JP2000220076A - Non-porous film type moisture-permeable waterproof coating agent for fabric and moisture-permeable waterproof fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a moisture-permeable waterproof coating agent and a moisture-permeable waterproof fabric which are excellent in chlorine resistance and moisture permeability. SOLUTION: This coating agent comprises a substantially linear polyurethane resin (A) having 40,000-500,000 number-average molecular weight and derived from an organic diisocyanate (a), a polymer polyol (b) comprising a polymer diol (b1) having 5,500-12,000 number-average molecular weight and at least 20 wt.% oxyethylene unit content and as necessary the other polymer diol (b2) and a chain extender (c), and oxyethylene unit content in the component A is 10-70 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-porous membrane-type moisture-permeable waterproof coating for fabric and a moisture-permeable waterproof fabric, and more particularly to a non-porous membrane-type moisture-permeable and waterproof fabric excellent in chlorine resistance. The present invention relates to a coating agent and a moisture-permeable waterproof fabric using the same.

[0002]

2. Description of the Related Art Conventionally, as a moisture-permeable material used for a moisture-permeable waterproof fabric, a film made by stretching a polytetrafluoroethylene resin to make it porous, or a microporous film such as a wet film made of a polyurethane resin is used. (For example, JP-A-59-15825) are known.
However, the conventional microporous film has a problem in that the film is clogged with sweat, dirt, etc., and the moisture permeability is reduced. As a solution to such problems, a non-porous polyurethane resin film has been proposed, and this moisture-permeable polyurethane resin film is a polyurethane resin containing a hydrophilic segment such as polyoxyethylene in a polyurethane resin. . As a method for imparting hydrophilicity to a polyurethane resin, it is well known that polyoxyethylene glycol or a block copolymer of polyoxyethylene and polyoxypropylene is used as a polyol component (Japanese Patent Publication No. 54-961). JP-A-64-63220,
Japanese Unexamined Patent Publication No. 4-180813, etc.).

[0003]

However, in the case of the non-porous polyurethane resin film containing the above-mentioned hydrophilic segment, clothing articles and the like using the same are repeated using sodium hypochlorite or the like. When the chlorine bleaching treatment is performed, the film is deteriorated due to insufficient chlorine resistance, and as a result, there is a problem that the water resistance is remarkably reduced.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have developed a non-porous fabric for fabrics which is excellent in chlorine resistance and has no problem of film deterioration due to repeated chlorine bleaching treatment using sodium hypochlorite or the like. As a result of intensive studies to obtain a membrane-type moisture-permeable and waterproof coating agent, the present invention has been achieved.

That is, the present invention relates to an organic diisocyanate (a) having a number average molecular weight of 5,500 to 12,000.
A polymer polyol (b) comprising a polymer diol (b1) having an oxyethylene unit content of at least 20% by weight and optionally another polymer diol (b2)
And a chain extender (c) having a number average molecular weight of 4
A non-woven fabric for fabrics comprising a substantially linear polyurethane resin (A) having a content of oxyethylene units of from 10 to 70% by weight. A porous film-type moisture-permeable waterproof coating agent; and a coating method according to any one of claims 1 to 3, which is applied to a releasable support, dried, and then adhered to a fiber cloth via an adhesive layer. The moisture-permeable waterproof fabric is manufactured by a transfer system or a dry system in which the coating agent is directly applied to a fiber fabric and dried.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, as the organic diisocyanate (a), those which have been conventionally used for producing polyurethane can be used. Such organic diisocyanates include aromatic diisocyanates having 6 to 20 carbon atoms (excluding carbon in the NCO group, the same applies hereinafter), and 2 to 2 carbon atoms.
To 18 aliphatic diisocyanates, alicyclic diisocyanates having 4 to 15 carbon atoms, araliphatic diisocyanates having 8 to 15 carbon atoms, modified products of these diisocyanates (modified carbodiimide, modified urethane, modified uretdione, etc.) and A mixture of two or more of these is included.

