JPS6059178A - Moisture permeable waterproof cloth - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a moisture-permeable waterproof fabric that has excellent light resistance, hydrolysis resistance, and water resistance.

Outdoor work involves rain and sunlight, so clothing made of waterproof fabric is used. In recent years, there has been a growing need to eliminate the discomfort caused by wearing waterproof clothing, such as stuffiness and stickiness. Various so-called moisture-permeable waterproof fabrics that emit moisture have been proposed. These moisture-permeable waterproof fabrics are mainly classified into the following four types.

■A fibrillar microporous structure film of tetrafluoroethylene resin laminated on a fabric, ■A fabric made of ultrafine fibers such as split composite fibers with a high density structure, ■A dimethylformamide solution of polyurethane resin A microporous film is formed by coating a fabric and coagulating it in water (wet-processed fabric). ■A fabric with a film layer made of a special polyurethane resin whose non-porous film itself is moisture permeable. The one formed on top (
Dry-processed fabric) Among these, processed fabric (①) has the disadvantage of having a hard texture and being expensive. In addition, the treated fabric (■) has the disadvantage that its waterproof properties are not necessarily sufficient. The microporous structure described in (2) has the disadvantage that the micropores become clogged with sweat and dirt, resulting in a decrease in moisture permeability.

The present invention relates to the above-mentioned moisture-permeable waterproof fabric which does not have such drawbacks. However, the above ■
Breathable waterproof fabrics also have drawbacks. In other words, waterproof fabrics using polyurethane resin, including the fabric processed in item (2) above, cannot be used with the polyurethane resin side facing up because the polyurethane resin originally has a problem with light resistance. It was used as a table. However, when the fabric side is exposed, water-repellent treatment is required to prevent the fabric from getting wet with water, and it also has the disadvantage of being easily stained. If a polyurethane resin with excellent light resistance is used, this problem can be solved because the polyurethane resin side can be used facing up, but polyurethane resins with excellent light resistance are generally susceptible to hydrolysis and cannot be used for long periods of time. When exposed to heavy rain or sweat, the surface becomes sticky and cracks, resulting in a sudden drop in water resistance. For example, polyurethane resin is made of polymeric diols such as polyester diol and polyether diol, and organic diincyanate.
They are synthesized from chain extenders such as low-molecular-weight diols and low-molecular diamines, but those using high-molecular diols and polyester diols have excellent light resistance, but are susceptible to hydrolysis. , resulting in poor water resistance. On the other hand, products using polyether diol as the polymeric diol have excellent hydrolysis resistance, but have poor light resistance, and after long-term use, many cracks occur in the resin, resulting in poor water resistance. Become something.

Additionally, in order to impart moisture permeability to a polyurethane resin, it is sufficient to introduce a hydrophilic group into the polyurethane molecule, but generally speaking, when a hydrophilic group is introduced into the polyurethane molecule, the polyurethane resin tends to swell with water; Water-resistant cloth coated with such a resin will cause wrinkles on the surface due to water, which will significantly reduce its commercial value. Water-swollen resin also has poor surface properties such as secondary abrasion resistance.
Furthermore, it becomes more susceptible to hydrolysis due to the moisture present inside.

That is, among the conventionally known moisture-permeable waterproof fabrics in which a non-porous polyurethane resin layer is formed on the surface of the fabric layer,
Materials with excellent light resistance have poor hydrolysis resistance, and conversely, materials with excellent hydrolysis resistance have poor light resistance, and in the end, after long-term use, their water resistance rapidly decreases. However, those that still had excellent moisture permeability were likely to swell with water, while those that did not swell with water had low moisture permeability.

The present invention relates to a breathable waterproof fabric in which a non-porous polyurethane resin layer is formed on a fabric layer, and it is a novel waterproof fabric that satisfies all of these conflicting requirements and cannot be predicted by conventional common sense. It is related to processed cloth.

