JP5479296B2 - Aqueous polyurethane resin, hydrophilic resin and film - Google Patents

Description

  The present invention relates to an aqueous polyurethane resin, a hydrophilic resin containing the aqueous polyurethane resin (first aqueous resin) and a second aqueous resin, and a film obtained from the hydrophilic resin.

  Fibers are known to be moisture-permeable and waterproof so as to block rainwater while allowing moisture (water vapor) such as sweat to pass through. It is known to use a wet resin.

  For example, 1,3- (bisisocyanatomethyl) cyclohexane, polyethylene glycol, and polyoxyethylene side chain-containing polyol are reacted to obtain an isocyanate group-terminated prepolymer, and the isocyanate group-terminated prepolymer is dispersed in water. After that, an aqueous polyurethane resin is obtained by reacting the prepolymer with amines (ethylenediamine, monoethanolamine, diethanolamine, amino alcohol, etc.), and further, a hydrophilic resin containing the aqueous polyurethane resin is obtained. (For example, refer to Patent Document 1 (Examples 16 to 18)).

International Publication Pamphlet WO2009 / 072561A1

  However, although the hydrophilic resin described in Patent Document 1 is excellent in moisture permeability, when its ethylene oxide content is high (such as 50% by mass or more), water resistance may be inferior.

  In addition, when obtaining a film from such a hydrophilic resin, it is required to improve the mechanical properties such as tensile strength and elongation of the film, to lower the initial modulus of the film, and to obtain a flexible texture. ing.

  An object of the present invention is to provide an aqueous polyurethane resin, an aqueous polyurethane resin (first aqueous resin), and an aqueous polyurethane resin that have excellent moisture permeability and water resistance, and are excellent in mechanical properties and capable of obtaining a flexible texture film. It is to provide a hydrophilic resin containing two aqueous resins and a film obtained from the hydrophilic resin.

  In order to achieve the above object, the aqueous polyurethane resin of the present invention does not contain an aromatic ring and an alicyclic ring, or contains 50% by mass or more of a polycyclic-free polyisocyanate containing one aromatic ring or alicyclic ring. Obtained by reacting at least a polyisocyanate, a polyoxyethylene polyol, and a polyoxyethylene side chain-containing active compound having two or more hydroxyl groups or isocyanate groups at the molecular ends and having a polyoxyethylene group in the side chain. Water-based polyurethane resin obtained by the reaction of the obtained isocyanate group-terminated prepolymer and a chain extender containing water, wherein 60 mol% or more of the isocyanate groups in the isocyanate group-terminated prepolymer are chain-extended with water. It is characterized by.

  In the aqueous polyurethane resin of the present invention, it is preferable that the viscosity of the aqueous dispersion having a solid concentration of 30% by mass is less than 5000 mPa · s.

  Moreover, in the water-based polyurethane resin of this invention, it is suitable that the polyoxyethylene group contains 50-90 mass%.

  In the aqueous polyurethane resin of the present invention, it is preferable that the polyoxyethylene polyol has a number average molecular weight of 600 to 6000.

  Moreover, in the water-based polyurethane resin of this invention, it is suitable for the polyoxyethylene side chain containing active compound that the number average molecular weight of a polyoxyethylene group is 600-6000.

  In the aqueous polyurethane resin of the present invention, it is preferable that the polyoxyethylene side chain-containing active compound has at least one chemical bond selected from a urea group, a urethane group and an allophanate group.

  The aqueous polyurethane resin of the present invention is preferably a hydrophilic modifier.

  The hydrophilic resin of the present invention is characterized by containing the above-mentioned aqueous polyurethane resin as the first aqueous resin.

  Moreover, it is preferable that the hydrophilic resin of the present invention contains a second aqueous resin.

  The hydrophilic resin of the present invention preferably contains a water-dispersible isocyanate curing agent.

  In the hydrophilic resin of the present invention, the second aqueous resin is at least one selected from the group consisting of polyester polyol, polycarbonate polyol, and polyoxyalkylene polyol having 3 to 10 carbon atoms in the alkylene group as a raw material. It is preferable that the hydrophobic macropolyol is contained, and the hydrophobic macropolyol is contained in an amount of 50% by mass or more based on the total amount of raw materials of the second aqueous resin.

