JP6726383B2 - Waterproof fabric - Google Patents

Description

The present invention relates to a urethane resin composition and a waterproof fabric using the same, and the urethane resin composition of the present invention has excellent moisture permeability, and a highly moisture-permeable waterproof fabric using the same. Is provided. Specifically, by combining with woven or knitted fabric, non-woven fabric, paper, porous film, etc., outdoor wear such as fishing wear and mountain clothing, ski related wear, windbreaker, athletic wear, golf wear, tennis wear, rainwear, casual coat. The present invention relates to a breathable waterproof cloth which can be suitably used in the field of indoor and outdoor work, clothing such as gloves and shoes, and clothing materials.

Conventionally, urethane resin has been used as a waterproof film by applying it to cloth due to its excellent mechanical properties, and has been used as a moisture-permeable waterproof film by making the polyurethane layer porous by a wet coagulation method. Focusing on the terminal group of the urethane resin, urethane resins having various characteristics have been invented, but the invention of the urethane resin terminal group that is a waterproof film-forming urethane resin that improves moisture permeability is It has not been.
For example, a water-based urethane resin for moisture-permeable waterproofing is disclosed as a urethane resin obtained by reacting a terminal isocyanate with an alkoxysilane to produce a moisture-permeable waterproof cloth without using an organic solvent. It was a porous membrane type, and the initial moisture permeability of the direct coating method was 13,000 g/m ² ·24 hrs (Test Example 6), and the moisture permeability was not sufficient (Patent Document 1).

Further, as a hydrophilic urethane resin having a hydroxyl group at the terminal group, a urethane resin containing at least one polymerization terminator selected from the group consisting of ethylene glycol, 1,4-butanediol, monoethanolamine and diethanolamine is disclosed. However, since it is a non-porous membrane type and is a method of laminating it on a polyester plain fabric with an adhesive after coating on release paper, the original moisture permeability of the urethane resin is not improved (Patent Document 2).

Furthermore, by using monoalcohols having 1 to 8 carbon atoms and monoamines having 1 to 10 carbon atoms as the reaction terminator, it is excellent in hydrophilicity and resin strength and has a small permanent set. And, a urethane resin capable of obtaining a moisture-permeable and waterproof material having excellent washing resistance is disclosed, but the moisture permeability is 10900 g/m ² ·24h at the maximum in the A-1 method, and the measurement evaluation by the B-1 method is performed. No (Patent Document 3).

In addition, as the polyol that constitutes the urethane resin, a polyol having an ester structure is mainly used from the viewpoint of satisfying the characteristics of flexibility, moisture permeability and waterproofness, and also in terms of raw material cost. However, the polyol having an ester structure is poor in hydrolysis resistance, and when used in a high temperature and high humidity environment, there is a problem in long-term use due to deterioration of the polyurethane layer. Therefore, in order to satisfy the durability, it is common to use a polyol having a carbonate structure, but as a urethane resin for moisture-permeable waterproofing that has both durability, moisture permeability and waterproof performance, Not invented.

For example, a polycarbonate-based polyurethane resin obtained by reacting a polycarbonate polyol, an alicyclic polyisocyanate, and an aromatic isocyanate may be a polyurethane resin useful for applications with high durability such as furniture and vehicle seats. Although disclosed (Patent Document 4), it cannot be said that the moisture-permeable and waterproof property is sufficient.

Further, it has been disclosed that a napped leather-like sheet material using a polyurethane resin composed of a polyol containing a polycarbonate diol has excellent durability such as light resistance and hydrolysis resistance (Patent Document 5, Patent In Document 6), it cannot be said that the moisture permeability and waterproofness are sufficient.

On the other hand, by overcoating a urethane resin dispersion liquid containing urethane fine particles having a carbonate group and an oxyethylene group on a porous moisture-permeable processed cloth, the moisture-permeable and waterproof cloth has excellent moisture permeability, water resistance, and lubricity. Is disclosed. However, since the resin composition which already has the moisture-permeable and waterproof property is overcoated on the cloth previously coated on the cloth, the moisture permeability cannot be said to be sufficient. (Patent Document 7)
Further, it is a polyurethane resin composition having a polyol containing an oxyalkylene structure-containing polyether polyol and a polycarbonate diol, and has durability such as adhesion to various substrates by coating agent or skin layer formation, heat resistance, hydrolysis resistance, etc. Although it is disclosed that a coating film that satisfies both requirements can be formed, it cannot be said that the water vapor transmission rate is sufficient (Patent Document 8).

JP, 2007-45866, A JP, 2010-215918, A JP, 2014-141643, A JP-A-3-244619 JP 2002-30579A JP-A-2002-61081 JP, 2007-169489, A International publication 2012/017724

The problem to be solved by the present invention is to provide a urethane resin and a waterproof cloth having moisture permeability, waterproofness, and durability.

As a result of intensive studies, the present inventors have found that a polyol compound having at least two hydroxyl groups reactive with an isocyanate group and a divalent aliphatic hydrocarbon group A and a diisocyanate compound having at least two isocyanate groups. And a functional group having an aliphatic hydrocarbon group B at the end of the chemical structure, and the hydrocarbon group B has a carbon number of divalent aliphatic carbon derived from the polyol compound. Urethane resin having 10 mol% or more of functional groups having a larger number of carbon atoms in the aliphatic hydrocarbon structure having the largest number of hydrogen groups A in the terminal functional groups, and urethane containing the urethane resin It was found that the above problems can be solved by a resin composition, and the present invention has been completed. It should be noted that the term "the largest number of structures" means that the largest number of the structures is included when the number of the aliphatic hydrocarbon groups having the largest number of structures giving the same number of carbons is compared, and is included in the structure. It does not mean that the carbon contained is the largest. Details will be described later.

Further, they have found that the above-mentioned problems can be solved by the following waterproof fabric, and have completed the present invention.
A waterproof cloth having a fiber cloth and a porous urethane resin layer containing a urethane resin composition containing a urethane resin on the surface of the fiber cloth,
The urethane resin is prepared by reacting a polyol compound having at least two hydroxyl groups reactive with an isocyanate group and a divalent aliphatic hydrocarbon group A with a diisocyanate compound having at least two isocyanate groups. What you get,
The urethane resin has a functional group having an aliphatic hydrocarbon group B having the following characteristics (i) to (iii) at the terminal of its molecular structure:
It is a waterproof fabric.
(I) The carbon number of the aliphatic hydrocarbon group B is larger than the carbon number of the maximum structural number aliphatic hydrocarbon group defined below.
Maximum number of structures Aliphatic hydrocarbon group: Divalent aliphatic hydrocarbon group A is classified according to the number of aliphatic carbons that compose the aliphatic hydrocarbon group, and divalent classified according to the number of carbons. Comparing the number of aliphatic hydrocarbon groups of, the divalent hydrocarbon group with the largest number.
(Ii) The aliphatic hydrocarbon group B has 8 to 22 carbon atoms.
(Iii) The aliphatic hydrocarbon group B is 10 mol% or more with respect to the terminal functional group of the polyurethane resin.

As another invention, a urethane resin having a functional group in which a part or all of hydrogen atoms of an aliphatic hydrocarbon group is substituted with a fluorine atom at the end of the chemical structure can be provided.

