KR960004914B1 - Moisture-permeable waterproof cloth and the production thereof - Google Patents

Abstract

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Description

[Name of invention]

Breathable waterproof fabric and manufacturing method thereof

Detailed description of the invention

[Technical Field]

The present invention relates to a moisture-permeable waterproof fabric and a method for manufacturing the same. In more detail, the present invention relates to a comfortable moisture-permeable waterproof fabric and a method for manufacturing the same that can control moisture permeability and warmth corresponding to the cold and heat bodily sensation.

[Background]

Conventionally, the manufacturing technology of the processing fabric with moisture-permeable waterproof is made mainstream to make moisture permeability high in order to be free from the moisture at the time of activity, maintaining waterproofness. However, the moisture-permeable waterproof fabric obtained by the prior art has a low heat retention and a cold because of its high moisture permeability even when the temperature of use is low, in other words, even when the body is not hot before the exercise or at the beginning of the exercise. In addition, when the use temperature is a high temperature, in other words, if the moisture-permeable waterproof fabric is hot, in other words, the body becomes hot during and after exercise, and even when the sweating amount is high, the moisture permeability is low, and the moisture is easy to get cold. Therefore, the processed fabric obtained by the conventional manufacturing technique does not have the function of true comfort, that is, the heat retention is high when the use temperature is low, and the moisture is hard to cool when the use temperature is high.

[Initiation of invention]

It is an object of the present invention to provide a moisture-permeable waterproof fabric having a genuine comfort and a method for producing the same, which is characterized by abundant heat retention when the use temperature is low and high moisture vapor permeability when the use temperature is high. It is done.

In order to achieve the above object, the present invention provides a polyurethane resin obtained by reacting an isocyanate, a polyol and a chain extender and having a glass transition point in the range of -20 ° C to 20 ° C and having an ethylene oxide unit of at least 7.0 mol / kg. Provided is a moisture-permeable waterproof fabric formed by providing a resin film containing on at least one side of a fabric.

The present invention is also a resin solution of a polar organic solvent obtained by reacting an isocyanate, polyol and chain extender and containing a polyurethane resin having a glass transition point in the range of -20 ° C to 20 ° C and having at least 7.0 mol / kg of ethylene oxide units. Is applied to at least one side of the fabric and wet-coagulated in a coagulation bath to form a film, or a resin solution of a volatile organic solvent containing the above resin is applied onto a release paper to form a resin film. It provides a method of manufacturing a moisture-permeable waterproof fabric comprising attaching to at least one side.

Best Mode for Carrying Out the Invention

The material of the fabric useful in the present invention may be chemical fibers such as polyester, polyamide, acrylic and rayon, natural fibers such as cotton or wool, or a mixture thereof, and these may be one of woven, knitted or nonwoven fabrics. .

The polyurethane resin obtained by reacting the isocyanate, polyol and chain extender used in the present invention has a glass transition point of -20 ° C. to 20 ° C. using a component having a rigid structure that suppresses molecular mobility to its constituents. By making it into a range, its moisture permeability is made to make temperature dependence high.

In the production of the polyurethane resin useful in the present invention, a known one used in conventional polyurethanes can be used as the isocyanate component. Preferred examples include 4,4'-diphenylmethane diisocyanate (MDI), hydrogenated MDI, isophorone diisocyanate, 1,3-xylene diisocyanate, 2,4-tolylene diisocyanate, m- Phenylene diisocyanate etc. can be mentioned, These can be used individually or as a mixture of 2 or more types. From the viewpoint of the rigidity of the molecular structure, MDI and hydrogenated MDI are more preferable.

Chain extenders may also be known. Examples of preferred chain extenders may include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, ethylenediamine, trimetalenediamine, isophoronediamine, water, and the like, which are alone or 2 It can be used as a mixture of species or more. Ethylene glycol, propylene glycol and water are particularly preferable in view of the rigidity of the molecular structure.

