JPH111611A - Moisture-permeable resin composition and moisture-permeable waterproof cloth using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an urethane composition excellent in moisture permeability and water pressure resistance by dispersing fine particles of an oligomer or polymer having urea bonds and being substantially incompatible with the organic solvent and the polyurethane resin in a polyurethane resin solution. SOLUTION: The polyurethane resin solution used herein is desirably one applicable to a wet-process film formation. Although not particularly limited, the concentration in use is suitably 15-40 % in consideration for economical profitability and workability. The fine particles of e.g. the oligomer having urea bonds has suitably a mean particle diameter of 5 μm or below and are desirably used in an amount of 0.1-40 wt.%. Although not particularly limited, the process for producing this composition is desirably one comprising simultaneously mixing for example an amino-containing compound (e.g. methylamine) and an isocyanate-containing compound (methyl isocyanate) and/or water by using a polyurethane resin solution as a medium to effect in situ formation of polyurea.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel highly moisture-permeable resin composition and a moisture-permeable waterproof cloth coated on a base material using the same as a main component.

[0002]

2. Description of the Related Art Conventionally, polyurethane resins have excellent mechanical strength and elasticity, so they have been used for coating agents, molding materials, synthetic leather, surface treatment agents, paints, films, etc. It has been used as.

[0003] However, a waterproof cloth coated with a usual polyurethane resin has a drawback that it becomes stuffy when worn due to poor moisture permeability. In order to solve this, a method in which the polyurethane resin solution is wet-coagulated to make it porous, or a method in which the polyol component of the polyurethane resin is introduced into the main chain using hygroscopic polyoxyethylene glycol or the like, A method has been proposed in which a mixture of wood powder, gelatin, protein powder, and the like having a hygroscopic property in a polyurethane resin solution is applied.

[0004] However, with the sophistication of the performance required for moisture permeability,
The moisture permeability was approaching its ultimate limit only by changing the polymer composition or improving the wet film forming formulation.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a polyurethane resin composition which breaks through such a limit value and has excellent moisture permeability and water pressure resistance, and a moisture permeable waterproof cloth using the same as a main component. It is intended.

[0006]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that in a polyurethane resin solution, an oligomer or a urea bond having a urea bond in a molecule, which is substantially incompatible with an organic solvent and a resin. It has been found that a polyurethane resin composition capable of overcoming the above-mentioned problems can be obtained by dispersing polymer fine particles, and the present invention has been completed.

That is, the present invention provides a polyurethane resin solution (A) in which oligomer or polymer fine particles (B) having a urea bond in a molecule, which are substantially incompatible with an organic solvent and a polyurethane resin, are dispersed. The present invention provides a wet resin composition, preferably an oligomer or polymer fine particle (B) having a urea bond in the molecule.
Provides a moisture-permeable resin composition having a content of 0.1 to 40% by weight based on the solid content of the polyurethane resin in the polyurethane resin solution (A).

In the polyurethane resin solution (A), a compound having at least one isocyanate group in a molecule is reacted with a compound having at least one amino group in a molecule and / or water. Do
Provided is a method for producing a moisture-permeable resin composition comprising oligomer or polymer fine particles having a urea bond in the molecule dispersed in the polyurethane resin solution (A).

It is another object of the present invention to provide a moisture-permeable waterproof cloth obtained by applying the moisture-permeable resin composition to a substrate. The moisture-permeable resin composition having such a configuration exhibits an effect that the moisture permeability is remarkably excellent while maintaining the same water resistance as the conventional one.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention relates to a polyurethane resin composition comprising a polyurethane resin solution in which fine particles such as oligomers having a urea bond in a molecule, which are substantially incompatible with an organic solvent and a resin, are dispersed. is there.

In the present invention, "substantially incompatible" means that the polyurethane resin organic solvent solution and the oligomer or polymer fine particles do not dissolve each other,
As a result, the fine particles are separated from the polyurethane resin solution and are dispersed in the polyurethane resin solution.