That is, the present invention provides a processed fabric in which a non-porous layer of polyurethane with a thickness of 20 to 100 microns is provided on a fabric layer, and the fabric has a moisture permeability of 1000 to 500 microns.
Within the range of 0 Q/1el-day, the area swelling rate after being left in water at 30°C for 24 hours must be 20% or less, and the water resistance before and after irradiation with a 200-hour sunshine carbon weather meter is respectively It is a moisture-permeable waterproof fabric characterized by having a resistance of 1000 to H20 or more and 500 to H20 or more, and according to the present invention, it has light resistance, hydrolysis resistance,
It has become possible to create waterproof fabrics that are water resistant, moisture permeable, and have low water swelling properties. Therefore, the moisture-permeable waterproof fabric of the present invention does not need to be sewn with the polyurethane resin layer on the inside unlike conventional polyurethane waterproof fabrics, and the polyurethane resin layer can be exposed on the outside, making the fabric layer water repellent. No processing is necessary.

Next, the above requirements of the present invention will be explained. As mentioned above, the moisture-permeable waterproof fabric of the present invention has a weight of 1,000 to 5,000 g/
It is essential to have a moisture permeability of yy/・day, and those with a moisture permeability of less than 10009/#'dtL7 may cause stuffiness when worn, and conversely, those with a moisture permeability of 5.
If the polyurethane resin layer exceeds 0.0097 m-day, the thickness of the polyurethane resin layer is extremely thin, or the polyurethane resin layer swells significantly with water, and thus does not meet the purpose of the present invention. Do not leave it in water at 50°C for 24 hours.
Even if a waterproof fabric having an areal swelling degree of more than 0.0 cm satisfies other requirements, it will cause wrinkles due to water swelling when worn, significantly impairing its appearance. In addition, in the present invention, the waterproof fabric has a water resistance of 1000 to H20 or higher, and this water resistance is 50 or higher even after 200 hours of sunshine carbon weather meter irradiation.
0 It is necessary to maintain a resistance of H20 or higher, but all conventional polyurethane-based waterproof fabrics have a resistance of 100 H20 before irradiation with the Sunshine Carbon Weather Meter.
Even if the polyurethane resin had a water resistance of 0 or more, the water resistance decreased significantly due to hydrolysis and photolysis after 200 hours of irradiation, resulting in several sets of H20 to several tens of NtRH20. If the water resistance is less than 500 H20 as measured by a 200-hour sunshine carbon weather meter, it cannot be said to be suitable for long-term use.

Next, preferred configurations for achieving the present invention will be explained in detail.

First, the fabric (fibrous substrate) constituting the present invention includes, for example, woven fabric, silk fabric, non-woven fabric, etc., and its constituent fibers include natural fibers such as cotton, silk, and wool, acetate,
Any of chemical fibers such as viscose rayon and cupra, synthetic fibers such as polyester fibers, polyamide fibers, polyvinyl alcohol fibers, and polyacrylic fibers may be used, or a mixture thereof may be used. Generally, the fabric layer may be impregnated with a resin within a range that does not significantly impair moisture permeability.

Next, a non-porous layer made of polyurethane is formed on the fabric, and this non-porous layer consists of an adhesive layer and a surface layer, and the adhesive layer is in contact with the fabric layer. It is preferable to have the following.

In particular, the polyurethane constituting the surface layer is as follows (1
) to (3) or the following compounds (1) to (4) (ethylene oxide structural unit ÷ CH2CH20q in the molecule)
or a diol mixture containing this polymer diol, the proportion of ethylene oxide structural units in the total polymer diol is 10 to 50.
% by weight, and the average molecular weight of all polymeric diols is 5.
00 to 5000 (however, the above n
is the average number of repetitions), (2) aliphatic or alicyclic organic diincyanate, (3
) aliphatic or alicyclic diamine, (4) hydrazine or organic acid dihydrazide, and the polyurethane constituting the adhesive layer is one of the following (1) to (5) or Compound (1) of the following (1) to (4) is a polymeric diol having an ethylene oxide structural unit←CH2CH20% in the molecule or a polymeric diol mixture containing this polymeric diol, which is The proportion of ethylene oxide structural units in is 5 to 40% by weight, and the average molecular weight of all polymeric diols is 500 to 5.
000 (however, the above m is the average value of the repeating number), (2) organic diisocyanate, (3) low molecular weight organic compound having one or more active hydrogen atoms, (4) hydrazine, The object of the present invention can be more effectively achieved by using a polyurethane synthesized by a method or a curable polyurethane obtained by reacting this polyurethane with an intermolecular crosslinking agent.