  In the hydrophilic resin of the present invention, it is preferable that the second aqueous resin further contains a carboxylic acid group-containing polyol as a raw material.

  In the hydrophilic resin of the present invention, it is preferable that the isocyanate curing agent is a blocked isocyanate in which the isocyanate is blocked with a blocking agent.

  In the hydrophilic resin of the present invention, it is preferable that the blocked isocyanate is water-dispersed with an external emulsifier.

  In the hydrophilic resin of the present invention, in the blocked isocyanate, it is preferable that the isocyanate is a polyisocyanate containing one aromatic ring or a modified product thereof.

  In the hydrophilic resin of the present invention, in the blocked isocyanate, the blocking agent is preferably 3,5-dimethylpyrazole.

  In addition, the hydrophilic resin of the present invention is preferably a coating agent for moisture permeation and waterproofing.

  Moreover, the film of this invention is obtained from said hydrophilic resin, It is characterized by the above-mentioned.

  In the polyurethane resin of the present invention, since 60 mol% or more of the isocyanate groups in the isocyanate group-terminated prepolymer are chain-extended with water, the hydrophilic resin of the present invention containing such an aqueous polyurethane resin is made of ethylene. Even when the oxide content is high (such as 50% by mass or more), it is possible to combine excellent moisture permeability and water resistance.

  Moreover, the hydrophilic resin of the present invention including the aqueous polyurethane resin of the present invention is excellent in mechanical properties and can provide a film having a soft texture.

  Therefore, the hydrophilic resin of the present invention can be suitably used as a coating agent for moisture permeable and waterproof processing.

  And the film of this invention obtained from the hydrophilic resin of this invention has the outstanding moisture-permeable waterproof performance.

  The aqueous polyurethane resin of the present invention can be obtained by a reaction between an isocyanate group-terminated prepolymer and a chain extender, and the isocyanate group-terminated prepolymer contains a polyisocyanate, a polyoxyethylene polyol, and a polyoxyethylene side chain. The active compound can be obtained by reacting at least.

  In the present invention, the polyisocyanate contains a multi-ring-free polyisocyanate in an amount of 50% by mass or more, preferably 55% by mass or more, and more preferably 60% by mass or more. When the blending ratio of the polyisocyanate containing no plural rings is less than the above lower limit, when the isocyanate group-terminated prepolymer and the chain extender are reacted, the viscosity of the aqueous dispersion increases, and the handling property decreases. In some cases, it becomes difficult to obtain an aqueous dispersion of an aqueous polyurethane resin by gelation. Moreover, the coating film obtained as the mixture ratio of polycyclic-free polyisocyanate is less than the above lower limit becomes hard and the texture may be impaired.

  Multi-ring-free polyisocyanate is a polyisocyanate that does not contain an aromatic ring and an alicyclic ring or contains one aromatic ring or alicyclic ring in one molecule, and contains, for example, an aromatic ring and an alicyclic ring. Non-aliphatic diisocyanates, for example, mono-aromatic ring-containing diisocyanates containing one aromatic ring, for example, mono-alicyclic ring-containing diisocyanates containing one alicyclic ring.

  Examples of the aliphatic diisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (abbreviation: HDI), 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate and the like can be mentioned.

  Examples of the monoaromatic ring-containing diisocyanate include 2,4- or 2,6-tolylene diisocyanate or a mixture thereof (abbreviation: TDI), 4,4′-toluidine diisocyanate, 1,3- or 1,4-xylylene diene. An isocyanate or a mixture thereof (abbreviation: XDI), tetramethylxylylene diisocyanate, and the like can be given.

Examples of monoisocyanate-containing diisocyanates include 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, (Abbreviation: IPDI), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane or a mixture thereof (abbreviation: H ₆ XDI) Is mentioned.

