JPH11124497A - Resin composition for moisture permeable waterproof cloth and moisture permeable waterproof cloth using the same - Google Patents

Abstract

(57) [Problem] To provide a resin composition for a moisture-permeable waterproof cloth and a moisture-permeable waterproof cloth which are excellent in storage stability, improved in moisture permeability and water pressure resistance, and excellent in antifouling properties. A polyurethane resin solution (A) in which oligomer or polymer fine particles (B) having a urea bond and an organopolysiloxane group in a molecule, which are substantially incompatible with an organic solvent and a polyurethane resin, are dispersed. The present invention relates to a resin composition for a wet waterproof cloth, a method for producing the same, and a moisture permeable waterproof cloth.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel resin composition for a high-pressure, water-resistant, moisture-permeable waterproof cloth, and a moisture-permeable waterproof cloth coated on a base material using the resin composition 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 an object of the present invention, in particular, to improve both the moisture permeability and the reduction in water pressure resistance, but to improve both of them and to impart antifouling property.

[0006]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that a urea bond and an organopolysiloxane group in a molecule are substantially incompatible with an organic solvent and a resin in a polyurethane resin solution. It has been found that a polyurethane resin composition capable of overcoming the above-mentioned problems can be obtained by dispersing an oligomer or a polymer having the formula (1), thereby completing the present invention.

That is, the present invention relates to an oligomer or polymer fine particle (B) having a urea bond and an organopolysiloxane group in a molecule which is substantially incompatible with an organic solvent and a polyurethane resin in a polyurethane resin solution (A).
It is intended to provide a resin composition for a moisture-permeable waterproof cloth, wherein the organopolysiloxane group is preferably a tetraalkyldisiloxane group or a polydialkylsiloxane group, and preferably has a urea bond in the molecule. An object of the present invention is to provide a resin composition for a moisture-permeable waterproof cloth, wherein the oligomer or polymer fine particles (B) having an organopolysiloxane group are 0.1 to 40% by weight per solid content of the polyurethane resin solution (A). .

In a polyurethane resin solution, a compound having at least one isocyanate group and an organopolysiloxane group in a molecule, a compound having at least one amino group in a molecule, or a compound having an amino group and an organopolysiloxane in a molecule. A method for producing a resin composition for a moisture-permeable waterproof cloth, comprising oligomers or polymer fine particles having a urea bond and an organopolysiloxane group dispersed in a molecule, characterized by reacting a compound having a group and / or water. Or in a polyurethane resin solution, reacting a compound having at least one isocyanate group in the molecule with a compound having at least one amino group and an organopolysiloxane group in the molecule. Oligomers having urea bonds and organopolysiloxane groups Stone are those polymer particles to provide a method for producing a moisture-permeable waterproof fabric resin composition obtained by dispersing.

Further, the present invention provides a moisture-permeable waterproof cloth obtained by applying the resin composition for a moisture-permeable waterproof cloth to a substrate.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a polyurethane resin obtained by dispersing, in a polyurethane resin solution, particles such as oligomers having a urea bond and an organopolysiloxane group in a molecule, which are substantially incompatible with an organic solvent and a polyurethane resin. The present invention relates to a 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.

The resin composition for a moisture-permeable and waterproof cloth according to the present invention requires that the polyurethane resin solution and the oligomer or polymer fine particles are not substantially compatible with each other. The above structure can be contained in the oligomer or polymer fine particles having a bond.

The oligomer or polymer of the present invention has a urea bond and an organopolysiloxane group in the molecule. However, the tetraalkyldisiloxane group or the polydialkylsiloxane group is preferred in view of availability of raw materials and cost. preferable.

The average particle size of the oligomer or polymer fine particles having a urea bond and an organopolysiloxane group in the molecule is not particularly limited, but the storage stability in a practically finally obtained polyurethane resin composition. In consideration of the above, it is preferable to be as small as possible.
μm or less is applied. 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 an organopolysiloxane group obtained in the present invention have a lower specific gravity than inorganic materials such as silica and are uniformly dispersed in a coexisting polyurethane resin solution. Even during storage, it has the characteristic that the tendency to settle and separate is extremely low.

The polyurethane resin solution of the present invention refers to a solution of a polyurethane resin in an organic solvent. This polyurethane resin solution is dispersed fine particles having a urea bond, which are substantially incompatible with an organic solvent and a resin when a moisture-permeable waterproof cloth is produced by wet-forming the resin composition for a moisture-permeable waterproof cloth of the present invention. Acts also as a film-forming property improver, and is therefore preferably a polyurethane resin solution applicable to wet film formation.