To explain in more detail about the polyurethane resin that constitutes the surface layer, the polymer diol used to synthesize the polyurethane used for the surface layer is a polymer that has an ethylene oxide structural unit + CH2CH20q in the molecule. A diol or a diol mixture containing this polymeric diol, in which the proportion of ethylene oxide structural units in the total polymeric diol is 10 to 50% by weight.
It is preferable that If the proportion of ethylene oxide structural units is less than 10% by weight, the moisture permeability will be insufficient, and if it exceeds 50% by weight, the resulting waterproof fabric will swell too much with water, reducing its commercial value. This will cause a significant loss. Moreover, in a water-containing state, the surface properties deteriorate significantly and become easily scratched. In the present invention, particularly, the polymer diol having an ethylene oxide structural unit is a block copolymer diol of ethylene oxide and propylene oxide, and the ethylene oxide structural unit in the block copolymer diol is from 20 to 80. weight%
This material is suitable for use as a surface layer in terms of moisture permeability, water swelling property, and NOx gas resistance.

Polymer diol components used with polymer diols containing ethylene oxide structural units include cibolycarbonate diol, polycarbonate polyester diol, polycaprolactone diol, and polyβ-methyl-δ-valerolactone in terms of hydrolysis resistance and light resistance. A polyester diol obtained by condensation polymerization of a diol, a dicarboxylic acid having 4 or more carbon atoms, and a glycol having 4 or more carbon atoms is used. Further, it is preferable from the viewpoint of physical properties and texture that the average molecular weight of all the polymeric diols is within the range of 500 to 5,000.

In the present invention, the average number of edge warps n1m of the ethylene oxide structural units is 10 or more, especially 12 or more in both the surface layer and the adhesive layer, even if the ethylene oxide content is the same. It is also preferable because it has good moisture permeability and a low water swelling rate. However, if the polymeric diol having an ethylene oxide structural unit is a block copolymer diol of ethylene oxide and propylene oxide, sufficient moisture permeability can be obtained even if n is less than 10.

Generally, when a polymeric diol having an ethylene oxide structural unit is used, the moisture permeability of the resulting polyurethane is improved, but the surface layer of the present invention,
When polyurethane, such as that used for the adhesive layer, is used, its water swelling property is relatively low despite having an ethylene oxide structural unit in the molecule. In addition, polyurethane resins with high water swelling properties are more susceptible to hydrolysis due to the moisture contained inside, but the polyurethane used in the present invention is not only inherently resistant to hydrolysis, but also Since it has low swelling property, it is also less susceptible to hydrolysis.

As the aliphatic or alicyclic organic diincyanate, inphorone diisocyanate, dicyclohexylmethane-
Examples include 4,4'-diisocyanate, hexamethylene diisocyanate, isopropylidenecyclohexane diisocyanate, hydrogenated xylylene diisocyanate, cyclohexane diisocyanate, and hydrogenated tolylene diisocyanate.

The aliphatic or alicyclic organic diamines used in the present invention include isophorone diamine, 4,4'-diaminodicyclohexylmethane, cyclohexylene diamine,
Examples include hexamethylene diamine and ethylene diamine.

In general, when aromatic diisocyanates or aromatic diamines are used, the resulting polyurethane resin turns light yellow, whereas aliphatic, alicyclic diisocyanates or aliphatic,
It is known that when an alicyclic diamine is used, light resistance is improved.

