JPH1160940A - Moisture-permeable resin composition and moisture-permeable waterproof fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent in moisture permeability and resistance to hydraulic pressure by dispersing specific oligomer or polymer microparticles in a polyurethane resin solution. SOLUTION: This composition is obtained by reaction, in a solution of a polyurethane resin (e.g. polyester-based urethane resin), between a compound bearing at least one isocyanate group and fluoroalkyl and/or fluoroalkylene group(s) [ e.g. a reaction product from isophorone diisocyanate and C8 F17 SO2 N (C2 H4 OH)2 ] and a compound bearing at least one amino group (e.g. methylamine) or a compound bearing amino group and fluoroalkyl and/or fluoroalkylene group(s) [e.g. bis-(4-aminocyclohexyl)methane], and/or water. This composition is such one that oligomer or polymer microparticles bearing in the molecule urea linkage and fluoroalkyl and/or fluoroalkylene group(s) are dispersed in the polyurethane resin solution.

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, a urea bond and a fluoroalkyl group are 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 oligomer or polymer fine particles having a group and / or a fluoroalkylene group, thereby completing the present invention.

That is, the present invention relates to an oligomer or a urea bond and a fluoroalkyl group and / or a fluoroalkylene group in a molecule which are substantially incompatible with an organic solvent and a polyurethane resin in a polyurethane resin solution (A). The present invention provides a moisture-permeable resin composition obtained by dispersing polymer fine particles (B), wherein the fluoroalkyl group and / or the fluoroalkylene group is preferably a perfluoroalkyl group or a perfluoroalkylene group, and Moisture-permeable resin in which the oligomer or polymer fine particles (B) having a urea bond and a fluoroalkyl group and / or a fluoroalkylene group is 0.1 to 40% by weight based on the solid content of the polyurethane resin in the polyurethane resin solution (A) It provides a composition.

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 and a fluoroalkyl group and / or a fluoroalkylene group 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]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a polyurethane resin solution comprising fine particles such as oligomers having a urea bond and a fluoroalkyl group and / or a fluoroalkylene group in a molecule which are substantially incompatible with an organic solvent and a resin. The present invention relates to a dispersed polyurethane resin composition.

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 oligomer or polymer of the present invention contains a urea bond and either or both of a fluoroalkyl group and a fluoroalkylene group in the molecule. Also, the fluoroalkyl group and the fluoroalkylene group may be an alkyl group, a perfluoroalkyl group in which all hydrogens of the alkylene group are substituted by fluorine, or a perfluoroalkylene group, or a partially substituted fluorine, From the viewpoint of improving the water pressure resistance of the moisture-permeable waterproof cloth, a perfluoroalkyl group or a perfluoroalkylene group having the highest water repellency is preferred.

The average particle diameter of the oligomer or polymer fine particles having a urea bond and a fluoroalkyl group and / or a fluoroalkylene group in the molecule is not particularly limited, but the average particle diameter of the polyurethane resin composition finally obtained for practical use is not limited. In consideration of the storage stability at room temperature, it is preferable that the size is as small as possible.
In order to increase the water pressure resistance, which is one of the required performances of the moisture-permeable waterproof cloth of the present invention, fine particles of 1 μm or less are more preferable.

The oligomer or polymer fine particles having a urea bond and a fluoroalkyl group and / or a fluoroalkylene group obtained by the present invention have a lower specific gravity than an inorganic substance such as silica, and are homogeneous in a coexisting polyurethane resin solution. It has a feature that it has a very low tendency to settle and separate even during storage.

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, as a polyol used for producing a polyurethane resin, 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.

