JP2016176040A - Urethane resin composition, waterproof fabric and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an urethane resin having moisture permeability, waterproofness and durability, and a waterproof-finished fabric.SOLUTION: Provided is an urethane resin composition containing an urethane resin obtained by reacting a polyol compound having at least two or more hydroxyl groups having reactivity with an isocyanate group and having a bivalent aliphatic hydrocarbon group and a diisocyanate compound having at least two isocyanate groups, and having a bivalent aliphatic hydrocarbon group in the skeleton of the molecule, being an urethane resin having a functional group with an aliphatic hydrocarbon group at the terminal of the molecular structure, being a functional group in which the carbon number of the hydrocarbon group is higher than the carbon number of an aliphatic hydrocarbon structure whose structural number is highest in the bivalent aliphatic hydrocarbon group by 10 mol% or higher to the functional group at the terminal, and also provided is a fabric obtained by applying the same to a fiber fabric to form an urethane resin layer and performing a waterproof-finish. Further, the urethane resin may be the one in which, in the terminal, a part or the whole of hydrogen is substituted with fluorine.SELECTED DRAWING: None

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 an excellent moisture permeability and a highly moisture-permeable waterproof fabric using the same. Is to provide. Specifically, by combining with woven / knitted fabric, non-woven fabric, paper, porous film, etc., outdoor wear such as fishing wear and mountaineering clothing, ski-related wear, windbreaker, athletic wear, golf wear, tennis wear, rainwear, casual coat The present invention relates to a moisture-permeable waterproof fabric that can be suitably used in indoor and outdoor work clothes, clothing such as gloves and shoes, and clothing materials.

Conventionally, urethane resin is used as a waterproof film by applying it to a cloth because of its excellent mechanical properties, and is used as a moisture permeable waterproof film by making a polyurethane layer porous by a wet coagulation method. Focusing on the end group of the urethane resin, a urethane resin having various characteristics has been invented. However, the invention is a urethane resin for wet film formation having waterproofness, and the invention of the urethane resin end group that improves moisture permeability. It has not been.
For example, a urethane resin obtained by reacting a terminal isocyanate with an alkoxysilane can produce a moisture-permeable waterproof fabric without using an organic solvent. Further, 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 performance was not sufficient (Patent Document 1).

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

Furthermore, by using monoalcohols having 1 to 8 carbon atoms and monoamines having 1 to 10 carbon atoms as a reaction terminator, it has excellent hydrophilicity and resin strength and has a small permanent strain. And urethane resin from which a moisture-permeable waterproof material excellent in washing resistance can be obtained is disclosed. However, the moisture permeability is a maximum of 10900 g / m ² · 24 h by the A-1 method, and the measurement evaluation by the B-1 method is performed. (Patent Document 3).

  In addition, the polyol constituting the urethane resin is mainly used as a polyol having an ester structure from the viewpoint of raw material cost, satisfying the properties of flexibility, moisture permeability and waterproofness. However, polyols having an ester structure have poor hydrolysis resistance, and there has been a problem in long-term use due to deterioration of the polyurethane layer when used in a high temperature and high humidity environment. Therefore, in order to satisfy the durability, it is common to use a polyol having a carbonate structure, but it is still a urethane resin for moisture-permeable waterproof processing that has 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 is a polyurethane resin useful for applications having high durability such as furniture and vehicle seats. Although disclosed (Patent Document 4), moisture permeability and waterproofness was not sufficient.

  Further, it is disclosed that napped leather-like sheet-like material using a polyurethane resin comprising a polyol containing a polycarbonate diol is excellent in durability such as light resistance and hydrolyzability (Patent Document 5, Patent) Reference 6), moisture permeability and waterproofness was not sufficient.

On the other hand, by overcoating a urethane resin dispersion containing urethane fine particles having carbonate groups and oxyethylene groups on a porous moisture permeable cloth, the moisture permeable and waterproof cloth is excellent in moisture permeability, water resistance and slipperiness. Is disclosed. However, since the resin composition having moisture permeability and waterproof performance is already overcoated on the cloth coated on the cloth in advance, the moisture permeability cannot be said to be sufficient. (Patent Document 7)
Furthermore, it is a polyurethane resin composition having a polyol containing a polyether polyol having an oxyalkylene structure and a polycarbonate diol, and has durability such as adhesion to various substrates due to coating agent and skin layer formation, heat resistance, hydrolysis resistance, etc. Although it has been disclosed that a film that balances the above can be formed, the water vapor transmission rate was not sufficient (Patent Document 8).

JP 2007-45866 A JP 2010-215918 A JP 2014-141463 A JP-A-3-244619 JP 2002-30579 A JP 2002-61081 A 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 fabric having moisture permeability, water resistance and durability.

  As a result of intensive studies, the present inventors have determined that a polyol compound having at least two hydroxyl groups reactive with isocyanate groups and having a divalent aliphatic hydrocarbon group A and a diisocyanate compound having at least two isocyanate groups. And having a functional group having an aliphatic hydrocarbon group B at the end of the chemical structure, and the carbon number of the hydrocarbon group B is divalent aliphatic carbonization derived from the polyol compound Urethane resin having 10 mol% or more of functional groups that are larger than the carbon number of the aliphatic hydrocarbon structure having the largest number of structures among hydrogen groups A, and urethane containing the urethane resin The present inventors have found that the above problems can be solved by the resin composition, and have completed the present invention. Here, “the largest number of structures” means that when the number of aliphatic hydrocarbon groups having a large number of structures that give the same number of carbons is compared, the number of structures is the largest, and included in the structure. This does not mean that the carbon produced is the largest. Details will be described later.

