JP2007045866A - Aqueous polyurethane resin composition for nonporous film type moisture-permeable, waterproof finish and method for producing moisture-permeable, waterproof finish fabric - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an aqueous polyurethane resin composition for a nonporous film type moisture-permeable, waterproof finish, which forms a moisture-permeable layer having excellent feeling, water resistance, moisture permeability, washing resistance, etc. <P>SOLUTION: The aqueous polyurethane resin composition for a nonporous film type moisture-permeable, waterproof finish is obtained by reacting (A component) an organic polyisocyanate component with (B component) a first polyol component containing a polyoxyethylene group composed of four or more oxyethylene units and at least two or more active hydrogens with reactivity to an NCO group and having 800-22,000 number-average molecular weight and (C component) a second polyol component containing at least two or more active hydrogens with reactivity to an NCO group as constituent components in the ratio NCO/OH (molar ratio) of 1.03-1.12 to give a polyurethane prepolymer containing a terminal isocyanate group and further adding (D component) an alkoxysilane compound to the polyurethane prepolymer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a water-based polyurethane resin composition for non-porous membrane-type moisture-permeable waterproof processing that uses water-based polyurethane resin and exhibits high moisture permeability, water resistance, good surface condition, excellent texture and high durability, and The present invention relates to a method for producing a nonporous membrane-type moisture-permeable waterproof fabric using the same.

  2. Description of the Related Art Conventionally, some outdoor clothing and the like have been used a fabric that has been subjected to a non-porous membrane-type moisture-permeable waterproof process. This non-porous membrane-type moisture-permeable waterproof fabric is manufactured by forming a moisture-permeable film made of polyurethane resin on the fabric and then treating with a waterproofing agent. As the polyurethane resin used for forming the moisture permeable film, a solvent-based one has been used so far, for example, polyoxyethylene glycol or polyoxyethylene / polyoxypropylene is randomly or block copolymerized in the polyurethane resin. It is widely known to use one (for example, Patent Documents 1 to 4).

  However, when a solvent-based polyurethane resin is used, organic products such as dimethylformamide (DMF), toluene, and methyl ethyl ketone (MEK) are contained in the product, and this organic solvent is discharged into the atmosphere during processing into a fabric. Or remains in the fabric and has a great influence on air pollution and water pollution.

On the other hand, in recent years, water-based polyurethane resins not containing an organic solvent have been attracting attention from the viewpoints of the global environment, safety, and hygiene. As for non-porous membrane-type moisture-permeable waterproofing agents, conversion from organic solvent-based polyurethane resins to water-based polyurethane resins has been studied, and various non-porous moisture-permeable waterproofing agents have been proposed (for example, patents) References 5 and 6). The water-based urethane resin has a great feature that it can reduce adverse effects on the environment, but the problem is that the formed moisture-permeable layer has tack, and that moisture accumulates in a liquid state on the moisture-permeable layer during the moisture-permeable test. There is a problem of water leakage. Moreover, the actual situation is that it is greatly inferior to the nonporous moisture-permeable waterproofing agent using a solvent-based resin in terms of texture, water resistance, moisture permeability, washing resistance and the like.
Japanese Patent Publication No.54-961 Japanese Unexamined Patent Publication No. 64-62320 Japanese Patent Laid-Open No. 3-203920 JP-A-4-180813 JP-A-6-220399 JP 2004-300188 A

  The present invention has been made to solve the above-described problems of the prior art, and the object of the present invention is to provide a moisture-permeable layer that is excellent in terms of texture, water resistance, moisture permeability, washing resistance, and the like. It is providing the manufacturing method of the water-based polyurethane-resin composition for non-porous membrane type moisture-permeable waterproof processes which can form, and a moisture-permeable waterproof fabric using the same.

  The water-based polyurethane resin composition for non-porous membrane-type moisture-permeable and waterproof processing of the present invention contains (A component) an organic polyisocyanate component and (B component) a polyoxyethylene group composed of 4 or more oxyethylene units. And a first polyol component containing at least two active hydrogens reactive with NCO groups and having a number average molecular weight in the range of 800 to 22000, and (C component) active hydrogens reactive with NCO groups. A polyurethane prepolymer having a terminal isocyanate group obtained by reacting in the range of NCO / OH ratio (molar ratio) = 1.03 to 1.12. Using at least two second polyol components as constituent components On the other hand, it is characterized in that it is obtained by water-dispersing a prepolymer obtained by adding (D component) alkoxysilane compound.

  Moreover, the non-porous membrane-type moisture-permeable waterproof water-based polyurethane resin composition of the present invention comprises (A component) an organic polyisocyanate component and (B component) a polyoxyethylene group composed of 4 or more oxyethylene units. A first polyol component that contains at least two active hydrogens that are reactive with NCO groups and have a number average molecular weight in the range of 800 to 22000, and (C component) an activity reactive with NCO groups Polyurethane having a terminal isocyanate group obtained by reacting in the range of NCO / OH ratio (molar ratio) = 1.03 to 1.12 with a second polyol component containing at least two hydrogens as a constituent component It is characterized by being obtained by further adding (D component) an alkoxysilane compound to a prepolymer obtained by dispersing the prepolymer in water.

