JP2012201042A - Moisture permeable waterproof fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a moisture permeable waterproof fabric which has excellent water pressure resistance, moisture permeable waterproof and durability (washing durability) and has an excellent appearance even in hard rain.SOLUTION: The moisture permeable waterproof fabric has a polyurethane based resin film formed on one surface of fiber fabric and satisfies the following (I) to (V). (I) The polyurethane based resin film includes a dry microporous film and a dry non-porous film, the dry microporous film is provided on a surface to be in contact with the fiber fabric, and the dry non-porous film is provided on a surface on the opposite side of the fiber fabric in the dry microporous film. (II) The main component of the dry non-porous film is ether based polyurethane. (III) The dry microporous film contains a fluorine water repellent. (IV) The dry non-porous film has a swelling ratio of 5-15%, and the swelling ratio of the dry microporous film is lower than that of the dry non-porous film. (V) The moisture permeable waterproof fabric has a water pressure resistance of 60-500 kPa, a moisture permeability of 4,000-10,000 g/m24hrs measured according to JIS L-1099 A-1 method, and a moisture permeability of 8,000-15,000 g/m24hrs measured according to JIS L-1099 B-1 method.

Description

  The present invention relates to a moisture-permeable and waterproof fabric that is suitably used for sports, outdoor use and the like.

  A moisture-permeable and waterproof fabric having both moisture permeability and waterproof properties is suitably used in sports clothing, cold clothing, and the like. Moisture permeability is a property that releases water vapor from sweating from the body to the outside of the clothes, and waterproofness is a property that prevents moisture such as rain from entering the clothes.

  As a structure of such a moisture permeable waterproof fabric, a structure in which a microporous film or a nonporous film made of a resin such as polyurethane, polyester, polyamide, or polytetrafluoroethylene is formed on one side of a fiber cloth is widely known. ing.

  In order to obtain a microporous membrane, a wet method is generally used. However, when the microporous membrane is obtained using a hydrophilic resin by a wet method, there are problems such as slow solidification of the hydrophilic resin. Therefore, a technique of forming a microporous wet film by using a hydrophobic resin, such as an ester polyurethane resin, to form a solidified film is employed. When the moisture permeability of the hydrophobic microporous membrane thus obtained is measured by the JIS L-1099 A-1 method (calcium chloride method), it is recognized that the moisture permeability is excellent. However, when microporous wet membranes are obtained by a wet method, the site conditions of processing sites are generally limited due to high equipment and recovery costs and the need for large amounts of water and groundwater. There was a problem of being.

  On the other hand, in order to obtain a nonporous membrane, a dry method is generally used. However, when a nonporous membrane is obtained by a dry method using a hydrophobic resin, there is a problem that moisture permeability and the like are insufficient. Therefore, a technique of forming a nonporous film by forming a dry film using a hydrophilic resin such as an ether-based polyurethane resin has been adopted. When the moisture permeability of the hydrophilic nonporous membrane obtained by the dry method is measured by the JIS L-1099 B-1 method (potassium acetate method), it is recognized that the moisture permeability is excellent. In addition, the wet method has an advantage that it is superior in cost and the like. However, since the hydrophilic non-porous membrane obtained by the dry method is easily swelled, there is a problem that the appearance of the moisture-permeable and waterproof fabric obtained by simply using the membrane is easily impaired.

  For example, Patent Document 1 proposes a moisture-permeable and waterproof fabric including a resin film layer mainly composed of a water-swellable polymer material for the purpose of obtaining higher moisture-permeable and waterproof properties. Specifically, in Example 1 of Patent Document 1, a microporous membrane is formed on one side of a polyester fabric, and a nonporous membrane mainly composed of a polyurethane resin having a water swelling degree of 17% is used. A moisture-permeable and waterproof fabric is obtained by thermocompression bonding on the porous membrane. The moisture-permeable and waterproof fabric obtained in Patent Document 1 is used for applications such as clothes and tents.

  Patent Document 2 has a configuration in which a resin film having a swelling rate of 15 to 25% is formed on a fiber fabric, and another resin film having a swelling rate of 0 to 12% is arranged on the resin film. A method for producing a moisture-permeable and waterproof laminate fabric has been proposed.

JP 2001-239623 A JP 2003-20574 A

  However, in the case of the invention described in Patent Document 1, since the layer exposed to the outside air is a film that swells greatly, when sweating or when the number of times of washing increases, in addition to the durability of the film, moisture permeability and waterproofness There was a problem that the appearance and quality of the fabric deteriorated. In general, in the field of moisture-permeable and waterproof fabrics, nylon fabrics are frequently used as the fiber fabrics as the base material. The decline in quality tends to be remarkable.

  In the case of Patent Document 2, a moisture-permeable and waterproof laminate fabric whose appearance is unlikely to change is obtained because a resin film having a high swelling ratio is covered with a resin film having a low swelling ratio. Such a moisture-permeable and waterproof laminate fabric has a high water pressure resistance and is therefore excellent in washing durability. However, since only a non-porous film is used as the resin film, there is a problem that the permeability is not sufficient, and in particular, the moisture permeability measured by the A-1 method is not sufficient.