Generally, urea bond has strong cohesive force,
Oligomer or polymer fine particles having a urea bond in the molecule are inherently hardly compatible with organic solvents and polyurethane resins, so that oligomers having a urea bond repeating unit in the molecule are compatible with the polyurethane resin solution. It is difficult to do.

When the fine particles such as oligomers have an asymmetric organic group such as a bulky alkyl group other than a urea bond,
When the distance between urea bonds is long, and when a structure similar to the constituent material of the urethane resin is included in many cases, the cohesive force tends to be lower than in the case of only urea bonds (which are relatively dense). Compatibility with organic solvents and the like is improved.

In the moisture-permeable resin composition of the present invention, it is necessary that the polyurethane resin solution and the oligomer or polymer fine particles are not substantially compatible with each other, but they have a urea bond as long as they are not substantially compatible with each other. The above structure can be contained in the oligomer or polymer fine particles.

The average particle size of the oligomer or polymer fine particles having a urea bond in the molecule is not particularly limited, but is practically limited in consideration of the storage stability in the finally obtained polyurethane resin composition. Smaller ones are preferable, and those having a size of 5 μm or less are usually applied.
In order not to remarkably reduce the water resistance, which is one of the required properties of the moisture-permeable waterproof cloth of the present invention, fine particles having a particle size of 1 μm or less are more preferable.

The oligomer or polymer fine particles having a urea bond obtained in the present invention have a lower specific gravity than inorganic substances such as silica and are uniformly dispersed in a coexisting polyurethane resin solution. It has the characteristic that the tendency to separate is extremely small.

The amount of the oligomer or polymer having a urea bond obtained in the present invention is preferably 0.1 to 40% by weight based on the solid content of the polyurethane resin. If the amount is less than 0.1% by weight, the effect of expressing moisture permeability can hardly be expected. On the other hand, when the content exceeds 40% by weight, the oligomer or polymer fine particles become bulky and the viscosity of the polyurethane resin composition increases, so that the stirring at the time of preparing the composition becomes insufficient, and an uneven dispersion is produced. Or generate
Further, the workability when actually producing a moisture-permeable waterproof cloth tends to deteriorate, and the required water pressure tends to decrease simultaneously with the moisture permeability.

Although the reason why the polyurethane resin composition obtained in the present invention exhibits high moisture permeability is not clear,
Electron microscopic observation of the cross section of the polyurethane film formed by wet film formation on the base cloth shows that fine particles such as oligomers having urea bonds finely dispersed are likely to have fallen off during film formation, or that fine particles were formed during film formation. Since voids are considered to have been generated due to the local ease of removal of the organic solvent in the surroundings, it is presumed that steam was easily released through these gaps.

The polyurethane resin solution of the present invention refers to a solution of a polyurethane resin in an organic solvent. When producing a moisture-permeable waterproof cloth by wet-forming the moisture-permeable resin composition of the present invention to form a moisture-permeable waterproof cloth, the polyurethane resin solution is formed of dispersed fine particles having a urea bond, which are substantially incompatible with an organic solvent and a resin. A polyurethane resin solution that can be applied to wet film formation is preferable because it also acts as a performance improver.

Although the concentration of the polyurethane resin solution is not limited, it is usually 15 to 15 in consideration of economy and workability.
40% applies. The polyurethane resin is generally obtained by reacting a polyol with a polyisocyanate, or a urethane prepolymer obtained by reacting a polyol with a polyisocyanate, and further elongating the chain with a polyamine. Generally, a copolymer of a high molecular polyol (number average molecular weight of about 400 to about 6000) and a low molecular polyol (number average molecular weight of less than 400) is used as the polyol used for polyurethane resin production.

Examples of the high-molecular polyol component include hydroxy-terminated polyester polyols, polycarbonate polyols, polyester carbonate polyols, polyether polyols, polyether carbonate polyols, polyester amide polyols, and the like. Those modified with fluorine may be mentioned. Of these, polyester polyols, polycarbonate polyols and polyether polyols are preferred.

Examples of the polyester polyol include a reaction product of a dihydric alcohol and a dibasic carboxylic acid. Instead of the free dibasic carboxylic acids, the corresponding anhydrides or diesters of lower alcohols or mixtures thereof can also be used in the preparation of the polyesters as the carboxylic acid component.