Specific examples of the aromatic diisocyanate include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate, 2,4'- and / or 4,
4'-diphenylmethane diisocyanate (hereinafter MDI
Abbreviation), 4,4'-diisocyanatobiphenyl, 3,
Examples include 3′-dimethyl-4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, and the like.

Specific examples of the above aliphatic diisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and 2,6-diisocyanatomethyl Examples thereof include aliphatic diisocyanates such as proate, bis (2-isocyanatoethyl) carbonate, and 2-isocyanatoethyl-2,6-diisocyanatohexanoate.

Specific examples of the alicyclic diisocyanate include isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, and bis (2-isocyanatoethyl) -4-cyclohexylene-isocyanate. 1,2-dicarboxylate, 2,5-
And / or 2,6-norbornane diisocyanate.

Specific examples of the araliphatic diisocyanate include m- and / or p-xylylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate.

[0011] Of these, preferred are aromatic diisocyanates and alicyclic diisocyanates, more preferred are aromatic diisocyanates, and particularly preferred is MDI.

In the present invention, the polymer diol (b1) having an oxyethylene unit content of at least 20% by weight
Examples include polyethylene glycol (hereinafter PEG)
Abbreviations), polyoxyethyleneoxypropylene block copolymerized diols, polyoxyethyleneoxytetramethylene block copolymerized diols; ethylene glycol,
Propylene glycol, 1,4-butanediol, 1,
6-hexamethylene glycol, neopentyl glycol, bis (hydroxymethyl) cyclohexane, 4,
Ethylene oxide adducts of low molecular weight glycols such as 4'-bis (2-hydroxyethoxy) -diphenylpropane; PEG having a molecular weight of 2,000 or less, and dicarboxylic acids [aliphatic dicarboxylic acids having 4 to 10 carbon atoms (for example, succinic acid, Condensed polyetherester diols obtained by reacting with at least one of adipic acid, sebacic acid, etc.), and an aromatic dicarboxylic acid having 8 to 15 carbon atoms (eg, terephthalic acid, isophthalic acid, etc.); Mixtures of more than one species are included. Preferred are PEG, polyoxyethyleneoxypropylene block copolymer diol and polyoxyethyleneoxytetramethylene block copolymer diol, and particularly preferred is PEG. The content of the oxyethylene unit in (b1) is usually at least 20% by weight, preferably 30% by weight or more, more preferably 40% by weight or more. When the content of the oxyethylene unit is less than 20% by weight, the moisture permeability becomes insufficient. The number average molecular weight of (b1) is usually from 5,500 to 1
It is 2,000, preferably 6,000 to 11,000. When the number average molecular weight is less than 5,500, the resulting polyurethane resin has a high modulus and a hard coating film, and when it exceeds 12,000, the strength of the coating film decreases. If necessary, another polymer diol (b2) can be used together with (b1) as long as moisture permeability is not impaired. The (b2) has a number average molecular weight of 600 to 50.
00.

Examples of other high molecular diols (b2) include polyether diol (a), polyester diol (b), polycarbonate diol (c) and the like, and mixtures thereof. As the polyether diol (a), those not containing an oxyethylene group, for example, polypropylene glycol, polyoxytetramethylene glycol (hereinafter abbreviated as PTMG), polyoxypropyleneoxytetramethylene block copolymerized diol and the like, and two or more of these Mixtures are mentioned.