However, when these aliphatic or alicyclic compounds are used, if a polyether such as polyethylene glycol is introduced to impart moisture permeability, there is no photoyellowing, but the photooxidation resistance deteriorates significantly compared to when aromatic compounds are used. It becomes defective. At this time, the light resistance can be significantly improved by using hydrazine or organic acid dihydrazide as part of the chain extender. Considering hydrolysis resistance, light resistance, physical properties, etc. comprehensively, the amount of hydrazine or organic acid dihydrazide should be in a molar ratio of 0.25 to the amount of the diamine.
The amount is preferably 4.0. Representative examples of the organic acid dihydrazide include isophthalic acid dihydrazide and adipic acid dihydrazide.

Next, the polymer diol used to synthesize the polyurethane used for the adhesive layer is a polymer diol having an ethylene oxide structural unit in the molecule or a polymer diol mixture containing this polymer diol. Preferably, the proportion of ethylene oxide structural units in the total polymeric diol is 5 to 40% by weight.

If the proportion of ethylene oxide structural units is less than 5% by weight, the moisture permeability will be insufficient, and if it exceeds 40% by weight, the resulting moisture-permeable waterproof fabric will swell too much with water, reducing its commercial value. This will cause a significant loss. In the present invention, the polymer diol having an ethylene oxide structural unit, particularly in the adhesive layer polyurethane, is a block copolymer diol of ethylene oxide and propylene oxide, and the ethylene oxide structural unit in the block copolymer diol is A content of 20 to 80% by weight is good in terms of moisture permeability, water swelling property, and NOx gas resistance.

Polymer diol components used together with polymer diols containing ethylene oxide structural units include hydrolysis-resistant face sheets, polytetramethylene diol, polypropylene diol, polycarbonate diol, polycaprolactone diol, and polyβ-methyl-δ- Preferred are valerolactone diol and polyester diol obtained by condensation polymerization of a dicarboxylic acid having 4 or more carbon atoms and a glycol having 4 or more carbon atoms. Further, the average molecular weight of all polymeric diols is preferably within the range of 500 to 500 from the viewpoint of physical properties and texture.

Examples of organic diincyanates include tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (
MDI), isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, isoglopylidene cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, cyclohexane diisocyanate, hydrogenated tolylene diisocyanate, etc., aliphatic and alicyclic groups, Examples include aromatic ones, but tolylene diisocyanate or inphorone diisocyanate is preferred.

In addition, examples of low-molecular organic compounds having one or more active hydrogen atoms include isophorone diamine, 4,4'-diaminodicyclohexylmethane, cyclohexylene diamine, hexamethylene diamine, ethylene diamine, piperazine, butanediol, ethylene glycol, hexamethylene diamine, Recall, N-(2-hydroxyethyl)propylenediamine, N-(2-hydroxyethyl)ethylenediamine, N-(2-hydroxypropyl)propylenediamine, monoethanolamine, impropaturamine, jetanolamine, diisopropylenediamine tool amine,
Examples include di-n-butylamine, isobutylamine, hexylamine, and the like. Particularly preferred L< is N-(2-hydroxyethyl)propylene diamine and monoethanolamine. When using a low-molecular organic compound having 1 or 6 or more active hydrogen atoms, 2 active hydrogen atoms are used.
It is preferable to use the polyurethane in combination with a low-molecular-weight compound, in terms of the strength, physical properties, flexibility, etc. of the resulting polyurethane.

In addition, if it is necessary to further increase the light resistance of the adhesive layer,
Preferably, hydrazine is used together with low molecular weight organic compounds having one or more active hydrogen atoms.

Incyanates obtained by reacting these synthesized polyurethanes with diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, or polyhydric alcohols such as these diisocyanates, nicrycerin, trimethylolpropane, and pentaerythritol. A curable polyurethane can also be obtained by reacting a polyisocyanate with trifunctional or higher functionality at the terminal. In particular, this curable polyurethane is particularly preferable for the moisture-permeable waterproof fabric of the present invention because it has excellent surface properties and water-swellability.

The surface layer is usually formed by evaporating the solvent from a polyurethane solution, and the thickness of this layer is approximately 5 to 6 mm.
A range of 0 microns is preferable. Further, the 100% modulus of the polyurethane constituting this surface layer at 20°C is preferably in the range of 20 to 130 kg7ci.