The dihydric alcohol is not particularly restricted but includes, for example, ethylene glycol, 1,3- and 1,2-propylene glycol, 1,4- and 1,3- and 2,3.
Butylene glycol, 1,6-hexane glycol,
1,8-octane glycol, neopentyl glycol, cyclohexanedimethanol, 1,4-bis (hydroxymethyl) -cyclohexane, 2-methyl-1,
3-propanediol, 2,2,4-trimethyl-1,3
-Pentanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, dibutylene glycol and the like. Further, the glycol component may have a mono- or polydimethylsiloxane skeleton or a fluorinated modified skeleton.

The dibasic carboxylic acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic and can be unsaturated or modified with, for example, silicon or fluorine. And may be further substituted with a halogen atom. These carboxylic acids include, but are not limited to, for example, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimetic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexa Hydrophthalic acid, tetrahydroisophthalic anhydride, hexahydroisophthalic anhydride, endmethylene tetrahydrophthalic anhydride, glutaric anhydride, maleic anhydride, maleic acid, fumaric acid,
Dimer fatty acids such as oleic acid dimer, dimethyl terephthalate, mixed terephthalate and the like can be mentioned.

As these polyester polyols, those having a part of a carboxyl terminal group can be used. Such polyester polyols include, for example, lactones such as ε-caprolactone, or polyesters of hydroxycarboxylic acids such as ε-hydroxycaproic acid.

As the polycarbonate polyol having a hydroxy group, for example, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, polyethylene glycol,
Reaction products of diols such as polypropylene glycol and / or polytetramethylene glycol with phosgene, diallyl carbonate (eg, diphenyl carbonate) or cyclic carbonate (eg, propylene carbonate).

As the polyether polyol, a compound having a reactive hydrogen atom and an alkylene oxide and an arylene oxide such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran and epichlorohydrin, or a mixture of these oxides are used. Reaction products. They may be modified with silicon or modified with fluorine.

Compounds having a reactive hydrogen atom include:
The dihydric alcohols described above as raw materials for producing water, bisphenol A and polyester polyol are exemplified.

Examples of the low molecular polyol include the above-mentioned dihydric alcohols and the like. Next, as a generally used polyisocyanate, a compound represented by the formula: R (NC
0) ₂ (wherein, R is an arbitrary divalent organic group).

Specific examples thereof include, but are not limited to, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, cyclohexane-1,3 and 1,4-diisocyanate, 1-isocyanato-3-isocyanatome. Cyl-3,5,5-trimethylcyclohexane (= isophorone diisocyanate), bis (4-isocyanatocyclohexyl) methane (= hydrogenated MDI), 2, and 4-isocyanatocyclohexyl 2'-isocyanatocyclohexylmethane, 1,3 And 1,4-bis- (isocyanatomethyl) -cyclohexane, bis (4-isocyanato-3-methylcyclohexyl) methane, 1,3 and 1,4-tetramethylxylidene diisocyanate, 2,4 and / or
Or 2,6-diisocyanatotoluene, 2,2 '-, 2,
4 'and / or 4,4' diisocyanatodiphenylmethane, 1,5 naphthalene diisocyanate, p- and m
-Phenylene diisocyanate, dimeryl diisocyanate, xylylene diisocyanate, diphenyl-4,4 'diisocyanate and the like.

The production conditions of the urethane polymer or urethane prepolymer are not particularly limited, but are usually from 0 to
These urethanizing raw materials are obtained by stirring and mixing at 120 ° C., preferably 40 to 100 ° C. in the presence of a suitable organic solvent and reacting them. In this case, the reaction is carried out without a catalyst or by using a known urethanation catalyst and, if necessary, adding a reaction retarder. Further, in the case of polymerization, a compound having a monofunctional active hydrogen can be added at or near the end point of the reaction to substantially eliminate unreacted isocyanate groups.