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 polyurethane resin composition of the present invention is not particularly limited. For example, 1) in a polyurethane resin solution, at least one isocyanate group and / or a fluoroalkyl group and / or a fluoroalkylene group in a molecule. With a compound having at least one amino group in the molecule, or a compound having an amino group and / or a fluoroalkyl group and / or a fluoroalkylene group, and / or water by a conventional method, 2) In a polyurethane resin solution, a compound having at least one isocyanate group in a molecule and a compound having at least one amino group and / or a fluoroalkyl group and / or a fluoroalkylene group in a molecule are reacted by a conventional method. It should be done. For example, taking a reaction between an isocyanate group-containing compound containing a fluoroalkyl group and / or a fluoroalkylene group and an amino group-containing compound as an example,
The following method can be used.

That is, first, a fluoroalkyl group and / or an isocyanate compound containing a fluoroalkylene group is dispersed or dissolved in a polyurethane resin solution.
Next, an amino group-containing compound is added here as a solvent solution, if necessary, or added in a lump or divided form, and a method of adjusting these two compounds by reacting them, or a polyurethane resin solution inside,
First, an amino group-containing compound is dispersed or dissolved, and then an isocyanate compound containing a fluoroalkyl group and / or a fluoroalkylene group is added dropwise as a solvent solution, if necessary, or in a lump or divided form. There is a method in which the mixture is added or adjusted by reacting both of these compounds.

In such a reaction, an amino group-containing compound and a fluoroalkyl group and / or a fluoroalkylene group-containing isocyanate compound are simultaneously mixed with the polyurethane resin solution as a medium, as generally applied. There is also a method of adjusting by instantaneous mixing.

At least one molecule in the molecule used in the present invention
Isocyanate groups and fluoroalkyl groups and / or
As an isocyanate compound having a loalkylene group
Is a perfluoroalkyl group or a perfluoroalkylene group
As an isocyanate compound having, for example, monofunctional
The property is CF_Three(CF_Two)₆CH_TwoOH, CF_Three
(CF_Two)_FiveSO_TwoN (CH_Three) C_TwoH_FourOH, CF_Three(C
F_Two)_FiveSO_TwoN (C_TwoH_Five) C _TwoH_FourOH, CF_Three(CF_Two)_Five
SO_TwoN (C_ThreeH₇) C_TwoH_FourOH, CF_Three(CF_Two)₇SO_Two
N (CH_Three) C_TwoH_FourOH, CF_Three(CF_Two)₇SO_TwoN (C_Two
H_Five) C_TwoH_FourOH, CF_Three(CF_Two)₇SO_TwoN (C_ThreeH₇)
C_TwoH_FourOH, (CF_Three)_ThreeCCOOC_TwoH_FourOH, CF
_Three(CF_Two)₆COOC_TwoH_FourOH, CF_Three(CF_Two)₈COO
C_TwoH_FourOH, CF_Three(CF_Two)₁₆COOC_TwoH_FourLike OH
Perfluoroalkyl group-containing monoalcohols
Equimolar reaction products with isocyanates.

Next, as the difunctional isocyanate compound, a dialkyl isocyanate at both ends obtained by reacting a fluoroalkyl group or a diol containing a fluoroalkylene group with a diol having a molar equivalent of twice the above-mentioned diisocyanate is used as the difunctional isocyanate compound. Compounds.