  In the present invention, the balance between hydrophilicity and hydrophobicity is adjusted by using two types of polyol components (component B) and component (C), and the texture is excellent as a moisture-permeable layer of moisture-permeable and waterproof fabric. Water resistance, moisture permeability, washing resistance, etc. are exhibited.

  In the above, the total content of oxyethylene units contained in the first polyol component (component B) is in the range of 10 to 35% by weight, with the solid content in the aqueous polyurethane resin being 100% by weight. It is preferable that

  The component (D) is preferably an alkoxysilane containing two or more alkoxy groups in one molecule, and the content thereof is 1 to 10 based on 100% by weight of the solid content in the aqueous polyurethane resin. A range of% by weight is preferred.

  The method for producing a moisture-permeable and waterproof fabric of the present invention comprises forming the moisture-permeable layer by applying the water-based polyurethane resin composition for non-porous membrane-type moisture-permeable and waterproof treatment described above to a release paper and performing a drying treatment. Then, an adhesive composition obtained by adding an isocyanate crosslinking agent to the water-based polyurethane resin composition is applied onto the moisture-permeable layer and dried, and then the fabric is bonded and further subjected to a water-repellent treatment. To obtain a moisture permeable waterproof fabric.

  Alternatively, the water-based polyurethane resin composition for non-porous membrane-type moisture-permeable and waterproof processing described above may be applied to a fabric and dried, and then the fabric may be bonded and further subjected to a water-repellent treatment.

  According to the present invention, it is difficult to obtain with a conventional water-based polyurethane resin, and it is excellent in texture, moisture permeability, water resistance, and washing resistance, and enables non-porous moisture-permeable waterproof processing that does not cause tackiness or leakage. A water-based moisture-permeable waterproofing agent and a method for producing a moisture-permeable waterproof fabric using the same are provided.

  There is no restriction | limiting in particular as an organic polyisocyanate component of A component used in this invention, A well-known thing can be used in the field | area of the urethane industry. For example, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymeric MDI, hexamethylene diisocyanate (HMDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), isophorone diisocyanate (IPDI), hydrogenated MDI Organic polyisocyanate compounds such as (H12MDI) can be mentioned, but when non-yellowing is required, aliphatic isocyanates such as HMDI, alicyclic isocyanates such as IPDI and H12MDI, and alicyclic rings such as XDI and TMXDI Group isocyanates are preferred.

  As the first polyol component, which is the B component used in the present invention, those known in the field of the urethane industry are used as long as they contain a polyoxyethylene group composed of 4 or more oxyethylene units. For example, mention may be made of polyether polyols.

  Examples of the polyether polyol that can be used as the component B in the present invention include a polyoxyethylene glycol polymer and a block-like or random ethylene oxide copolymer containing hydroxyl end groups (preferably an ethylene oxide / propylene oxide copolymer). Product). As a starting material for obtaining a block-like or random ethylene oxide copolymer containing hydroxyl end groups, triols such as glycerin, hexanetriol, trimethylolethane, trimethylolpropane, triethanolamine, triisopropanolamine, Examples include alkanolamines such as tributanolamine. An example of the tetrafunctional alcohol component is pentaerythritol. Using these polyhydric alcohols as starting materials, polyether polyols are synthesized by polyadding ethylene oxide and, if necessary, other alkylene oxides in the presence of a basic catalyst. Examples of other alkylene oxides include propylene oxide and butylene oxide.

  The number average molecular weight of the polyol compound having a polyoxyethylene group as the component B is required to be 800 to 22000, and preferably 3000 to 12000. When the number average molecular weight of the polyol compound having an oxyethylene group is less than 800, the sticky feeling of the film formed from the obtained polyurethane resin becomes strong. On the other hand, when the molecular weight of the polyethylene glycol exceeds 22000, the flexibility of the film formed from the resulting polyurethane resin is lowered, and sufficient moisture permeability cannot be obtained.

  The content of the polyoxyethylene group contained in the polyol compound having a polyoxyethylene group as component B in the polyurethane resin is preferably 10 to 35% by weight, where the solid content in the water-based polyurethane resin is 100% by weight. When the content is less than 10% by weight, sufficient moisture permeability may not be obtained. On the other hand, if it exceeds 35% by weight, the viscosity of the emulsifying system increases when the resin is made aqueous, and as a result, the solid content may decrease.

  As a 2nd polyol component which is C component used in this invention, polyether polyol, polyester polyol, and polycarbonate polyol can be mentioned, for example.

  Examples of the polyether polyol that can be used as the component C in the present invention include polyoxypropylene glycol and polyoxytetramethylene glycol. These polyether polyols are starting materials such as glycerol, hexanetriol, trimethylolethane, trimethylolpropane and other triols, triethanolamine, triisopropanolamine, tributanolamine and other alkanolamines, and pentaerythritol. It is obtained by polyaddition of propylene oxide, butylene oxide, etc. to these polyhydric alcohols in the presence of a basic catalyst.