The thickness of the adhesive layer is preferably in the range of 10 to 80 microns, and the thickness of the polyurethane constituting this adhesive layer is preferably 10 to 80 microns.
100% modulus at °C is 10-80 kg/c
It is preferable from the viewpoint of hand feel and moisture permeability that it is within the range of d and is at least 10 kg/cd lower than the 100 thimodules of the polyurethane constituting the surface layer.

The 100% modulus of polyurethane can generally be achieved by changing the molar ratio of polymeric diol and diisocyanate used in polyurethane synthesis, and by changing the average molecular weight of polymeric diol, as well as by changing the selection of polyurethane raw materials, etc. It can be changed arbitrarily.

In particular, in the present invention, it is important that the total thickness of the surface layer and adhesive layer formed on the fabric layer is within the range of 20 to 100 microns, and if it is less than 20 microns, the physical properties (surface physical properties, If the thickness exceeds 100 microns, the moisture permeability becomes insufficient and the texture becomes hard.

Pigments are usually added to the surface layer for coloring, but if a dye is also added at this time, the light resistance is further improved. The dyes to be blended include metal-containing complex dyes, acid dyes, vat dyes, and sulfur dyes, with metal-containing complex dyes being particularly preferred. There is nothing wrong with adding a pigment to the adhesive layer, or the above-mentioned dye may be added in place of the pigment for coloring. Further, a highly hydrophilic moisture permeability imparting substance such as a polyvinylpyrrolidone derivative may be added to the polyurethane layer in order to improve moisture permeability. Furthermore, it is preferable to provide a water repellent agent or a polyurethane resin layer containing a water repellent agent on the non-porous polyurethane layer, since water droplets will not adhere to the layer and the waterproof effect will be significant. Examples of water repellents used include fluororesin represented by DickGuard F520 (manufactured by Dainippon Ink) and silicone resin represented by Poron Coat (Shin-Etsu Chemical Exhibition). Further, as the polyurethane resin used together with the water repellent, polyurethane resins used for the surface layer are preferred from the viewpoint of light resistance and moisture permeability.

A typical method for manufacturing the moisture-permeable waterproof fabric of the present invention is as follows: First, a polyurethane solution corresponding to the surface layer was applied onto the release paper, and after drying, a polyurethane solution corresponding to the adhesive layer was applied and moistened. It can be obtained by pasting it on a fabric in a dry or semi-dry state, drying it, and then peeling it off from a release paper.

The waterproof fabric obtained by the present invention has a good texture, excellent waterproofness, water resistance, and moisture permeability, and also has excellent durability such as light resistance and hydrolysis resistance. It also has low water swelling properties, so it can be used in commercial raincoats worn under harsh weather conditions, mountaineering raincoats, fishing clothes, as well as general sports clothing such as ski wear, golf wear, and cold protection clothing. It can be applied to a wide range of applications such as

In the present invention, sunshine carbon weather meter irradiation is performed using a sunshine carbon arc lamp type light resistance tester described in JIS B7753-1977, with a black panel temperature of 65±3°C, and a spray cycle of 1 in 120 minutes.
This means that the polyurethane resin side of the sample was irradiated for the required time of 8 minutes, and the moisture permeability was still below JI.
Moisture permeability test method described in S Z 020B-1976 (
Cup method) under constant temperature and humidity conditions at a temperature of 40±0.5
It was measured by the test method of 90±2% relative humidity at 60°C.The area swelling rate after standing in water at 60°C for 24 hours is 3°C.
The area increase rate after immersion in water for 24 hours is 10
0% modulus is measured by punching out a film using a No. 3 dumbbell and testing it at 2°C1 using a TMM type universal tensile tester.
This is the value obtained when pulling at a pulling speed of 30 cm and Aim.

In addition, water resistance is the value measured using the hydrostatic pressure method in Method A (low water pressure method) using the water resistance test method described in JIS L 1092-1977 Waterproof Test Methods for Textile Products, that is, the water pressure that the sample can withstand. (llH20).