  In order to solve such problems, the present invention has excellent water pressure resistance, moisture permeable waterproofness and durability (washing durability), and has a moisture permeable waterproof fabric excellent in appearance even during heavy rain. The purpose is to provide.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the gist of the present invention is as follows.
(1) A moisture-permeable waterproof fabric having non-swelling properties, wherein a polyurethane-based resin film is formed on one side of a fiber fabric and satisfies the following (I) to (V):
(I) The polyurethane-based resin membrane includes a dry microporous membrane and a dry nonporous membrane, and the dry microporous membrane is provided on a surface in contact with the fiber fabric, and the dry nonporous membrane is a dry microporous membrane. It is provided on the surface of the wet film opposite to the fiber fabric.
(II) The dry nonporous membrane is mainly composed of ether polyurethane.
(III) The dry microporous membrane contains a fluorine-based water repellent.
(IV) The dry nonporous membrane has a swelling rate of 5 to 15%, and the dry microporous membrane has a lower swelling rate than the dry nonporous membrane.
(V) Water pressure resistance of 60 to 500 kPa, moisture permeability of 4000 to 10000 g / m ² · 24 hrs measured according to JIS L-1099 A-1 method, and 8000 to 15000 g measured according to JIS L-1099 B-1 method It has a water vapor transmission rate of / m ² · 24 hrs.
(2) The moisture-permeable and waterproof fabric according to (1), wherein the dry microporous membrane and / or the dry nonporous membrane has a two-layer structure.
(3) The moisture-permeable and waterproof fabric according to (1) or (2), wherein the water pressure retention after 100 washings is 60% or more.

  The moisture-permeable and waterproof fabric of the present invention has excellent moisture-permeable and waterproof properties, water pressure resistance and durability by laminating a dry microporous membrane and a dry nonporous membrane. Moreover, since the texture is soft and the fabric as a whole is non-swellable, it has a remarkable effect that it is possible to suppress deterioration of the appearance.

Hereinafter, the present invention will be described in detail.
The moisture-permeable and waterproof fabric of the present invention has a polyurethane resin film formed on one side of a fiber fabric. The polyurethane resin film includes a microporous film (hereinafter referred to as dry microporous film) formed by a dry coating method and a nonporous film (hereinafter referred to as dry nonporous film) formed by a dry coating method. Is included. The dry microporous membrane is provided on the fiber fabric, and the dry nonporous membrane is provided on the opposite surface of the fiber fabric in the dry microporous wet membrane.

  Examples of the fiber fabric used in the present invention include woven fabrics, knitted fabrics, and nonwoven fabrics made of fibers. Examples of the fibers include polyamide synthetic fibers such as nylon 6 and nylon 66; polyester synthetic fibers such as polyethylene terephthalate; polyacrylonitrile synthetic fibers; synthetic fibers such as polyvinyl alcohol synthetic fibers; and semisynthetics such as triacetate. Examples of fibers include mixed fibers such as nylon 6 / cotton and polyethylene terephthalate / cotton. Among these, polyamide-based synthetic fibers are preferable from the viewpoint of the texture and fastness of the moisture-permeable and waterproof fabric, and polyester-based synthetic fibers are preferable from the viewpoint of the waterproof property of the moisture-permeable and waterproof fabric. In addition, when compared with the fiber cloth of the same standard, the waterproofness of the moisture-permeable waterproof cloth can be increased by about 10 to 20% when the polyester-based synthetic fiber is used compared to the case where the polyamide-based synthetic fiber is used.

  In the present invention, before the polyurethane resin film is formed on one side of the fiber cloth, the surface of the fiber cloth is subjected to water repellent treatment in order to prevent the resin forming the dry microporous film from penetrating into the fiber cloth. Is preferably applied.

  The water-repellent treatment can be performed by a known method after the fiber fabric is subjected to treatment such as scouring and dyeing. The method is not particularly limited, and examples thereof include a padding method, a coating method, a gravure coating method, and a spray method.

  Examples of the water repellent used in the water repellent processing include ordinary ones, and examples include paraffinic water repellents, polysiloxane water repellents, and fluorine water repellents. Among these, a fluorine-based water repellent is preferable from the viewpoint of water repellency durability. In particular, from the viewpoint of the environment, a perfluorooctanoic acid-free fluorine-based water repellent mainly comprising a perfluoroalkyl group having 1 to 6 carbon atoms is particularly preferred.

  In addition, the perfluorooctanoic acid-free fluorine-based water repellent in the present invention means the following water repellent. That is, it means a water repellent that does not contain perfluorooctanoic acid and its related substances or precursor substances thereof. Alternatively, it means a water repellent which cannot qualify perfluorooctanoic acid and its related substances or precursor substances when measured by a high performance liquid chromatograph mass spectrometer.

  As the fluorine-based water repellent containing no perfluorooctanoic acid, a commercially available product can be suitably used. For example, trade names “Asahi Guard AG-E061”, “Asahi Guard AG-E082”, “Asahi” manufactured by Asahi Glass Co., Ltd. Guard AG-E500D "; Daikin Industries, Ltd., trade names" Unidyne TG-5521 "," Unidyne TG-5541 "," Unidyne TG-5601 "; Clariant Japan, trade names" NUVA N2114 LIQ "," NUVA N2116 LIQ " Etc.

  Further, for the purpose of improving water repellency, a triazine compound, an isocyanate compound or the like may be used in combination with a water repellent. Among these, an isocyanate compound is preferable from the environmental viewpoint. In particular, from the viewpoint of processing stability when a water repellent is used as an aqueous solution, a thermally dissociated blocked isocyanate compound in which an isocyanate group is blocked with acetoxime, phenol, caprolactam or the like may be used in combination.

  When the water repellent finish is applied to the surface of the fiber fabric, the amount of the water repellent applied is preferably 0.1 to 3% by mass, more preferably 0.3 to 2% by mass in terms of solid content with respect to the entire fiber fabric. . If the application amount is less than 0.1% by mass, sufficient water repellency may not be provided. On the other hand, if it exceeds 3% by mass, the moisture-permeable waterproof fabric finally obtained becomes hard and the texture is lowered, the adhesion between the fiber fabric and the dry microporous membrane is lowered, or finally obtained. This is not preferable because the moisture-permeable performance of the moisture-permeable and waterproof fabric is reduced.