As the polyol component, a known one can be used, for example, polyethylene glycol which is an addition polymer of ethylene oxide alone and ethylene oxide adduct of tetrahydrofuran which is a copolymer of ethylene oxide and other compounds, ethylene oxide adduct of bisphenol A, Ethylene oxide-containing polymer diols such as condensates of adipic acid and ethylene oxide, ethylene oxide adducts of polybutylene glycol adipate diol or polypropylene glycol adipate diol, and polytetramethylene glycol, polypropylene ether glycol, poly And polymer diols that do not contain ethylene oxide, such as caprolactone glycol, polybutyrolactone glycol, polypropylene glycol adipate diol, and polybutylene glycol adipate diol. These may be used alone or as a mixture of two or more thereof.

It is preferable that the polyol has a molecular weight of 500 to 3,000. When the molecular weight is less than 500, the elastomer performance of the obtained polyurethane resin is not enough, which may result in poor durability at the time of use. In addition, when the molecular weight is 3,000 or more, the synthetic conditions are restricted, and when the obtained polyurethane resin is formed into a film, there is a problem that foreign matters of opaque or fish eye are likely to occur.

In the present invention, in particular, it is preferable to use a mixture of polyethylene glycol and polytetramethylene glycol or a mixture of polyethylene glycol and an ester of ethylene oxide and adipic acid as a polyol, and the molecular weight thereof is preferably in the range of 500 to 3,000.

In the present invention, the ethylene oxide fraction in the polyurethane resin obtained by blending these polyols with isocyanates and chain extenders can be maintained at 7.0 mol / kg or more.

The polyurethane resin used in the present invention can be produced in the absence of a solvent (bulk polymerization) or in a solvent (solution polymerization) by a one-shot method or a prepolymer method.

In this invention, the said polyurethane resin can be used in mixture with another urethane resin. Examples of other urethane resins include conventional ether-based urethane resins, ester-based urethane resins, polycarbonate-based urethane resins, amino acid-modified urethane resins, fluorine-modified urethane resins, and the like having a glass transition point of -20 ° C or lower. .

In the products obtained from the fabrics of the present invention, especially garments, the moisture vapor transmission rate at high temperatures and the low temperature conditions in terms of controlling the comfort resulting from being released from moisture in a high temperature and high humidity environment and controlling other comforts in warming in a low temperature environment. It is preferable that the ratio of water vapor transmission rate is 1.4 or more. In the present specification, the water vapor transmission rate (g / m 2 · 24hrs · mmHg) is a value obtained by dividing the water vapor transmission rate (g / m 2 · 24hrs) at the measurement temperature by the partial pressure of water vapor at the measurement temperature (mmHg). In addition, low-temperature time is 0 degreeC-20 degreeC at the clothing temperature, and high temperature time is 20 degreeC-50 degreeC at the clothing temperature. Since the ratio of the water vapor transmission rate is consistently high in conventional moisture-permeable waterproof fabrics, it is easy to be comfortable by actively releasing water vapor out of the garment at high temperatures, and at the same time releasing the latent heat of water out of the garment, but at low temperatures. Because of its high water vapor transmission rate, the latent heat of vapor is released out of the garment, so it lacks warmth. Further, in the conventional low moisture-permeable waterproof fabric, the water vapor transmission rate is constantly low. Therefore, at low temperatures, water vapor is not released much out of the garments, so it accumulates in the garment as latent heat and retains heat retention, but at high temperatures, moisture permeability is low, and thus moisture or stickiness is likely to occur.

The higher the water vapor transmission rate at high temperature, the smaller the water vapor transmission rate at low temperature, and the higher the water vapor transmission rate, the more active the vapor at high temperature, so that the clothing is not occupied with moisture, and at low temperature, the moisture permeation of water vapor is suppressed to exert warmth. A moisture-permeable waterproof fabric having a large temperature dependency is obtained.

In the present invention, the moisture permeability (g / m 2 · 24hrs) is measured according to the JIS L 1099 A-1 method, and a temperature of 5 ° C. and a relative humidity of 90% are employed as a low temperature environment, and a temperature of 40 ° C., as a high temperature environment. 90% relative humidity is adopted.