The present invention will be specifically explained below using Examples.

In the examples, the light resistance was evaluated by performing the aforementioned sunshine carbon weather meter irradiation for 200 hours and 500 hours, and determining the resulting change in water resistance and the presence or absence of surface cracks. In addition, hydrolysis resistance was determined by examining surface cracks, adhesion, etc. that occurred when the waterproof fabric was left in an ambient atmosphere with a relative humidity of 95% and a temperature of 70° C. (jungle test conditions) for 6 weeks. Moisture permeability, water swelling rate and water resistance were measured by the test methods described above. The surface properties were determined using a fold abrasion tester (Custom type), which is the A-3 method (fold method) for evaluating abrasion strength, using the general textile testing method described in JIS L 1096-1979 at a load of 0.454 and 4 f.
This is the result of observing the degree of surface wear on the polyurethane resin side when subjected to 1000 friction cycles. In addition, the fabrics used in the Examples and Comparative Examples used 150 denier polyester yarn as the warp and 150 denier polyester yarn as the weft, and had a warp of 70 threads/1 nch and a weft thread of 50 threads/inch.
It is woven into the tissue of nch.

In addition, the polymer diols, diincyanate compounds, chain extenders, etc. that were the raw materials for the polyurethane resins used in the Examples and Comparative Examples are indicated using abbreviations, but the relationship between the abbreviations and the compounds PEG Polyethylene ether glycol PPG Polypropylene Ether glycol PCL Polycaglodictone glycol PI (A Polyhexamethylene adipate glycol PTG Polytetramethylene ether glycol IPDI Isophorone diincyanate H,2MDI Dicyclohexylmethane-4,4'-diisocyanate HDI Hexamethylene diincyanate TDI Tolylene diincyanate H6XD I Water-containing xylylene diisocyanate MDI Diphenylmethane-4,4'-diisocyanate IPDA Isophorone diamine H12DAM 4p4'-diaminodicyclohexylmethane dish Hydrazine-Hitler ADH Adipic dihydrazide HKPDA N-(2-hy)'oxyethyl)propylene diamine A Monoethanolamine DBA Di-n-butylamine BD 1,4-butanediol TMP Trimethylolglopan Examples 1-11. Comparative Examples 1 to 8 A release paper was coated with a polyurethane solution using a doctor knife, and dried for 3 minutes in a hot air dryer at 120°C to obtain a resin layer for the surface layer.

Furthermore, a 60% solution of polyurethane for the adhesive layer was coated on top with a doctor knife, and semi-dried at 80°C.
The fabric was laminated onto it while the adhesive remained.

After roller pressing, it was dried at 120°C for 5 minutes and further cured at 150°C for 1 minute. After cooling, it was peeled off from the release paper. The polyurethanes used for the surface layer and adhesive layer are shown in Tables 3 and 4.
The raw materials for these polyurethanes are shown in Tables 1 and 2, respectively.
This is shown in the table.

The light resistance, hydrolysis resistance, moisture permeability, degree of area swelling with water, surface properties, texture, etc. of the obtained moisture-permeable waterproof fabrics were compared. The results are shown in Tables 5 and 4. Regarding surface properties, texture, and overall evaluation, ×, ○, and ◎ indicate the degree of quality. ◎ represents a state that is not necessarily satisfactory, and a state that is extremely suitable as a waterproof fabric for clothing.

From Table 1, it can be seen that the moisture-permeable waterproof fabric of the present invention has light resistance,
It can be seen that it has excellent hydrolysis resistance and moisture permeability, and also has little swelling due to water, and has good physical properties and texture.