  Further, when the fiber fabric is crushed together with the above, the penetration of the polyurethane resin into the fiber fabric can be further suppressed. The crushing process can be performed using a general method. For example, using a known calender machine, run the fabric between a mirror roll having a temperature control function and a cotton roll or plastic roll so that the mirror roll side is the side on which the polyurethane resin film is formed. What is necessary is just to crush from the mirror surface roll side.

  In the present invention, as described above, the dry microporous membrane is formed on one side of the fiber fabric, and then the dry nonporous membrane is formed on the dry microporous membrane. By having such a configuration, the water pressure resistance and water permeability are excellent. In addition, by forming a microporous film and a nonporous film by a dry method, cost can be reduced and, in addition, moisture permeability can be improved.

The dry microporous membrane is described below.
The dry microporous membrane has a polyurethane resin as a main component. When a resin other than the polyurethane resin is used as a main component, a microporous film is not formed. A conventionally well-known thing can be used as a polyurethane resin, For example, the polyurethane resin obtained by making a polyisocyanate component and a polyol component react is mentioned. In the present invention, the main component means that the content is 70% by mass or more based on the entire film.

  Examples of the polyisocyanate component include aromatic diisocyanate, aliphatic diisocyanate, and alicyclic diisocyanate. Specific examples include tolylene-2,4-diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, or 1,4-cyclohexane diisocyanate. A tri- or higher functional polyisocyanate may be used. These may be used alone or in combination of two or more.

  On the other hand, examples of the polyol component include polyether polyol and polyester polyol. Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, and polytetraethylene glycol. As the polyester polyol, a reaction product of a diol such as ethylene glycol or propylene glycol and a dibasic acid such as adipic acid or sebacic acid, a ring-opening polymer such as caprolactone, an oxyacid monomer or a prepolymer thereof is used. be able to.

  The method for forming the dry microporous membrane is not particularly limited, and examples thereof include the following methods. That is, a resin solution for forming a dry microporous membrane is prepared, and the resin solution is applied to the fiber fabric using a known means such as a comma coater or a roll-on knife coater. Then, the method of evaporating an organic solvent and water and forming a microporous film | membrane is mentioned.

  As a resin solution for forming a microporous membrane, for example, a small amount of emulsifier or hydrophilic polyurethane resin is used, and W / O type in which polyurethane fine particles are emulsified and dispersed in an organic solvent such as methyl ethyl ketone or toluene. An (oil-in-oil type) emulsion can be used. The particle diameter of the polyurethane fine particles in the emulsion is preferably about 0.05 to 5 μm.

  In addition, after applying a resin solution for forming a microporous film, water is evaporated to form a film once, and then a specific component (eluting component) is eluted from the resin film to form a microporous film. A method is also mentioned. In the resin solution used in such a method, an O / W type (oil-in-water type) emulsion in which polyurethane fine particles are dispersed in water with an emulsifier or the like, or an O / W dispersed by self-emulsification without using an emulsifier. What added the elution component to either type | mold emulsion is suitable. As the elution component, a mixture of glue, starch, water-soluble polyurethane resin or the like that can be eluted with water, hot water or hot water is used. After film formation, these components can be eluted by soaping with water at a temperature of 20 to 100 ° C. for about 5 to 20 minutes.

  Further, a method of forming a dry microporous film by mixing a gas foaming agent or the like in a solution in which a polyurethane resin is dissolved in water and / or an organic solvent and foaming at the time of dry film formation can be employed. In addition, a method of forming a dry microporous film by adding a surfactant, a foaming agent, or the like to the polyurethane resin solution to stably generate bubbles can be employed.

  The dry microporous membrane can contribute to improving the texture of the moisture-permeable and waterproof fabric, but tends to be inferior in membrane strength. Therefore, it is preferable to contain 1 to 12% by mass of an isocyanate-based crosslinking agent in the solid content of the resin solution forming the microporous membrane from the viewpoint of improvement in membrane strength and adhesiveness to the fiber fabric. It is more preferable to make it contain by mass%. If the content of the isocyanate-based crosslinking agent is less than 1% by mass, the strength of the microporous film and the improvement of the adhesive strength with the fabric body may not be expected. On the other hand, if it exceeds 12% by mass, the texture of the microporous membrane may become hard.

  Examples of the isocyanate-based crosslinking agent include tolylene 2,4-diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate. Triisocyanates obtained by addition reaction of these diisocyanates with a compound containing active hydrogen are also used. Examples of the compound containing active hydrogen include trimethylolpropane and glycerin.

  In particular, in the present invention, blocked isocyanate can be preferably used as the isocyanate-based crosslinking agent from the viewpoint of the stability of the resin solution for forming the microporous film and the pot life. As the blocked isocyanate, a type that is usually dissociated by heat treatment is preferable, and specifically, those obtained by forming an additional block with phenol, lactam, methyl ketoxime, or the like are preferable.

  The thickness of the dry microporous membrane is preferably 10 to 100 μm, and more preferably 15 to 60 μm. If it is less than 10 μm, the fiber fabric may not be completely covered, and thus the water pressure resistance may be insufficient. On the other hand, when it exceeds 100 μm, not only the improvement effect of the water pressure resistance is saturated, but it is difficult to obtain good moisture permeability even if measured by either the A-1 method or the B-1 method, and the cost and texture are reduced. May be inferior. In addition, when the dry microporous membrane has a two-layer structure as described later, the total thickness is taken as the thickness of the dry microporous membrane.