Examples of the polyester diol (b) include a condensed polyester diol obtained by reacting a low molecular weight diol and / or a polyether diol having a molecular weight of 1,000 or less with at least one of the above-mentioned dicarboxylic acids, and a polyester diol having 4 carbon atoms. And polylactone diols obtained by ring-opening polymerization of lactones of No. 1 to No. 12. Examples of the low molecular diol include the low molecular glycol exemplified in the section of the oxyethylene unit-containing polyether diol (b1). Examples of the polyether diol having a molecular weight of 1,000 or less include polypropylene glycol and PTMG. Examples of the lactone include ε-caprolactone and γ-valerolactone. Specific examples of (b) include polyethylene adipate diol, polybutylene adipate diol, polyneopentylene adipate diol, and poly (3-methyl-1,5
-Pentylene adipate) diol, polyhexamethylene adipate diol, polycaprolactone diol and mixtures of two or more thereof. Examples of the polycarbonate diol (c) include polyhexamethylene carbonate diol.

When (b1) and (b2) are used in combination as the polymer polyol (b), the amount of (b1) is usually at least 50% by weight, preferably at least 70% by weight. Further, the content of the oxyethylene unit in (b) is at least 20% by weight, preferably 30% by weight or more. If it is less than 20% by weight, the moisture permeability becomes insufficient.

Examples of the chain extender (c) include those having 2 carbon atoms.
To 10 low molecular weight diols [eg, ethylene glycol (hereinafter abbreviated as EG), propylene glycol, 1,4-
Butanediol (hereinafter abbreviated as 14BG), diethylene glycol (hereinafter abbreviated as DEG), 1,6-hexamethylene glycol, etc .; diamines [aliphatic diamines having 2 to 6 carbon atoms (eg, ethylenediamine, 1,2-propylenediamine, etc.) ), An alicyclic diamine having 6 to 15 carbon atoms (eg, isophoronediamine, 4,4′-diaminodicyclohexylmethane, etc.), an aromatic diamine having 6 to 15 carbon atoms (eg, 4,4′-diaminodiphenylmethane, etc.)] Monoalkanolamine (eg, monoethanolamine), hydrazine or a derivative thereof (eg, adipic acid dihydrazide), and a mixture of two or more thereof. Preferred among these are low molecular weight diols, and particularly preferred are E
G, DEG and 14BG.

The equivalent ratio of the organic diisocyanate (a), the polymer polyol (b) and the chain extender (c) constituting the polyurethane resin (A) in the present invention is as follows:
The equivalent ratio of (a) / (b) is usually 10 to 30/1, preferably 11 to 28/1. If the ratio of (a) is less than 10 equivalents, the chlorine resistance will be insufficient, and if it exceeds 30 equivalents, the modulus will be high and the coating film will have a hard texture. The equivalent ratio of (a) / [(b) + (c)] is usually 0.9 to
1.1 / 1, preferably 0.95 to 1.05 / 1. If it is outside this range, the polyurethane resin will not have a sufficiently high molecular weight, and it will be difficult to produce a polyurethane resin having practically useful physical properties. The number average molecular weight of the polyurethane resin (A) is usually from 40,000 to 50
0000, particularly preferably 50,000 to 400,000.
00. If it is less than 40,000, the strength of the coating film will be low, and if it exceeds 500,000, the solution viscosity will be high and the coatability will be poor, and a uniform coating film will not be obtained. (A) needs to be a polyurethane resin having a substantially linear structure. With a three-dimensional structure, a uniform solvent solution having good coatability cannot be obtained.

The polyurethane resin (A) can be produced by a usual method, for example, a one-shot method in which an organic diisocyanate (a), a polymer polyol (b) and a chain extender (c) are simultaneously reacted, A prepolymer method in which (a) and (b) are reacted first, and then (c) is continuously reacted. The production of (A) can be performed in the presence or absence of a solvent inert to isocyanate groups. When the reaction is carried out in the presence of a solvent, suitable solvents include amide solvents [dimethylformamide (hereinafter abbreviated as DMF), dimethylacetamide, etc.]
Sulfoxide solvents (dimethylsulfoxide etc.), ketone solvents [methyl ethyl ketone (hereinafter abbreviated as MEK), methyl isobutyl ketone etc.], aromatic solvents (toluene, xylene etc.), ether solvents (dioxane, tetrahydrofuran etc.), ester solvents Solvents (such as ethyl acetate and butyl acetate) and mixtures of two or more thereof. Among these, preferred are amide solvents, ketone solvents, aromatic solvents and mixtures of two or more of these.