  The polyester polyol that can be used as the C component in the present invention is typically one obtained by reacting a dibasic acid component with a dihydric alcohol component. Examples of the dibasic acid component include aromatic dibasic acids such as adipic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid. As the dihydric alcohol component constituting the polyester polyol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl- Aliphatic glycols such as 1,5-pentadiol, alicyclic glycols such as cyclohexanediol, and aromatic glycols such as bisphenol A alkylene oxide adducts. These dibasic acid components and dihydric alcohol components are subjected to a condensation reaction to obtain a polyester polyol.

  Examples of the polycarbonate polyol that can be used as the component C in the present invention include polytetramethylene carbonate diol, polyhexamethylene carbonate diol, and poly-1,4-cyclohexanedimethylene carbonate diol.

  In preparing the aqueous polyurethane resin composition of the present invention, a chain extender may be used in combination as long as the effects of the present invention are not impaired. Examples of the chain extender include polyhydric alcohols such as ethylene glycol, diethylene glycol, butanediol, propylene glycol, hexanediol, trimethylolpropane, glycerin and pentaerythritol, and low molecular chain extenders such as oxyalkylene derivatives. Can be used.

  In addition, examples of the chain extender component include low molecular chain extenders such as bisfer A, bisphenol B, hydrogenated bisphenol A, dibromobisphenol A, cyclohexanediol, cyclohexanedimethanol, hydroquinone, and hydroquinone dihydroxyethyl ether. These can be used within a range not impairing the effects of the present invention.

  The reaction of the organic polyisocyanate of component A with the polyols of component B and component C can be carried out by a known method, and the molar ratio of NCO groups / active hydrogen groups during the reaction is 1.03. The polyurethane prepolymer is obtained by performing the reaction at 30 to 130 ° C. for 30 minutes to 50 hours. The polyurethane prepolymer preferably contains at least 0.2% by weight to 2.0% by weight of free isocyanate groups, and has 0.5 to 1.5% by weight of free isocyanate groups. More preferably.

  In the synthesis of the urethane prepolymer, a solvent that is inactive with respect to isocyanate and that can dissolve the urethane prepolymer may be used. Examples of the solvent that can be used include dioxane, methyl ethyl ketone, dimethylformamide, tetrahydrofuran, N-methyl-2-pyrrolidone, toluene, and propylene glycol monomethyl ether acetate. Moreover, you may use together the solution or emulsion of antioxidant or a light-resistant agent in urethane prepolymer aqueous solution.

  Examples of the antioxidant include a solution or emulsion of an antioxidant such as a hindered phenol type or a semicarbazide type. Examples of the light fastener include solutions or emulsions of light fasteners such as hindered amine (HALS), benzophenone, and benzotriazole.

  After obtaining the polyurethane prepolymer as described above, the alkoxysilane compound of component D is added. The D component is added before or after the dispersion of the polyurethane prepolymer in water. As the alkoxysilane compound, an alkoxysilane containing two or more alkoxy groups in one molecule is preferably used. Examples of the alkoxysilane containing two or more alkoxy groups in one molecule include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. , Γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ -Methacryloxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrie Toxisilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane and the like can be mentioned.

  In the present invention, an amine extender may be further used after the addition of the alkoxysilane compound of component D. Examples of amine extenders include ethylenediamine, propylenediamine, trimethylenediamine, hexamethylenediamine, 4,4'-diaminodicyclohexylmethane, piperazine, 2-methylpiperazine, isophoronediamine, diethylenetriamine, triethylenetetramine, hydrazine, adipic acid dihydrazide, etc. And low molecular weight polyamines.

  The manufacturing method of the moisture-permeable waterproof fabric of the present invention is to obtain the moisture-permeable waterproof fabric by the dry laminating method using the non-porous membrane-type water-permeable polyurethane resin composition for moisture-permeable and waterproof processing. That is, the moisture-permeable layer is formed by applying the water-based polyurethane resin composition for non-porous membrane-type moisture-permeable and waterproof processing to a release paper and performing a heat drying process using a pin tenter or the like. Thereafter, an adhesive composition obtained by adding an isocyanate crosslinking agent to the water-based polyurethane resin composition is applied onto the moisture permeable layer, dried using a pin tenter or the like, and then the fabric is bonded to the pin tenter or the like. Use to heat. Next, the moisture-permeable and waterproof fabric is obtained by removing the release paper and performing a water repellent treatment.

  Moreover, according to the manufacturing method of the moisture-permeable waterproof fabric of this invention, you may apply | coat and dry-process the said water-based polyurethane resin composition for non-porous membrane type moisture-permeable waterproof processes directly to a fabric.

  EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.