The mixing ratio of the polyisocyanate and the polyol is usually NCO / OH equivalent ratio in the case of polymerization, 0.95 to 1.05, and in the case of prepolymerization,
Usually, 1.05 to 2.5 is used.

An organic diamine or the like can be used as a chain extender for the urethane prepolymer. The organic diamine is not particularly limited, for example, diaminoethane, 1,2 or 1,3 diaminopropane,
1,2 or 1,3 or 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, piperazine, N, N'-bis (2-aminoethyl) piperazine, 1-amino-3-aminomethyl-3,5,5- Trimethyl-cyclohexane (= isophoronediamine), bis (4-aminocyclohexyl) methane, bis (4-amino-3-butylcyclohexyl) methane, 1,2
-1,3- and 1,4-diaminocyclohexane and the like, and hydrazine, amino acid hydrazide, hydrazide of semi-carbazide carboxylic acid, bis (hydrazide) and bis (semicarbazide) can also be used. The organic diamine, hydrazine, hydrazide, or semicarbazide compound may have a mono- or polydimethylsiloxane skeleton or a fluorinated skeleton.

In this case, the conditions for the chain extension reaction include:
Although not particularly limited, it is usually 80 ° C. or lower, preferably 0 to
It is carried out at a temperature of 70 ° C. under good stirring conditions. As the organic solvent used in the polyurethane resin solution of the present invention,
For example, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, alcohols such as methanol, ethanol, propanol and butanol, ethylene glycol monomethyl ether and the like Ethers, ethylene glycol monomethyl ether acetate, ether esters such as ethylene glycol monoethyl ether acetate, dimethylformamide, diethylformamide, dimethylacetamide,
Dimethyl sulfoxide, dioxane, tetrahydrofuran and the like can be mentioned. In particular, a water-soluble organic solvent applicable to wet film formation is preferably used.

These organic solvents may be used in their entirety at the beginning of the urethanization reaction, may be partially used in the course of the reaction, or may be used alone or in combination of two or more. Is also good.

In producing the polyurethane resin of the present invention,
At any point in the urethanization reaction, stabilizers such as antioxidants, lubricants, pigments, fillers, antistatic agents, and other additives can be added as needed.

The method for producing the moisture-permeable resin composition of the present invention is not particularly limited. For example, 1) an oligomer or a polymer having a urea bond in a molecule is dissolved in the same water-soluble organic solvent as the polyurethane resin solution. A method of blending a dispersed resin and a polyurethane resin solution,
2) a method of dispersing an oligomer or polymer having a urea bond in a molecule by an in situ ureation reaction in an organic solvent at any point in the resin production step, as long as the polyurethane conversion reaction of the polyurethane resin is not inhibited. 3) There is a method in which an amino group-containing compound and an isocyanate group-containing compound are simultaneously and instantaneously mixed using the polyurethane resin solution as a medium. Among these, from the viewpoint of preventing aggregation of dispersed particles and the storage stability of the dispersed composition, the method of in-situ polyurea formation in the polyurethane resin solution described in 2) and 3) above is preferred.

The in situ polyureation reaction method, which is a preferred embodiment for producing the polyurethane resin composition of the present invention, comprises the steps of:
The compound having at least one isocyanate group in the molecule may be reacted with a compound having at least one amino group in the molecule and / or water by a conventional method, and is not particularly limited. Taking the reaction of a compound with an amino group-containing compound as an example, the reaction can be performed as follows.

That is, the isocyanate group-containing compound is first dispersed or dissolved in the polyurethane resin solution, and then the amino group-containing compound is added dropwise thereto as a solvent solution, if necessary, or the solution is subjected to batch or division. Either by charging in the form or adjusting by reacting both of these compounds, or first dispersing or dissolving the amino group-containing compound in the polyurethane resin solution, and then adding the isocyanate group-containing compound May be added, if necessary, as a solvent solution or added in a lump or divided form, and the reaction may be adjusted by reacting these two compounds.