The specific temperature and humidity at the time of high temperature and low temperature environment are not specifically limited, It is good to determine the range of temperature and humidity of the clothing to be changed according to the intended use, and to determine the temperature and humidity of the high temperature environment and the low temperature environment. Do. The ratio of water vapor transmission rate at high temperature and water vapor transmission rate at low temperature may be large.

In the moisture-permeable waterproof fabric of the present invention, the water vapor transmission rate at a temperature of 40 ° C. and a relative humidity of 90% is preferable at a temperature of 8,000 g / m 2 · 24 hrs or higher at high temperature. It is preferable that the water vapor transmission rate at the temperature of 5 degreeC and 90% of a relative humidity at low temperature environment is less than 1,000 g / m <2> * 24hrs. In addition, the water pressure is preferably not less than 1,000㎜H ₂ O.

The temperature at which the steam is actively released and the temperature at which the thermal insulation is exerted can be adjusted according to the use by the glass transition point of the polyurethane resin, and used in the present invention from the viewpoint of human comfort in normal work or exercise. The glass transition point of the polyurethane resin is in the range of -20 ° C to 20 ° C.

Since the moisture-permeable waterproof fabric of the present invention has such a configuration, it exhibits excellent moisture permeability under high temperature and high humidity environment, suppresses moisture permeability under low temperature environment, and exerts excellent heat retention, thereby actively controlling the temperature and humidity environment in the product.

Next, the manufacturing method of the moisture-permeable waterproof fabric of this invention is demonstrated.

In the manufacturing method according to the wet method, for example, a solution of the polar organic solvent containing the polyurethane resin is applied to at least one side of the fabric, preferably in an amount of 3 to 50 g / m 2, and the coagulation and desolvent are applied. And dry. At this time, it is preferable that the coating amount of a polyurethane resin is 3-10 g / m <2> after drying from a viewpoint of maintaining a favorable base. Moreover, in the use where water pressure is important, it is preferable to form a polyurethane resin film by wet coagulation | solidification or a dry method again on the film formed as mentioned above. As a polar organic solvent used as a solvent of a polyurethane resin, water-soluble polar organic compounds, such as dimethylformamide (hereinafter, DMF), dimethylacetamide, and N-methylpyrrolidone, in terms of solubility in the resin, ease of coagulation and desolvent. It is preferable to select a solvent as a main agent. Moreover, an isocyanate type crosslinking agent, surfactant, etc. can be added to a resin solution. Isocyanate-based crosslinking agent forms a crosslinked structure in the film by heat treatment after film formation, thereby contributing to the strength and durability of the film.

Coagulation and desolvent are good according to known wet coagulation methods. As a coagulation bath, the above-mentioned aqueous solution and water of a solvent are used preferably. The solidification temperature is preferably in the range of 5 to 50 ° C. in view of adjusting the pore diameter of the fine pores formed in the resin film to an appropriate range. It is preferable to use water as a desolvent, and the range of 10-80 degreeC is selected suitably as temperature of a desolvent. The desolvated fabric is then dried according to conventional methods, with a drying temperature in the range of 60 to 140 ° C being preferably selected. In addition, if necessary, after drying, water repellent treatment may be performed to impart durable water repellency, and a known water repellent may be used in the water repellent treatment. It is also desirable to perform a finish set again to improve the quality of the textile product. In addition, before the resin is applied, the fabric can be subjected to a water repellent treatment or a calendar treatment.

The resin film obtained by the wet method can be easily microporous to obtain a moisture-permeable waterproof fabric having good moisture permeability.

In the manufacturing method according to the dry method, for example, a solution of the volatile organic solvent containing the polyurethane resin is applied onto a release paper, preferably in an amount of 50 to 200 g / m 2, to obtain a resin coating. Subsequently, an adhesive resin is added to the obtained resin film, it is dried at 40-150 degreeC as needed, it adheres to at least one side of a fabric, and then a release paper is peeled off. The coating amount of the polyurethane resin after drying is preferably 10 to 50 g / m 2, and as the volatile solvent, toluene, methyl ethyl ketone, isopropyl alcohol, dimethylformamide and the like are preferably used. Moreover, a ultraviolet absorber, antioxidant, a foaming agent, etc. can be added to a resin solution. In the case of the dry method, a resinous film of any of microporous and nonporous can be obtained. Moreover, an isocyanate type crosslinking agent, surfactant, etc. can be added to a resin solution. Isocyanate-based crosslinking agent forms a crosslinked structure in the film by heat treatment after film formation, thereby contributing to the strength and durability of the film.