For example, CF_Three(CF_Two)_FiveSO_TwoN (C_TwoH_Four
OH)_Two, CF_Three(CF_Two)₇SO_TwoN (C_TwoH_FourOH)_Two, C
F_Three(CF_Two)₈CON (C_TwoH_FourOH)_Two, CF_Three(CF_Two)
₇SO_TwoN (C_TwoH_FourOH) (C_ThreeH₆OH), CF_Three(C
F_Two)₇C_TwoH_FourSO_TwoN (C_TwoH _FourOH)_Two, CF_Three(CF_Two)
₈0C₆H_FourSO_TwoN (C_TwoH_FourOH)_Two, CF_Three(CF_Two)₈0
C₆H_FourCON (C_TwoH_FourOH)_Two, CF_Three(CF_Two)₇SO_Two
N (CH_Three) [CH_TwoCH (OH) CH_TwoOH], CF
_Three(CF_Two)₈CON (C_ThreeH₇) [CH_TwoCH (OH) CH
_TwoOH], CF_Three(CF_Two)₈0C₆H_FourSO_TwoNH [CH_TwoC
H (OH) CH_TwoOH], CF_Three(CF_Two)₈C_TwoH_FourNH
[CH_TwoCH (OH) CH_TwoOH], CF_Three(CF_Two)₇C_Two
H_FourO [CH_TwoCH (OH) CH_TwoOH], CF_Three(C
F_Two)₇C_TwoH_FourS [CH_TwoCH (OH) CH_TwoOH], HO
CH_Two(CF_Two)_ThreeCH_Two0H, HOCH_Two(CF_Two)₈CH_Two
OH, HOC_TwoH_FourOCO (CF_Two)_FourCOOC_TwoH_FourOH,
HOC_TwoH_FourOCO (CF_Two)₈COOC_TwoH_FourOH, C₆F
_Ten(COOC_TwoH_FourOH)_TwoAnd the like.

On the other hand, an equimolar reaction product of the above-mentioned diisocyanate trimer (isocyanurate) with the above-mentioned fluoroalkyl group or fluoroalkylene group-containing monoalcohol can also be used as the bifunctional diisocyanate in the present invention. .

Examples of the compound having three or more functionalities include a trimer (isocyanurate) of a diisocyanate containing a fluoroalkyl group or a fluoroalkylene group described above. Further, a terminal isocyanate group composed of the above-mentioned fluoroalkyl group or fluoroalkylene group-containing diisocyanate and a compound having an active hydrogen atom having two or more functionalities (for example, the above-mentioned dihydric alcohols, glycerin, trimethylolpropane, pentaerythritol, etc.) And a urethane prepolymer having the following formula:

These compounds having a fluoroalkyl group or a fluoroalkylene group and an isocyanate group can be obtained by reacting an oligomer or a polymer having a urea bond, which is finally obtained by the reaction with a compound having an amino group, with an organic solvent and / or a resin. They may be used alone or in combination of two or more as long as they do not dissolve.

The compound having at least one isocyanate group which does not contain a fluoroalkyl group or a fluoroalkylene group and which is used in the present invention includes, for example, monofunctional compounds such as methyl isocyanate, ethyl isocyanate and n-propyl isocyanate. , N-butyl isocyanate, phenyl isocyanate, benzyl isocyanate and 2-phenylethyl isocyanate, and the difunctional isocyanate described above. 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, etc.) are also included. No.

On the other hand, as the compound having at least one amino group in the molecule applied 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

The compound 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 / or the resin. Or two or more of them may be used in combination.

The amino compound having at least one amino group and a fluoroalkyl group and / or a fluoroalkylene group in the molecule to be used in the present invention includes at least one amino group and a perfluoroalkyl group or a perfluoroalkyl group in the molecule. The compound having a fluoroalkylene group, for example, a monofunctional compound is obtained by reacting the above-mentioned monofunctional perfluoroalkyl group or perfluoroalkylene group-containing isocyanate with an equivalent or more of water.

The difunctional compound can also be obtained by dropping the above-mentioned difunctional perfluoroalkyl group or diisocyanate containing a perfluoroalkylene group into a large excess of water. Examples of the compound having two amino groups include the following.

That is, CF_Three(CF_Two)_FiveSO_TwoN (C_TwoH_FourN
H_Two)_Two, CF_Three(CF_Two)₇SO_TwoN (C_TwoH_FourNH_Two)_Two, C
F_Three(CF_Two)₇SO_TwoN [CH_TwoCH (OH) CH_TwoN
H_Two]_Two, CF_Three(CF_Two)₈CON [CH_TwoCH (OH) C
H_TwoNH_Two]_Two, CF_Three(CF_Two)₈OC₆H_FourCON [CH_Two
CH (OH) CH_TwoNH_Two]_Two, H_TwoNCH_Two(CF_Two)_FourC
H _TwoNH_Two, H_TwoNCH_Two(CF_Two)₈CH_TwoNH_TwoAnd so on.