The compound having at least one isocyanate group in the molecule used in the present invention includes, for example,
Monofunctional ones include methyl isocyanate, ethyl isocyanate, n-propyl isocyanate, n-
Examples thereof include butyl isocyanate, phenyl isocyanate, benzyl isocyanate and 2-phenylethyl isocyanate, and examples of the bifunctional one include the above-described diisocyanates. In addition, examples of the trifunctional or higher functional group include the above-mentioned diisocyanate trimer (isocyanurate).

Further, urethane prepolymers having terminal isocyanate groups comprising diisocyanate and a compound having an active hydrogen atom having two or more functionalities (for example, the above-mentioned dihydric alcohols, glycerin, trimethylolpropane, pentaerythritol and the like) are also available. No.

These compounds having an isocyanate group may be used alone as long as the oligomer or polymer having a urea bond finally obtained by the reaction with the compound having an amino group is not compatible with the organic solvent and the resin. Or two or more of them may be used in combination.

On the other hand, as the compound having at least one amino group in the molecule used in the present invention, for example, monofunctional compounds include methylamine, ethylamine,
Examples include propylamine, butylamine, hexylamine, aniline, benzylamine and 2-phenylethylamine, and examples of the bifunctional one include the above-mentioned organic diamines. Examples of those having three or more functionalities include various polyfunctional amines such as polyalkylene polyamines such as diethylenetriamine and hydrazines.

Further, compounds having an oxirane ring capable of reacting with an organic diamine, triamine or higher polyamines or hydrazines (eg, ethylene oxide, propylene oxide, butylene oxide, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether) , Neopentyl glycol diglycidyl ether, glycerin triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, etc.) or a compound having a terminal amino group obtained by a reaction with the aforementioned isocyanate group-terminated urethane prepolymer. Can be

These compounds having an amino group may be used alone as long as the oligomer or polymer having a urea bond finally obtained by the reaction with the compound having an isocyanate group is not compatible with the organic solvent and the resin. Or two or more of them may be used in combination.

The water of the present invention can produce an oligomer or a polymer having a urea bond by reacting the organic polyisocyanate or the compound having a plurality of terminal isocyanate groups in an amount less than the equivalent amount.

In this manner, the polyurethane resin composition of the present invention, which is a dispersion of an oligomer or a polymer having a urea bond in the molecule and substantially incompatible with the organic solvent and the resin, is obtained. The molecular weight of the oligomer or polymer is not particularly limited as long as it is not compatible with the organic solvent and the resin.

The polyurethane resin composition of the present invention can be used as it is, but when there is no problem with compatibility with other polyurethane resins, these polyurethane resins are mixed and used at an arbitrary ratio. be able to.

The moisture-permeable waterproof cloth of the present invention is prepared by applying a moisture-permeable resin composition containing the polyurethane resin composition obtained by the above method as a main component to a base material and then wet-drying it in a coagulation bath by a conventional method. It is obtained by forming a film.

As a method of applying the polyurethane resin composition to the base material, for example, a method of directly applying the polyurethane resin composition to the base material with a doctor knife coater, a roll coater, or the like, or a method of applying the polyurethane resin to a support having releasability. Forming a film,
It can also be obtained by bonding the film to a substrate.

As the substrate, for example, woven fabric, non-woven fabric, knitted fabric, synthetic resin foam and the like can be mentioned. Examples of the cloth used in the present invention include a woven cloth of natural or synthetic fibers such as cellulose, polyester, and nylon.

[0052]

Next, embodiments of the present invention will be described with reference to specific examples, but the present invention is not limited to these examples. Parts and percentages in the examples are by weight unless otherwise indicated.

The method for preparing a polyurethane resin coating, the method for testing moisture permeability and water pressure resistance, the method for testing storage stability and the method for measuring particle size distribution are as follows. [Preparation Method of Polyurethane Resin Coating Material] A polyurethane resin composition to which dimethylformamide was added so that the solid content concentration of the polyurethane resin became 20% was applied to a polyester cloth with a bar coater or the like so that the thickness became 150 μm. .
Next, it was immersed in an aqueous solution of 20 ° C. containing 10% dimethylformamide to solidify for 2 minutes, and then sufficiently desolvated in warm water and dried in a hot air dryer at 50 ° C. Then, a coating material having a coating thickness of about 30 μm was prepared.