In the production of the polyurethane resin (A), the reaction temperature may be the same as that usually used for the polyurethane-forming reaction, and when a solvent is used, it is usually 20 to 100 ° C.
In the case of no solvent, the temperature is usually from 20 to 220 ° C.

If necessary for accelerating the reaction, a catalyst usually used for the polyurethane reaction [eg, an amine catalyst (eg, triethylamine, triethylenediamine, etc.);
Tin-based catalysts (such as dibutyltin dilaurate)].

If necessary, a polymerization terminator such as a monohydric alcohol (such as ethanol, isopropyl alcohol or butanol) or a monovalent amine (such as dimethylamine or dibutylamine) can be used.

The production of the polyurethane resin (A) can be carried out by a production apparatus usually employed in the relevant industry. When no solvent is used, a production apparatus such as a kneader or an extruder can be used. The polyurethane resin (A) produced in this manner usually has a solution viscosity of 10 to 10,000 poise / 20 ° C. measured as a 30% by weight (solid content) DMF solution, and is preferably 100 to 2 poise in practical use. 2,000 poise / 20 ° C.

The coating agent of the present invention comprises a solution of the polyurethane resin (A) in the organic solvent. The amount of the organic solvent is such that the resin solid content of the resin solution is usually 5 to 50% by weight, preferably 10 to 40% by weight.

The coating agent of the present invention may contain various stabilizers for improving weather resistance and heat deterioration, a crosslinking agent such as a polyfunctional isocyanate compound, a coloring agent, an inorganic filler, an organic modifier, etc., if necessary. And the like.

In the production of a moisture-permeable waterproof fabric using the coating agent of the present invention, a coating agent is applied on a releasable support, heated and dried to form a resin film, and then applied via an adhesive layer. It is manufactured by a dry transfer method in which the fiber cloth is peeled off from the release support, or a dry method in which a coating agent is directly applied to the fiber cloth and dried to form a resin film on the fiber cloth.

In order to apply the coating agent on the release support, it is applied by a usual coating method, for example, using a knife over roll or the like, and after dry film formation, is bonded to a fiber cloth with a polyurethane adhesive. I just need. In addition, in order to apply directly to the fiber cloth, for example, an application method using a knife coater or a comma coater may be used.

As the release support, for example, release paper or polyester film can be used. As the fiber cloth, for example, all of natural fibers and synthetic fibers can be used. Specific examples include cotton, socks, polyester,
Nylon, acrylic and a blend of two or more of these may be used. Examples of the form include a woven fabric, a knitted fabric, a nonwoven fabric, and a raised fabric. Alternatively, a laminated substrate having a polyurethane resin porous film on one surface of a fiber cloth may be used. These fiber cloths may be subjected to a water repellent treatment with a silicone resin, a fluorine resin or the like.

The thickness of the polyurethane resin film to which the coating agent has been applied is usually 1 to 200 μm, preferably 5 to 100 μm as a resin solid content.

[0029]

The present invention will be further described below with reference to examples, but the present invention is not limited to these examples. Parts in Examples and Comparative Examples represent parts by weight, and% represents% by weight.