(Example 1 ... Preparation of water-based polyurethane resin composition)
274.6 parts of polyester polyol (1,4-butanediol / adipic acid, Nippon Polyurethane Industry Co., Ltd., Mw = 1000, hydroxyl value = 112.2), polyethylene glycol (Daiichi Kogyo Seiyaku Co., Ltd., Mw) = About 1000, hydroxyl value = 112.2) 49.7 parts, 4,4'-dicyclohexylmethane diisocyanate 53.2 parts, 4,4'-diphenylmethane diisocyanate 50.7 parts, trimethylolpropane 4.4 parts, methyl ethyl ketone 80 parts and 0.05 part of dioctyltin dilaurate were added and reacted at 70 to 75 ° C. for 90 minutes (NCO / OH = 1.10). At this time, the free isocyanate group content (in terms of solid content) was 0.68% by weight. Next, 94.5 parts of methyl ethyl ketone was added to bring the temperature of the system to 40 ° C., and this prepolymer was diluted with water with stirring, and further N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane (Shin-Etsu Chemical). 6.2 parts of Kogyo Co., Ltd., KBM-602) was added, and disappearance of free NCO (% by weight) was confirmed. Thereafter, MEK was distilled off to obtain an aqueous polyurethane resin composition A having a pure content of 25% by weight (content of polyethylene glycol (Mw = about 1000) with respect to the solid content in the aqueous polyurethane resin composition A = 11.3). % By weight (theoretical value), content of alkoxysilane = 1.4% by weight (theoretical value)).

(Example 2: Preparation of aqueous polyurethane resin composition)
109.3 parts of polypropylene glycol (“PML S-X4001” manufactured by Asahi Glass Co., Ltd., Mw = 2000, hydroxyl value = 56.1), polyethylene glycol (produced by Daiichi Kogyo Seiyaku Co., Ltd., Mw = about 20000, hydroxyl value) = 5.6) 49.7 parts, 2.6 parts of trimethylolpropane, 23.3 parts of 3-methyl-1,5-pentadiol, 39.8 parts of 4,4′-dicyclohexylmethane diisocyanate, 4,4 ′. -38.0 parts of diphenylmethane diisocyanate, 100 parts of methyl ethyl ketone, and 0.02 part of dioctyltin dilaurate were added and reacted at 70 to 75 ° C for 90 minutes (NCO / OH = 1.06). At this time, the free isocyanate group content (in terms of solid content) was 0.70% by weight. Next, 124 parts of methyl ethyl ketone was added, the temperature of the system was 40 ° C., and 23.6 parts of γ-glycidoxypropylmethyldiethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-403) was added, This prepolymer was diluted with water under stirring, 2.8 parts of dipropylene triamine was further added, and 4.1 parts of was added, and disappearance of free NCO (wt%) was confirmed. Thereafter, MEK was distilled off to obtain an aqueous polyurethane resin composition B having a pure content of 25% by weight (content of polyethylene glycol (Mw = about 20000) relative to the solid content in the aqueous polyurethane resin composition B = 17.2). % By weight (theoretical value), content of alkoxysilane = 8.2% by weight (theoretical value)). This water-based polyurethane resin composition B has a free imino group in the state of an aqueous dispersion, but it is intended that the imino group is crosslinked with the epoxy group of the silane coupling agent during film formation.

(Example 3 ... Preparation of aqueous polyurethane resin composition)
274.6 parts of polytetramethylene glycol (PolyTHF1000, manufactured by BASF Corporation, Mw = 1000, hydroxyl value = 112.2), polyoxyethylene propylene random copolymer glycol (Polyhardener D-340W, Daiichi Kogyo Seiyaku Co., Ltd.) ), Mw = about 3400, ethylene oxide content of about 78% by weight, hydroxyl value = 33.0) 108.0 parts, trimethylolpropane 4.4 parts, 3-methyl-1,5-pentadiol 2.6 Part, 4,4'-dicyclohexylmethane diisocyanate 51.0 parts, 4,4'-diphenylmethane diisocyanate 48.7 parts, methyl ethyl ketone 110 parts, dioctyltin dilaurate 0.02 parts, and reacted at 70-75 ° C for 90 minutes (NCO / OH = 1.03). The free isocyanate group content (in terms of solid content) at this time was 0.40% by weight. Next, 75 parts of methyl ethyl ketone was added, the temperature of the system was adjusted to 40 ° C., and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-303) was added to 5.2. The prepolymer was diluted with water under stirring, and 2.8 parts of dipropylene triamine was further added to confirm the disappearance of free NCO (% by weight). Thereafter, MEK was distilled off to obtain an aqueous polyurethane resin composition C having a pure content of 25% by weight (content of polyethylene polypropylene random glycol (Mw = about 3400) relative to the solid content in the aqueous polyurethane resin composition C) = 21. 0.7% by weight (theoretical value), content of alkoxysilane = 1.0% by weight (theoretical value)). Although this water-based polyurethane resin composition C has a free imino group in the state of an aqueous dispersion, it is intended that the imino group crosslinks with an epoxy group of a silane coupling agent during film formation.