  In the present invention, the dry microporous film needs to contain a fluorine-based water repellent. By including such a water repellent, the resulting dry microporous membrane can be made more hydrophobic, and the durability of the membrane can be improved along with the waterproofness of the membrane. Further, by making the membrane more hydrophobic, there is an advantage that durability can be improved while suppressing changes in the appearance of the fabric.

  Examples of the method for containing the water repellent in the dry microporous membrane include a method in which the water repellent is contained in the resin solution for forming the dry microporous membrane. For example, if this resin solution is a W / O type (water-in-oil type) emulsion, a water repellent agent may be dispersed in water in advance, and later mixed in oil little by little to form an emulsion. When the resin solution is a water-soluble type such as an O / W type (oil-in-water type), a water repellent may be directly added to the resin solution.

  The addition amount of the water repellent is preferably 0.5 to 15% by mass, more preferably 1 to 12% by mass in terms of solid content with respect to the dry microporous membrane. If it is less than 0.5% by mass, the resulting dry microporous membrane may be poor in durability, and if it exceeds 15% by mass, the durability improving effect may be saturated and the stability of the resin solution may also be reduced.

  The swelling rate of the dry microporous membrane needs to be lower than the swelling rate of the dry nonporous membrane described later. When the swelling rate is higher than the swelling rate of the nonporous membrane, the moisture-permeable and waterproof fabric easily swells, which is not preferable from the viewpoint of maintaining a good appearance of the fabric.

  The microporous membrane may contain various additives such as a pigment, a filler, an antibacterial agent, a deodorant, and a flame retardant, as necessary, within a range not impairing the effects of the present invention.

  Next, the dry nonporous membrane will be described. The dry nonporous membrane is composed of an ether-based polyurethane resin. The ether-based polyurethane resin in the present invention exhibits appropriate water absorption and water retention when formed into a film. For this reason, the obtained nonporous membrane exhibits moderate moisture permeability and has suppressed swelling property.

  In the present invention, the dry microporous membrane is formed, and then a dry nonporous membrane is laminated thereon. This lamination is preferably performed quickly. Promptly, there is an advantage that the adhesion between the dry microporous membrane and the dry nonporous membrane is improved, and the water pressure resistance and durability of the moisture permeable waterproof fabric finally obtained are easily improved. For example, when the dry non-porous membrane is not laminated immediately after the formation of the dry microporous membrane, for example, after 2 to 3 days have elapsed, the cross-linking of the microporous membrane proceeds. And the adhesiveness of both may fall.

  The method for forming the dry nonporous film is not particularly limited. For example, a solvent-type polyurethane resin solution in which an organic solvent is a main solvent and a polyurethane resin is dissolved in the main solvent is used with a comma coater, a floating knife coater, or the like. The method of forming by evaporating an organic solvent after apply | coating is mentioned. In addition, an O / W emulsion in which polyurethane fine particles are dispersed in water with an emulsifier or the like, or an O / W emulsion in which a resin is self-emulsified without using an emulsifier is applied in the same manner as described above, and then water or A method of forming a nonporous film by evaporating the organic solvent can also be employed.

  In the present invention, by using an ether-based polyurethane resin, it is possible to impart appropriate moisture permeability to the dry non-porous membrane. However, in order to further improve moisture permeability, polyethylene glycol, polyoxypropylene / polyoxyethylene An ether-based polyurethane resin containing a copolymer or the like may be used. However, if the polyurethane resin is excessively contained, the non-porous membrane may have a tacky feeling, or the membrane may be greatly swollen, resulting in the appearance of the moisture-permeable and waterproof fabric being impaired. For this reason, when the resin is contained in the nonporous membrane, it is preferable to adjust the content so that a good texture and appearance can be maintained.

  The thickness of the dry nonporous membrane is preferably 2 to 15 μm, more preferably 3 to 13 μm. If it is less than 2 μm, the water pressure resistance may be inferior. On the other hand, when it exceeds 15 μm, an excellent water pressure resistance can be obtained, but it is not preferable because moisture permeability measured by the A-1 method tends to decrease. When the dry nonporous membrane has a two-layer structure as described later, the total thickness is taken as the thickness of the dry nonporous membrane.

In the dry nonporous membrane, the swelling rate is suppressed within a predetermined range by the composition of the resin. Specifically, it becomes 5 to 15%. Here, in the case of a film having a swelling rate of less than 5%, that is, a film that is difficult to absorb and retain water excessively, moisture permeability tends to be lowered, and specifically, measured by the B-1 method as a moisture-permeable and waterproof fabric. Moisture permeability may be less than 8000 g / m ² · 24 hrs. On the other hand, in the case of a film having a swelling rate exceeding 15%, that is, a film that swells greatly, problems such as deterioration of the appearance of water due to water permeation into the clothes during raining or the like occur.

  In order to obtain a high water pressure resistance, when the dry nonporous film is formed thick, for example, 10 to 15 μm, the swelling rate of the nonporous film is 3 to 12% from the viewpoint of maintaining the appearance of the moisture-permeable and waterproof fabric. It is preferable to keep it at a minimum. In addition, the swelling rate in this invention means the swelling rate of the length direction when a 10 micrometers-thick film (2 cm width x 15 cm length) is immersed in the water of temperature 25 degreeC, and the calculation method is explained in full detail in an Example. .