[Test Method for Moisture Permeability] The coating material prepared by the above method was measured according to the B-1 method of JIS L-1099.

[Hydraulic pressure test method] The coating material prepared by the above method was measured according to the method B (high water pressure method) of JIS L-1092.

[Storage Stability Test Method] The cloudy polyurethane resin composition was placed in a glass bottle, kept at room temperature (25 ° C.), and the number of days until a precipitate was formed at the bottom of the bottle was checked.

[Method of Measuring Particle Size Distribution] One drop of the clouded polyurethane resin composition was taken on a glass rod, dissolved in 20 ml of dimethylformamide, and the particle size distribution was measured with a particle size distribution analyzer. The measured value was an average value after five measurements.

REFERENCE EXAMPLE 1 In a reactor equipped with a stirrer, a reflux condenser and a thermometer, 200 parts of poly (1,4-butylene adipate) having an average molecular weight of 2,000, 18.6 parts of ethylene glycol and dimethyl were added. Formamide 2
Charge 12.4 parts, dissolve uniformly, then
100 parts of 4'-diisocyanatodiphenylmethane was added, and the mixture was reacted at 70 ° C. for 8 hours while increasing the viscosity and further adding dimethylformamide.
A colorless and transparent resin solution having a viscosity of 800 poise (25 ° C., hereinafter the same temperature) at 0% was obtained.

Reference Example 2 In the same reactor as Reference Example 1,
200 parts of polytetramethylene glycol having an average molecular weight of 2,000, 9.3 parts of ethylene glycol, 13.5 parts of 1,4-butylene glycol and 215.2 parts of dimethylformamide are charged and uniformly dissolved. 100 of 4,4'-diisocyanatodiphenylmethane
The reaction was continued for 8 hours while increasing the viscosity at 70 ° C. and further adding dimethylformamide to obtain a colorless and transparent resin solution having a nonvolatile content of 30% and a viscosity of 880 poise.

Reference Example 3 In the same reactor as Reference Example 1,
200 parts of poly (1,6-hexane carbonate) diol having an average molecular weight of 2000 and dimethylformamide 1
After charging 58.5 parts and uniformly dissolving, 37.8 parts of isophorone diisocyanate and 0.05 part of dibutyltin dilaurate as a reaction catalyst are added thereto, and the mixture is maintained at 65 ° C. for 5 hours, and the nonvolatile content is 60%. Thus, a urethane prepolymer having an isocyanate group equivalent of 566 was obtained. Next, 594.8 parts of dimethylformamide was added thereto, and
After cooling to below ℃, 11.8 parts of bis (4-aminocyclohexyl) methane is added and reacted at below 50 ° C. for 30 minutes. Next, 1.5 parts of bis (4-aminocyclohexyl) methane was added, and after sufficient stirring, 5 parts of methanol as a reaction terminator and 2 parts of dimethylformamide 2 were added.
Add 51.1 parts and stir further. Thus, a colorless and transparent solution having a nonvolatile content of 20% and a viscosity of 100 poise was finally obtained.

Example 1 In a reactor equipped with a stirrer, a reflux condenser and a thermometer, 500 parts of the polyester-based urethane resin solution obtained in Reference Example 1, 250 parts of dimethylformamide and bis- (4-isocyanate) 8.3 parts of (natocyclohexyl) methane were charged, uniformly dissolved, and kept at room temperature (25 ° C.). Further, a solution consisting of 6.0 parts of bis (4-aminocyclohexyl) methane and 57.2 of dimethylformamide, which had been mixed in advance, was added all at once, and the mixture was sufficiently mixed and reacted at room temperature for 30 minutes.
Next, 0.5 part of methanol was added, the temperature was further raised to 70 ° C., and the mixture was stirred and stirred at that temperature for 1 hour. Thus, a cloudy resin solution having a nonvolatile content of 20% and a viscosity of 45 poise was finally obtained. Regarding the particle size distribution of the dispersed fine particles, those having a central peak value of 0.72 μm were 95% by weight.