Further, the resin film according to the present invention can be provided on the resin film surface of the moisture-permeable waterproof fabric obtained from a known urethane resin by a dry method. The waterproof fabric obtained according to this method has a water pressure of at least 10,000 mmH ₂ O.

The moisture-permeable waterproof fabric according to the present invention has a temperature dependence on the moisture permeability, and when the use temperature is low, it inhibits the movement of water vapor, that is, the latent heat, maintains heat retention, and when the use temperature is high temperature, actively passes water vapor through the latent heat. Release to prevent moisture and prevent temperature rise. Therefore, when the moisture-permeable waterproof fabric of the present invention is used in windproof facilities, ski suits, work clothes, shoes, etc., it is waterproof and has abundant warmth when the body is not warmed up before or during the exercise, and when the body is warm during exercise or after exercise. High water vapor permeability and difficulty in getting moisture can provide a cool and pleasant garment material with good texture.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated more concretely based on an Example.

In this specification, the water vapor transmission rate and the water pressure resistance are measured according to the JIS L 1099 A-1 method and JIS L 1092 (low water pressure method and higher water pressure method if the water pressure is 2,000 mmH ₂ O or less), respectively.

Example 1

A 10% aqueous solution of the fluorine-based water repellent Ashhi Gard AG 710 was padded and dried on a polyester ponzee fabric (75D-72F for both warp and weft yarns, inclined density: 101 / inch, and weft density: 80 / inch). Next, it is cured.

The polyol is stirred and dissolved in DMF at 50 ° C., then diisocyanate is added and then stirred for about 1 hour to obtain a prepolymer. Subsequently, the chain extender is added dropwise to cause a polymerization reaction to obtain a 25 wt% DMF solution of polyurethane resin. MDI as diisocyanate, polyethylene glycol with a molecular weight of 2,000 as polyol, polyethylene glycol adipate diol with a molecular weight of 1,200, and ethylene glycol as a chain extender are combined in a molar ratio of 3.4: 0.5: 0.5: 2.5. The glass transition point of the obtained polyurethane resin was 0.2 ° C. and the fraction of ethylene oxide in the polymer was 8.4 mol / kg.

10 parts by weight of DMF and 1 part by weight of isocyanate-based crosslinking agent Rezamin NE (manufactured by Daiichi Seika Co., Ltd.) were added to 100 parts by weight of the solution, and a mixed resin solution was applied to one side of the fabric in an amount of 15 g / m 2, and then an aqueous solution. Allow to coagulate for 5 minutes. Thereafter, the solvent is removed with water at 25 ° C, washed and dried, followed by fluoric oil-based water repellent treatment, and a processing set at 150 ° C to obtain a coated fabric. The coating amount of the polyurethane resin is 5 g / m 2 after drying. The ratio of water vapor permeability, water pressure and water vapor transmission rate (environmental dependence of water vapor permeability from a low temperature environment to a high temperature environment) is measured for the obtained fabric. The results are shown in Table 1.

Example 2

Padded 10% aqueous solution of fluorine-based water repellent Asahi Guard AG 710 in polyester ponsy fabric (75D to 72F for both warp and weft, warp density: 101 / inch, weft density: 80 / inch), dried and cured .

The polyol is dissolved by stirring in DMF at 50 ° C., then diisocyanate is added and stirred for about 1 hour to obtain a prepolymer. Subsequently, the chain extender is added dropwise to cause a polymerization reaction to obtain a 25 wt% DMF solution of polyurethane resin. MDI as diisocyanate, polyethylene glycol with a molecular weight of 2,000 as polyol, polyethylene glycol adipate diol with a molecular weight of 1,200, and 1,4-butanediol as a chain extender are blended in a molar ratio of 1.2: 0.7: 0.2: 0.2. The glass transition point of the obtained polyurethane resin is 3.0 ° C. and the fraction of ethylene oxide in the polymer is 11.3 mol / kg.