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 polyesters, polycarbonates, polyester carbonates, polyethers, polyether carbonates, polyester amides and the like.
A polymer in which the inside of a polymer main chain or the inside of a branch is modified with silicon and / or fluorine is exemplified. Among them, polyester, polycarbonate and polyether 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, alicyclic, aromatic and / or heterocyclic and can be unsaturated or, for example, silicon-modified or fluorine-modified. Or 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 dimer, dimethyl terephthalate and mixed terephthalate And the like.

As these polyester polyols, those having a part of carboxyl terminal groups can be used. For example, such polyester polyols include:
For example, a lactone such as ε-caprolactone or a polyester of a hydroxycarboxylic acid such as ε-hydroxycaproic acid can be used.

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

The polyether polyol includes a starting compound having a reactive hydrogen atom and, for example, ethylene oxide,
Examples include reaction products of propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran, alkylene oxides such as epichlorohydrin, and allylene oxides or mixtures of these oxides. Further, these may be modified with silicon or modified with fluorine.

Compounds having a reactive hydrogen atom include:
Water, bisphenol A, and the dihydric alcohols described above for producing polyester polyols. Examples of the low molecular polyol include the above-mentioned dihydric alcohols and the like.

Next, as a generally used polyisocyanate, there may be mentioned a diisocyanate represented by the formula: R (NC0) ₂ (where R is any 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. In this case, the reaction is carried out without a catalyst or using a known urethanation catalyst, and if necessary, a reaction retardant is added. Further, in the case of polymerization, at or near the end point of the reaction, a compound having a monofunctional active hydrogen can be added 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. Further, 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,
Examples thereof include dimethyl sulfoxide, dioxane, and tetrahydrofuran. Among them, a water-soluble organic solvent which is particularly 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, if necessary, as long as it does not inhibit the in situ ureation reaction in the resin solution,
Stabilizers such as antioxidants, lubricants, pigments, fillers, antistatic agents, and other additives can be added.

The method for producing the polyurethane resin composition of the present invention is not particularly limited. For example, 1) a compound having at least one isocyanate group and an organopolysiloxane group in a molecule and a molecule in a polyurethane resin solution; A compound having at least one amino group alone or a compound having an organopolysiloxane group and / or water by a conventional method, or 2) a compound having at least one isocyanate group in a molecule in a polyurethane resin solution And a compound having at least one amino group and an organopolysiloxane group in the molecule may be reacted by a conventional method. For example, the reaction between an isocyanate group-containing compound containing an organopolysiloxane group and an amino group-containing compound can be performed as follows.

That is, an isocyanate group-containing compound containing an organopolysiloxane group is first dispersed or dissolved in a polyurethane resin solution, and then the amino group-containing compound is added dropwise as a solvent solution, if necessary. Or put them in batches or splits,
A method of adjusting these two compounds by reacting them, or in a polyurethane resin solution, first disperse or dissolve the amino group-containing compound, then the isocyanate group-containing compound containing an organopolysiloxane group, As needed, there is a method in which the compound is adjusted by reacting these two compounds by dropping the solution as a solvent solution or adding it in a lump or divided form.

Further, as generally used in such a reaction, an amino group-containing compound and an isocyanate group-containing compound containing an organopolysiloxane group are simultaneously instantaneously mixed using the polyurethane resin solution as a medium. Adjustment method.

The compound having at least one isocyanate group and an organopolysiloxane group in the molecule applied in the present invention is, for example, a monofunctional compound.
HOC ₃ H ₆ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₃ , HOC ₃ H ₆
− {Si (CH ₃ ) ₂ O} n−Si (CH ₃ ) ₃ (where n ≧
2) and the like, an equimolar reaction product of an organopolysiloxane group-containing monoalcohol and the above-mentioned diisocyanate. As the alkyl group, a methyl group is mainly used from the viewpoint of cost, but an alkyl group having 2 or more carbon atoms may be partially mixed or a phenyl group may be partially mixed.

Next, as the bifunctional one, a dialkyl isocyanate obtained by reacting a diol containing a tetraalkyldisiloxane group or a polydialkylsiloxane group as shown below with twice the molar equivalent of the above-mentioned diisocyanate is used. And a terminal diisocyanate compound.