Example 2 In a reactor similar to that of Example 1,
500 parts of the polyester-based urethane resin solution obtained in Reference Example 1, 250 parts of dimethylformamide and 7.1 parts of isophorone diisocyanate were charged, uniformly dissolved, and kept at room temperature (25 ° C.). Further, a solution consisting of 6.0 parts of bis (4-aminocyclohexyl) methane and 52.4 parts of dimethylformamide, which had been mixed in advance, was added all at once, and the mixture was thoroughly mixed at room temperature for 30 minutes. Then, 0.5 part of methanol is added and a further 70 parts are added.
C. and the mixture was stirred at that temperature for 1 hour. Thus, a cloudy resin solution having a non-volatile content of 20% and a viscosity of 40 poise was finally obtained. Regarding the particle size distribution of the dispersed particles, those having a center peak value of 0.85 μm were 90% by weight.

Example 3 In a reactor similar to that in Example 1,
500 parts of the polyether-based urethane resin solution obtained in Reference Example 2, 250 parts of dimethylformamide and 4,4
'7.9 parts of diisocyanatodiphenylmethane was charged, uniformly dissolved and kept at room temperature (25 ° C). Furthermore, isophorone diamine which has been previously mixed here 7.
A solution consisting of 8 parts of dimethylformamide and 62.8 parts of dimethylformamide was added all at once, and the mixture was sufficiently mixed and reacted at room temperature for 30 minutes.
And the mixture was stirred at that temperature for 1 hour. Thus, a cloudy resin solution having a non-volatile content of 20% and a viscosity of 50 poise was finally obtained. Regarding the particle size distribution of the dispersed particles, those having a central peak value of 0.93 μm were 88% by weight.

Example 4 In a reactor similar to that of Example 1,
In 500 parts of the polycarbonate-based urethane resin solution obtained in Reference Example 3, 8.3 parts of bis- (4-isocyanatocyclohexyl) methane was charged and uniformly dissolved to obtain 50 parts.
C. was maintained. Further, a previously mixed solution of 6.0 parts of bis (4-aminocyclohexyl) methane and 57.2 parts of dimethylformamide was added thereto all at once, and the mixture was sufficiently mixed and reacted at 50 to 55 ° C. for 30 minutes. Then, 0.5 part of methanol was added, the temperature was further raised to 70 ° C., and the mixture was stirred and stirred at that temperature for 1 hour. Thus,
Finally, a cloudy resin solution having a nonvolatile content of 20% and a viscosity of 120 poise was obtained. Regarding the particle size distribution of the dispersed particles, those having a central peak value of 1.1 μm were 93% by weight.

[Examples 5 to 8] In the same reactor as in Example 1, bis- (4-isocyanatocyclohexyl) methane and dimethylformamide were added to 500 parts of the polyester-based urethane resin solution obtained in Reference Example 1. Charge the amount shown in Table 1 of the attached sheet, dissolve it uniformly and room temperature (25 ° C)
Held. Further, a solution prepared by previously mixing bis- (4-aminocyclohexyl) methane and dimethylformamide in the amounts shown in Table 1 at once or in portions is added thereto, and after the addition, the mixture is added at room temperature for 30 minutes. The reaction was sufficiently mixed.

In Example 8, the generated polyurea powder became bulky and hard to disperse with normal stirring power, so that it was necessary to further increase the stirring power. Next, the amount of methanol shown in Table 1 was added, the temperature was further raised to 70 ° C., and the mixture was mixed and stirred at that temperature for 1 hour. Thus, a cloudy resin solution having a nonvolatile content of 20% and a viscosity as shown in Table 1 was finally obtained. Also, the particle size distribution of the dispersed particles,
The results were as shown in Table 1.

Comparative Example 1 In a reactor similar to that of Example 1,
In a place where 250 parts of dimethylformamide was added and uniformly dissolved in 500 parts of the polyester-based urethane resin solution obtained in Reference Example 1, 15 parts of silica powder was previously dispersed in 60 parts of dimethylformamide. The solution was added and the whole was further dispersed in a ball mill for 24 hours to obtain a cloudy resin solution having a nonvolatile content of 20% and a viscosity of 43 poise. The particle size distribution of the dispersed particles has a central peak value of 2.5.
μm was 75% by weight.