Examples of the compound having three or more amino groups include an equimolar reaction product of an organic polyamine (tetrafunctional or higher) and the above-mentioned monofunctional perfluoroalkyl group or perfluoroalkylene group-containing isocyanate. Can be

Further, compounds having a terminal amino group obtained by the reaction of an organic diamine, a triamine or higher polyamine or a hydrazine with the above-mentioned perfluoroalkyl group or perfluoroalkylene group-containing isocyanate are also applicable to the present invention. it can.

As described above, the present invention is a dispersion of an oligomer or polymer having a urea bond and a fluoroalkyl group and / or a fluoroalkylene group in a molecule, which is substantially incompatible with an organic solvent and / or a resin. The polyurethane resin composition is obtained, but the molecular weight of the oligomer or polymer is not particularly limited as long as it is substantially incompatible with the organic solvent and the resin.

The water used in the present invention is capable of forming an oligomer or polymer having a urea bond by reacting the above-mentioned organic polyisocyanate or the compound having a plurality of terminal isocyanate groups in an amount less than the equivalent. it can.

The polyurethane resin composition of the present invention may be used as such, or when there is no problem with compatibility with other polyurethane resins, these polyurethane resins are mixed with these various polyurethane resins at an arbitrary ratio. May be used.

The oligomer or polymer obtained in the present invention has a specific gravity smaller than that of an inorganic substance such as silica, which is usually used for producing a fine particle dispersion, and is present in a coexisting polyurethane resin solution. Since the resin composition is uniformly and finely dispersed, even when the resin composition in which the resin composition is dispersed is stored, the resin composition has a feature that the tendency of sedimentation and separation is extremely small.

The amount of the oligomer or polymer having a urea bond and a fluoroalkyl group and / or a fluoroalkylene group 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 exhibiting moisture permeability is hardly expected. If the amount exceeds 40% by weight, the dispersion becomes bulky and the viscosity of the polyurethane resin composition increases greatly. Therefore, the stirring at the time of adjusting the composition becomes insufficient, and not only an uneven dispersion is generated, but also the workability at the time of actually creating a moisture-permeable waterproof cloth is deteriorated or moisture-permeable. At the same time, the required water pressure tends to decrease.

As to why the polyurethane resin composition obtained in the present invention exhibits high moisture permeability, observation of an electron micrograph of a cross section of a polyurethane film formed by wet film formation on a base fabric shows that the polyurethane resin composition is finely dispersed. Vapors that seemed to have formed due to the particles having urea bonds that had fallen off during film formation, or cavities that appeared to have formed due to local ease of organic solvent leakage around the particles during film formation were observed. It is presumed that it was easy to escape through the gap.

In the present invention, since finely dispersed particles contain a fluoroalkyl group or a fluoroalkylene group having water repellency, when the moisture permeability is improved, the water pressure resistance usually decreases. It is unique that the water pressure resistance does not decrease but rather increases.

Further, in the case of a wet-type polyurethane resin composition, dispersed particles having a urea bond and a fluoroalkyl group and / or a fluoroalkylene group obtained in the present invention and which are incompatible with a solvent and a resin are formed. This is convenient because it also acts as a film property improver.

The moisture-permeable waterproof cloth of the present invention is obtained by applying a polyurethane resin solution containing the polyurethane resin composition obtained by the above method as a main component to a substrate, and then wet-coating in a coagulation bath by a conventional method. To be obtained.

As a method of applying the polyurethane resin solution to the substrate, for example, a method of directly applying the polyurethane resin solution to the substrate with a doctor knife coater, a roll coater, or the like, or a method of coating a polyurethane resin film on a mold having releasability. And bonding the coating to a substrate.