  In addition, as the polyisocyanate, for example, a multimer (for example, dimer, trimer (for example, aliphatic diisocyanate, monoaromatic ring-containing diisocyanate and monoalicyclic ring-containing diisocyanate) described above) , Isocyanurate-modified products, iminooxadiazinedione-modified products, etc.), pentamers, heptamers, etc.), allophanate-modified products (for example, allophanate-modified products formed by the reaction of polyisocyanates containing no rings and alcohols) Etc.), polyol-modified products (for example, polyol-modified products produced by the reaction of polycyclic-free polyisocyanates with low molecular weight polyols (described later) or high molecular weight polyols (described later)), biuret-modified products (for example, multiple rings). By reaction of polyisocyanate containing no water with amines Biuret-modified products), urea-modified products (for example, urea-modified products produced by the reaction of a polycyclic-free polyisocyanate and diamine), oxadiazine triones (for example, multi-ring-free polyisocyanates and carbon dioxide) And carbodiimide modified products (carbodiimide modified products formed by decarboxylation condensation reaction of polyisocyanate containing no plural rings), and the like.

Multiple ring-free polyisocyanates can be used alone or in combination of two or more. From the viewpoints of strength, yellowing and texture, monoalicyclic ring-containing diisocyanates are preferable, and IPDI and H ₆ XDI are more preferable.

  As long as the polyisocyanate contains a multi-ring-free polyisocyanate in the above proportion, a multi-ring-containing polyisocyanate can be used in combination.

  The multi-ring-containing polyisocyanate is a polyisocyanate containing two or more aromatic rings and / or alicyclic rings in one molecule, for example, a multi-aromatic ring-containing diisocyanate containing two or more aromatic rings, such as fat A multi-alicyclic ring-containing diisocyanate containing two or more rings is exemplified.

  Examples of the multi-aromatic ring-containing diisocyanate include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate (abbreviation: MDI), 4, Examples include 4'-diphenyl ether diisocyanate.

Examples of the diisocyanate containing a plurality of alicyclic rings include 4,4′-methylenebis (cyclohexyl isocyanate) (abbreviation: H ₁₂ MDI), 2,5 (2,6) -bis (isocyanatomethyl) bicyclo [2.2.1]. ] Heptane etc. are mentioned.

  Furthermore, for example, multimers, allophanate modified products, biuret modified products, urea modified products, oxadiazine trione, carbodiimide modified products of the above-mentioned multiple ring-containing polyisocyanates (that is, multiple aromatic ring-containing diisocyanates and multiple alicyclic ring-containing diisocyanates). Etc. can also be used.

  Multiple ring-containing diisocyanates can be used alone or in combination of two or more.

  In the present invention, the polyoxyethylene polyol can be obtained, for example, by addition polymerization of ethylene oxide using a low molecular weight polyol (described later) as an initiator. Preferably, polyethylene glycol is used.

  The number average molecular weight of the polyoxyethylene polyol is, for example, 600 to 6000, preferably 600 to 3000.

  In addition, the number average molecular weight of each raw material of the water-based polyurethane resin can be calculated from the hydroxyl equivalent of the raw material (determined from JIS K1557-1 (2007)) and the number of functional groups.

  In addition, the polyoxyethylene polyol is a total amount of the polyoxyethylene side chain-containing active compound and a high-molecular-weight polyol containing an oxyethylene group such as polypropylene polyethylene glycol, which will be described later, in the aqueous polyurethane resin. It mix | blends so that a polyoxyethylene group may be 50-90 mass%, for example, Preferably, it is 55-85 mass%, More preferably, it is 60-85 mass%, More preferably, it is 60-80 mass%. . By setting the polyoxyethylene group in the aqueous polyurethane resin in the above range, the moisture permeability of the film can be improved.

  Further, if the polyoxyethylene group in the aqueous polyurethane resin can be within the above range, a high molecular weight polyol or a low molecular weight polyol can be used in combination with the polyoxyethylene polyol.