Comparative Example 2 The same reactor as in Example 1 was used.
To 500 parts of the polyester-based urethane resin solution obtained in Reference Example 1, 37.5 parts of bis (4-isocyanatocyclohexyl) methane and 250 parts of dimethylformamide were charged, uniformly dissolved, and kept at room temperature (25 ° C.). did. Further, a solution composed of 27.0 parts of bis (4-aminocyclohexyl) methane and 258 parts of dimethylformamide, which had been mixed in advance, was added in three portions. At this time, the generated polyurea was bulky with a normal stirring force, and was more difficult to disperse than in Example 8. Therefore, although the stirring force was further increased, a part was unevenly dispersed. After completion of the addition, a sufficient mixing reaction was performed at room temperature for 30 minutes. Next, 2.5 parts of methanol was added, the temperature was further raised to 70 ° C., and the mixture was stirred and stirred at that temperature for 1 hour. In this way, a highly cloudy resin solution having a nonvolatile content of 20% and a viscosity of 250 poise was finally obtained. The particle size distribution of the dispersed particles was 75% by weight with a central peak value of 1.5 μm and 15% by weight with a central peak value of 3.7 μm.

[0069]

[Table 1] Note: H12MDI = bis- (4-isocyanatoatocyclohexyl) methane H12MDA = bis- (4-aminocyclohexyl) methane IPDI = isophorone diisocyanate MDI = 4,4′-diisocyanatodiphenylmethane IPDA = isophorone diamine *; central peak value ( The weight percentage of the central peak value distribution) The clear polyurethane resin solution obtained in each of the above examples, the polyurethane resin composition solution of the present invention, and the silica fine particle-dispersed polyurethane resin solution for control were described above in [Polyurethane Resin Coating]. Production Method], about 30 μm of a porous layer coating material was prepared on a polyester cloth.

The values of the moisture permeability and the water pressure resistance of the coating product obtained in the B-1 method were determined together with the storage stability of the solution of each example.
The results are shown in Table-2.

[0071]

[Table 2] As apparent from these, the polyurethane resin composition obtained by uniformly dispersing the polyurea compound incompatible with the solvent and the resin in a specific range constituting the present invention not only exhibits excellent storage stability, but also It can be seen that by applying a polyurethane resin composition containing (A) as a main component, an excellent waterproof cloth having significantly improved moisture permeability and holding water resistance can be obtained.

[0072]

The wet-type polyurethane resin composition obtained by uniformly dispersing a polyurea compound substantially incompatible with a solvent and a resin in a specific range obtained by the present invention has excellent storage stability. An excellent waterproof fabric that not only exhibits water resistance but also has a significantly improved moisture permeability and a water pressure retention by applying a polyurethane resin composition containing this as a main component to a base fabric and forming a film by a conventional method. Is very useful as a waterproof cloth.

Claims (5)

[Claims] 1. A moisture-permeable resin composition comprising a polyurethane resin solution (A) in which oligomer or polymer fine particles (B) having a urea bond in a molecule and substantially incompatible with an organic solvent and a polyurethane resin are dispersed. . 2. The composition according to claim 1, wherein the polyurethane resin solution (A) is applied to a wet film formation method. 3. An oligomer or polymer fine particle (B) having a urea bond in the molecule is present in an amount of 0.1 to 40 per solid content of the polyurethane resin in the polyurethane resin solution (A).
3. The composition according to claim 1, which is in weight%. 4. A method comprising reacting a compound having at least one isocyanate group in a molecule with a compound having at least one amino group in a molecule and / or water in a polyurethane resin solution. A method for producing a moisture-permeable resin composition comprising oligomer or polymer fine particles having a urea bond in the molecule dispersed in the polyurethane resin solution (A). 5. A moisture-permeable waterproof cloth obtained by applying the moisture-permeable resin composition according to claim 1 to a substrate.