Examples of the substrate include a woven fabric, a nonwoven fabric, a knitted fabric, and a synthetic resin foam. Examples of the cloth used in the present invention include a woven cloth of natural or synthetic fibers such as cellulose, polyester, and nylon.

[0068]

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, and the method for testing storage stability are as follows. [Preparation Method of Polyurethane Resin Coating Material] Polyurethane resin composition comprising dimethylformamide solution to which dimethylformamide is added so as to have a solid content concentration of 20% is polyester-coated with a bar coater or the like so as to have a thickness of 150 μm. Apply to cloth. Next, it was immersed in an aqueous solution containing 10% dimethylformamide at 20 ° C. to solidify for 2 minutes, and then sufficiently desolvated in warm water.
The coating was dried in a hot-air dryer at a temperature of about 30 ° C. to form a coating having a coating thickness of about 30 μm.

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

[Hydraulic Resistance 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] A 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.

Synthesis 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 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.

[Synthesis Example 2] In the same reactor as in Synthesis 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.

[Synthesis Example 3] In the same reactor as in Synthesis 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 Synthesis Example 1, 250 parts of dimethylformamide and bis- (4-isocyanate) (Natocyclohexyl) methane / C ₈ F ₁₇ SO ₂ N (C ₂ H ₄ OH) ₂ = 2/1
(Molar ratio), and 42.7 parts of a 30% concentration solution of fluorine-containing diisocyanate (hereinafter abbreviated as solution-I) obtained by reaction in dimethylformamide was charged and uniformly dissolved at room temperature (25%). (° C). Further, a premixed solution of 2.2 parts of bis (4-aminocyclohexyl) methane and 45.1 parts of dimethylformamide was added all at once, and the mixture was sufficiently mixed and reacted at room temperature for 30 minutes. And then add 0.2 parts of methanol,
The temperature was further raised to 70 ° C., and the mixture was stirred at that temperature for 1 hour. Thus, finally, the nonvolatile content is 20% and the viscosity is 40%.
A cloudy resin solution of poise was obtained.

Example 2 In a reactor similar to that of Example 1,
500 parts of the polyester-based urethane resin solution obtained in Synthesis Example 1, 250 parts of dimethylformamide and isophorone diisocyanate / C ₈ F ₁₇ SO ₂ N (C ₂ H ₄ OH)
₂ = 2/1 (molar ratio), 30% of the fluorine-containing diisocyanate obtained by reaction in dimethylformamide
42.7 parts of a concentration solution (hereinafter abbreviated as solution-II) is charged, uniformly dissolved, and kept at room temperature (25 ° C.).
Further, a solution consisting of 2.4 parts of bis (4-aminocyclohexyl) methane and 46.1 parts of dimethylformamide, which have been mixed in advance, is added all at once, and the solution is added at room temperature to 30 parts.
After thoroughly mixing and reacting for 0.2 min.
The mixture was further heated to 70 ° C., and mixed and stirred at that temperature for 1 hour. Thus, finally, the nonvolatile content is 20%
Thus, a cloudy resin solution having a viscosity of 37 poise was obtained.

Example 3 In the same reactor as in Example 1,
500 parts of the polyether-based urethane resin solution obtained in Synthesis Example 2, 250 parts of dimethylformamide, and 44.0 parts of Solution-I used in Example 1 were charged and uniformly dissolved to obtain room temperature (25 ° C.). To be kept. Further, a solution consisting of 1.9 parts of isophoronediamine and 44.7 parts 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. Two parts were 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 of 45 poise was finally obtained.