In a preferred embodiment of the invention, the polyol compound has a structure containing a carbonate group and a divalent aliphatic hydrocarbon group A and/or a structure containing an ether bond and a divalent aliphatic hydrocarbon group A. You can

The following are more preferable embodiments.
A urethane resin composition containing the urethane resin.
A urethane resin layer obtained by wet coagulation of the urethane resin composition is a fiber cloth and a waterproof cloth having the surface of the fiber cloth.
The urethane resin layer is preferably a porous film.
A non-porous film may be provided on the urethane resin layer. The non-porous membrane preferably has moisture permeability.
The waterproof fabric preferably has a water pressure resistance of 10 kPa or more.
It is preferable that the waterproof cloth has a water vapor permeability of 104 g/m ² ·hr or more according to JIS L 1099 B-1 method.
In the hydrolyzability evaluation test under the conditions of the temperature of 70° C. and the humidity of 95%, the waterproof fabric preferably has a water pressure resistance retention rate of 80% or more after 5 weeks.
The method for producing the waterproof fabric includes a step of applying a liquid composition of a urethane resin composition containing any one of the urethane resins to a fiber cloth, and then forming a urethane resin layer from the liquid composition. is there.
The step of forming the urethane resin layer is preferably a wet coagulation method.
The method for manufacturing the waterproof cloth may include a step of joining the urethane resin layer and the fiber cloth with an adhesive.

According to the urethane resin composition of the present invention, a urethane resin, a urethane resin film, and a waterproof cloth having good moisture permeability and waterproofness are provided.

Further, the fiber cloth and the waterproof cloth having the urethane resin layer formed on the surface of the fiber cloth have the comfort that can be suitably used for outdoor sports clothes, rain clothes and the like.
Further, the polyol compound of the urethane resin composition has a structure containing a carbonate group and a divalent aliphatic hydrocarbon group A and/or a structure containing an ether bond and a divalent aliphatic hydrocarbon group A, thereby improving durability. It is a urethane resin layer that has both moisture resistance and moisture permeability. The waterproof cloth made of a urethane resin layer having both durability and moisture permeability can be used for waders, salopette clothes and the like, and can be suitably used for fishing, rain clothes, work clothes and the like.

The urethane resin of the present invention comprises a polyol compound (A) having at least two hydroxyl groups reactive with an isocyanate group, an isocyanate compound having an isocyanate structure and at least two isocyanate groups (B), and if necessary. It is a urethane resin that can be obtained by reacting the chain extender (C) added as a reaction in the solvent (D) and terminating the polymerization with the reaction terminator (E).

The urethane resin referred to in the present invention includes not only a polyurethane resin having only a urethane bond but also a polyurethane/polyurea resin having a urea bond. The urea bond can be obtained by reacting the isocyanate compound (B) with a compound having an amino group, which can be optionally added in the present invention.

Moreover, the polyol compound (A) and the chain extender (C) are similar to each other and have two or more hydroxyl groups reactive with an isocyanate group in the molecular chain. Is a divalent aliphatic hydrocarbon group A, which is formed by combining two or more units of this functional group with an ester bond, a carbonyl group such as a carbonate group, or an ether bond in the middle of the skeleton. It has two or more hydroxyl groups in its molecular chain, and the chain extender (C) is composed of one unit of a divalent aliphatic hydrocarbon group, and the entire compound has two hydroxyl groups in its molecular chain. The above shall be possessed.

Examples of the polyol compound (A) include a polyester polyol having a structure containing an ester bond and a divalent aliphatic hydrocarbon group A, and a polyether polyol having a structure containing an ether bond and a divalent aliphatic hydrocarbon group A. A polycarbonate polyol having a structure containing a carbonate group and a divalent aliphatic hydrocarbon group A can be mentioned.

The polyester polyol is generally obtained by reacting a dibasic acid component and a dihydric alcohol component. Examples of the dibasic acid component include adipic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 6-hydroxyadipic acid. Examples of the dihydric alcohol component include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol. And the like, and alicyclic glycols such as cyclohexanediol, and aromatic glycols such as alkylene oxide adducts of bisphenol A. A polyester polyol is obtained by subjecting these dibasic acid component and dihydric alcohol component to a condensation reaction.

Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyneopentyl glycol, and copolymer polyether polyols.

Polycarbonate polyol forms a polymer chain linked through a carbonate bond, and has a hydroxyl group in the polymer chain. Polycarbonate polyol can be obtained by transesterification reaction of alkylene glycol and carbonic acid ester, reaction of phosgene or chloroformic acid ester with alkylene glycol, and the like. Examples of the alkylene glycol include linear alkylene glycols such as ethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol and 1,10-decanediol. And branched alkylene glycols such as neopentyl glycol, 3-methyl-1,5-pentanediol, and 2-methyl-1,8-octanediol. Examples of the carbonic acid ester used in the transesterification reaction include diethyl carbonate and diphenyl carbonate.

Examples of the above-mentioned isocyanate compound (B) include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymeric MDI, hexamethylene diisocyanate (HMDI), xylylene diisocyanate (XDI), tetramethyl xylylene diisocyanate (TMXDI), Examples of the isocyanate compound include isophorone diisocyanate (IPDI) and hydrogenated MDI.

Examples of the chain extender (C) include ethylene glycol, 1,4-butanediol, 1,3-butanediol (1,3-butylene glycol), neopentyl glycol, 1,5-pentanediol, methylpentanediol, Aliphatic diols such as 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol and 1,10-decanediol, 1,4-cyclohexanediol, hydrogenated xylyl Examples thereof include alicyclic diols such as len glycol and aromatic diols such as xylylene glycol.

Examples of the solvent (D) include amide solvents (dimethylformamide (DMF), dimethylacetamide, etc.), sulfoxide solvents (dimethylsulfoxide, etc.), ketone solvents (methylethylketone (MEK), etc.), aromatic solvents (toluene, Xylene etc.), ether type solvents (dioxane, tetrahydrofuran etc.), ester type solvents (ethyl acetate, butyl acetate etc.).

The above reaction terminator (E) is used in the urethane resin polymerization reaction so as to react with the terminal of the chemical structure to terminate the polymerization at the target viscosity.
As the reaction terminator (E), monohydric and polyhydric alcohols, monohydric amines and the like can be used. Examples thereof include monohydric and polyhydric alcohols (methanol, ethanol, butanol, propylene glycol, higher alcohols, higher fatty acid esters having a hydroxyl group, etc.), and monovalent amines (methylamine, butylamine, etc.). Here, propylene glycol has two hydroxyl groups, but a primary alcohol reacts with an isocyanate, and a secondary alcohol has poor reactivity due to steric hindrance, and as a result does not cause chain extension, it can be used as a reaction terminator. it can.

The divalent aliphatic hydrocarbon group A in the present invention may contain a carbon-carbon double bond or triple bond. Further, some or all of hydrogen may be replaced with other atoms or functional groups. Carbons that give a structure branched from the divalent aliphatic hydrocarbon group A or an alicyclic group structure are also counted in the carbon number. However, the carbonyl group, the ester bond, and the ether bond are not treated as structures in the divalent aliphatic hydrocarbon group A in the present invention, and the aromatic hydrocarbon group is a carbon atom even if it is monovalent or divalent or more. Not included in the number. When counting the number of carbon atoms at the branch from the skeleton side, if there is no next carbon to count and it becomes a bond of oxygen or nitrogen, count the carbons before oxygen and nitrogen. Similarly, when the number of carbons is counted, if a carbonyl group comes, count the carbons before the carbonyl group. Similarly, when counting the number of carbons, if aromatic carbons come, count them before the aromatic carbons. Here, the chemical formula of the divalent aliphatic hydrocarbon group A is illustrated, and the carbon number thereof is shown.

It is assumed that the atom bonded to the free chemical bond in the chemical formula is not the carbon constituting the aliphatic hydrocarbon group. The divalent hydrocarbon group of the formula (1) has 3 carbon atoms. Similarly, the number of carbon atoms in the formula (2) is 4. The number of carbon atoms in the formula (3) is 3. The number of carbon atoms in the formula (4) is 2. The number of carbon atoms in formula (5) is four. The number of carbon atoms in the formula (6) is 2. The number of carbons in formula (7) is four. In formula (8), there are two divalent hydrocarbon groups, which are methylene groups, each of which has 1 carbon atom.