The evaluation of chlorine resistance and moisture permeability in the test examples was performed according to the following methods. (1) Chlorine resistance Test solution preparation: sodium hypochlorite (active ingredient 5
%) And 2 g of Zab ([detergent manufactured by Kao Corporation]) were dissolved in distilled water in a total amount of 1,000 ml to prepare a test solution having an effective chlorine concentration of 1,500 ppm. × 10 cm film) was placed in 200 ml of the test solution, immersed for 360 minutes at room temperature with stirring, washed with water, and dried.The test piece after the test was immersed in DMF to extract the polyurethane resin, and gel permeation was performed. The weight molecular weight of the polyurethane resin was measured by emission chromatography (hereinafter abbreviated as GPC), and the molecular weight retention of the polyurethane resin after the test was 1 to 2 with respect to the weight molecular weight of the polyurethane resin before the test.
Less than 0%: Grade 1, 20 to less than 40%: Grade 2, Grade 40 to less than 60%: Grade 3, Grade 60 to less than 80%: Grade 4,
80% or more: Grade 5 was evaluated on a 5-point scale. (2) Moisture permeability The moisture permeability was measured according to JIS-Z0208 (condition B).

Example 1 A four-necked flask equipped with a stirrer and a thermometer was charged with PEG (b) 5 having a number average molecular weight (calculated from the OH value) of 6,000.
7.4 parts, EG (c) 8.0 parts, MDI (a) 34.7
And 233 parts of DMF, and reacted at 70 ° C. for 10 hours in a dry nitrogen atmosphere to obtain a resin concentration of 30% and a viscosity of 60%.
A polyurethane resin (A1) solution of 0 poise (20 ° C.) was obtained. (A) of the obtained polyurethane resin (A1) /
(B) The equivalent ratio is 14.5, (a) / [(b) + (c)]
The equivalent ratio is 1.0, and the oxyethylene group (abbreviated as OE group) content is 57%. 100 parts of the polyurethane resin (A1) is diluted with 150 parts of DMF, and the polyurethane resin concentration is 12 parts.
% Of the coating agent was obtained.

Example 2 46.0 parts of PEG (b) having a number average molecular weight of 6,000, D
15.5 parts of EG (c), 38.5 parts of MDI (a) and 233 parts of DMF were charged and reacted at 70 ° C. for 10 hours in a dry nitrogen atmosphere to obtain a polyurethane having a resin concentration of 30% and a viscosity of 500 poise (20 ° C.). A resin (A2) solution was obtained. The (a) / (b) equivalent ratio of the obtained polyurethane resin (A2) was 20.1, the (a) / [(b) + (c)] equivalent ratio was 1.0, and the OE group content was 46%. is there. 100 parts of the polyurethane resin (A2) was diluted with 150 parts of DMF to obtain a coating agent having a polyurethane resin concentration of 12%.

Example 3 55.2 parts of PEG (b) having a number average molecular weight of 8,000, E
8.6 parts of G (c), 36.2 parts of MDI (a) and DM
F233 parts, and 10 ° C. at 70 ° C. in a dry nitrogen atmosphere.
After reacting for 30 hours, the resin concentration is 30% and the viscosity is 800 poise (2
(0 ° C.) to obtain a polyurethane resin (A3) solution. The (a) / (b) equivalent ratio of the obtained polyurethane resin (A3) is 20.0, and the (a) / [(b) + (c)] equivalent ratio is 1.
0, OE group content is 55%. Polyurethane resin (A
3) 100 parts were diluted with 150 parts of DMF to obtain a coating agent having a polyurethane resin concentration of 12%.

Example 4 52.3 parts of PEG (b) having a number average molecular weight of 8,000, D
EG (c) 9.2 parts, MDI (a) 38.6 parts and D
Charge 233 parts of MF at 70 ° C under dry nitrogen atmosphere.
The reaction was carried out for 0 hour to obtain a polyurethane resin (A4) solution having a resin concentration of 30% and a viscosity of 700 poise (20 ° C.). The resulting polyurethane resin (A4) had an (a) / (b) equivalent ratio of 23.6, an (a) / [(b) + (c)] equivalent ratio of 1.0, and an OE group content of 52%. is there. 100 parts of the polyurethane resin (A4) was diluted with 150 parts of DMF to obtain a coating agent having a polyurethane resin concentration of 12%.