For example, HOC ₃ H ₆ Si (CH ₃ ) ₂ OSi
(CH ₃ ) ₂ C ₃ H ₆ OH, HOC ₃ H _6- ｛Si (CH ₃ )
₂ O｝ n-Si (CH ₃ ) ₂ C ₃ H ₆ OH (where n ≧ 2), C _{2
H 5 -C (CH 2 OH)} 2 -CH 2 OC 3 H 6 - {Si (C
H ₃ ) ₂ O｝ m-Si (CH ₃ ) ₃ (where m ≧ 1), CH ₃ −
C (CH ₂ OH) ₂ —CH ₂ OC ₃ H ₆ — ｛Si (CH ₃ ) ₂
—O｝ m—Si (CH ₃ ) ₃ , CH (OH) —C (CH _{2
OH) -CH 2 OC 3 H 6} - {Si (CH 3) 2 -O} m-
Si (CH ₃ ) _{3 and the} like. In addition, as the alkyl group, a methyl group is mainly used from the viewpoint of price,
An alkyl group having 2 or more carbon atoms may be partially mixed, or a phenyl group may be partially mixed.

On the other hand, an equimolar reaction product of the above-mentioned diisocyanate trimer (isocyanurate) and the above-mentioned organopolysiloxane group-containing monoalcohol can also be applied as the bifunctional diisocyanate in the present invention.

Examples of the trifunctional or higher functional groups include the above-mentioned trimers (isocyanurates) of diisocyanates containing an organopolysiloxane group. Further, a urethane having a terminal isocyanate group consisting of the above-mentioned organopolysiloxane 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.) A prepolymer and the like.

The compound having an organopolysiloxane group and an isocyanate group is used 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. They may be used alone or in combination of two or more.

The compound having at least one isocyanate group which does not contain an organopolysiloxane group and which is used in the present invention includes, for example, monofunctional compounds such as methyl isocyanate, ethyl isocyanate and n-isocyanate.
Examples include -propyl isocyanate, n-butyl isocyanate, phenyl isocyanate, benzyl isocyanate and 2-phenylethyl isocyanate, and the difunctional is the above-mentioned diisocyanate. 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, a trifunctional or higher polyamine or a hydrazine (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.

Next, a compound having at least one amino group and an organopolysiloxane group in a molecule applied in the present invention is, for example, a monofunctional compound such as H ₂
It is obtained by reacting NC ₃ H ₆ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₃ or the above-mentioned isocyanate containing a monofunctional tetraalkyldisiloxane group or polydialkylsiloxane group with an equivalent or more of water.

The difunctional compound can also be obtained by dropping the above-mentioned difunctional organopolysiloxane group-containing diisocyanate into a large excess of water. For example, the following are included.

That is, H ₂ NC ₃ H ₆ Si (CH ₃ ) ₂ OSi (C
H ₃ ) ₂ C ₃ H ₆ NH ₂ , H ₂ NC ₃ H _6- {Si (CH ₃ ) ₂ O}
n-Si (CH ₃ ) ₂ C ₃ H ₆ NH ₂ (where n ≧ 2).
As the alkyl group, a methyl group is mainly used from the viewpoint of cost, but an alkyl group having 2 or more carbon atoms may be partially mixed or a phenyl group may be partially mixed.

Examples of the compound having three or more amino groups include, for example, an equimolar reaction product of an organic polyamine (tetrafunctional or higher) and the above-mentioned monofunctional tetraalkyldisiloxane group or polydialkylsiloxane group-containing isocyanate. No.

Further, organic diamines, triamine or higher functional polyamines or hydrazines and compounds having a terminal amino group obtained by the reaction of the above-mentioned organopolysiloxane group-containing isocyanate can also be applied to the present invention.

In this manner, the polyurethane resin composition of the present invention, which is a dispersion of an oligomer or polymer having a urea bond and an organopolysiloxane group in the molecule, which is substantially incompatible with the organic solvent and the resin, is obtained. However, 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 resin compatibility with other polyurethane resins, these polyurethane resins can be mixed with these various polyurethane resins at an arbitrary ratio. You may use it.

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 generally 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 an organopolysiloxane group obtained in the present invention is 0.1 to 0.1% based on the solid content of the polyurethane resin.
40% by weight is preferred.

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 an organopolysiloxane group having water repellency, when the moisture permeability is improved, the water pressure is normally lowered. It is specific that the siloxane chain does not decrease, but rather improves, and that the siloxane chain also exerts antifouling properties.

Further, in the case of a wet type polyurethane resin composition, the dispersed particles having a urea bond and an organopolysiloxane group, which are not compatible with a solvent and a resin, obtained in the present invention can also be used as a film-forming improver. It is convenient because it works.

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] The translucent 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.