(Example 4 ... Preparation of water-based polyurethane resin composition)
Polypropylene glycol ("PML S-X4001" manufactured by Asahi Glass Co., Ltd., Mw = 2000, hydroxyl value = 56.1) 82.0 parts, polyethylene glycol (Daiichi Kogyo Seiyaku Co., Ltd., Mw = approximately 10,000, hydroxyl value) = 11.2) 56.2 parts, 9.7 parts of 3-methyl-1,5-pentanediol, 1.3 parts of trimethylolpropane, 41.1 parts of 4,4′-dicyclohexylmethane diisocyanate, 100 parts of methyl ethyl ketone, Dioctyltin dilaurate 0.02 part was added, and it was made to react for 90 minutes at 70-75 degreeC (NCO / OH = 1.03). At this time, the free isocyanate group content (in terms of solid content) was 1.50% by weight. Next, 60 parts of methyl ethyl ketone, 0.8 part of dimethylolpropionic acid and 0.6 part of triethylamine were added and reacted at 65 to 70 ° C. for 1 hour. At this time, the content of free isocyanate groups (in terms of solid content) was 1.20% by weight. The system was cooled and 50 parts of methyl ethyl ketone was added to bring the temperature of the system to 40 ° C. Under stirring, γ-aminopropyltriethoxysilane (KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to this prepolymer. After adding 1 part, it diluted with water, and also 1.5 parts of dipropylene triamines were added, and the loss | disappearance of free NCO (weight%) was confirmed. Thereafter, MEK was distilled off to obtain an aqueous polyurethane resin composition D having a pure content of 20% by weight (the content of polyethylene glycol (Mw = about 10,000) relative to the solid content in the aqueous polyurethane resin composition D was 34.4% by weight). % (Theoretical value), content of alkoxysilane = 2.5% by weight (theoretical value), acid value 1.9 mgKOH / g).

(Example 5: Preparation of water-based polyurethane resin composition)
Polytetramethylene glycol (PolyTHF2000, manufactured by BASF Corporation, Mw = 2000, hydroxyl value = 56.1) 82.0 parts, polyethylene glycol (Daiichi Kogyo Seiyaku Co., Ltd., Mw = about 10,000, hydroxyl value = 11) .2) 49.7 parts, 2.0 parts of trimethylolpropane, 12.2 parts of 1,4-butanediol, 59.7 parts of hexamethylene diisocyanate, 100 parts of methyl ethyl ketone, 0.02 part of dioctyltin dilaurate, The reaction was carried out at 70 to 75 ° C. for 90 minutes (NCO / OH = 1.11). The free isocyanate group content (in terms of solid content) at this time was 2.0% by weight. Next, 60 parts of methyl ethyl ketone and 3.0 parts of N-methyldiethanolamine were added and reacted at 70 to 75 ° C. for 2 hours. At this time, the free isocyanate group content (in terms of solid content) was 0.60% by weight. The system was cooled to 40 ° C., 1.5 parts of acetic acid was added, 50 parts of methyl ethyl ketone was further added, and under stirring, this prepolymer was added to γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE). After adding 4.1 parts of -903), it was diluted with water, and 1.2 parts of dipropylene triamine was further added to confirm the disappearance of free NCO (% by weight). Thereafter, MEK was distilled off to obtain an aqueous polyurethane resin composition E having a pure content of 25% by weight (content of polyethylene glycol (Mw = about 10,000) with respect to the solid content in the aqueous polyurethane resin composition E was 25.2% by weight). % (Theoretical value), content of alkoxysilane = 2.1% by weight (theoretical value), amine value 7.2 mgKOH / g).
(Synthesis example: Preparation of adhesive composition)
160.0 parts of polyester polyol (1,4-butanediol / adipic acid, Nippon Polyurethane Industry, Mw = 2000, hydroxyl value = 56.1), polyethylene glycol (Daiichi Kogyo Seiyaku, Mw = 1000, hydroxyl value = 112.2) 300.0 parts, methyl ethyl ketone 180.0 parts, and tolylene diisocyanate (manufactured by Nippon Polyurethane Industry, TDI-80) 70.5 parts were added and reacted at 70 to 75 ° C. for 90 minutes (NCO / OH = 1.07). The free isocyanate group content (in terms of solid content) at this time was 1.00% by weight. Next, 91.3 parts of methyl ethyl ketone, 5.4 parts of dimethylolpropionic acid, and 2.0 parts of triethylamine were added and reacted at 60 to 65 ° C. for 20 minutes. At this time, the free isocyanate group content (in terms of solid content) was 0.10% by weight. Next, 124 parts of methyl ethyl ketone was added, the temperature of the system was 40 ° C., this prepolymer was diluted with water under stirring, MEK was distilled off, and a nonionic polyurethane prepolymer water dispersion having a pure content of 25% by weight was dispersed. The body BR was obtained.