Example 5 PEG (b1) having a number average molecular weight of 10,000 40.9
Parts, 10.3 parts of polybutylene adipate (b2) having a number average molecular weight of 2000, 12.1 parts of 14BG (c), MD
36.7 parts of I (a) and 233 parts of DMF were charged and reacted at 70 ° C. for 10 hours in a dry nitrogen atmosphere to obtain a polyurethane resin (A5) solution having a resin concentration of 30% and a viscosity of 600 poise (20 ° C.). The obtained polyurethane resin (A
5) (a) / (b1) + (b2) equivalent ratio is 15.9;
(A) / [(b1) + (b2) + (c)] equivalent ratio is 1.
0, OE group content is 41%. Polyurethane resin (A
5) 100 parts were diluted with 150 parts of DMF to obtain a coating agent having a polyurethane resin concentration of 12%.

Comparative Example 1 58.1 parts of PEG (b) having a number average molecular weight of 2,000, E
G (c) 6.8 parts, MDI (a) 35.2 parts and DM
F233 parts, and 10 ° C. at 70 ° C. in a dry nitrogen atmosphere.
After reacting for 30 hours, resin concentration is 30% and viscosity is 600 poise (2
(0 ° C.) to obtain a polyurethane resin (H1) solution. (A) / (b) equivalent ratio of the obtained polyurethane resin (H1) is 4.9, (a) / [(b) + (c)] equivalent ratio is 1.0,
The OE group content is 58%. Polyurethane resin (H1)
100 parts were diluted with 150 parts of DMF to obtain a comparative coating agent having a polyurethane resin concentration of 12%.

Comparative Example 2 Tetrahydrofuran / ethylene oxide copolymerized diol having a number average molecular weight of 6,000 (0E group content: 15%)
(B) 56.9 parts, EG (c) 8.0 parts, MDI (a)
35.1 parts and 233 parts of DMF were charged and reacted at 70 ° C. for 10 hours in a dry nitrogen atmosphere to obtain a resin concentration of 30%.
Polyurethane resin with a viscosity of 800 poise (20 ° C) (H
3) A solution was obtained. (A) / (b) equivalent ratio of the obtained polyurethane resin (H3) was 14.8, and (a) / [(b) +
(C)] The equivalent ratio is 1.0, and the OE group content is 8.5%. 100 parts of polyurethane resin (H2) in DMF150
The resulting mixture was diluted with a portion to obtain a coating agent having a polyurethane resin concentration of 12%.

Performance Test Example <Preparation of Adjustment Solution and Preparation and Evaluation of Test Piece> Example 1
To 5 and each of the coating agents obtained in Comparative Examples 1 and 2 were applied on a polyester fabric to a thickness of about 150 μm,
After drying at 100 ° C for 20 minutes, the basis weight of the polyurethane resin was 1
A moisture-permeable waterproof cloth of ² g / m ² (solid content) was obtained. Using the obtained moisture-permeable waterproof cloth, chlorine resistance and moisture permeability were evaluated according to the above-mentioned evaluation methods. Table 1 shows the results.

[0039]

[Table 1]

As is clear from Table 1, the coating films comprising the coating agents of Examples 1 to 5 of the present invention have significantly improved chlorine resistance as compared with the conventional one (Comparative Example 1), and have a high water vapor transmission rate. Is also at a high level. Further, Comparative Example 2 has good chlorine resistance, but has low moisture permeability and cannot be put to practical use.

[0041]

The coating agent of the present invention gives a coating film having excellent chlorine resistance and good moisture permeability as compared with the conventional coating agent. Because of the above effects, the coating agent of the present invention is extremely useful as a moisture-permeable waterproof coating agent for fabrics such as clothing, umbrellas, canvas, and tents.