  The dry non-porous membrane may contain various additives such as pigments, fillers, antibacterial agents, deodorants, and flame retardants as necessary within the range not impairing the effects of the present invention.

  In the present invention, the dry microporous membrane and / or the dry nonporous membrane may have a two-layer structure. For example, when a fiber fabric having a low density and easily penetrated by a resin is applied, if a thin film having a thickness of 5 μm or less is formed as the first dry microporous film, this film becomes the target and the second layer The penetration of the resin can be suppressed during the formation. Further, if a concave portion is formed on the surface of the first layer and then smoothened by forming the second layer, not only the peel resistance between the fiber fabric and the dry microporous membrane but also moisture permeability The water pressure resistance of the waterproof fabric can also be improved.

  On the other hand, when the dry nonporous film has a two-layer structure, it is effective, for example, when a thick film of about 8 to 15 μm is laminated. In order to secure a desired film thickness by a single application, a comma coater that can provide a clearance is usually used. However, if a clearance is provided, defects such as coating streaks and application spots tend to occur. In this regard, if the coating is performed twice, a direct type knife coater that does not require a clearance can be used, and as a result, a uniform film can be easily formed. If the nonporous membrane is uniform, there is an advantage that the adhesion to the dry microporous membrane is improved and the tightness of the dry nonporous membrane is also improved. Furthermore, there is an advantage that a high water pressure can be easily obtained because defects such as pinholes are hardly generated.

The moisture-permeable and waterproof fabric of the present invention is difficult to swell as a whole fabric.
Specifically, after water is sprayed on a part of the back surface of the fabric (the surface where the polyurethane resin film is not formed in the moisture permeable waterproof fabric), the water is visually observed from the surface, and the water is not sprayed. In comparison, it is judged that the smaller the change in appearance is, the more difficult it is to swell.

  More specifically, when evaluated by the following method, if it is grade 3 or higher, it is assumed that there are few problems in appearance even when worn as a moisture permeable waterproof fabric during rainfall or sweating.

<Evaluation method>
According to JIS L-1092 spray method, the following five-step evaluation is performed. However, the amount of water to be sprayed is 100 ml.
Grade 5: Swelling of the spray part is small and not noticeable from the surface.
Fourth grade: The spray part is slightly swollen but hardly noticeable from the surface.
Third grade: The spray part is swollen and slightly noticeable from the surface.
Second grade: The spray part and its surroundings are clearly swollen and quite noticeable from the surface.
First grade: The sprayed part and its surroundings are significantly swollen and noticeable from the surface.

  In the moisture permeable waterproof fabric of the present invention, the dry microporous membrane and the dry nonporous membrane are sequentially laminated on the fiber fabric, so that both waterproofness and moisture permeability are excellent.

  Water resistance is evaluated by water pressure resistance. Specifically, the water pressure resistance is required to be 60 to 500 kPa, and more preferably 100 to 500 kPa. In addition, the measuring method of water pressure resistance is measured according to JIS L1092 (high water pressure method).

On the other hand, as moisture permeability, in the case of moisture permeability measured according to JIS L-1099 A-1, it is necessary to be 4000 to 10000 g / m ² · 24 hrs, and is 6000 to 10000 g / m ² · 24 hr. It is more preferable. On the other hand, in the case of moisture permeability measured according to the B-1 method, it is necessary to be 8000 to 15000 g / m ² · 24 hrs. In any measurement method, if the moisture permeability range is below the above range, the surface of the resin film is likely to condense, and the comfort of clothing as a garment is reduced. Sex cannot be obtained.

  Moreover, the moisture permeable waterproof fabric of the present invention preferably has a water pressure retention after 100 washings of 60% or more, and more preferably 80% or more. Although a desired water pressure resistance retention rate can be obtained, depending on the type of resin, etc., it is generally possible to include a fluorine-based water repellent in the dry microporous film. Moreover, it is advantageous for the improvement of the water pressure resistance retention rate that the thickness of the dry nonporous film is 5 μm or more. In addition, the measuring method of a water-resistant pressure retention rate is explained in full detail in an Example.

  The moisture-permeable and waterproof fabric according to the present invention can be used not only for various clothing materials but also for filter applications. In addition, because it is excellent in water pressure resistance, moisture permeability and waterproofness, durability and appearance, in addition to sports clothing and cold clothing, as well as materials for mountaineering equipment such as tents, various products that require moisture permeability and waterproofness are also available. It can also be used as a material.

EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.
In addition, the physical property evaluation of the fabric obtained by the Example and the comparative example was performed with the following method.

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

(2) Water pressure resistance retention The water pressure resistance (B) of the fabric after washing 100 times according to JIS L-0217 (Method 103) was measured, and the water pressure resistance before washing (A) according to the following formula: The retention rate of the water pressure resistance (B) after washing with respect to was calculated, and this value was taken as the water pressure resistance retention rate of the fabric.
Water pressure retention rate (%) = (B / A) × 100

(3) Water vapor permeability Measured according to JIS L-1099 A-1 method (calcium chloride method) and B-1 method (potassium acetate method).

(4) Peel resistance The peel strength of the longitudinal resin film was measured according to JIS L-1089 method.

(5) Swelling rate of dry non-porous membrane Films were prepared on the release surface of release paper (manufactured by Lintec Corporation, 130TPD (trade name)) so that each formulation solution had a thickness of 10 μm. After standing for a whole day and night, the degree of swelling in the vertical direction when a film in which the length × width size was cut to 2 cm × 15 cm was immersed in water at a temperature of 25 ° C. was defined as the swelling ratio (%).
Swelling rate (%) = (length after swelling−15) / 15 × 100

(6) Appearance change of moisture-permeable and waterproof fabric The evaluation was made based on the method described above. That is, according to the JIS L-1092 spray method, the appearance change of the moisture-permeable and waterproof fabric was evaluated in the above five steps.