When ethylene glycol, diethylene glycol, triethylene glycol, or polyethylene glycol is used as a raw material for the polyester polyol, polycarbonate polyol, or polyether polyol, the divalent aliphatic hydrocarbon group A has 2 carbon atoms. When propylene oxide or trimethylene glycol is used, the number of carbon atoms is 3, when 1,4-butanediol is used, the number of carbon atoms is 4, and when 1,5-pentanediol is used, the number of carbon atoms is 5. When 1,,6-hexanediol is used, the carbon number is 6.

“Molecule skeleton” refers to the space between the urethane bond (mostly a urea bond) existing closest to the end of the molecule and the urethane bond (sometimes urea bond) existing near the other end of the molecule. To tell.

The term “functional group at the terminal of the molecular structure” refers to a functional group located at the end of a urethane bond (or a urea bond in some cases) existing near the end of the molecule. The functional group at the end of the molecular structure contains a functional group having an aliphatic hydrocarbon group having a specific number or more of carbon atoms in a specific ratio or more.

The specific or more carbon number that the aliphatic hydrocarbon group B has is the carbon number of the divalent aliphatic hydrocarbon group A in the skeleton of the molecule (in the case where an aliphatic hydrocarbon structure having a plurality of carbon atoms is present, Means that the number of carbon atoms in the structure is larger than that of the aliphatic hydrocarbon group having a large number of structures. For example, of the divalent aliphatic hydrocarbon groups A, those giving 4 carbon atoms (here, the difference in chemical structure does not matter) are 60 mol% and those giving 6 carbon atoms (the difference in chemical structure does not matter) ) Is 20 mol% and the one giving 2 carbon atoms is 20 mol%, "the carbon number of the aliphatic hydrocarbon structure having the largest number of structures giving the same number of carbons in the divalent aliphatic hydrocarbon group A is The number is four.

The aliphatic hydrocarbon group B may contain a carbon-carbon double bond or a triple bond. Further, hydrogen of the hydrocarbon group may be replaced with another element or another functional group (for example, hydroxyl group). By definition, an aliphatic hydrocarbon group does not include a carbonyl group, an ester bond, or an ether bond, but even if the terminal functional group includes a carbonyl group, an ester bond, or an ether bond, if an aliphatic hydrocarbon group is present, , Judge that there is an aliphatic hydrocarbon group. However, the carbon number of the carbonyl group is not counted in the carbon number of the aliphatic hydrocarbon group.

When methyl alcohol is used as the reaction terminator, the number of carbon atoms in the aliphatic hydrocarbon group B is 1. When ethyl alcohol was used, the carbon number was 2, when propylene glycol was used, the carbon number was 3, and when cyclohexanol was used, the carbon number was 6, and lauryl alcohol (also known as 1-dodecanol) was used. In this case, the carbon number is 12. When diethyl carbinol (also known as 3-methyl-3-pentanol) is used, it has 6 carbon atoms. When an ester of ricinoleic acid (also known as 12-hydroxy-9-octadecenoic acid, having 18 carbon atoms and one hydroxyl group) and a lower alkyl alcohol is used, the number of hydrocarbon groups is 17. When octylamine is used, the aliphatic hydrocarbon group B has 8 carbon atoms.

The terminating agent usually has an aliphatic hydrocarbon group in its structure, and the number of carbon atoms in the hydrocarbon group is the same as that of the polyol compound (A) and the chain extender (C). Among the hydrogen structures, it has a carbon-hydrogen group larger than the number of carbon atoms of the aliphatic hydrocarbon structure having the largest number. This makes it possible to obtain a urethane resin having a high hydrophobicity at the molecular end, as compared with a conventional urethane resin composition.

The divalent aliphatic hydrocarbon structure A having the maximum number of structures, which is derived from the polyol compound in the skeleton of the urethane resin molecule, preferably has 2 to 9 carbon atoms, and more preferably has 2 to 6 carbon atoms from the viewpoint of polymerization reactivity.
The number of carbon atoms of the aliphatic hydrocarbon group B, which is larger than the number of carbon atoms of the aliphatic hydrocarbon structure having the largest structure number among the divalent aliphatic hydrocarbon groups A, is preferably 8 to 22. The hydrocarbon group having a specific number of carbon atoms does not need to be present in all the terminal functional groups, and if the terminal functional group (whether or not an aliphatic hydrocarbon group is present) is 10 mol% or more, The effects of the invention can be obtained. More preferably, it is 30 mol% or more. When the urethane resin is polymerized, a reaction terminator is finally added, but a reaction terminator that gives an aliphatic hydrocarbon group having a high carbon number is added in advance, and almost all of the reaction terminator is added. It can be obtained by reacting with an isocyanate group and then adding another reaction terminator if necessary. Further, in the second invention, a part or all of hydrogen of the aliphatic hydrocarbon group contained in the terminal group is substituted with a fluorine atom.

With this terminal structure, a urethane resin film having good moisture permeability is formed in the urethane resin layer. This is because the urethane resin of the present invention has an aliphatic hydrocarbon group having a large number of carbon atoms at the end of the chemical structure, or a functional group in which some or all of the hydrogen atoms of the hydrocarbon group are substituted with fluorine atoms. It is considered that the phase separation of the urethane resin layer molded by the wet coagulation method easily occurs uniformly.

It is considered that the reason is that the above-mentioned functional group improves the hydrophobicity of the end of the urethane resin structure to induce uniform phase separation to form a homogeneous and fine porous body. These homogeneous and fine porous materials improve both properties compared to the conventional water vapor permeability and water resistance (water resistance and water vapor permeability) in the porous shape caused by phase separation induced by solvent substitution. be able to.

The components (A) to (E) may be used alone, or two or more of them may be mixed and used. In the production of polyurethane, the reaction temperature may be the same as the temperature usually adopted in the urethanization reaction, and is usually 30 to 90°C when a solvent is used and 30 to 220°C when no solvent is used.

Further, in order to accelerate the reaction, a catalyst usually used in a urethane reaction, for example, an amine-based catalyst such as triethylamine or triethylenediamine can be used if necessary.

The urethane resin produced in this way has a solution viscosity at 30° C. measured as a 25% by mass (solid content) DMF solution of usually from 1,000 to 1,000,000 mPa·s, preferably from 10,000 to practically. It is 200,000 mPa·s.

The urethane resin of the present invention may contain the organic solvents listed above as examples, and the amount thereof is usually such that the resin solid content concentration of the urethane resin is 5 to 50% by mass, and preferably 10 The amount is about 40% by mass.

In the resin composition containing the urethane resin of the present invention, as necessary, various stabilizers for improving weather resistance, heat deterioration and the like, crosslinking agents such as polyfunctional isocyanate compounds, colorants, inorganics such as silica. Fillers, organic modifiers, other additives and the like can be included.

(2) Waterproof Fabric and Method for Producing the Same The waterproof fabric of the present invention using the urethane resin preferably has a water pressure resistance of 10 kPa or more from the viewpoint of practical waterproofing.

From the viewpoint of practical durability, it is preferable that the durability retention rate after 5 weeks in the hydrolysis evaluation test (jungle test: temperature 70° C., humidity 95% RH) is 80% or more.

In the present invention, a polycarbonate polyol having a structure containing a carbonate group and a divalent aliphatic hydrocarbon group A as a component of the polyol compound (A) and/or a structure containing an ether bond and a divalent aliphatic hydrocarbon group A By using the polyether polyol that is possessed, it is easy to make the retention rate of the waterproof cloth 5% or more after 5 weeks of the hydrolytic hydrolysis evaluation test 5 weeks. Further, even after 10 weeks, a waterproof fabric having a water pressure resistance retention rate of 50% or more, which is 5 times or more as compared with the case of using a normal polyester polyol, can be obtained.