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

As a preferred embodiment of the invention, the polyol compound may have 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. .
Further preferred embodiments include the following.
It is 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 a surface of the fiber cloth.
The urethane resin layer is preferably a microporous film.
A non-porous film may be provided on the urethane resin layer. It is preferable that the non-porous film has moisture permeability.
The waterproof pressure resistance of the waterproof fabric is preferably 10 kPa or more.
The waterproof fabric preferably has a water vapor transmission rate of 104 g / m ² · hr or more according to JIS L 1099 method B-1.
In the hydrolyzability evaluation test of the waterproof fabric at a temperature of 70 ° C. and a humidity of 95%, it is preferable that the retention rate of water pressure resistance after 80 weeks is 80% or more.
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 fabric, and then a step of 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 producing the waterproof fabric can include a step of joining the urethane resin layer and the fiber fabric using an adhesive.

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

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

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

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

  The polyol compound (A) and the chain extender (C) are similar and have two or more hydroxyl groups reactive with isocyanate groups in the molecular chain. The polyol compound (A) referred to in the present invention. Has a divalent aliphatic hydrocarbon group A, and is composed of two or more units of this functional group and a carbonyl group such as an ester bond or carbonate group or an ether bond in the middle of the skeleton. It is assumed that the molecular chain has two or more hydroxyl groups, and the chain extender (C) is composed of one unit of a divalent aliphatic hydrocarbon group, and has two hydroxyl groups in the molecular chain of the entire compound. It shall have the above.

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

  The polyester polyol is generally obtained by reacting a dibasic acid component with 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. Dihydric alcohol components include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol And an aliphatic glycol such as cyclohexanediol, and an aromatic glycol such as an alkylene oxide adduct of bisphenol A. A polyester polyol is obtained by a condensation reaction between these dibasic acid component and dihydric alcohol component.

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

  Polycarbonate polyol forms a polymer chain connected through a carbonate bond, and has a hydroxyl group in the polymer chain. The polycarbonate polyol can be obtained by transesterification of an alkylene glycol and a carbonate ester or a reaction of phosgene or chloroformate ester with an alkylene glycol. Examples of alkylene glycols 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 isocyanate compound (B) include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymeric MDI, hexamethylene diisocyanate (HMDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), Examples include isocyanate compounds such as 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, 1,10-decanediol, 1,4-cyclohexanediol, hydrogenated xylyl Examples thereof include alicyclic diols such as lenglycol, and aromatic diols such as xylylene glycol.

  Examples of the solvent (D) include amide solvents (such as dimethylformamide (DMF) and dimethylacetamide), sulfoxide solvents (such as dimethyl sulfoxide), ketone solvents (such as methyl ethyl ketone (MEK)), and aromatic solvents (toluene, Xylene), ether solvents (dioxane, tetrahydrofuran, etc.) and ester solvents (ethyl acetate, butyl acetate, etc.).

The reaction terminator (E) is used in the urethane resin polymerization reaction to react with the end of the chemical structure to stop the polymerization at the target viscosity.
As the reaction terminator (E), monovalent and polyhydric alcohols, monovalent 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 the primary alcohol reacts with the isocyanate, and the secondary alcohol has poor reactivity due to steric hindrance, and as a result does not extend the chain, it can be used as a reaction terminator. it can.

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

Note that an atom bonded to a free chemical bond in the chemical formula is not a carbon constituting an aliphatic hydrocarbon group. The carbon number which comprises the bivalent hydrocarbon group of Formula (1) is 3. 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 the formula (5) is 4. The number of carbon atoms in the formula (6) is 2. The number of carbon atoms in the formula (7) is 4. In Formula (8), there are two divalent hydrocarbon groups, which are methylene groups, each having 1 carbon.

  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.

  “Molecular backbone” is the distance between the urethane bond that is closest to the end of the molecule (in some cases a urea bond) and the urethane bond that is closest to the other end of the molecule (in some cases, the urea bond). say.

  In addition, the “functional group at the end of the molecular structure” refers to a functional group at the end of the urethane bond (in some cases, a urea bond) that exists near the end of the molecule. And the functional group in the terminal of molecular structure contains more than a specific ratio the functional group which has an aliphatic hydrocarbon group of carbon number more than specific.

The number of carbons more than a specific value that the aliphatic hydrocarbon group B has is the number of carbon atoms of the divalent aliphatic hydrocarbon group A in the molecular skeleton (when there is an aliphatic hydrocarbon structure having a plurality of carbon numbers). Means larger than the carbon number of the aliphatic hydrocarbon group having a large number of carbon structures.
For example, among the divalent aliphatic hydrocarbon groups A, those that give 4 carbon atoms (wherein the chemical structure does not matter) are 60 mol% and those that give 6 carbon atoms (no difference in chemical structure) ) Is 20 mol%, and those that give 2 carbon atoms are 20 mol%, “of the divalent aliphatic hydrocarbon group A, the carbon of the aliphatic hydrocarbon structure having the largest number of structures giving the same number of carbon atoms. The “number” is four.