(7) Texture It evaluated by the following four steps by handling.
A: Very soft.
○: Soft.
Δ: Slightly hard
X: Hard.

Example 1
A plain structure woven fabric having a warp density of 115 / 2.54 cm and a weft density of 95 / 2.54 cm was woven using nylon 6 multifilament 78 dtex / 68f for both the warp and the weft. The obtained woven fabric was scoured and then dyed with 1.0% omf of an acidic dye (“Kayanol Blue N2G” manufactured by Nippon Kayaku Co., Ltd.). Thereafter, a 6% by mass aqueous dispersion of a fluorine-based water repellent emulsion shown in Formula 1 below was applied to the woven fabric by a padding method (wet pickup rate 40%), and after drying, heat treated at 170 ° C. for 40 seconds. Subsequently, using a calendar processing machine having a mirror surface roll, the fabric was crushed and processed under conditions of a temperature of 170 ° C., a pressure of 300 kPa, and a speed of 30 m / min.

(Prescription 1)
Asahi Guard AG-E500D 60 parts by mass (Asahi Glass Co., Ltd., fluorine-based water repellent emulsion)
Meikanate WEB 10 parts by mass (manufactured by Meisei Chemical Co., Ltd., block type isocyanate)
Isopropyl alcohol 10 parts by weight Water 920 parts by weight

  Next, in preparing a W / O type polyurethane emulsion (solid content concentration 14% by mass) having the composition shown in Formula 2 below, first, Heimlen ATX-10 (trade name), Resamine X (trade name) and methyl ethyl ketone / A mixed resin solution was prepared by mixing with a toluene mixed solvent. Subsequently, while rotating and stirring this at 500 rpm using a disper-type stirrer, the water / methyl ethyl ketone mixed solvent was poured into the mixed resin solution twice with an interval of about 3 minutes, and further water / fluorine repellent properties were added. The W / O-type polyurethane emulsion (containing 2% by mass of a fluorine-based water repellent) was obtained by adding the liquid emulsion mixture twice with an interval of about 3 minutes. The viscosity of this emulsion was 8000 mPa · s / 25 ° C.

Next, the W / O type polyurethane emulsion obtained on the crushed surface of the woven fabric is applied with a comma coater at an application amount of 180 g / m ² , and then dried at 80 ° C. for 3 minutes to form a microporous membrane. Formed. The thickness of the microporous film was about 45 μm.

(Prescription 2)
Heimlen ATX-10 (trade name) 100 parts by mass
(Daiichi Seika Kogyo Co., Ltd., W / O type polyurethane resin with a solid content of 26% by mass)
Rezamin X (trade name) 2 parts by mass (manufactured by Dainichi Seika Kogyo Co., Ltd., isocyanate crosslinking agent)
Methyl ethyl ketone / toluene 20 parts by weight / 25 parts by weight Water / Methyl ethyl ketone 25 parts by weight / 5 parts by weight Water / Asahi Guard AG-E081 (trade name) 20 parts by weight / 2 parts by weight (Asahi Guard AG-E082 (trade name): Asahi Glass Fluorine-based water repellent emulsion with a solid content of 30% by mass)

  Subsequently, each composition was rotated and stirred at 300 rpm using a Disper type stirrer to prepare a solvent-type polyurethane resin solution having the composition shown in Formula 3 below. This resin solution had a solid content concentration of 22% by mass and a viscosity of 4000 mPa · s / 25 ° C.

Thereafter, this resin solution is applied onto the microporous film with a floating knife coater at an application amount of 20 g / m ^{2 and then} dried at 100 ° C. for 2 minutes to form a nonporous film having a thickness of 4 to 5 μm. Furthermore, it set-processed for 1 minute at 170 degreeC, and the moisture-permeable waterproof fabric of this invention was obtained. At this time, the swelling ratio of the nonporous membrane was 5%.

(Prescription 3)
Heimlen Y237NS (trade name) 100 parts by mass
(Daiichi Seika Kogyo Co., Ltd., solvent-type polyurethane resin solution with a solid content of 25%)
Methyl ethyl ketone 15 parts by mass

(Example 2)
According to the same method as in Example 1, except that a solvent-type polyurethane resin solution having a composition shown in Formula 4 below (solid content concentration 22 mass%, viscosity 3500 mPa · s / 25 ° C.) is used instead of Formulation 3. A moisture permeable waterproof fabric was obtained. At this time, the swelling ratio of the nonporous film was 10%.

(Prescription 4)
Heimlen Y237NS (trade name) 50 parts by mass
(Daiichi Seika Kogyo Co., Ltd., solvent-type polyurethane resin solution with a solid content of 25% by mass)
Heimlen Y261-1NS (trade name) 50 parts by mass
(Daiichi Seika Kogyo Co., Ltd., solvent-type polyurethane resin solution with a solid content of 30% by mass)
Methyl ethyl ketone 25 parts by mass

(Example 3)
The same method as in Example 1 was used except that a solvent-type polyurethane resin solution having a composition shown in Formula 5 below (solid content concentration 22 mass%, viscosity 3000 mPa · s / 25 ° C.) was used instead of Formulation 3. A moisture permeable waterproof fabric was obtained. At this time, the swelling ratio of the nonporous membrane was 14%.