Waterproof fabric of the present invention, 104 g ^{/ m} 2 · hr or more in JIS standard L1099A-1 method as moisture permeability, and / or preferably has a higher 104 g ^{/ m} 2 · hr at the same standard B-1 method.

In the present invention, a polycarbonate polyol having a structure containing a carbonate group and a divalent aliphatic hydrocarbon group A as a component of the polyol compound (A) and/or a structure containing an ether bond and a divalent aliphatic hydrocarbon group A Higher water vapor transmission rate can be obtained by using the polyether polyol.

Moisture permeability can be imparted to the urethane resin film by forming the urethane resin into a porous film by a wet method. Furthermore, it is preferable to form a microporous film by a wet method.
By laminating a non-porous film having moisture permeability on a porous film or a microporous film, higher water pressure resistance or moisture permeability can be obtained.

The method for producing the waterproof cloth of the present invention can be obtained by forming a urethane resin layer on the surface of the fiber cloth. A method of applying a liquid composition containing the urethane resin composition to a fiber cloth (a direct coating method), or after forming the urethane resin layer alone, using the urethane resin layer and the fiber cloth with an adhesive. There is a method of joining (joining method). This urethane resin layer is preferably a porous film or a microporous film.

If necessary, the liquid composition containing the urethane resin composition may be mixed with an additive that can serve as a nucleus (inducer) during phase separation.

Examples of the additive include fine particles of inorganic materials and organic compounds, and silica fine powder is preferable. The method for producing silica is not particularly limited, and examples thereof include a gas phase reaction method and a sol-gel method, and examples of the silica raw material include tetrafunctional silane, trifunctional silane, and bifunctional silane.

In the direct coating method, various coating methods such as knife coating, knife over roll coating and reverse rule coating can be used, but the method is not limited thereto.

In the joining method, for example, a method in which a urethane resin layer formed by coating or the like on a release paper is laminated on a fiber cloth by an adhesive or by dot or whole surface adhesion and then the release paper is peeled off is not limited to this.

As a preferred embodiment of the method for laminating a urethane resin having moisture permeability and waterproofness, the urethane resin of the present invention is represented by a water-soluble polar solvent (dimethylformamide:DMF, dimethylsulfoxide:DMSO, etc.). A liquid composition containing a urethane resin composition dissolved in water is coated on a fiber cloth and wet gelated in water or an aqueous solution containing a polar solvent to have both moisture permeability and waterproofness. This is a method of forming a porous film.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

The following methods were used as methods for measuring various performances in the present specification and the like including the following examples.
(Measuring method)
(1) Water pressure resistance: Measured according to JIS-L1092 (2009).
(2) Water vapor transmission rate: measured according to the A-1 and B-1 methods of JIS-L1099 (2012).
(3) Hydrolysis test (jungle test): Hydrolysis is promoted in a high temperature and high humidity tank at 70° C. and a relative humidity of 95%, and the water pressure resistance retention rate (the ratio of the water pressure resistance after the test to the water pressure before the test, Unit %).

[Example 1]
<Polymerization of polyurethane resin solution (1)>
Polyester polyol (ethylene glycol adipate, structure of divalent aliphatic hydrocarbon group A, maximum carbon number: 4, manufactured by Nippon Polyurethane Industry Co., Ltd., "Nipporan" (registered trademark; the same applies hereinafter) 4060) 75 g, polyester polyol ( Butylene glycol adipate, structure of divalent aliphatic hydrocarbon group A Maximum carbon number: 4, Nippon Polyurethane Industry Co., Ltd., "Nipporan" 4010) 35 g, polyester polyol (neopentyl glycol adipate, divalent aliphatic carbonization) Hydrogen group A structure maximum carbon number: 5, Hitachi Chemical Co., Ltd., "Teslac" 2471) 47g, polyester polyol (hexylene glycol caprolactone, divalent aliphatic hydrocarbon group A structure maximum carbon number: 6, Daicel Co., Ltd., PCL-205 (28 g) and dimethylformamide (hereinafter, "DMF") 245 g were put into 2 liters of separable corbene to dissolve, and diphenylmethane diisocyanate 137 g was added while controlling the temperature to 50°C. The reaction was carried out at ℃ for about 1 hour to obtain a prepolymer. Thereafter, the temperature was raised to 60° C., ethylene glycol (20 g and DMF 65 g were added, a chain extension reaction was carried out at 60° C., and polymerization was carried out while DMF 611 g was added portionwise in accordance with the increase in viscosity. The carbon number of the structural unit of the divalent aliphatic hydrocarbon group A, which has the largest number of carbon atoms in the coalesce, is 6. Analyze the residual amount of isocyanate during the polymerization to determine the residual amount of the isocyanate at the end of the polymerization. Glycerin-monodiolate corresponding to 66 mol% (mixing ratio of glycerin-monooleate/glycerin-diolate 50%/50% (mol/mol)) (maximum carbon number of aliphatic hydrocarbon group B provided by this compound: 17) , Riken Vitamin Co., Ltd., OL-200V) (5.5 g) was added and reacted for 30 minutes, and then propylene glycol (carbon number of hydrocarbon group: 3) 10 g and DMF 137 g were added in about 6 to 8 hours. After the reaction was completed, a liquid composition of a urethane resin composition having a urethane resin concentration of 25.4% and a viscosity of 41,000 mPa·s (30° C.) was obtained.

[Example 2]
<Polymerization of polyurethane resin solution (2)>
Polyester polyol (ethylene glycol adipate, structure of divalent aliphatic hydrocarbon group A, maximum carbon number: 4, Nippon Polyurethane Industry Co., Ltd., "Nipporan" 4060) 79 g, polyester polyol (butylene glycol adipate, divalent fat) Maximum structure carbon number of group hydrocarbon group A: 4, Nippon Polyurethane Industry Co., Ltd., "Nipporan" 4010) 28 g, polyester polyol (neopentyl glycol adipate, divalent aliphatic hydrocarbon group A structure maximum number of carbon atoms : 5, Hitachi Chemical Co., Ltd., "Teslac" 2471) 50 g, polyester polyol (hexylene glycol caprolactone, divalent aliphatic hydrocarbon group A structure maximum carbon number: 6, Daicel Corporation, PCL-205 ) 28 g and 245 g of dimethylformamide were put into 2 liters of separable corbene and dissolved, and 137 g of diphenylmethane diisocyanate was added while controlling the temperature at 50° C. and reacted at 50° C. for about 1 hour to obtain a prepolymer. Then, the temperature was raised to 60° C., 20 g of ethylene glycol and 65 g of DMF were added, a chain length extension reaction was carried out at 60° C., and polymerization was carried out while D584 of DMF was added in portions in accordance with the increase in viscosity. The divalent aliphatic hydrocarbon group A having the largest number of carbon atoms in the polymer has 6 carbon atoms in the structural unit. The amount of isocyanate remaining was analyzed during the polymerization, and at the end of the polymerization, 3.6 g of behenyl alcohol (carbon number of aliphatic hydrocarbon group B: 22, NOA-422 manufactured by NOF CORPORATION) corresponding to 67 mol% of the amount of remaining isocyanate. Was added to 27 g of DMF and reacted for 30 minutes, and then 10 g of propylene glycol (carbon number of hydrocarbon group: 3) and 137 g of DMF were added. The reaction was completed in about 6 to 8 hours, and a urethane resin solution having a urethane resin concentration of 25.4% and a viscosity of 55,000 mPa·s (30° C.) was obtained.