  The aliphatic hydrocarbon group B may contain a carbon-carbon double bond or triple bond. Moreover, the hydrogen of the hydrocarbon group may be substituted with another element or another functional group (for example, a hydroxyl group). By definition, an aliphatic hydrocarbon group does not include a carbonyl group, an ester bond, or an ether bond. However, even if the terminal functional group includes a carbonyl group, an ester bond, or an ether bond, an aliphatic hydrocarbon group exists. It is judged that there is an aliphatic hydrocarbon group. However, the carbon 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 aliphatic hydrocarbon group B has 1 carbon atom. When ethyl alcohol is used, the carbon number is 2, when propylene glycol is used, the carbon number is 3, and when cyclohexanol is used, the carbon number is 6, and lauryl alcohol (also known as 1-dodecanol) is used. In this case, the carbon number is 12. When diethyl carbinol (also called 3-methyl-3-pentanol) is used, the carbon number is 6. 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 terminator usually has an aliphatic hydrocarbon group in its structure, and the hydrocarbon group has all the carbon atoms of the polyol compound (A) and the chain extender (C). Among hydrogen structures, it has a carbon hydrogen group larger than the carbon number of the most aliphatic hydrocarbon structure. Thereby, compared with the conventional urethane resin composition, the urethane resin with high molecular terminal hydrophobicity can be obtained.

The maximum number of divalent aliphatic hydrocarbon structures A derived from the polyol compound in the molecular skeleton of the urethane resin is preferably 2 to 9, and more preferably 2 to 6 from the viewpoint of polymerization reactivity.
Of the divalent aliphatic hydrocarbon group A, the aliphatic hydrocarbon group B having a larger number of carbon atoms in the aliphatic hydrocarbon structure having the largest structure number preferably has 8 to 22 carbon atoms. The hydrocarbon group having a specific number of carbon atoms need not be present in all of the terminal functional groups, and if the terminal functional group (with or without an aliphatic hydrocarbon group) is at least 10 mol%, The effects of the invention can be obtained. More preferably, it is 30 mol% or more. When polymerization of urethane resin is occurring, a reaction stopper is finally added, but a reaction stopper that gives an aliphatic hydrocarbon group having a high carbon number is added in advance, and almost all of the reaction stopper is added. It can be obtained by reacting with an isocyanate group and then adding another reaction terminator if necessary. In the second invention, part or all of the 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 has an aliphatic hydrocarbon group having a large number of carbons at the end of the chemical structure of the urethane resin composition of the present invention, or a functional group in which part or all of hydrogen of the hydrocarbon group is substituted with a fluorine atom. This is considered to be because phase separation of the urethane resin layer formed by the wet coagulation method easily occurs uniformly.

  The reason is considered to be that uniform phase separation is induced by the improvement in hydrophobicity of the urethane resin structure end by the functional group, and a homogeneous and fine porous body is formed. These homogeneous and fine porous bodies improve both properties compared to conventional moisture-permeable and waterproof properties (water resistance of water and water vapor permeability) in the porous form induced by phase separation in solvent substitution. be able to.

  The above components (A) to (E) may be used singly, but two or more types may be mixed and used in each component. In the production of polyurethane, the reaction temperature may be the same as that usually employed in the urethanization reaction, and is usually 30 to 90 ° C. when a solvent is used, and usually 30 to 220 ° C. when no solvent is used.

  Moreover, in order to accelerate | stimulate reaction, the catalyst normally used for urethane reaction, for example, amine catalysts, such as a triethylamine and a triethylenediamine, can be used as needed.

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

  The urethane resin of the present invention may contain the above-exemplified organic solvents, and the amount thereof is usually an amount such that the resin solid content concentration of the urethane resin is 5 to 50% by mass, preferably 10 It is the quantity which becomes -40 mass%.

  In the resin composition containing the urethane resin of the present invention, various stabilizers for improving weather resistance, heat resistance deterioration, etc., crosslinking agents such as polyfunctional isocyanate compounds, colorants, inorganics such as silica, etc. 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 after 5 weeks in the hydrolyzability 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 and / or a structure containing an ether bond and a divalent aliphatic hydrocarbon group A as a component of the polyol compound (A). By using the polyether polyol which has, it is easy to make 80% or more of the retention after 5 weeks of the hydrolytic property evaluation test of the waterproof pressure of the waterproof fabric. Further, even after 10 weeks, a highly durable waterproof fabric having a water pressure resistance retention rate of 50% or more, which is 5 times or more that of a normal polyester polyol, is obtained.

The waterproof fabric of the present invention preferably has a moisture permeability of 104 g / m ² · hr or more according to the JIS standard L1099A-1 method and / or 104 g / m ² · hr or more according to the 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 and / or a structure containing an ether bond and a divalent aliphatic hydrocarbon group A as a component of the polyol compound (A). By using the polyether polyol having, a higher moisture permeability can be obtained.

It is possible to impart moisture permeability to the urethane resin film by making the urethane resin into a porous film by a wet method. Further, it is preferable to form a microporous film by a wet method.
By laminating a non-porous film having moisture permeability on the porous film or the microporous film, higher water pressure resistance or moisture permeability can be obtained.