(Comparative Example 1 ... Preparation of water-based polyurethane resin composition)
201.2 parts of polypropylene glycol (“PML S-X4001”, Asahi Glass Co., Ltd., Mw = 2000, hydroxyl value = 56.1), polyethylene glycol (Daiichi Kogyo Seiyaku Co., Ltd., Mw = about 1000, hydroxyl value) = 112.2) 21.0 parts, 0.7 parts of trimethylolpropane, 36.3 parts of 4,4′-dicyclohexylmethane diisocyanate, 80 parts of methyl ethyl ketone, 0.02 part of dioctyltin dilaurate were added, and 70 to 75 ° C. For 90 minutes (NCO / OH = 1.07). At this time, the free isocyanate group content (in terms of solid content) was 0.50% by weight. Next, 100 parts of methyl ethyl ketone is added, the temperature of the system is 40 ° C., this prepolymer is diluted with water under stirring, and 0.6 part of dipropylene triamine is further added to eliminate the disappearance of free NCO (% by weight). confirmed. Thereafter, MEK was distilled off to obtain an aqueous polyurethane resin composition a having a pure content of 25% by weight (content of polyethylene glycol (Mw = about 1000) based on the solid content of the aqueous polyurethane resin composition a was 8.0% by weight). (Theoretical value), content of alkoxysilane = 0 wt%).

(Comparative Example 2 ... Preparation of water-based polyurethane resin composition)
82.0 parts of polytetramethylene glycol (PolyTHF2000, manufactured by BASF Corporation, Mw = 2000, hydroxyl value = 56.1), polyethylene glycol (produced by Daiichi Kogyo Seiyaku Co., Ltd., Mw = about 10,000, hydroxyl value = 11) .2) 49.7 parts, 2.0 parts of trimethylolpropane, 16.0 parts of 1,6-hexanediol, 70.3 parts of 4,4′-dicyclohexylmethane diisocyanate, 100 parts of methyl ethyl ketone, 0.02 of dioctyltin dilaurate Part was added and reacted at 70-75 ° C. for 90 minutes. The free isocyanate group content (in terms of solid content) at this time was 2.0% by weight. Next, 60 parts of methyl ethyl ketone and 3.0 parts of N-methyldiethanolamine were added and reacted at 70 to 75 ° C. for 2 hours. At this time, the free isocyanate group content (in terms of solid content) was 0.60% by weight. The system was cooled to 40 ° C., 1.5 parts of acetic acid was added, 50 parts of methyl ethyl ketone was further added, and under stirring, this prepolymer was added to γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE). After adding 4.1 parts of -903), it was diluted with water, and further 2.3 parts of dipropylenetriamine was added to confirm the disappearance of free NCO (% by weight). Thereafter, MEK was distilled off to obtain an aqueous polyurethane resin composition b having a pure content of 25% by weight (NCO / OH = 1.17; polyethylene glycol relative to the solid content of the aqueous polyurethane resin composition b (Mw = about 10,000). Content of 22.0% by weight (theoretical value), content of alkoxysilane = 1.8% by weight, amine value 6.3 mgKOH / g).

(Comparative Example 3 ... Preparation of water-based polyurethane resin composition)
180 parts of polytetramethylene glycol (PolyTHF1000, manufactured by BASF Corp., Mw = 1000, hydroxyl value = 112.2), polyoxyethylene propylene random copolymer glycol (Polyhardener D-340W, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Mw = 3400, hydroxyl value = 33.0) 20 parts of 1,4-butanediol 3.8 parts, 3.8 parts of trimethylolpropane and 100 parts of methyl ethyl ketone are added with 79.9 parts of dicyclohexylmethane diisocyanate, The reaction was carried out at 75 ° C. for 90 minutes to obtain a 1.1 wt% urethane polymer containing a free isocyanate group.

  After adding 14.4 parts of polyoxyethylene arylphenol ether type nonionic surfactant (HLB = 15) which is an ethylene oxide adduct of distyrenated phenol to this prepolymer (5.0% by weight of solid content) and mixing, Water was added and emulsified and dispersed, and 42.4 parts of a 5 wt% aqueous solution of ethylenediamine was added thereto, and disappearance of free NCO (wt%) was confirmed. Thereafter, MEK was distilled off to obtain an aqueous polyurethane resin composition c having a pure content of 25% by weight (NCO / OH = 1.13; content of hydrophilic polyether component with respect to the solid content of the aqueous polyurethane resin composition c) 7.0% by weight, content of alkoxysilane = 0% by weight).

(Comparative Example 4 ... Preparation of water-based polyurethane resin composition)
Polypropylene glycol ("PML S-X4001" manufactured by Asahi Glass Co., Ltd., Mw = 2000, hydroxyl value = 56.1) 82.0 parts, polyethylene glycol (Daiichi Kogyo Seiyaku Co., Ltd., Mw = 400, hydroxyl value = 280.6) 65.2 parts, 37.7 parts of hexamethylene diisocyanate, 100 parts of methyl ethyl ketone and 0.02 part of dioctyltin dilaurate were added and reacted at 70 to 75 ° C. for 90 minutes (NCO / OH = 1.06). ). At this time, the free isocyanate group content (in terms of solid content) was 1.50% by weight. Next, 60 parts of methyl ethyl ketone, 0.8 part of dimethylolpropionic acid and 0.6 part of triethylamine were added and reacted at 65 to 70 ° C. for 1 hour. At this time, the free isocyanate group content (in terms of solid content) was 0.60% by weight. The system was cooled, 50 parts of methyl ethyl ketone was further added, the temperature of the system was adjusted to 40 ° C., and γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-903) was added to this prepolymer under stirring. After adding 4.1 parts, it diluted with water, and also 1.1 parts of dipropylene triamines were added, and the loss | disappearance of free NCO (weight%) was confirmed. Thereafter, MEK was distilled off to obtain an aqueous polyurethane resin composition d having a pure content of 20% by weight (the content of polyethylene glycol was 34.4% by weight and the content of alkoxysilane = the solid content of the aqueous polyurethane resin composition d = 2.2% by weight, acid value 1.8 mg KOH / g).