[Example 3]
<Polymerization of polyurethane resin solution (3)>
77 g of polyester polyol (ethylene glycol adipate, structure of divalent aliphatic hydrocarbon group A: maximum carbon number: 4, Nippon Polyurethane Industry Co., Ltd., "Nipporan" 4060), polyester polyol (butylene glycol adipate, divalent fat) Maximum structure carbon number of group hydrocarbon group A: 4, Nippon Polyurethane Industry Co., Ltd. product, "Nipporan" 4010) 29 g, polyester polyol (neopentyl glycol adipate, divalent aliphatic hydrocarbon group A maximum structure carbon number : 5, Hitachi Chemical Co., Ltd., "Teslac" 2471) 45 g, polyester polyol (hexylene glycol caprolactone, divalent aliphatic hydrocarbon group A structure maximum carbon number: 6, Daicel Corporation, PCL-205 ) 35 g and 245 g of dimethylformamide were put into 2 liters of separable corbene and dissolved, and 137 g of diphenylmethane diisocyanate was added while controlling the temperature at 50° C. and reacted at 50° C. for about 1 hour to obtain a prepolymer. Then, the temperature was raised to 60° C., 20 g of ethylene glycol and 65 g of DMF were added, a chain length extension reaction was carried out at 60° C., and polymerization was carried out while adding 611 g of DMF in accordance with the increase in viscosity. The divalent aliphatic hydrocarbon group A having the largest number of carbon atoms in the polymer has 6 carbon atoms in the structural unit. The amount of isocyanate remaining is analyzed during the polymerization, and propylene glycol monooleate corresponding to 66 mol% of the amount of the remaining isocyanate at the end of the polymerization (carbon number of aliphatic hydrocarbon group B: 17, Riken Vitamin Co., Ltd., PO-100V) After adding 3.7 g and reacting for 30 minutes, 10 g of propylene glycol (carbon number of hydrocarbon group: 3) and 137 g of DMF were added. The reaction was completed in about 6 to 8 hours, and a urethane resin solution having a urethane resin concentration of 25.4% and a viscosity of 85,000 mPa·s (30° C.) was obtained.

[Example 4]
<Polymerization of polyurethane resin solution (4)>
Polycarbonate polyol (hexamethylene carbonate diol, structural carbon number of divalent aliphatic hydrocarbon group A: 6, Nippon Polyurethane Industry Co., Ltd., "Nipporan" 980R) 108 g, polyether polyol (polytetramethylene glycol, divalent The number of structural carbon atoms of the aliphatic hydrocarbon group A is 4, 4, 27 g of PTMG-2000M (manufactured by Sanyo Chemical Industry Co., Ltd.), and 163 g of dimethylformamide are dissolved in 2 liters of separable Kolben and the temperature is adjusted to 50°C. Meanwhile, 87 g of diphenylmethane diisocyanate was added and reacted at 50° C. for about 1 hour to obtain a prepolymer. Then, the temperature was raised to 60° C., 17 g of ethylene glycol and 40 g of DMF were added, a chain length extension reaction was carried out at 60° C., and polymerization was carried out while adding 435 g of DMF in divided portions according to the increase in viscosity. The divalent aliphatic hydrocarbon group A having the largest number of carbon atoms in the polymer has 6 carbon atoms in the structural unit. The residual amount of isocyanate is analyzed during the polymerization, and propylene glycol monooleate (the number of carbon atoms of the aliphatic hydrocarbon group B: 17, which is 100 mol% or more (excess amount) of the residual amount of the isocyanate at the end of the polymerization, manufactured by Riken Vitamin Co., Ltd., After adding 4.7 g of PO-100V) and reacting for 30 minutes, 7 g of propylene glycol (carbon number of hydrocarbon group: 3) and 83 g of DMF were added. The reaction was completed in about 6 to 8 hours, and a urethane resin solution having a urethane resin concentration of 25.0% and a viscosity of 82,000 mPa·s (30° C.) was obtained.

[Example 5]
<Polymerization of polyurethane resin solution (5)>
Polycarbonate polyol (hexamethylene carbonate diol, structural carbon number of divalent aliphatic hydrocarbon group A: 6, Nippon Polyurethane Industry Co., Ltd., "Nipporan" 980R) 130 g, polyether polyol (polytetramethylene glycol, divalent The number of structural carbon atoms of the aliphatic hydrocarbon group A is 4; Sanyo Kasei Co., Ltd., PTMG-2000M 32g, and dimethylformamide 250g are dissolved in 2 liters of separable Kolben, and the temperature is adjusted to 50°C. Meanwhile, 87 g of diphenylmethane diisocyanate was added and reacted at 50° C. for about 1 hour to obtain a prepolymer. Thereafter, the temperature was raised to 60° C., 16 g of ethylene glycol and 40 g of DMF were added, a chain length extension reaction was carried out at 60° C., and polymerization was carried out while adding 400 g of DMF in divided portions according to the increase in viscosity. The divalent aliphatic hydrocarbon group A having the largest number of carbon atoms in the polymer has 6 carbon atoms in the structural unit. Analyzing the residual amount of isocyanate during the polymerization, ricinoleic acid alkyl ester corresponding to 46 mol% of the residual amount of the isocyanate at the end of the polymerization (carbon number of aliphatic hydrocarbon group B: 17, Ito Oil Co., Ltd., URICH-31S) After adding 1.5 g and reacting for 30 minutes, 8 g of propylene glycol (carbon number of hydrocarbon group: 3) and 110 g of DMF were added. The reaction was completed in about 6 to 8 hours, and a urethane resin solution having a urethane resin concentration of 25.0% and a viscosity of 90,000 mPa·s (30° C.) was obtained.

[Example 6]
<Polymerization of polyurethane resin solution (6)>
Polyester polyol (ethylene glycol adipate, structure of divalent aliphatic hydrocarbon group A, maximum carbon number: 4, Nippon Polyurethane Industry Co., Ltd., "Nipporan" 4060) 79 g, polyester polyol (butylene glycol adipate, divalent fat) Maximum structure carbon number of group hydrocarbon group A: 4, Nippon Polyurethane Industry Co., Ltd., "Nipporan" 4010) 31 g, polyester polyol (neopentyl glycol adipate, structure maximum carbon number of divalent aliphatic hydrocarbon group A) : 5, Hitachi Chemical Co., Ltd., "Teslac" 2471) 47 g, polyester polyol (hexylene glycol caprolactone, divalent aliphatic hydrocarbon group A structure maximum carbon number: 6, Daicel Corporation, PCL-205 ) 28 g and 245 g of dimethylformamide were put into 2 liters of separable corbene and dissolved, and 137 g of diphenylmethane diisocyanate was added while controlling the temperature at 50° C. and reacted at 50° C. for about 1 hour to obtain a prepolymer. Then, the temperature was raised to 60° C., 20 g of ethylene glycol and 65 g of DMF were added, a chain extension reaction was carried out at 60° C., and polymerization was carried out while adding 611 g of DMF in accordance with the increase in viscosity. The divalent aliphatic hydrocarbon group A having the largest number of carbon atoms has 6 carbon atoms in the structural unit. Analyzing the isocyanate remaining in the polymerization, C6 fluorinated alcohol corresponding to 75 mol% of the isocyanate remaining at the end of polymerization (2- (perfluorohexyl) _{ethanol, F (CF 2) 6 CH} 2 CH 2 OH, UNIMATEC ( Ltd., "CHEMINOX" (registered trademark, the same applies hereinafter) 4.5 g of FA-6) was added and reacted for 30 minutes, and then 11 g of propylene glycol (carbon number of hydrocarbon group: 3) and 137 g of DMF were added. The reaction was completed in about 6 to 8 hours, and a urethane resin solution having a urethane resin concentration of 25.4% and a viscosity of 49,000 mPa·s (30° C.) was obtained.