  About the manufacturing method of the waterproof fabric of this invention, it is obtained by forming a urethane resin layer in the fiber fabric surface. A method of applying a liquid composition containing the urethane resin composition to a fiber fabric (direct coating method), or after forming a urethane resin layer alone, and then using an adhesive between the urethane resin layer and the fiber fabric. There is a method of joining (joining method). The urethane resin layer is preferably a porous film or a microporous film.

  In the liquid composition containing the urethane resin composition, if necessary, an additive that can be a nucleus (inducing agent) at the time of phase separation can be blended.

  Examples of the additive include fine particles of an inorganic material and an organic compound, and a fine powder of silica 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. 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 are not limited thereto.

  In the bonding method, for example, a method is used in which a urethane resin layer formed on a release paper by coating or the like is laminated on a fiber fabric by dots or full adhesion with an adhesive, and then the release paper is peeled off, but is not limited thereto.

  As a method for laminating a urethane resin having moisture permeability and waterproofness, as an example of a preferable embodiment, the urethane resin of the present invention is represented by a polar solvent (dimethylformamide: DMF, dimethylsulfoxide: DMSO, etc.) soluble in water. A liquid composition containing a urethane resin composition dissolved in (1) is coated on a fiber fabric, and this is wet-gelled in water or in an aqueous solution containing a polar solvent, so that it has both moisture permeability and waterproofness. This is a method of forming a porous film.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by a following example.

In addition, the following was used as a measuring method of various performance in this-application specification etc. including a following example.
(Measuring method)
(1) Water pressure resistance: Measured according to JIS-L1092 (2009).
(2) Moisture permeability: Measured according to A-1 method and B-1 method of JIS-L1099 (2012).
(3) Hydrolysis test (jungle test): promotes hydrolysis in a high-temperature and high-humidity tank at 70 ° C. and a relative humidity of 95%, and maintains the water pressure resistance (the ratio of the water pressure resistance after the test to the water pressure before the test, (%).

[Example 1]
<Polymerization of polyurethane resin solution (1)>
Polyester polyol (ethylene glycol adipate, divalent aliphatic hydrocarbon group A, structural maximum carbon number: 4, Nippon Polyurethane Industry Co., Ltd., “Nipporan” (registered trademark, the same applies hereinafter) 4060) 75 g, polyester polyol ( Butylene glycol adipate, divalent aliphatic hydrocarbon group A, structural maximum carbon number: 4, Nippon Polyurethane Industry Co., Ltd., “Nipporan” 4010) 35 g, polyester polyol (neopentyl glycol adipate, divalent aliphatic carbonization) Maximum structure carbon number of hydrogen group A: 5, 47 g of Hitachi Chemical Co., Ltd., “Teslac” 2471), Polyester polyol (hexylene glycol caprolactone, structure carbon number of divalent aliphatic hydrocarbon group A: 6, Daicel Corporation, PCL-205) 28 g and dimethylforma 245 g (hereinafter referred to as “DMF”) was dissolved in 2 liters of separable colben, 137 g of diphenylmethane diisocyanate was added while adjusting the temperature to 50 ° C., and reacted at 50 ° C. for about 1 hour to obtain a prepolymer. . Thereafter, the temperature was raised to 60 ° C., ethylene glycol (20 g 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 portions as the viscosity increased. The carbon number of the structural unit of the divalent aliphatic hydrocarbon group A having the largest number of carbon structures in the coalescence is 6. The amount of isocyanate remaining during the polymerization is analyzed, and the amount of isocyanate remaining at the end of the polymerization is analyzed. Glycerol-monodiolate equivalent to 66 mol% (mixing ratio of glycerol-monooleate / glycerin-diolate 50% / 50% (mol / mol)) (the number of carbon atoms of the largest aliphatic hydrocarbon group B provided by this compound: 17 After adding 5.5 g of Riken Vitamin Co., Ltd. (OL-200V) and reacting for 30 minutes, propylene glycol (carbon number of hydrocarbon group: 3) 10 And it was added DMF137g. Approximately ending the reaction at for 6-8 hours, urethane resin concentration 25.4%, the liquid composition of the urethane resin composition having a viscosity 41,000mPa · s (30 ℃) was obtained.