(Comparative Example 5 ... Preparation of water-based polyurethane resin composition)
Polypropylene glycol ("PML S-X4001" manufactured by Asahi Glass Co., Ltd., Mw = 2000, hydroxyl value = 56.1) 82.0 parts, polyethylene glycol (Daiichi Kogyo Seiyaku Co., Ltd., Mw = approximately 10,000, hydroxyl value) = 11.2) 67.4 parts, 9.7 parts of 3-methyl-1,5-pentanediol, 1.3 parts of trimethylolpropane, 41.8 parts of 4,4′-dicyclohexylmethane diisocyanate, 100 parts of methyl ethyl ketone, Dioctyltin dilaurate 0.02 part was added, and it was made to react at 70-75 degreeC for 90 minutes. At this time, the free isocyanate group content (in terms of solid content) was 1.50% by weight. Next, 60 parts of methyl ethyl ketone, 2.2 parts of dimethylolpropionic acid, and 0.6 parts of triethylamine were added and reacted at 65 to 70 ° C. for 1 hour. At this time, the free isocyanate group content (in terms of solid content) was 0.60% by weight. The system was cooled, 50 parts of methyl ethyl ketone was further added, the temperature of the system was adjusted to 40 ° C., and γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-903) was added to this prepolymer under stirring. After adding 4.1 parts, it diluted with water, and also 1.1 parts of dipropylene triamines were added, and the loss | disappearance of free NCO (weight%) was confirmed. Thereafter, MEK was distilled off to obtain an aqueous polyurethane resin composition e having a pure content of 25% by weight (content of polyethylene glycol 37.9% by weight, content of alkoxysilane relative to the solid content of the aqueous polyurethane resin composition e = 2.3 wt%, acid value 5.5 mg KOH / g).

(Creation of moisture permeable waterproof fabric for evaluation test)
<Preparation of adhesive>
100 parts of nonionic polyurethane prepolymer aqueous dispersion BR prepared in Synthesis Example, 5 parts of Aquanate 210 (water-dispersed isocyanate cross-linking agent, manufactured by Nippon Polyurethane Industry), and associative thickener M-2005A (Daiichi Kogyo) An adhesive was obtained by blending 0.5 part of Pharmaceutical Co., Ltd.

<Test Examples 1 to 5, Comparative Test Examples 1 to 5 ... Creation of moisture-permeable and waterproof fabric by dry lamination method>
The release paper is coated with the aqueous polyurethane resin compositions A to E and a to e prepared in Examples 1 to 5 and Comparative Examples 1 to 5 so as to have a dry film thickness of 15 μm, and is 80 ° C. with a pin tenter (dryer). After the treatment for 3 minutes, heat treatment was further performed at 150 ° C. for 3 minutes to form a moisture-permeable polyurethane resin film on the release paper. On this polyurethane resin film, the adhesive prepared above is coated with a bar coater so as to have a dry film thickness of 20 μm, heat-treated with a pin tenter (dryer) at 90 ° C. for 4 minutes, and immediately adhered to a polyester fabric (taffeta). In addition, the laminate was laminated using a calender under the conditions of a temperature of 90 ° C. and a pressure of 2 MPa, and then aged at a temperature of 45 ° C. for 48 hours. Next, the release paper is peeled off, immersed in a 1% aqueous solution of Erasgard W-70 (Fluorine-based water repellent; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), squeezed, and then 120 with a pin tenter (dryer). It processed for 3 degreeC *, and the moisture-permeable waterproof fabric of Test Examples 1-5 and Comparative Test Examples 1-5 was obtained.

<Test Example 6 ... Creation of moisture permeable waterproof fabric by direct coating method>
A water-based polyurethane resin A having moisture permeability and waterproofness prepared in Example 1 is coated on a lightly water-repellent polyester woven fabric (taffeta) so as to have a dry film thickness of 30 μm, and a pin tenter (dryer) at 80 ° C. × After the treatment for 3 minutes, heat treatment was further performed at 150 ° C. for 3 minutes to form a polyurethane resin film having moisture permeability on a polyester fabric (taffeta). Further, after being immersed in a 1% aqueous solution of Elastogard W-70 (fluorinated water repellent; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) A porous moisture-permeable waterproof fabric was obtained.

(Evaluation test of moisture permeable waterproof fabric)
The moisture permeable waterproof fabrics of Test Examples 1 to 6 and Comparative Test Examples 1 to 5 prepared above were evaluated for moisture permeability, water pressure resistance, wash resistance and texture. The evaluation method is as follows.