[Example 7]
<Polymerization of polyurethane resin solution (7)>
Polyester polyol (ethylene glycol adipate, structure of divalent aliphatic hydrocarbon group A, maximum carbon number: 4, Nippon Polyurethane Industry Co., Ltd., "Nipporan" 4060) 79 g, polyester polyol (butylene glycol adipate, divalent fat) Maximum structure carbon number of group hydrocarbon group A: 4, Nippon Polyurethane Industry Co., Ltd., "Nipporan" 4010) 31 g, polyester polyol (neopentyl glycol adipate, structure maximum carbon number of divalent aliphatic hydrocarbon group A) : 5, Hitachi Chemical Co., Ltd., "Teslac" 2471) 47 g, polyester polyol (hexylene glycol caprolactone, divalent aliphatic hydrocarbon group A structure maximum carbon number: 6, Daicel Corporation, PCL-205 ) 28 g and 245 g of dimethylformamide were put into 2 liters of separable corbene and dissolved, and 137 g of diphenylmethane diisocyanate was added while controlling the temperature at 50° C. and reacted at 50° C. for about 1 hour to obtain a prepolymer. Then, the temperature was raised to 60° C., 20 g of ethylene glycol and 65 g of DMF were added, a chain extension reaction was carried out at 60° C., and polymerization was carried out while adding 611 g of DMF in accordance with the increase in viscosity. The divalent aliphatic hydrocarbon group A having the largest number of carbon atoms has 6 carbon atoms in the structural unit. The remaining amount of isocyanate is analyzed during the polymerization, and C4/C5 fluorine-substituted alcohol (3,3,4,4,5,5,6,6,7,7,9 corresponding to 65 mol% of the remaining amount of the isocyanate at the end of the polymerization. , 9,10,10,11,11,12,12,12- nonadecamethylene fluoro _{dodecanol, F (CF 2) 4 CH} 2 (CF 2) 5 CH 2 CH 2 OH,
After 5.8 g of "CHEMINOX" FA-45 (Unimatec Co., Ltd.) was added and reacted for 30 minutes, 11 g of propylene glycol (carbon number of hydrocarbon group: 3) and 137 g of DMF were added. The reaction was completed in about 6 to 8 hours, and a urethane resin solution having a urethane resin concentration of 24.9% and a viscosity of 57,000 mPa·s (30° C.) was obtained.

[Example 8]
<Polymerization of polyurethane resin solution (8)>
77 g of polyester polyol (ethylene glycol adipate, structure of divalent aliphatic hydrocarbon group A: maximum carbon number: 4, Nippon Polyurethane Industry Co., Ltd., "Nipporan" 4060), polyester polyol (butylene glycol adipate, divalent fat) Maximum number of carbon atoms of group hydrocarbon group A: 4, Nippon Polyurethane Industry Co., Ltd., “Nipporan” 4010, 29 g, polyester polyol (neopentyl glycol adipate, structure of maximum C number of divalent aliphatic hydrocarbon group A) : 5, Hitachi Chemical Co., Ltd., "Teslac" 2471) 45 g, polyester polyol (hexylene glycol caprolactone, structure of divalent aliphatic hydrocarbon group A: maximum carbon number: 6, Daicel Corporation, PCL-205 ) 35 g and 245 g of dimethylformamide were put into 2 liters of separable corbene and dissolved, and 137 g of diphenylmethane diisocyanate was added while controlling the temperature at 50° C. and reacted at 50° C. for about 1 hour to obtain a prepolymer. Then, the temperature was raised to 60° C., 20 g of ethylene glycol and 65 g of DMF were added, a chain extension reaction was carried out at 60° C., and polymerization was carried out while adding 611 g of DMF in accordance with the increase in viscosity. The divalent aliphatic hydrocarbon group A having the largest number of carbon atoms has 6 carbon atoms in the structural unit. The remaining amount of isocyanate is analyzed during the polymerization, and C4/C5 fluorine-substituted alcohol (3,3,4,4,5,5,6,6,7,7,9) corresponding to 32 mol% of the remaining amount of the isocyanate at the end of the polymerization. , 9,10,10,11,11,12,12,12- nonadecamethylene fluoro _{dodecanol, F (CF 2) 4 CH} 2 (CF 2) 5 CH 2 CH 2 OH, UNIMATEC (Ltd.), "CHEMINOX" After adding 1.2 g of FA-45) and reacting for 15 minutes, 1.0 g of propylene glycol monooleate (carbon number of aliphatic hydrocarbon group B: 17, Riken Vitamin Co., Ltd., PO-100V) is added. After reacting for 15 minutes, 10 g of propylene glycol (carbon number of hydrocarbon group: 3) and 137 g of DMF were added. The reaction was completed in about 6 to 8 hours, and a urethane resin solution having a urethane resin concentration of 25.4% and a viscosity of 55,000 mPa·s (30° C.) was obtained.

[Example 9]
<Polymerization of polyurethane resin solution (9)>
Polycarbonate polyol (hexamethylene carbonate diol, structure of divalent aliphatic hydrocarbon group A maximum carbon number: 6, Nippon Polyurethane Industry Co., Ltd., "Nipporan" 980R) 130 g, polyether polyol (polytetramethylene glycol, 2 Structure of valent aliphatic hydrocarbon group A Maximum carbon number: 4, Sanyo Kasei Kogyo Co., Ltd., PTMG-2000M 32g, and dimethylformamide 250g were put into 2 liters of separable Kolben and dissolved, and at 50°C. While controlling the temperature, 87 g of diphenylmethane diisocyanate was added and reacted at 50° C. for about 1 hour to obtain a prepolymer. Then, the temperature was raised to 60° C., 16 g of ethylene glycol and 40 g of DMF were added, a chain extension reaction was carried out at 60° C., and polymerization was carried out while D435 of 435 g was added in portions in accordance with the increase in viscosity. The divalent aliphatic hydrocarbon group A having the largest number of carbon atoms has 6 carbon atoms in the structural unit. The remaining amount of isocyanate is analyzed during the polymerization, and C4/C5 fluorine-substituted alcohol (3,3,4,4,5,5,6,6,7,7,9) corresponding to 36 mol% of the remaining amount of the isocyanate at the end of the polymerization. , 9,10,10,11,11,12,12,12- nonadecamethylene fluoro _{dodecanol, F (CF 2) 4 CH} 2 (CF 2) 5 CH 2 CH 2 OH, UNIMATEC (Ltd.), "CHEMINOX" DFTA-103) 1.2 g was added and reacted for 15 minutes, and then an ester of ricinoleic acid and a lower alkyl alcohol (carbon number of aliphatic hydrocarbon group B: 17, Ito Oil Co., Ltd., URICH-31S). After 0.8 g was added and reacted for 15 minutes, 8 g of propylene glycol (carbon number of hydrocarbon group: 3) and DMF of 83 g were added. The reaction was completed in about 6 to 8 hours, and a urethane resin solution having a urethane resin concentration of 25.0% and a viscosity of 80,000 mPa·s (30° C.) was obtained.

[Example 10]
<Molding of waterproof fabric (1)>
Nylon lip taffeta composed of 50 denier nylon filament yarn is diluted with 30 g/l of a fluorine-based water repellent (“Dykin Industry Co., Ltd., “Unidyne” (registered trademark; the same applies hereinafter) TG-5521). After immersing and squeezing with a mangle so that the squeezing ratio would be 40%, it was dried at 120° C., heat-treated at 130° C. for 30 seconds, and subjected to water repellent treatment.

Next, 80 parts by weight of the polyurethane resin solution (1) prepared in Example 1 was mixed with silica fine powder (manufactured by Tokuyama Corp., ""Roleoseal" (registered trademark; the same applies hereinafter) MT-10 and dimethyldichlorosilane gas. 6 parts by weight of phase-reactive silica), was fully immersed in 50 parts by weight of DMF, dispersed and stirred with a homomixer for about 15 minutes, and then stirred to obtain a liquid composition of a polyurethane resin composition.