Example 4 In the same reactor as in Example 1,
In 500 parts of the polycarbonate-based urethane resin solution obtained in Synthesis Example 3, bis (4-isocyanatocyclohexyl) methane / HOCH ₂ (CF ₂ ) ₈ CH ₂ OH = 2/1
(Molar ratio) and charged with 42.3 parts of a 30% concentration solution of fluorine-containing diisocyanate (hereinafter abbreviated as solution III) obtained by reaction in dimethylformamide, uniformly dissolved and kept at 50 ° C. Keep it. Further, a premixed solution of 2.5 parts of bis (4-aminocyclohexyl) methane and 46.4 parts of dimethylformamide was added all at once, and the mixture was sufficiently mixed and reacted at 50 to 55 ° C. for 30 minutes. And then add 0.2 parts of methanol,
The temperature was further raised to 70 ° C., and the mixture was stirred at that temperature for 1 hour. Thus, finally, the non-volatile content is 20% and the viscosity is 11
A cloudy resin solution of 0 poise was obtained.

Example 5 In the same reactor as in Example 1,
500 parts of the polyether-based urethane resin solution obtained in Synthesis Example 2, 250 parts of dimethylformamide and 5.6 parts of bis (4-isocyanatocyclohexyl) methane are charged, uniformly dissolved, and brought to room temperature (25 ° C.). Keep it.

Further, the H ₂ NC previously mixed therein
A solution consisting of 9.4 parts of H ₂ (CF ₂ ) ₈ CH ₂ NH ₂ and 60.0 parts of dimethylformamide was added all at once, and the mixture was thoroughly mixed and reacted at room temperature for 30 minutes. Two parts were added, the temperature was further raised to 70 ° C., and the mixture was mixed and stirred at that temperature for 1 hour. Thus, finally, the nonvolatile content 2
A 0%, cloudy resin solution having a viscosity of 42 poise was obtained.

[Examples 6 to 9] In the same reactor as in Example 1, 500 parts of the polyester-based urethane resin solution obtained in Synthesis Example 1 was added with Solution-I and dimethylformamide in amounts shown in Table 1. At room temperature (25
(° C). Further, a solution of bis- (4-aminocyclohexyl) methane and dimethylformamide, which have been mixed in advance, in the amounts shown in Table 1 of the separate sheet are added all at once or in portions. The mixture was sufficiently mixed for minutes.

In Example 9, the generated polyurea powder was bulky and difficult to disperse with normal stirring power, so that it was necessary to further increase the stirring power. Next, methanol was added in the amount shown in Table 1 of the attached sheet, 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 as shown in Table 1 of the attached paper was obtained.

[0084]

[Table 1]

Notes: 1) Solution-I: H ₁₂ MDI / C ₈ F ₁₇
DM with SO ₂ N (C ₂ H ₄ OH) ₂ = 2/1 (molar ratio)
F (NV = 30%)
₁₂ MDI = bis- (4-isocyanatocyclohexyl)
Methane 2) H ₁₂ MDA: bis- (4-aminocyclohexyl)
Methane 3) solution _{-II: IPDI / C 8 F 17} SO 2 N (C 2 H 4 O
H) ₂ = _2/1 (solution (NV = 30% obtained by reacting in DMF molar ratio)) where IPDI = isophorone diisocyanate 4) IPDA = isophoronediamine 5) solution -III: H ₁₂ MDI / HOCH ₂ (CF ₂ ) ₈ CH ₂
OH = 2/1 solution (NV = 30%) obtained by reacting in DMF as (molar ratio) 6) H ₁₂ MDI = bis - (4-isocyanatocyclohexyl) methane 7) F-containing DA: H ₂ NCH ₂ (CF ₂ ) ₈ CH ₂ NH ₂ [Comparative Example 1] In a reactor similar to that of Example 1, 500 parts of the polyester urethane resin solution obtained in Synthesis Example 1, 250 parts of dimethylformamide and bis- 8.3 parts of (4-isocyanatocyclohexyl) methane are 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 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 was added, the temperature was further raised to 70 ° C., and the mixture was stirred at that temperature for 1 hour. Thus, finally, the non-volatile content is 20% and the viscosity is 45.
A cloudy resin solution of poise was obtained.