[Anti-fouling test method] The coated material prepared by the above method was marked with an aqueous magic ink and immediately wiped off with a paper towel, and at room temperature (about 20 ° C).
2 weeks later, the state of wiping with a paper towel was compared.

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) 3.3 parts of natocyclohexyl) methane are charged, uniformly dissolved and kept at room temperature (20 ° C.). Further, a solution consisting of 11.7 parts of α, ω-bis- (3-aminopropyl) polydimethylsiloxane (molecular weight = 1000) and 60.0 parts of dimethylformamide, which have been previously mixed, is added all at once to the mixture at room temperature. After 30 minutes of sufficient mixing and reaction, 0.2 parts of methanol 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 translucent resin solution having a non-volatile content of 20% and a viscosity of 32 poise was finally 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 0.8 parts of bis (4-isocyanatocyclohexyl) methane are charged, uniformly dissolved, and brought to room temperature (20 ° C.). Keep it. Further, 14.2 parts of α, ω-bis- (3-aminopropyl) polydimethylsiloxane (molecular weight = 5000) and dimethylformamide 60.
0 parts of the solution was added all at once, and the mixture was thoroughly mixed at room temperature for 30 minutes. Then, 0.1 parts of methanol was added, and the mixture was further heated to 70 ° C. and mixed at that temperature for 1 hour. Stirred. Thus, a translucent resin solution having a non-volatile content of 20% and a viscosity of 30 poise was finally obtained.

Example 3 In a reactor similar to that in Example 1,
500 parts of the polyether-based urethane resin solution obtained in Synthesis Example 2, 250 parts of dimethylformamide and 7.8 parts of bis- (4-isocyanatocyclohexyl) methane were charged and uniformly dissolved to obtain room temperature (20 ° C.). To be kept. Furthermore, the 1,3-bis-
A solution consisting of 7.2 parts of (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane 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. Then, 0.2 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, the non-volatile content is 20% and the viscosity is 3
An 8-poise translucent resin solution was obtained.

Example 4 In a reactor similar to that of Example 1,
In 500 parts of the polycarbonate urethane resin solution obtained in Synthesis Example 3, bis (4-isocyanatocyclohexyl) methane / HOC ₃ H _6- {Si (CH ₃ ) ₂ O} n-Si
(CH ₃ ) ₂ C ₃ H ₆ OH (molecular weight = 1000) = 2/1
(Molar ratio), and 30.0 parts of a 30% concentration solution of siloxane chain-containing diisocyanate (hereinafter abbreviated as solution-I) obtained by reacting in dimethylformamide was charged and uniformly dissolved at 30 ° C. Keep it. Furthermore, bis- (4-aminocyclohexyl) previously mixed here
A solution consisting of 1.0 part of methane and 55.0 parts of dimethylformamide was added all at once, and the mixture was thoroughly mixed and reacted at 50 to 55 ° C. for 30 minutes. C. and the mixture was stirred at that temperature for 1 hour. Thus, finally, the nonvolatile content is 20% and the viscosity is 7
A translucent 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 isophorone diisocyanate / HOC ₃ H _6- ｛Si (CH ₃ )
₂ O｝ n-Si (CH ₃ ) ₂ C ₃ H ₆ OH (molecular weight = 100
0) = 2/1 (molar ratio) and 44.0 of a 30% concentration solution of siloxane chain-containing diisocyanate (hereinafter abbreviated as solution-II) obtained by reaction in dimethylformamide.
A part is charged, uniformly dissolved, and kept at room temperature (20 ° C.).

Further, a solution consisting of 1.8 parts of bis (4-aminocyclohexyl) methane and 82.0 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. After the reaction, 0.2 part of methanol was added, and the temperature was further raised to 70 ° C., and the mixture was stirred and stirred at that temperature for 1 hour. Thus, a translucent resin solution having a nonvolatile content of 20% and a viscosity of 35 poise was finally obtained.

Examples 6 to 10 Bis (4-isocyanatocyclohexyl) methane and dimethylformamide were added to 500 parts of the polyester-based urethane resin solution obtained in Synthesis Example 1 in the same reactor as in Example 1. Charge by the amount shown in Table 1, dissolve uniformly, and keep at room temperature (20 ° C.). Further, a solution in which α, ω-bis- (3-aminopropyl) polydimethylsiloxane (molecular weight = 1000) and dimethylformamide, each of which has been previously mixed, are added in batches or in portions is added. After that, a sufficient mixing reaction was performed at room temperature for 30 minutes.