10 parts by weight of DMF and 1 part by weight of isocyanate-based crosslinking agent Rezamin NE (manufactured by Daiichi Seika Co., Ltd.) were added to 100 parts by weight of the solution, and the mixed resin solution was applied to one side of the fabric in an amount of 15 g / m 2, Allow to coagulate for 5 minutes. The solvent is then removed with water at 25 ° C., washed and dried, then subjected to a fluorine-based oil and water repellent treatment and subjected to a processing set at 150 ° C. to obtain a coated fabric. The coating amount of the polyurethane resin is 5 g / m 2 after drying. The ratio of water vapor permeability, water pressure and water vapor transmission rate (environmental dependence of water vapor permeability from a low temperature environment to a high temperature environment) is measured for the obtained fabric. The results are shown in Table 1.

Example 3

Pad a 10% aqueous solution of the fluorine-based water repellent agent Asahi Guard AG 710 on polyester pongee fabric (75D-72F for both warp and weft, warp density: 101 pieces / inch, weft density: 80 pieces / inch), dry and cure. .

The polyol is dissolved by stirring in DMF at 50 ° C., then diisocyanate is added and stirred for about 1 hour to obtain a prepolymer. Subsequently, the chain extender is added dropwise to cause a polymerization reaction to obtain a 25 wt% DMF solution of polyurethane resin. MDI as diisocyanate, polyethylene glycol having a molecular weight of 2,00 as polyol, polytetramethylene glycol having a molecular weight of 2,000, and ethylene glycol as a chain extender are blended in a molar ratio of 3.3: 0.5: 0.5: 2.4. The glass transition point of the obtained polyurethane resin is -8.5 ° C and the fraction of ethylene oxide in the polymer is 7.4 mol / kg.

20 parts by weight of methyl ethyl ketone and 80 parts by weight of toluene were added to 100 parts of such a solution, and the mixed resin solution was applied on a release paper in an amount of 80 g / m 2 and dried at 120 ° C. Subsequently, a resin solution obtained by adding 60 parts by weight of toluene and 10 parts by weight of isocyanate-based crosslinking agent Rezamin NE (manufactured by Daiichi Seika Co., Ltd.) to 100 parts by weight of the ether-based polyurethane resin as a binder resin was applied onto the obtained resin film. It is bonded to one side of the fabric mentioned above. After aging day and night, the release paper is peeled off to obtain a laminate fabric. The coating amount of the polyurethane resin is 15 g / m 2 after drying. The moisture permeability, water pressure, and the ratio of the water vapor transmission rate at low and high temperatures are measured for the obtained fabric. The results are shown in Table 1.

Example 4

A polyester knitted fabric (Tricoat of 30 d, 20 gauge) was used as the fabric, and MDI as the diisocyanate, polyethylene glycol with a molecular weight of 2,000 as polyol, polytetramethylene glycol with a molecular weight of 2,000 and ethylene glycol as the chain extender were used in a molar ratio of 3.30: A laminate fabric was obtained in the same manner as in Example 3 except that 0.55: 0.45: 2.40 was used. The glass transition point of the polyurethane resin at this time is -18 degreeC, and the fraction of ethylene oxide in a polymer is 7.8 mol / kg. The moisture permeability, water pressure, and the ratio of the water vapor transmission rate at low and high temperatures are measured for the obtained fabric. The results are shown in Table 1.

Example 5

The same fabric as in Example 4 was used as the fabric, and a mixed resin solution of the following composition was applied to one side and solidified in an aqueous solution for 5 minutes. Then, the solvent was desolvated with water at 25 ° C. and dried to obtain a fabric having a fine porous membrane having an application amount of 27 g / m 2.

100 parts of ester polyurethane resin

Dimethylformamide 80 parts

Rezamin NE [product made by Daiichi Seika Co., Ltd.]