(Prescription 5)
Heimlen Y261-1NS (trade name) 100 parts by mass
(Daiichi Seika Kogyo Co., Ltd., solvent-type polyurethane resin solution with a solid content of 30% by mass)
Methyl ethyl ketone 35 parts by mass

Example 4
Using a polyester multifilament 156 dtex / 68f as the warp and a polyester high multifilament 156 dtex / 136f as the weft, a plain fabric with a warp density of 86 yarns / 2.54 cm and a weft density of 70 yarns / 2.54 cm was woven. The obtained woven fabric was scoured and then dyed with 0.5% omf of a disperse dye (“Dianix Blue UN-SE” manufactured by Dystar Japan). Thereafter, the fabric was water-repellent and crushed in the same manner as in Example 1.

  Next, in preparing a W / O type polyurethane emulsion (solid content concentration 16% by mass) having the composition shown in Formula 6 below, first, XOLTEX PX-550 (trade name) and a methyl ethyl ketone / toluene mixed solvent are mixed. The combined resin solution was obtained. Subsequently, while rotating and stirring this at 1000 rpm using a disper-type stirrer, the water / methyl ethyl ketone mixed solvent was poured into the mixed resin solution twice with an interval of about 3 minutes, and further water / fluorine repellent properties were added. The W / O type polyurethane emulsion (containing 2.1% by mass of a fluorine-based water repellent) was obtained by adding the liquid emulsion mixture twice with an interval of about 3 minutes. The viscosity of this emulsion was 6500 mPa · s / 25 ° C.

Next, the W / O type polyurethane emulsion obtained on the crushed surface of the fabric is applied with a comma coater at an application amount of 160 g / m ² , and then dried at 80 ° C. for 3 minutes to form a microporous membrane. Formed. The thickness of the microporous film was about 45 μm.

(Prescription 6)
XOLTEX PX-550 (trade name) 100 parts by mass
(Made by DIC, polyurethane resin solution for W / O type having a solid content of 31% by mass)
Rezamin X (trade name) 2 parts by mass (manufactured by Dainichi Seika Kogyo Co., Ltd., isocyanate crosslinking agent)
Methyl ethyl ketone / toluene 20 parts by weight / 25 parts by weight Water / Methyl ethyl ketone 25 parts by weight / 5 parts by weight Water / Asahi Guard AG-E082 (trade name) 25 parts by weight / 3 parts by weight (Asahi Guard AG-E082 (trade name): Asahi Glass Fluorine-based water repellent emulsion with a solid content of 20% by mass)
Thereafter, the same procedure as in Example 2 was performed to obtain a moisture-permeable and waterproof fabric of the present invention.

(Example 5)
A moisture-permeable waterproof fabric of the present invention was obtained by the same method as in Example 4 except that the microporous membrane had a two-layer structure. Here, the microporous film is formed by the following method. That is, a W / O type polyurethane emulsion is applied onto a woven fabric with a floating knife coater at an application amount of 10 g / m ² , and then dried at 80 ° C. for 1 minute to form a thin film (first layer) ) Was formed. On the thin film, the emulsion was applied at a coating amount of 150 g / m ² with a comma coater, and then dried at 80 ° C. for 3 minutes to form a thick film (second layer).

  Since the surface of the first layer was smooth, the second layer could be formed with high accuracy. The thickness of the microporous membrane (sum of the two layers) was about 45 μm.

(Example 6)
A solvent-type polyurethane resin solution (solid content: 24 mass%, viscosity: 4800 mPa · s / 25 ° C.) having the composition shown in the following formula 7 is used in place of the formula 4, and the coating amount is changed to 35 g / m ² to obtain a thickness of 8 A moisture-permeable and waterproof fabric of the present invention was obtained by the same method as in Example 5 except that a non-porous membrane of ˜9 μm was formed. At this time, the swelling ratio of the nonporous film was 10%.

(Prescription 7)
Heimlen Y237NS (trade name) 50 parts by mass
(Daiichi Seika Kogyo Co., Ltd., solvent-type polyurethane resin solution with a solid content of 25% by mass)
Heimlen Y261-1NS (trade name) 50 parts by mass
(Daiichi Seika Kogyo Co., Ltd., solvent-type polyurethane resin solution with a solid content of 30% by mass)
16 parts by mass of methyl ethyl ketone

(Example 7)
A solvent type polyurethane resin solution (solid content: 25 mass%, viscosity: 6000 mPa · s / 25 ° C.) having the composition shown in the following formulation 8 is used instead of the formulation 4, and the coating amount is changed to 50 g / m ² , and the thickness is 13 μm. The moisture-permeable and waterproof fabric of the present invention was obtained in the same manner as in Example 4 except that the nonporous membrane was formed. At this time, the swelling ratio of the nonporous film was 10%.

(Prescription 8)
Heimlen Y237NS (trade name) 50 parts by mass
(Daiichi Seika Kogyo Co., Ltd., solvent-type polyurethane resin solution with a solid content of 25% by mass)
Heimlen Y261-1NS (trade name) 50 parts by mass
(Daiichi Seika Kogyo Co., Ltd., solvent-type polyurethane resin solution with a solid content of 30% by mass)
8 parts by mass of methyl ethyl ketone

(Example 8)
A 20 g / m ² solvent-type polyurethane resin solution having the composition shown in Formula 7 is applied on the non-porous film using a floating knife coater and then dried at 100 ° C. for 2 minutes to form a non-porous film having a thickness of 4 to 5 μm. Furthermore, set processing was performed at 170 ° C. for 30 seconds to obtain a moisture-permeable and waterproof fabric of the present invention. The thickness of the nonporous membrane (the total of the two layers) was about 13 μm.