The above water repellent nylon lip taffeta was coated with a knife over roll coater at a coating amount of 150 g/m ² , and an aqueous solution containing 20% by weight of DMF was immersed in a gelling bath for 2 minutes and washed with water for 10 minutes, It was dried with hot air at 140°C to obtain a waterproof fabric.
The obtained cloth was evaluated for water pressure resistance and water vapor transmission rate (A-1, B-1). After performing a jungle test (70° C., 95% for 5 weeks), the water pressure resistance was measured to determine the retention rate. The results are shown in Table 1 or Table 2.

Further, the same processing and evaluation were performed on the liquid compositions (2), (3) and (6) to (8) of the polyurethane resin composition prepared in each of the above Examples.

[Example 11]
<Molding of waterproof fabric (2)>
Nylon lip taffeta composed of 50 denier nylon filament yarn was dipped in a 30 g/l dilution of a fluorine-based water repellent ("Unidyne" TG-5521, Daikin Industries, Ltd.) to obtain a squeezing ratio of 40%. After squeezing with a mangle so that it was dried at 120° C., heat treatment was performed at 130° C. for 30 seconds to perform water repellent treatment.

Next, to 80 parts by weight of the polyurethane resin solution (4) prepared in the above Example, 5 parts by weight of silica fine powder ("Roleoseal" MT-10, a gas phase reaction silica of dimethyldichlorosilane, manufactured by Tokuyama Corporation) was added. Then, it was sufficiently immersed in 60 parts by weight of DMF, dispersed and stirred with a homomixer for about 15 minutes, and then stirred to obtain a liquid composition of a polyurethane resin composition.
The above water repellent nylon lip taffeta was coated with a knife over roll coater at a coating amount of 150 g/m ² , and an aqueous solution containing 20% by weight of DMF was immersed in a gelling bath for 2 minutes and washed with water for 10 minutes, It was dried with hot air at 140°C to obtain a waterproof fabric.

The obtained cloth was evaluated for water pressure resistance and water vapor transmission rate (A-1, B-1). After performing a jungle test (70° C., 95% for 5 weeks), the water pressure resistance was measured to determine the retention rate. The results are shown in Table 1 or Table 2. Further, the same processing and evaluation were carried out for the polyurethane resin solutions (5) and (9) for the moisture-proof processed cloth.

[Example 12]
<Molding of waterproof fabric having a non-porous membrane having moisture permeability>
25 parts by weight of MEK and 25 parts by weight of toluene were added to 100 parts by weight of a polyether polyurethane solution ("Heimlen" Y-262 manufactured by Dainichiseika Kogyo Co., Ltd.) and mixed by a mixer to obtain a polyurethane compounding liquid.

This was coated on the urethane resin film obtained in Example 10 or 11 by a floating method at a coating amount of 15 g/m ² and dried with hot air at 80° C. to form a porous film having a non-porous film having moisture permeability. A waterproof/moisture permeable cloth having a waterproof/moisture permeable layer on one surface was obtained. The obtained cloth was evaluated for water pressure resistance and water vapor transmission rate (A-1, B-1). The results are shown in Table 1 or Table 2.
<Molding of waterproof fabric (1) having a microporous membrane>
To 80 parts by weight of the polyurethane resin solution (1) prepared in the above Example, 8 parts by weight of silica fine powder (“Roleoseal MT-10, a gas phase reaction silica of dimethyldichlorosilane” manufactured by Tokuyama Corporation) was added, and DMF50 was added. A liquid composition of a polyurethane resin composition was obtained after sufficiently dipping in parts by weight and dispersing and stirring with a homomixer for about 15 minutes.

The above water-repellent nylon lip taffeta was coated with a knife over roll coater at a coating amount of 150 g/m2, and an aqueous solution containing 25% by weight of DMF was immersed in a gelling bath at 35°C for 2 minutes. The polyurethane resin-containing coating solution was wet-coagulated, washed with warm water of 50° C. for 10 minutes, and dried with hot air at 120° C. to form a microporous moisture-permeable waterproof layer. The obtained fabric was evaluated for water pressure resistance and water vapor transmission rate (A-1, B-1). The results are shown in Table 1 or Table 2.

Further, the same processing and evaluations were carried out for the polyurethane resin solutions (2), (3) and (6) to (8) for the cloth for preventing moisture permeation.

[Example 14]
<Molding of waterproof fabric (2) having a microporous membrane>
To 80 parts by weight of the polyurethane resin solution (4), 8 parts by weight of silica fine powder (“Lorocile” MT-10, manufactured by Tokuyama Corp., gas phase reaction silica of dimethyldichlorosilane) was added, and fully immersed in 60 parts by weight of DMF. Then, the mixture was dispersed and stirred with a homomixer for about 15 minutes to obtain a liquid composition of a polyurethane resin composition.

The above water-repellent nylon lip taffeta was coated with a knife over roll coater at a coating amount of 150 g/m2, and an aqueous solution containing 25% by weight of DMF was dipped in a gelling bath at 35°C for 2 minutes. The polyurethane resin-containing coating solution was wet-coagulated, washed with hot water at 50° C. for 10 minutes, and dried with hot air at 120° C. to form a microporous moisture-permeable waterproof layer. The obtained cloth was evaluated for water pressure resistance and water vapor transmission rate (A-1, B-1). The results are shown in Table 1 or Table 2.

Further, the polyurethane resin solutions (5) and (9) were also processed and evaluated in the same manner.

[Example 15]
<Molding of waterproof fabric using adhesive>
Polyester taffeta composed of 50 denier polyester filament yarn is dipped in a 30 g/lmp diluted solution of a fluorine-based water repellent (“Unidyne” TG470B manufactured by Daikin Industries, Ltd.) and squeezed with a mangle at a squeezing rate of 40% After that, it was dried at 120° C., heat-treated at 130° C. for 30 seconds, and calendered at 160° C. with a calendering machine having a mirror surface roll to obtain a release cloth.

The polyurethane resin compounded solution obtained in Example 10 or 11 was coated with a knife over roll coater at a coating amount of 150 g/m 2 with the calendar surface of the release cloth as the coating surface, and an aqueous solution containing 20% by weight of DMF was gelled. It was washed with water for 10 minutes in a bath containing a chemical bath and dried with hot air at 140° C. to form a microporous urethane film on the surface of the release cloth.

Next, a nylon lip taffeta composed of a 50 denier nylon filament yarn was dipped in a 30 g/1 dilution of a fluorine-based water repellent (Daikin Industries, Ltd., "Unidyne" TG-5521), and the squeezing ratio was reduced. After squeezing with a mangle at 40%, it was dried at 120°C, heat-treated at 130°C for 30 seconds, and water-repellent treated. The resulting water-repellent treated cloth was melted at 100°C using a 30-mesh gravure roll. Moisture-curable polyurethane hot melt adhesive (NH-124, manufactured by DIC Co., Ltd.) was applied, and a microporous urethane film on the surface of the release cloth was adhered and aged with the pressure applied for 24 hours at 40° C. The mold cloth was peeled off to obtain a moisture permeable waterproof fabric in a laminated mode of "fiber fabric/adhesive/moisture permeable waterproof film".

The obtained fabric was evaluated for water pressure resistance and moisture permeability (A-1, B-1). After performing a jungle test (70° C., 95% for 5 weeks), the water pressure resistance was measured to determine the retention rate. The results are shown in Table 1 or Table 2.