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[Procedure amendment]

[Submission date] April 5, 2000 (200.4.5)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0031

[Correction method] Change

[Correction contents]

Example 1 A four-necked flask equipped with a stirrer and a thermometer was charged with PEG (b) 5 having a number average molecular weight (calculated from the OH value) of 6,000.
7.4 parts, EG (c) 8.0 parts, MDI (a) 34.7
And 233 parts of DMF, and reacted at 70 ° C. for 10 hours in a dry nitrogen atmosphere to obtain a resin concentration of 30% and a viscosity of 60.
A polyurethane resin (A1) solution of 0 poise (20 ° C.) was obtained. (A) of the obtained polyurethane resin (A1) /
(B) The equivalent ratio is 14.5, (a) / [(b) + (c)]
The equivalent ratio is 1.0, and the oxyethylene group (abbreviated as OE group) content is 57%. 100 parts of this solution was diluted with 150 parts of DMF to obtain a coating agent having a polyurethane resin concentration of 12%.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0032

[Correction method] Change

[Correction contents]

Example 2 A reaction vessel similar to that of Example 1 was charged with a number average molecular weight of 6,000.
46.0 parts of PEG (b), 15.5 parts of DEG (c),
38.5 parts of MDI (a) and 233 parts of DMF were charged and reacted at 70 ° C. for 10 hours in a dry nitrogen atmosphere to obtain a polyurethane resin (A2) solution having a resin concentration of 30% and a viscosity of 500 poise (20 ° C.). (A) / (b) equivalent ratio of the obtained polyurethane resin (A2) is 20.1, (a)
/ [(B) + (c)] equivalent ratio is 1.0, OE group content is 4
6%. 100 parts of this solution was diluted with 150 parts of DMF to obtain a coating agent having a polyurethane resin concentration of 12%.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0033

[Correction method] Change

[Correction contents]

Example 3 A number-average molecular weight of 8,000 was placed in the same reaction vessel as in Example 1.
PEG (b) 55.2 parts, EG (c) 8.6 parts, MD
36.2 parts of I (a) and 233 parts of DMF were charged and reacted at 70 ° C. for 10 hours in a dry nitrogen atmosphere to obtain a polyurethane resin (A3) solution having a resin concentration of 30% and a viscosity of 800 poise (20 ° C.). The obtained polyurethane resin (A
3) (a) / (b) equivalent ratio is 20.0, (a) /
[(B) + (c)] equivalent ratio is 1.0, OE group content is 55
%. 100 parts of the solution is diluted with 150 parts of DMF,
A coating agent having a polyurethane resin concentration of 12% was obtained.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0034

[Correction method] Change

[Correction contents]

Example 4 A reaction vessel similar to that of Example 1 was charged with a number average molecular weight of 8,000.
52.3 parts of PEG (b), 9.2 parts of DEG (c), M
DI (a) 38.6 parts and DMF 233 parts were charged,
The reaction was carried out at 70 ° C. for 10 hours in a dry nitrogen atmosphere to obtain a polyurethane resin (A4) solution having a resin concentration of 30% and a viscosity of 700 poise (20 ° C.). (A) / (b) equivalent ratio of the obtained polyurethane resin (A4) was 23.6, and (a) /
[(B) + (c)] equivalent ratio is 1.0, OE group content is 52
%. 100 parts of the solution is diluted with 150 parts of DMF,
A coating agent having a polyurethane resin concentration of 12% was obtained.

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Correction contents]

Example 5 A reaction vessel similar to that of Example 1 was charged with a number average molecular weight of 10,000.
00.9 PEG (b1) 40.9 parts, number average molecular weight 2000
10.3 parts of polybutylene adipate (b2), 14B
12.1 parts of G (c), 36.7 parts of MDI (a) and D
Charge 233 parts of MF at 70 ° C under dry nitrogen atmosphere.
The reaction was carried out for 0 hour to obtain a polyurethane resin (A5) solution having a resin concentration of 30% and a viscosity of 600 poise (20 ° C.). (A) / (b1) + of the obtained polyurethane resin (A5)
(B2) The equivalent ratio is 15.9, (a) / [(b1) + (b
2) + (c)] The equivalent ratio is 1.0, and the OE group content is 41%. 100 parts of this solution was diluted with 150 parts of DMF to obtain a coating agent having a polyurethane resin concentration of 12%.