(Comparative Example 1)
A moisture-permeable and waterproof fabric was obtained in the same manner as in Example 1 except that Asahi Guard AG-E081 (trade name) in Formulation 2 was omitted.

(Comparative Example 2)
A moisture-permeable and waterproof fabric was obtained by the same method as in Example 1 except that the nonporous membrane was formed directly on the fabric without forming the microporous membrane.

(Comparative Example 3)
A moisture-permeable waterproof fabric was obtained in the same manner as in Example 1 except that the nonporous film was not formed.

(Comparative Example 4)
A moisture-permeable and waterproof fabric was obtained in the same manner as in Example 4 except that Asahi Guard AG-E082 (trade name) in Formulation 6 was omitted.

(Comparative Example 5)
A moisture-permeable and waterproof fabric was obtained in the same manner as in Example 4 except that the nonporous membrane was formed directly on the fabric without forming the microporous membrane.

(Comparative Example 6)
A moisture-permeable waterproof fabric was obtained in the same manner as in Example 4 except that the nonporous film was not formed.

(Comparative Example 7)
Instead of formulation 4, a solvent-type polyurethane resin solution (solid content: 26% by mass, viscosity: 8000 mP · s / 25 ° C.) shown in the following formulation 9 is used, and the thickness is changed to about 20 μm to form a nonporous film. Except for this, a moisture-permeable and waterproof fabric was obtained by the same method as in Comparative Example 5.

(Prescription 9)
Heimlen Y237NS (trade name) 50 parts by mass
(Daiichi Seika Kogyo Co., Ltd., solvent-type polyurethane resin solution with a solid content of 25%)
Heimlen Y261-1NS (trade name) 50 parts by mass
(Daiichi Seika Kogyo Co., Ltd., solvent-type polyurethane resin solution with a solid content of 30%)
Methyl ethyl ketone 5 parts by mass

(Comparative Example 8)
Example 1 except that a solvent-type polyurethane resin solution (prepared at 300 rpm with a disper-type stirrer, solid content concentration 21 mass%, viscosity 4000 mPa · s / 25 ° C.) having the composition shown in the following formulation 10 in place of formulation 3 In the same manner as above, a moisture-permeable and waterproof fabric was obtained. At this time, the swelling ratio of the nonporous membrane was 0%.

(Prescription 10)
Heimlen NPU-5 (trade name) 100 parts by mass
(Daiichi Seika Kogyo Co., Ltd., solvent-type polyurethane resin solution with a solid content of 25%)
Toluene / isopropyl alcohol 10 parts by mass / 10 parts by mass

(Comparative Example 9)
A solvent-type polyurethane resin solution (prepared at 300 rpm with a disper-type stirrer, solid concentration 40 mass%, viscosity 4200 mPa · s / 25 ° C.) having the composition shown in the following formula 11 in place of formula 3 is used, and the coating amount is 10 g. A moisture-permeable and waterproof fabric was obtained by the same method as in Example 1 except that the nonporous membrane having a thickness of 4 to 5 μm was formed by changing to / m ² . At this time, the swelling ratio of the nonporous film was 20%.

(Prescription 11)
Heimlen Y265-2 (trade name) 100 parts by mass
(Daiichi Seika Kogyo Co., Ltd., solvent type polyurethane resin solution with a solid content of 50%)
Methyl ethyl ketone / N, N-dimethylformamide 20 parts by mass / 5 parts by mass

  The performance of each fabric obtained in the above examples and comparative examples is shown in Table 1 below.

  As is apparent from the results in Table 1, the moisture-permeable and waterproof fabric of the present invention has a high moisture-permeable and waterproof performance, washing durability, etc., which are not conventional, while the manufacturing method is a dry method, Was non-swelling and was confirmed to be excellent in practical use. On the other hand, although the fabrics of Comparative Examples 1 and 4 had substantially good performance, the water pressure retention rate was slightly inferior to that of the present invention. Furthermore, in Comparative Examples 2, 3, 5 and 6, since only one of the nonporous film and the microporous film was formed, the water pressure resistance was particularly inferior. Further, Comparative Example 7 has a problem in terms of moisture permeability and texture, Comparative Example 8 has a point of B-1 moisture permeability, and Comparative Example 9 has a difficulty in maintaining a change in appearance.

Claims (3)

A moisture-permeable and waterproof fabric having non-swellability, wherein a polyurethane-based resin film is formed on one side of the fiber fabric and satisfies the following (I) to (V):
(I) The polyurethane-based resin membrane includes a dry microporous membrane and a dry nonporous membrane, and the dry microporous membrane is provided on a surface in contact with the fiber fabric, and the dry nonporous membrane is a dry microporous membrane. It is provided on the surface of the wet film opposite to the fiber fabric.
(II) The dry nonporous membrane is mainly composed of ether polyurethane.
(III) The dry microporous membrane contains a fluorine-based water repellent.
(IV) The dry nonporous membrane has a swelling rate of 5 to 15%, and the dry microporous membrane has a lower swelling rate than the dry nonporous membrane.
(V) Water pressure resistance of 60 to 500 kPa, moisture permeability of 4000 to 10000 g / m ² · 24 hrs measured according to JIS L-1099 A-1 method, and 8000 to 15000 g measured according to JIS L-1099 B-1 method It has a water vapor transmission rate of / m ² · 24 hrs.   The moisture-permeable and waterproof fabric according to claim 1, wherein the dry microporous membrane and / or the dry nonporous membrane has a two-layer structure.   The moisture-permeable and waterproof fabric according to claim 1 or 2, wherein the water pressure retention after 100 washings is 60% or more.