In addition, all the waterproof fabrics obtained in these Examples and Comparative Examples were 1
Water resistance of 500mH20+/''/'

Claims (1)

[Scope of Claims] 1. A processed fabric comprising a fabric layer provided with a non-porous layer made of polyurethane and having a thickness of 20 to 100 microns,
The moisture permeability of the processed cloth is 1000~s o o o q/r
The area swelling rate after being left in water at 30°C for 24 hours within the range of d-day must be 20% or less, and the water resistance before and after irradiation with the Sunshine Carbon Weathermeter for 200 hours is 11,000 RI l ( 2Q or more and 50
0. A moisture-permeable waterproof fabric characterized by having a resistance of 0 M11H20 or more. 2. The moisture-permeable waterproof fabric according to claim 1, wherein the non-porous layer does not include an adhesive layer and a surface layer, and the adhesive layer is in contact with the fabric layer. 5. The 100 timodilous (hereinafter referred to as M1oo) at 20'C of the polyurethane constituting the surface layer is 20
~150 kg/c-, Mloo of the polyurethane constituting the adhesive layer is 10-80 kg/c-, and Mono of the polyurethane constituting the surface layer.
) The moisture-permeable waterproof fabric according to claim 2, which has a lower kti/d of 10 kti/d or more. 4. The polyurethane constituting the surface layer is as follows (1)
- (3) or the following (1) - (4) Compound (1) Ethylene oxide structural unit -C-CH2CH20 in the molecule
% or a diol mixture containing this polymer diol, wherein the proportion of ethylene oxide structural units in the total polymer diol is 10 to 10%.
50% by weight, and the average molecular weight of all polymeric diols is 500 to 5000 (however, the above n is the average value of the repeating number), (2) aliphatic or alicyclic organic diisocyanate, (3
3. The moisture-permeable waterproof fabric according to claim 2, which is a thermoplastic polyurethane substantially synthesized from aliphatic or alicyclic organic diamine, and (4) hydrazine or organic acid dihydrazide. 5. By condensation polymerization of a polymer diol mixture, polycarbonate diol, polycarbonate polyester diol, polycaprolactone diol, polyβ-methyl-δ-valerolactone diol, and a dicarboxylic acid having 4 or more carbon atoms and a glycol having 4 or more carbon atoms. The moisture-permeable waterproofing treatment according to claim 4, which is a mixture of at least one polymer diol selected from the group consisting of polyester diols obtained and a polymer diol having an ethylene oxide structural unit in the molecule. cloth. 6. The polyurethane constituting the adhesive layer is as follows (1)
～(3) or the following (1)～(4) Compound (1) has an ethylene oxide structural unit (-CH2CH20%
or a polymer diol mixture containing this polymer diol, wherein the proportion of ethylene oxide structural units in the total polymer diol is 5.
-40% by weight of polymeric diol and the average molecular weight of all polymeric diols is 500 to 5000 (however, the above m is the average value of the number of repeats), (2) organic diisocyanate, (3) active hydrogen Claim 2, which is a polyurethane substantially synthesized from a low-molecular organic compound having one or more atoms, (4) hydrazine, which is still a curable polyurethane obtained by reacting this polyurethane with an intermolecular crosslinking agent. Breathable waterproof fabric as described. 7. The moisture-permeable waterproof fabric according to claim 4 or 6, wherein n or m is 10 or more. 8. Claim 4, wherein the polymeric diol having an ethylene oxide structural unit is a block copolymer diol of ethylene oxide and propylene oxide.
The moisture-permeable waterproof fabric according to item 6 or item 6. 9. The moisture-permeable waterproof fabric according to claim 6, wherein the organic diisocyanate is isophorone diisocyanate or tolylene diisocyanate. 10. The moisture-permeable waterproof fabric according to claim 6, wherein the low-molecular organic compound having one or more active hydrogen atoms is N-(2-hydroxyethyl)propylene diamine or monoethanolamine. 11. The moisture permeable waterproof fabric according to claim 8, wherein a moisture permeability imparting substance is added to the non-porous layer. 12. The moisture-permeable waterproof fabric according to claim 1, wherein a water repellent agent or a layer containing a water repellent agent is provided on the non-porous layer. 13. The moisture-permeable waterproof fabric according to claim 2, wherein a pigment or dye is added to the surface layer. 14. The dye is a metal-containing complex dye, an acid dye, a vat dye,
The moisture-permeable waterproof fabric according to claim M13, which is any one of sulfur dyes.