Comparative Example 2 The same reactor as in Example 1 was used.
500 parts of the polyester-based urethane resin solution obtained in Synthesis Example 1, 250 parts of dimethylformamide, and Solution-I
Was charged in an amount of 213.5 parts, and was uniformly dissolved at room temperature (25%).
(° C). Further, a solution consisting of 11.0 parts of bis (4-aminocyclohexyl) methane and 300 parts of dimethylformamide mixed in advance was added to 3
Added in portions. At this time, the generated polyurea was bulky with normal stirring power, and became more difficult to disperse than in Example 9. Therefore, although the stirring power 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, 1.0 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.
In this way, a highly cloudy resin solution having a nonvolatile content of 20% and a viscosity of 240 poise was finally obtained.

Each of the clear polyurethane resin solution obtained in each of the above examples and the polyurethane resin composition solution of the present invention was coated on a polyester cloth with a porous layer coating material of about 30 μm in accordance with the above-mentioned polyurethane resin coating material preparation method. It was created.

The values of the moisture permeability and the water pressure resistance of the coating material 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.

[0089]

[Table 2]

* Solid content with respect to polyurethane resin As is apparent from the above, a specific amount of a fluoroalkyl group or a polyurea compound containing a fluoroalkylene group, which is incompatible with a solvent and a resin, constituting the present invention is uniformly dispersed. Not only does the resulting polyurethane resin composition exhibit excellent storage stability, but by applying the polyurethane resin composition containing the polyurethane resin composition as a main component, excellent moisture permeability and excellent waterproofness with improved water pressure resistance are obtained. It can be seen that a cloth is obtained.

[0091]

The wet-type polyurethane resin composition of the present invention not only exhibits excellent storage stability, but also applies a polyurethane resin composition containing this as a main component to a base fabric,
By forming a film by an ordinary method, an excellent waterproof cloth having significantly improved moisture permeability and improved water pressure resistance can be obtained.

Claims (8)

[Claims] An oligomer or polymer fine particle (B) having a urea bond and a fluoroalkyl group and / or a fluoroalkylene group in a molecule, which is substantially incompatible with an organic solvent and a polyurethane resin, in a polyurethane resin solution (A). ) Is dispersed therein. 2. The composition according to claim 1, wherein the fluoroalkyl group is a perfluoroalkyl group. 3. The composition according to claim 1, wherein the fluoroalkylene group is a perfluoroalkylene group. 4. The composition according to claim 1, wherein the polyurethane resin solution (A) is applied to a wet film forming method. 5. An oligomer or polymer fine particle (B) having a urea bond and a fluoroalkyl group and / or a fluoroalkylene group in the molecule is contained in an amount of 0.1 to 40 per solid content of the polyurethane resin in the polyurethane resin solution (A).
The composition according to any one of claims 1 to 4, which is% by weight. 6. A compound (a-1) having at least one isocyanate group and / or a fluoroalkyl group and / or a fluoroalkylene group in a molecule of a polyurethane resin solution, and at least one amino group in a molecule of the polyurethane resin solution. Wherein the compound (b-1) having the formula (b-1) or a compound (b-2) having an amino group and a fluoroalkyl group and / or a fluoroalkylene group, and / or water (c) is reacted. A method for producing a moisture-permeable resin composition comprising oligomer or polymer fine particles having a urea bond and a fluoroalkyl group and / or a fluoroalkylene group dispersed in the polyurethane resin solution (A). 7. A compound (a-2) having at least one isocyanate group in a molecule and a compound (b-2) having an amino group and a fluoroalkyl group and / or a fluoroalkylene group in a polyurethane resin solution. And / or water (c), wherein oligomer or polymer fine particles having a urea bond and a fluoroalkyl group and / or a fluoroalkylene group in the molecule are dispersed in the polyurethane resin solution (A). A method for producing a moisture-permeable resin composition comprising: 8. A moisture-permeable waterproof cloth obtained by applying the moisture-permeable resin composition according to any one of claims 1 to 5 to a substrate.