[Example 2]
<Polymerization of polyurethane resin solution (2)>
Polyester polyol (ethylene glycol adipate, divalent aliphatic hydrocarbon group A structure maximum carbon number: 4, Nippon Polyurethane Industry Co., Ltd., “Nipporan” 4060) 79 g, polyester polyol (butylene glycol adipate, divalent fat) Structure carbon number of aromatic hydrocarbon group A: 4, Nippon Polyurethane Industry Co., Ltd., “Nipporan” 4010) 28 g, polyester polyol (neopentylglycol adipate, divalent aliphatic hydrocarbon group A structure maximum carbon number : 5, Hitachi Chemical Co., Ltd., "Teslac" 2471) 50g, polyester polyol (hexylene glycol caprolactone, divalent aliphatic hydrocarbon group A structure maximum carbon number: 6, Daicel Corporation, PCL-205 2 liters of 28 g and 245 g of dimethylformamide Dissolved placed in separable flask, adding diphenylmethane diisocyanate 137g while controlling the temperature to 50 ° C., allowed to react for approximately 1 hour at 50 ° C., and a prepolymer. Thereafter, 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 584 g of DMF in portions as the viscosity increased. This polymer has 6 carbon atoms in the structural unit of the divalent aliphatic hydrocarbon group A having the largest number of carbon structures. The amount of isocyanate remaining during the polymerization was analyzed, and behenyl alcohol corresponding to 67 mol% of the amount of isocyanate remaining at the end of the polymerization (carbon number of aliphatic hydrocarbon group B: 22, NOA Corporation, NAA-422) 3.6 g Was dissolved in 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)>
Polyester polyol (ethylene glycol adipate, divalent aliphatic hydrocarbon group A structure maximum carbon number: 4, Nippon Polyurethane Industry Co., Ltd., “Nipporan” 4060) 77 g, polyester polyol (butylene glycol adipate, divalent fat) Structure carbon number of aromatic hydrocarbon group A: 4, Nippon Polyurethane Industry Co., Ltd., "Nipporan" 4010) 29g, polyester polyol (neopentylglycol adipate, divalent aliphatic hydrocarbon group A structure maximum carbon number : 5, Hitachi Chemical Co., Ltd., "Teslac" 2471) 45g, polyester polyol (hexylene glycol caprolactone, divalent aliphatic hydrocarbon group A structure maximum carbon number: 6, Daicel Corporation, PCL-205 2 g of 35 g and 245 g of dimethylformamide Dissolved placed in separable flask, adding diphenylmethane diisocyanate 137g while controlling the temperature to 50 ° C., allowed to react for approximately 1 hour at 50 ° C., and a prepolymer. Thereafter, 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 portions as the viscosity increased. This polymer has 6 carbon atoms in the structural unit of the divalent aliphatic hydrocarbon group A having the largest number of carbon structures. The amount of isocyanate remaining during the polymerization was analyzed, and at the end of the polymerization, propylene glycol monooleate corresponding to 66 mol% of the amount of isocyanate remaining (carbon number of aliphatic hydrocarbon group B: 17, manufactured by 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 aliphatic hydrocarbon group A has a structural carbon number of 4, 27 g of Sanyo Chemical Industries, Ltd. (PTMG-2000M), and 163 g of dimethylformamide are dissolved in 2 liters of separable colben and adjusted to 50 ° C. Then, 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., 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 proportion to the increase in viscosity. This polymer has 6 carbon atoms in the structural unit of the divalent aliphatic hydrocarbon group A having the largest number of carbon structures. Analyzing the remaining amount of isocyanate during the polymerization, propylene glycol monooleate (carbon number of aliphatic hydrocarbon group B: 17, manufactured by Riken Vitamin Co., Ltd.) which is 100 mol% or more (excess amount) of the remaining amount of isocyanate at the end of the polymerization, 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 aliphatic hydrocarbon group A has a structural carbon number of 4, 32 g of Sanyo Kasei Kogyo Co., Ltd., PTMG-2000M), and 250 g of dimethylformamide are dissolved in 2 liters of separable colben and adjusted to 50 ° C. Then, 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 portions as the viscosity increased. This polymer has 6 carbon atoms in the structural unit of the divalent aliphatic hydrocarbon group A having the largest number of carbon structures. The amount of isocyanate remaining during the polymerization was analyzed, and an alkyl ester of ricinoleic acid corresponding to 46 mol% of the amount of remaining isocyanate at the end of the polymerization (carbon number of aliphatic hydrocarbon group B: 17, manufactured by 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, divalent aliphatic hydrocarbon group A structure maximum carbon number: 4, Nippon Polyurethane Industry Co., Ltd., “Nipporan” 4060) 79 g, polyester polyol (butylene glycol adipate, divalent fat) Structure carbon number of aromatic hydrocarbon group A: 4, Nippon Polyurethane Industry Co., Ltd., “Nipporan” 4010) 31 g, polyester polyol (neopentylglycol adipate, divalent aliphatic hydrocarbon 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 Corporation, PCL-205 2 liters of 28 g and 245 g of