<Moisture permeability>
The measurement was performed according to JIS L-1099 4.1.1B-1 (potassium acetate method).

<Water pressure resistance>
The measurement was performed according to JIS L-1092 B method (high water pressure method).

<Washing resistance>
Washing was performed according to method 103 of JIS L 0217, and the moisture permeability and water pressure resistance were measured before and after 10 washings.

<Texture>
Evaluation was made by touch. The evaluation criteria are “◯” for “soft”, “Δ” for “slightly hard”, and “×” for “hard”.

<Result>
The result of the evaluation test about the moisture-permeable waterproof fabric of Test Examples 1-6 is shown in Table 1, and the result of the evaluation test about the moisture-permeable waterproof fabric of Comparative Test Examples 1-5 is shown in Table 2, respectively.

  From the comparison of Table 1 and Table 2, the moisture-permeable waterproof fabric of each test example shows high moisture permeability and no water leakage, whereas the moisture-permeable waterproof fabric of each comparative example has insufficient moisture permeability. It can be seen that there are many things, and even those with high moisture permeability cause water leakage. As for the washing resistance, the moisture-permeable waterproof fabrics of each test example showed a slight decrease in moisture permeability, but almost no decrease in water resistance. On the other hand, the moisture permeable and waterproof fabrics of Comparative Test Examples 1 to 5 do not endure the use because the initial moisture permeability and low water resistance are not improved even after the 10th washing. It was. As for the texture, each of the moisture permeable and waterproof fabrics of each test example and each comparative test example was evaluated as “good”. However, the moisture permeable waterproof fabric of Comparative Test Example 4 using the water-based polyurethane resin composition d had tack.

  If the water-based polyurethane resin composition for non-porous membrane-type moisture-permeable and waterproof processing of the present invention is used, a moisture-permeable and waterproof fabric can be produced without using an organic solvent, so that it can be used in the field of textile processing. is there.

Claims (7)

(Component A) an organic polyisocyanate component;
(Component B) A polyoxyethylene group comprising 4 or more oxyethylene units and at least two active hydrogens reactive with NCO groups and having a number average molecular weight in the range of 800 to 22,000. 1 polyol component;
(Component C) In the range of NCO / OH ratio (molar ratio) = 1.03 to 1.12. Using as a constituent component a second polyol component containing at least two active hydrogens reactive with NCO groups For the polyurethane prepolymer having a terminal isocyanate group obtained by the reaction,
(D component) A water-based polyurethane resin composition for non-porous membrane-type moisture-permeable waterproofing process obtained by water-dispersing a prepolymer obtained by adding an alkoxysilane compound. (Component A) an organic polyisocyanate component;
(Component B) A polyoxyethylene group comprising 4 or more oxyethylene units and at least two active hydrogens reactive with NCO groups and having a number average molecular weight in the range of 800 to 22,000. 1 polyol component;
(Component C) In the range of NCO / OH ratio (molar ratio) = 1.03 to 1.12. Using as a constituent component a second polyol component containing at least two active hydrogens reactive with NCO groups For the prepolymer obtained by water-dispersing the polyurethane prepolymer having terminal isocyanate groups obtained by the reaction,
(D component) A water-based polyurethane resin composition for non-porous membrane-type moisture-permeable and waterproof processing obtained by adding an alkoxysilane compound.   The total content of oxyethylene units contained in the first polyol component of the (B component) is 10 to 35 wt%, where the solid content in the aqueous polyurethane resin is 100 wt%. Item 3. The water-based polyurethane resin composition for non-porous membrane-type moisture permeable waterproofing processing according to Item 1 or 2.   The aqueous system for non-porous membrane-type moisture-permeable and waterproof processing according to any one of claims 1 to 3, wherein (D component) is an alkoxysilane containing two or more alkoxy groups in one molecule. Polyurethane resin composition.   The content of the alkoxysilane containing two or more alkoxy groups in one molecule of the component (D) is 1 to 10% by weight, where the solid content in the aqueous polyurethane resin is 100% by weight. A water-based polyurethane resin composition for non-porous membrane-type moisture-permeable waterproof processing.   A water-permeable polyurethane resin composition for non-porous membrane-type moisture-permeable and waterproof processing according to any one of claims 1 to 5 is applied to a release paper and dried to form a moisture-permeable layer, and the moisture-permeable layer After applying an adhesive composition obtained by adding an isocyanate cross-linking agent to a water-based polyurethane resin composition and performing a drying treatment, the fabric is bonded together and further subjected to a water-repellent waterproofing treatment by water-repellent treatment. A method for producing a moisture-permeable and waterproof fabric, characterized in that the fabric is obtained. Applying the water-based polyurethane resin composition for non-porous membrane-type moisture-permeable waterproofing processing according to any one of claims 1 to 5 to a fabric and drying it, then bonding the fabric together, and further water-repellent treatment A method for producing a moisture permeable and waterproof fabric.