Then, a fabric having a fine porous membrane and a nonporous membrane was obtained according to the same resin and method as in Example 4. The moisture permeability, water pressure, and the ratio of the water vapor transmission rate at low and high temperatures are measured for the obtained fabric. The results are shown in Table 1.

Comparative Example 1

Except for setting the molar ratio of MDI, polyethylene glycol, polyethylene glycol adipate diol and 1,4-butaldiol to 3.3: 0.3: 0.7: 2.4, a coating fabric exactly the same as in Example 2 was obtained. The glass transition point of the polyurethane resin is 0.8 ° C. and the ethylene oxide fraction in the polymer is 4.54 mol / kg. The moisture permeability, water pressure, and the ratio of the water vapor transmission rate at low and high temperatures are measured for the obtained fabric. The results are shown in Table 1 together.

Comparative Example 2

Except for using a resin having a glass transition point of −50 ° C. as the polyurethane resin, a coating fabric exactly the same as in Example 2 was obtained. The moisture permeability, water pressure, and the ratio of the water vapor transmission rate at low and high temperatures are measured for the obtained fabric. The results are shown in Table 1 together.

Comparative Example 3

A coated fabric was obtained in the same manner as in Example 2 except for using a resin having a glass transition point of -50 ° C and a high moisture permeability as the polyurethane resin. The moisture permeability, water pressure, and the ratio of the water vapor transmission rate at low and high temperatures are measured for the obtained fabric. The results are shown in Table 1.

Comparative Example 4

A laminate fabric was obtained in the same manner as in Example 4 except for using a resin having a glass transition point of −50 ° C. as the polyurethane resin. The moisture permeability, water pressure, and the ratio of the water vapor transmission rate at low and high temperatures are measured for the obtained fabric. The results are shown in Table 1.

TABLE 1

* 1 unit is (g / ㎡ ・ 24hrs)

* 2 Humidity is 90% RH

* 3 unit (g / ㎡, 24hrs, mmHg)

Claims (9)

A resin film containing a polyurethane resin obtained by reacting isocyanates, polyols and chain extenders and having a glass transition point in the range of -20 ° C to 20 ° C and having ethylene oxide units of at least 7.0 mol / kg is installed on at least one side of the fabric. Breathable waterproof fabric. The moisture-permeable waterproof fabric according to claim 1, wherein the polyol is composed of a mixture of polyethylene glycol and polytetramethylene glycol and their molecular weight is in the range of 500 to 3,000. The moisture-permeable waterproof fabric according to claim 1, wherein the polyol is composed of a mixture of polyethylene glycol and an ester of ethylene oxide and adipic acid, and their molecular weight is in the range of 500 to 3,000. The moisture-permeable waterproof fabric according to any one of claims 1 to 3, wherein the resin film is microporous. The moisture-permeable waterproof fabric according to any one of claims 1 to 3, wherein the resin film is nonporous. The moisture-permeable waterproof fabric according to any one of claims 1 to 3, wherein a ratio of the water vapor transmission rate at low temperature and the water vapor transmission rate at high temperature is 1.4 or more. The moisture-permeable waterproof fabric according to any one of claims 1 to 3, wherein the water vapor transmission rate in a low temperature environment is less than 1,000 g / m 2 · 24 hrs and the water vapor transmission rate in a high temperature environment is 8,000 g / m 2 · 24 hrs or more. A resin solution of a polar organic solvent obtained by reacting an isocyanate, a polyol and a chain extender and containing a polyurethane resin having a glass transition point in the range of -20 ° C to 20 ° C and having an ethylene oxide unit of at least 7.0 mol / kg is fabricated at least on the fabric. A method of manufacturing a moisture-permeable waterproof fabric, which is applied to one side and wet-coagulated in a coagulation bath to form a film. Applying a resin solution of a volatile organic solvent containing a polyurethane resin obtained by reacting isocyanate, polyol and chain extender and having a glass transition point in the range of -20 ° C to 20 ° C and having at least 7.0 mol / kg of ethylene oxide units on a release paper. To form a resin film, and then attaching the resin film to at least one side of the fabric.