dimethylformamide Dissolved placed in separable flask, adding diphenylmethane diisocyanate 137g while controlling the temperature to 50 ° C., allowed to react for approximately 1 hour at 50 ° C., and a prepolymer. Thereafter, 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 portions as the viscosity increased. The structural unit of the divalent aliphatic hydrocarbon group A having the largest number of carbon structures has 6 carbon atoms. The amount of isocyanate remaining during the polymerization was analyzed, and C6 fluorine-substituted alcohol (2- (perfluorohexyl) ethanol, F (CF ₂ ) ₆ CH ₂ CH ₂ OH, Unimatic ( Co., Ltd., “CHEMINOX” (registered trademark, the same applies hereinafter) FA-6) 4.5 g 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, divalent aliphatic hydrocarbon group A structure maximum carbon number: 4, Nippon Polyurethane Industry Co., Ltd., “Nipporan” 4060) 79 g, polyester polyol (butylene glycol adipate, divalent fat) Structure carbon number of aromatic hydrocarbon group A: 4, Nippon Polyurethane Industry Co., Ltd., “Nipporan” 4010) 31 g, polyester polyol (neopentylglycol adipate, divalent aliphatic hydrocarbon 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 Corporation, PCL-205 2 liters of 28 g and 245 g of dimethylformamide Dissolved placed in separable flask, adding diphenylmethane diisocyanate 137g while controlling the temperature to 50 ° C., allowed to react for approximately 1 hour at 50 ° C., and a prepolymer. Thereafter, 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 portions as the viscosity increased. The structural unit of the divalent aliphatic hydrocarbon group A having the largest number of carbon structures has 6 carbon atoms. The amount of isocyanate remaining during the polymerization was analyzed, and C4 · C5 fluorine-substituted alcohol (3,3,4,4,5,5,6,6,7,7,9) corresponding to 65 mol% of the amount of isocyanate remaining at the end of the polymerization. , 9, 10, 10, 11, 11, 12, 12, 12-nonadecafluorododecanol, F (CF ₂ ) ₄ CH ₂ (CF ₂ ) ₅ CH ₂ CH ₂ OH, Unimatec Co., Ltd., “CHEMINOX” After adding 5.8 g of FA-45) and reacting 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)>
Polyester polyol (ethylene glycol adipate, divalent aliphatic hydrocarbon group A structure maximum carbon number: 4, Nippon Polyurethane Industry Co., Ltd., “Nipporan” 4060) 77 g, polyester polyol (butylene glycol adipate, divalent fat) Structure carbon number of aromatic hydrocarbon group A: 4, Nippon Polyurethane Industry Co., Ltd., "Nipporan" 4010) 29g, polyester polyol (neopentylglycol adipate, divalent aliphatic hydrocarbon group A structure maximum carbon number : 5, Hitachi Chemical Co., Ltd., "Teslac" 2471) 45g, polyester polyol (hexylene glycol caprolactone, divalent aliphatic hydrocarbon group A structure maximum carbon number: 6, Daicel Corporation, PCL-205 2 g of 35 g and 245 g of dimethylformamide Dissolved placed in separable flask, adding diphenylmethane diisocyanate 137g while controlling the temperature to 50 ° C., allowed to react for approximately 1 hour at 50 ° C., and a prepolymer. Thereafter, 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 portions as the viscosity increased. The structural unit of the divalent aliphatic hydrocarbon group A having the largest number of carbon structures has 6 carbon atoms. The amount of isocyanate remaining during the polymerization was analyzed, and C4 · C5 fluorine-substituted alcohol (3,3,4,4,5,5,6,6,7,7,9) corresponding to 32 mol% of the amount of isocyanate remaining at the end of the polymerization. , 9, 10, 10, 11, 11, 12, 12, 12-nonadecafluorododecanol, F (CF ₂ ) ₄ CH ₂ (CF ₂ ) ₅ CH ₂ CH ₂ OH, Unimatec Co., 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, manufactured by 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, divalent aliphatic hydrocarbon group A structure maximum carbon number: 6, Nippon Polyurethane Industry Co., Ltd., “Nipporan” 980R) 130 g, polyether polyol (polytetramethylene glycol, 2 Valent aliphatic hydrocarbon group A structure maximum carbon number: 4, Sanyo Kasei Kogyo Co., Ltd., PTMG-2000M (32 g), and dimethylformamide 250 g were dissolved in 2 liter separable colben and dissolved at 50 ° C. While adjusting the temperature, 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 extension reaction was carried out at 60 ° C., and polymerization was carried out while adding 435 g of DMF in proportion to the increase in viscosity. The structural unit of the divalent aliphatic hydrocarbon group A having the largest number of carbon structures has 6 carbon atoms. The amount of isocyanate remaining during the polymerization was analyzed, and C4 · C5 fluorine-substituted alcohol (3,3,4,4,5,5,6,6,7,7,9) corresponding to 36 mol% of the amount of isocyanate remaining at the end of the polymerization. , 9, 10, 10, 11, 11, 12, 12, 12-nonadecafluorododecanol, F (CF ₂ ) ₄ CH ₂ (CF ₂ ) ₅ CH ₂ CH ₂ OH, Unimatec Co., Ltd., “CHEMINOX” DFTA-103) After adding 1.2 g and reacting for 15 minutes, ester of ricinoleic acid and lower alkyl alcohol (carbon number of aliphatic hydrocarbon group B: 17, manufactured by Ito Oil Co., Ltd., URICH-31S) After adding 0.8 g and reacting for 15 minutes, 8 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 80,000 mPa · s (30 ° C.) was obtained.