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0036

[Correction method] Change

[Correction contents]

Comparative Example 1 A reaction vessel similar to that in Example 1 was charged with a number average molecular weight of 2,000.
58.1 parts of PEG (b), 6.8 parts of EG (c), MD
35.2 parts of I (a) and 233 parts of DMF were charged and reacted at 70 ° C. for 10 hours in a dry nitrogen atmosphere to obtain a polyurethane resin (H1) solution having a resin concentration of 30% and a viscosity of 600 poise (20 ° C.). The obtained polyurethane resin (H
(A) / (b) equivalent ratio of 4.9, (a) /
[(B) + (c)] equivalent ratio is 1.0, OE group content is 58
%. 100 parts of the solution is diluted with 150 parts of DMF,
A comparative coating agent having a polyurethane resin concentration of 12% was obtained.

[Procedure amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0037

[Correction method] Change

[Correction contents]

Comparative Example 2 A number-average molecular weight of 6,000 was placed in the same reaction vessel as in Example 1.
56.9 parts of tetrahydrofuran / ethylene oxide copolymerized diol (OE group content 15%) (b), EG
(C) 8.0 parts, MDI (a) 35.1 parts and DMF
233 parts were charged and reacted at 70 ° C. for 10 hours in a dry nitrogen atmosphere to obtain a resin concentration of 30% and a viscosity of 800 poise (20
° C) of a polyurethane resin (H2) solution. The (a) / (b) equivalent ratio of the obtained polyurethane resin (H2) is 1
4.8, (a) / [(b) + (c)] equivalent ratio is 1.0,
The OE group content is 8.5%. 100 parts of the solution is DMF
It was diluted with 150 parts to obtain a comparative coating agent having a polyurethane resin concentration of 12%.

Continued on the front page F term (reference) 4J034 BA07 BA08 CA02 CA04 CA13 CA15 CA17 CB01 CB03 CB05 CB07 CB08 CC03 CC07 CC08 CC12 CC23 CC26 CC45 CC52 CC61 CC62 CC65 CC67 CE03 DA01 DB04 DB07 DF02 DF11 DF12 DF16 DG14 DG22 DG03 DG15 DG16 DH02 DH06 DH10 HA01 HA07 HB12 HC03 HC09 HC12 HC13 HC17 HC22 HC46 HC52 HC53 HC61 HC64 HC67 HC71 HC73 JA01 JA02 JA42 KA01 KB02 KC17 KD02 KD12 KE02 QA05 QC03 RA07 4J038 DG101 DG111 DG111 DG121 DG121 4A CA50 CA70

Claims (4)

[Claims] 1. An organic diisocyanate (a), a high molecular weight diol (b1) having a number average molecular weight of 5,500 to 12,000 and an oxyethylene unit content of at least 20% by weight, and optionally another polymer Diol (b2)
Having a number average molecular weight of 40,000 to 500, derived from a polymer polyol (b) consisting of
000 of a substantially linear polyurethane resin (A), wherein the content of oxyethylene units in (A) is 10 to 7
A non-porous membrane-type moisture-permeable and waterproof coating agent for fabric, which is 0% by weight. 2. The coating agent according to claim 1, wherein the content of oxyethylene units in (b) is at least 20% by weight. 3. The equivalent ratio of (a), (b) and (c) constituting (A) is (a) / (b) = 10-30 / 1.
And (a) / [(b) + (c)] = 0.9 to 1.1
The coating agent according to claim 1, wherein the ratio is / 1. 4. A dry transfer method in which the coating agent according to any one of claims 1 to 3 is applied to a release support, dried, and then adhered to a fiber cloth via an adhesive layer. A moisture-permeable waterproof fabric manufactured by a dry method of directly applying and drying on a fiber fabric.