[Comparative Example 1]
<Polymerization of polyurethane resin solution (10)>
Polyester polyol (ethylene glycol adipate, structure of divalent aliphatic hydrocarbon group A, maximum carbon number: 4, Nippon Polyurethane Industry Co., Ltd., "Nipporan" 4060) 79 g, polyester polyol (butylene glycol adipate, divalent fat) Maximum structure carbon number of group hydrocarbon group A: 4, Nippon Polyurethane Industry Co., Ltd., "Nipporan" 4010) 31 g, polyester polyol (neopentyl glycol adipate, structure maximum carbon number of divalent aliphatic hydrocarbon group A) : 5, Hitachi Chemical Co., Ltd., "Teslac" 2471) 47 g, polyester polyol (hexylene glycol caprolactone, divalent aliphatic hydrocarbon group A structure maximum carbon number: 6, Daicel Corporation, PCL-205 ) 28 g and 245 g of dimethylformamide were put into 2 liters of separable corbene and dissolved, and 137 g of diphenylmethane diisocyanate was added while controlling the temperature at 50° C. and reacted at 50° C. for about 1 hour to obtain a prepolymer. Then, the temperature was raised to 60° C., 20 g of ethylene glycol and 65 g of DMF were added, a chain extension reaction was carried out at 60° C., and polymerization was carried out while adding 611 g of DMF in accordance with the increase in viscosity. The largest number of divalent aliphatic hydrocarbon group A in this polymer has 6 structural units. At the end of the polymerization, 15 g of propylene glycol (carbon number of hydrocarbon group: 3) and 137 g of DMF were added. The reaction was completed in about 6 to 8 hours, and a urethane resin solution having a urethane resin concentration of 25.4% and a viscosity of 49,000 mPa·s (30° C.) was obtained.

Using this, the same processing and evaluation as in Examples 10, 12, and 15 were performed. The results are shown in Table 2.

[Comparative example 2]
<Polymerization of polyurethane resin solution (11)>
Polycarbonate polyol (hexamethylene carbonate diol, structural carbon number of divalent aliphatic hydrocarbon group A: 6, Nippon Polyurethane Industry Co., Ltd., "Nipporan" 980R) 130 g, polyether polyol (polytetramethylene glycol, divalent The number of structural carbon atoms of the aliphatic hydrocarbon group A is 4; Sanyo Kasei Co., Ltd., PTMG-2000M 32g, and dimethylformamide 250g are dissolved in 2 liters of separable Kolben, and the temperature is adjusted to 50°C. Meanwhile, 87 g of diphenylmethane diisocyanate was added and reacted at 50° C. for about 1 hour to obtain a prepolymer. Thereafter, the temperature was raised to 60° C., 16 g of ethylene glycol and 40 g of DMF were added, a chain length extension reaction was carried out at 60° C., and polymerization was carried out while adding 400 g of DMF in divided portions according to the increase in viscosity. The largest number of divalent aliphatic hydrocarbon group A in this polymer has 6 structural units. At the end of the polymerization, 8 g of propylene glycol (carbon number of hydrocarbon group: 3) and 110 g of DMF were added. The reaction was completed in about 6 to 8 hours, and a urethane resin solution having a urethane resin concentration of 25.0% and a viscosity of 80,000 mPa·s (30° C.) was obtained.

Using this, the same processing and evaluation as in Examples 11, 12, and 15 were performed. The results are shown in Table 2.

[Comparative Example 3]
<Polymerization of polyurethane resin solution (12)>
70 g of polyester polyol (1,9-nonanediol, 3-methylpentanediol copolymerized adipate, structural carbon number of divalent aliphatic hydrocarbon group A: 9), and 117 g of dimethylformamide were placed in 2 liters of separable Kolben. Was dissolved, 44 g of diphenylmethane diisocyanate was added while controlling the temperature at 50° C., and the mixture was reacted at 50° C. for about 1 hour to obtain a prepolymer. Thereafter, the temperature was raised to 60° C., 8.3 g of ethylene glycol and 19 g of DMF were added, a chain length extension reaction was carried out at 60° C., and polymerization was carried out while adding 208 g of DMF in accordance with the increase in viscosity. The largest number of the divalent aliphatic hydrocarbon group A in this polymer has a structural unit of 9 carbon atoms. At the end of the polymerization, 4 g of propylene glycol (carbon number of hydrocarbon group: 3) and 64 g of DMF were added to complete the polymerization. Polymerization was completed in about 6 to 8 hours, and a urethane resin solution having a urethane resin concentration of 25.0% and a viscosity of 52,000 mPa·s (30° C.) was obtained.

Using this, the same processing and evaluation as in Example 13 were performed. The results are shown in Table 2.

From Tables 1 and 2, the waterproof cloths made of the urethane resin composition having an aliphatic hydrocarbon group having the characteristics of the present invention have improved moisture permeability (method B-1) in the processing and evaluation of Examples 10 to 15. Since the water pressure resistance is maintained, it can be seen that the performance of the moisture-permeable waterproof fabric is improved.

Since the urethane resin composition of the present invention can provide a urethane resin porous film having good moisture permeability, it can be suitably used for outdoor sports clothing, rain clothes and the like. Furthermore, by limiting the polyol compound of the urethane resin composition to a carbonate divalent aliphatic hydrocarbon group structure and/or an oxydivalent aliphatic hydrocarbon group structure, both durability and moisture permeation waterproofness are provided. Since the urethane resin layer can be provided, it can be used for waders, salopette clothes and the like, and can be preferably used for applications such as fishing, rain clothes and work clothes.

Claims (8)

A waterproof cloth having a fiber cloth and a porous urethane resin layer containing a urethane resin composition containing a urethane resin on the surface of the fiber cloth,
The urethane resin is prepared by reacting a polyol compound having at least two hydroxyl groups reactive with an isocyanate group and a divalent aliphatic hydrocarbon group A with a diisocyanate compound having at least two isocyanate groups. What you get,
The urethane resin has a functional group having an aliphatic hydrocarbon group B having the following characteristics (i) to (iii) at the terminal of its molecular structure:
Waterproof fabric.
(I) The carbon number of the aliphatic hydrocarbon group B is larger than the carbon number of the maximum structural number aliphatic hydrocarbon group defined below.
Maximum number of structures Aliphatic hydrocarbon group: The divalent aliphatic hydrocarbon group contained in the polyol having the divalent aliphatic hydrocarbon group A is classified according to the number of aliphatic carbons, and according to the number of carbons. Comparing the number of classified divalent aliphatic hydrocarbon groups, the largest number of divalent aliphatic hydrocarbon groups.
(Ii) The aliphatic hydrocarbon group B has 8 to 22 carbon atoms.
(Iii) Hydrocarbon group B is 10 mol% or more with respect to the terminal functional group of the polyurethane resin. A waterproof fabric in which the number of carbon atoms in the maximum aliphatic hydrocarbon group in the divalent aliphatic hydrocarbon group A is 2 to 9. The polyol compound which gives a polyurethane resin has a structure containing a carbonate group and a divalent aliphatic hydrocarbon group A and/or a structure containing an ether bond and a divalent aliphatic hydrocarbon group A. Waterproof fabric. The waterproof fabric according to any one of claims 1 to 3, wherein the step of forming the urethane resin layer on the surface of the fiber fabric is a wet coagulation method. The waterproof cloth according to any one of claims 1 to 4, which has a non-porous film on the urethane resin layer. The waterproof fabric according to any one of claims 1 to 4, which has a water pressure resistance of 10 kPa or more. The waterproof fabric according to any one of claims 1 to 5, which has a water vapor transmission rate according to JIS L 1099 B-1 method of 104 g/m ² ·hr or more. The waterproof fabric according to any one of claims 1 to 6, which has a retention rate of water pressure resistance of 80% or more after 5 weeks in a hydrolyzability evaluation test under conditions of a temperature of 70°C and a humidity of 95%.