[Example 10]
<Molding of waterproof fabric (1)>
Nylon lip taffeta composed of a 50 denier nylon filament yarn was added to a 30 g / l dilution of a fluorine-based water repellent (Daikin Industries, Ltd., “Unidyne” (registered trademark, the same applies hereinafter) TG-5521). After dipping and squeezing with a mangle so as to obtain a squeezing ratio of 40%, the film was dried at 120 ° C. and heat-treated at 130 ° C. for 30 seconds to perform a water repellent treatment.

  Next, 80 parts by weight of the polyurethane resin solution (1) prepared in Example 1 was mixed with silica fine powder (“Lelosil” (registered trademark, the same applies hereinafter) MT-10 and dimethyldichlorosilane, manufactured by Tokuyama Corporation. 6 parts by weight of phase reaction silica) was added, sufficiently 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.

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

  The same processing and evaluation were performed for 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)>
A nylon lip taffeta composed of a 50 denier nylon filament yarn is immersed in a 30 g / l dilution of a fluorine-based water repellent (Daikin Industries, Ltd., “Unidyne” TG-5521). After being squeezed with a mangle, it was dried at 120 ° C. and heat-treated at 130 ° C. for 30 seconds to perform a water repellent treatment.

Next, 5 parts by weight of silica fine powder (“Leosil” MT-10, gas phase reaction silica of dimethyldichlorosilane, manufactured by Tokuyama Corporation) is added to 80 parts by weight of the polyurethane resin solution (4) prepared in the above example. 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.
This was coated on the water-repellent nylon lip taffeta with a knife over roll coater at a coating amount of 150 g / m ² , an aqueous solution containing 20% by weight of DMF was immersed in a gelling bath for 2 minutes, washed with water for 10 minutes, It was dried with hot air at 140 ° C. to obtain a waterproof fabric.

  The obtained fabric was evaluated for water pressure resistance and moisture permeability (A-1, B-1). Further, after performing a jungle test (70 ° C. and 95% for 5 weeks), the water pressure resistance was measured, and the retention rate was obtained. The results are shown in Table 1 or Table 2. The same processing and evaluation were performed for the polyurethane resin solutions (5) and (9) for moisture permeation preventive fabric.

[Example 12]
<Molding of waterproof fabric having moisture-free multi-membrane>
25 parts by weight of MEK and 25 parts by weight of toluene were added to 100 parts by weight of a polyether-based polyurethane solution (manufactured by Dainichi Seika Kogyo Co., Ltd., “Himlen” Y-262), and mixed with a mixer to obtain a polyurethane compounded 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 , dried with hot air at 80 ° C., and laminated with a non-porous film having moisture permeability. A waterproof and moisture permeable fabric having a waterproof and moisture permeable layer of a membrane was obtained on one side. The obtained fabric was evaluated for water pressure resistance and moisture permeability (A-1, B-1). The results are shown in Table 1 or Table 2.

[Example 13]
<Molding of waterproof fabric (1) having a microporous membrane>
To 80 parts by weight of the polyurethane resin solution (1) prepared in the above examples, 8 parts by weight of silica fine powder (manufactured by Tokuyama Corporation, “Leosil” MT-10, gas phase reaction silica of dimethyldichlorosilane) was added, and DMF50 After sufficiently immersed in parts by weight and dispersed and stirred with a homomixer for about 15 minutes, a liquid composition of a polyurethane resin composition was obtained.

This was coated on the water-repellent nylon lip taffeta with a knife over roll coater at a coating amount of 150 g / m2, and immersed in a bath using an aqueous solution containing 25% by weight of DMF at 35 ° C. for 2 minutes. The polyurethane resin blend coating solution was wet coagulated, then 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 fabric was evaluated for water pressure resistance and moisture permeability (A-1, B-1). The results are shown in Table 1 or Table 2.

  The same processing and evaluation were performed for the polyurethane resin solutions (2), (3), and (6) to (8) for the moisture permeation preventive fabric.

[Example 14]
<Molding of waterproof fabric (2) having a microporous membrane>
8 parts by weight of silica fine powder (“Leosil” MT-10, vapor-phase reaction silica of dimethyldichlorosilane) manufactured by Tokuyama Co., Ltd. is added to 80 parts by weight of the polyurethane resin solution (4) and sufficiently immersed in 60 parts by weight of DMF. After stirring and stirring for about 15 minutes with a homomixer, a liquid composition of a polyurethane resin composition was obtained.

This was coated on the water-repellent nylon lip taffeta with a knife over roll coater at a coating amount of 150 g / m2, and immersed in a bath using an aqueous solution containing 25% by weight of DMF at 35 ° C. for 2 minutes. The polyurethane resin blend coating solution was wet coagulated, then 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 fabric was evaluated for water pressure resistance and moisture permeability (A-1, B-1). The results are shown in Table 1 or Table 2.

  The same processing and evaluation were performed for the polyurethane resin solutions (5) and (9).

[Example 15]
<Molding of waterproof fabric using adhesive>
A polyester taffeta composed of 50 denier polyester filament yarn is immersed 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 drawing rate of 40%. Then, 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 compound liquid obtained in Example 10 or 11 was coated with a knife over roll coater at a coating amount of 150 g / m 2 using the calender surface of the release cloth as the coating surface, and an aqueous solution containing 20% by weight of DMF was gelled. The bath was washed with water for 10 minutes in a bath for forming a 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 is immersed in a 30 g / 1 dilution of a fluorinated water repellent (Daikin Industries, Ltd., “Unidyne” TG-5521), and the drawing rate is reduced. After squeezing with mangle at 40%, drying at 120 ° C and heat-treating at 130 ° C for 30 seconds, water-repellent treatment cloth obtained was melted at 100 ° C using a 30 mesh gravure roll. Moisture-curing polyurethane hot melt adhesive (manufactured by DIC Corporation, NH-124) was applied, and the microporous urethane film on the surface of the release cloth was bonded and aged at 40 ° C. for 24 hours with pressure bonding. The mold cloth was peeled off to obtain a moisture-permeable and waterproof fabric having a laminated form of “fiber fabric / adhesive / moisture-permeable waterproof membrane”.