In the ninth and tenth embodiments,
Under normal stirring power, the generated polyurea powder became bulky and difficult to disperse, so that it was necessary to further increase the stirring force.
Next, methanol was added in the amount shown in Table 1 and a further 7
The temperature was raised to 0 ° C., and the mixture was stirred at that temperature for 1 hour. Thus, a translucent resin solution having a nonvolatile content of 20% and a viscosity as shown in Table 1 was finally obtained.

[0085]

[Table 1]

Note: 1) H ₁₂ MDI = bis- (4-isocyanatoatocyclohexyl) methane 2) BAPS-1 = α, ω-bis- (3-aminopropyl) polydimethylsiloxane (Mw = 1000) 3) BAPS -2 = α, ω-bis- (3-aminopropyl) polydimethylsiloxane (Mw = 5000) 4) BATMDS = 1,3-bis- (3-aminopropyl) -1,1,3,3-tetramethyl Disiloxane 5) Solution-I = H ₁₂ MDI / HOC ₃ H _6- ｛Si (C
_{H 3) 2 0} n-} Si (CH 3) 2 C 3 H 6 OH * = 2/1
(Molar ratio) as a solution (N
V = 30%) where * Mw = 1000 6) H ₁₂ MDA = bis- (4-aminocyclohexyl)
Methane 7) Solution-II = IPDI / HOC ₃ H _6- ｛Si (C
_{H 3) 2 0} n-} Si (CH 3) 2 C 3 H 6 OH * = 2/1
(Molar ratio) as a solution (N
V = 30%) However, IPDI = isophorone diisocyanate, * Mw = 1000 [Comparative Example 1] 500 parts of the polyester urethane resin solution obtained in Synthesis Example 1 in a reactor similar to Example 1; 250 parts of formamide and 8.3 parts of bis (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.

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

Table 2 shows the storage stability of the solutions of each example,
The values of the moisture permeability, the water pressure resistance and the degree of stain resistance of the coating product obtained in this way were shown.

[0089]

[Table 2]

* Solid content with respect to polyurethane resin ** ：: Very slight mark remains, Δ: Slight mark remains ×: Mark does not fall off: No wiping was performed As apparent from these, the present invention is constituted A polyurethane resin composition obtained by uniformly dispersing a polyurea compound containing an organopolysiloxane group that is incompatible with a solvent and a resin in a specific range, not only exhibits excellent storage stability, but also has a superior storage stability. It can be seen that by applying the polyurethane resin composition thus obtained, a waterproof cloth having remarkably improved moisture permeability, improved water pressure resistance and excellent antifouling property can be 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, a waterproof cloth having remarkably improved moisture permeability and improved water pressure resistance and excellent antifouling property can be obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI D06M 15/564 D06M 15/564 // (C08L 75/04 75:02)

Claims (7)

[Claims] 1. An oligomer or polymer fine particle (B) having a urea bond and an organopolysiloxane group in a molecule, which is substantially incompatible with an organic solvent and a polyurethane resin, is dispersed in a polyurethane resin solution (A). A resin composition for a moisture-permeable waterproof cloth. 2. The composition according to claim 1, wherein the organopolysiloxane group is a tetraalkyldisiloxane group or a dialkylsiloxane group. 3. The composition according to claim 1, wherein the polyurethane resin solution (A) is applied to a wet film forming method. 4. An oligomer or polymer fine particle (B) having a urea bond and an organopolysiloxane group in the molecule.
The composition according to any one of claims 1 to 3, which is 0.1 to 40% by weight based on the solid content of the polyurethane resin of the polyurethane resin solution (A). 5. In a polyurethane resin solution, a compound having at least one isocyanate group and an organopolysiloxane group in a molecule, a compound having at least one amino group in a molecule, or a compound having an amino group and an organopolysiloxane in a molecule. A method for producing a resin composition for a moisture-permeable and waterproof cloth, comprising an oligomer or polymer fine particles having a urea bond and an organopolysiloxane group dispersed in a molecule, characterized by reacting a compound having a siloxane group and / or water. . 6. A polyurethane resin solution comprising reacting a compound having at least one isocyanate group in a molecule with a compound having at least one amino group and an organopolysiloxane group in a molecule. A method for producing a resin composition for a moisture-permeable waterproof cloth, comprising oligomer or polymer fine particles having a urea bond and an organopolysiloxane group in the molecule dispersed therein. 7. A moisture-permeable waterproof cloth obtained by applying the resin composition for a moisture-permeable waterproof cloth according to claim 1 to a substrate.