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

[Comparative Example 1]
<Polymerization of polyurethane resin solution (10)>
Polyester polyol (ethylene glycol adipate, divalent aliphatic hydrocarbon group A structure maximum carbon number: 4, Nippon Polyurethane Industry Co., Ltd., “Nipporan” 4060) 79 g, polyester polyol (butylene glycol adipate, divalent fat) Structure carbon number of aromatic hydrocarbon group A: 4, Nippon Polyurethane Industry Co., Ltd., “Nipporan” 4010) 31 g, polyester polyol (neopentylglycol adipate, divalent aliphatic hydrocarbon 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 Corporation, PCL-205 2 liters of 28 g and 245 g of dimethylformamide Dissolved placed in separable flask, adding diphenylmethane diisocyanate 137g while controlling the temperature to 50 ° C., allowed to react for approximately 1 hour at 50 ° C., and a prepolymer. Thereafter, 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 portions as the viscosity increased. The largest number of structural units of the divalent aliphatic hydrocarbon group A possessed by this polymer has 6 carbon atoms. 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 aliphatic hydrocarbon group A has a structural carbon number of 4, 32 g of Sanyo Kasei Kogyo Co., Ltd., PTMG-2000M), and 250 g of dimethylformamide are dissolved in 2 liters of separable colben and adjusted to 50 ° C. Then, 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 portions as the viscosity increased. The largest number of structural units of the divalent aliphatic hydrocarbon group A possessed by this polymer has 6 carbon atoms. 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, divalent aliphatic hydrocarbon group A structural carbon number: 9) and 117 g of dimethylformamide are placed in 2 liters of separable colben. Then, 44 g of diphenylmethane diisocyanate was added while adjusting the temperature to 50 ° C., and 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 portions as the viscosity increased. The structural unit of the largest number of divalent aliphatic hydrocarbon groups A possessed by this polymer has 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. The 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 fabric made of the urethane resin composition having an aliphatic hydrocarbon group having the characteristics of the present invention has 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.

According to the urethane resin composition of the present invention, a urethane resin porous film having good moisture permeability can be provided, and therefore it can be suitably used for clothes for outdoor sports, 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 oxy divalent aliphatic hydrocarbon group structure, it has both durability and moisture permeability and waterproofness. Since the urethane resin layer can be provided, it can be used for waders, salopette clothes, and the like, and can be suitably used for applications such as fishing, rain clothes, and work clothes.

Claims (14)

A urethane resin obtained by reacting a polyol compound having at least two hydroxyl groups reactive with isocyanate groups and having a divalent aliphatic hydrocarbon group A and a diisocyanate compound having at least two isocyanate groups. There,
Having a functional group having an aliphatic hydrocarbon group B at the end of the molecular structure;
The number of carbon atoms of the aliphatic hydrocarbon group B is
Among the divalent aliphatic hydrocarbon group A derived from the polyol compound, a functional group having a larger number of structures giving the same number of carbons than the number of carbon atoms of the aliphatic hydrocarbon structure is the terminal functional group. A urethane resin having 10 mol% or more based on the group. 2. The carbon number of the aliphatic hydrocarbon group B having a carbon number larger than that of the aliphatic hydrocarbon structure having the largest structure among the divalent aliphatic hydrocarbon group A is 8 to 22. The urethane resin described. The urethane resin according to claim 1 or 2, wherein the aliphatic hydrocarbon structure having the largest structure number among the divalent aliphatic hydrocarbon group A has 2 to 9 carbon atoms. It is obtained by reacting a polyol compound having at least two hydroxyl groups reactive with isocyanate groups and a diisocyanate compound having at least two isocyanate groups, and a divalent aliphatic hydrocarbon group A is formed in the skeleton of the molecule. A urethane resin having a functional group in which a part or all of the hydrogen of the aliphatic hydrocarbon group is substituted with a fluorine atom at the end of the chemical structure. The urethane according to any one of claims 1 to 4, wherein 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. resin.   A waterproof fabric having a urethane resin layer of a urethane resin composition containing the urethane resin according to any one of claims 1 to 5 on a surface of the fiber fabric and the fiber fabric.   The waterproof fabric according to claim 6, wherein the urethane resin layer is a microporous membrane.   The waterproof fabric according to claim 6 or 7, further comprising a nonporous film on the urethane resin layer.   The waterproof fabric according to any one of claims 6 to 8, wherein the waterproof pressure is 10 kPa or more. The waterproof fabric according to any one of claims 6 to 9, wherein moisture permeability according to JIS L 1099 method B-1 is 104 g / m ² · hr or more. The waterproof fabric according to any one of claims 6 to 10, wherein in a hydrolyzability evaluation test under conditions of a temperature of 70 ° C and a humidity of 95%, the water pressure retention after 5 weeks is 80% or more. .   A method for producing a waterproof fabric, comprising: applying a liquid composition of a urethane resin composition containing the urethane resin according to any one of claims 1 to 5 to a fiber cloth, and then forming a urethane resin layer from the liquid composition. The method for producing a waterproof fabric according to claim 12, wherein the step of forming the urethane resin layer is a wet coagulation method.   The method for producing a waterproof fabric according to claim 12 or 13, further comprising a step of joining the urethane resin layer and the fiber fabric using an adhesive.