  Examples of the high molecular weight polyol include polyoxypropylene polyol (eg, polypropylene glycol, polypropylene polyethylene glycol (random or block copolymer of polypropylene oxide and polyethylene oxide)), polyoxybutylene polyol (eg, polytetramethylene ether glycol, etc.) ), Polyester polyol (eg, alkylene (ethylene and / or butylene) adipate, polycaprolactone polyol, etc.), polycarbonate polyol (eg, polycarbonate diol, etc.), and the like.

  The number average molecular weight of the high molecular weight polyol is, for example, 400 to 6000, and the blending ratio is, for example, 0.5 to 15% by mass with respect to the total amount of raw material of the aqueous polyurethane resin (total amount charged).

  The low molecular weight polyol is a polyol having a number average molecular weight of less than 400, for example, ethylene glycol, propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol. , Neopentyl glycol, 1,6-hexanediol, 3-methylpentanediol, dimethylolheptane (butylethylpropanediol), 1,12-hydroxystearyl alcohol, alkane (carbon number 7 to 22) diol, diethylene glycol, triethylene Glycol, dipropylene glycol, cyclohexanedimethanol, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, bishydroxyethoxyben , Xylene glycol, low molecular weight diols such as bishydroxyethylene terephthalate, such as glycerin, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2 , 6-hexanetriol, 1,1,1-tris (hydroxymethyl) propane (trimethylolpropane), low molecular weight triols such as 2,2-bis (hydroxymethyl) -3-butanol, and the like.

  Examples of the low molecular weight polyol include dimer alcohol, hydrogenated dimer alcohol (for example, dimer alcohol obtained by reduction of dimer acid) and the like in addition to the above polyol.

  The blending ratio of the low molecular weight polyol is, for example, 0.01 to 5% by mass with respect to the total amount of raw material of the aqueous polyurethane resin (total amount charged).

  In the present invention, the polyoxyethylene side chain-containing active compound is a compound having two or more hydroxyl groups or isocyanate groups at the molecular ends and having a polyoxyethylene group at the side chains, for example, two hydroxyl groups at the molecular ends. Polyoxyethylene side chain-containing polyol having a polyoxyethylene group in the side chain, such as a polyoxyethylene side chain containing two or more isocyanate groups at the molecular ends and having a polyoxyethylene group in the side chain Polyisocyanate etc. are mentioned.

  The polyoxyethylene side chain-containing polyol is, for example, firstly diisocyanate (the above-mentioned diisocyanate) and one-end blocked polyoxyethylene glycol (alkoxyethylene glycol whose one end is sealed with an alkyl group of C1 to 20). After the urethanization reaction at a ratio where the isocyanate group of the diisocyanate is excessive with respect to the hydroxyl group of the polyoxyethylene glycol, if necessary, the unreacted diisocyanate is removed to synthesize a polyoxyethylene chain-containing monoisocyanate, Next, the polyoxyethylene chain-containing monoisocyanate and dialkanolamine (C1-20 dialkanolamine) can be obtained by a urea reaction.

  In the preparation of the polyoxyethylene side chain-containing polyol, the one-end blocked polyoxyethylene glycol is preferably methoxyethylene glycol, and the diisocyanate is preferably an aliphatic diisocyanate (for example, HDI). Examples of dialkanolamine include diethanolamine.

  The polyoxyethylene side chain-containing polyol thus obtained has, for example, a urethane group and a urea group, and is represented by the following formula (1).

(Wherein X ₁ is a diisocyanate residue (part other than the isocyanate group of diisocyanate), X ₂ is an alkyl group having 1 to 20 carbon atoms, X ₃ is an alkylene group having 1 to 20 carbon atoms, and n is Indicates an integer of 13 to 140.)
The blending ratio of the polyoxyethylene side chain-containing polyol is, for example, 5 to 40% by mass with respect to the total amount of raw material (total amount charged) of the aqueous polyurethane resin.

  Polyoxyethylene side chain-containing polyisocyanate is, for example, firstly diisocyanate (the above-mentioned diisocyanate) and one-end blocked polyoxyethylene glycol (alkoxyethylene glycol having one end sealed with an alkyl group of C1-20) at one end. After the urethanation reaction in an excess ratio of the isocyanate group of the diisocyanate with respect to the hydroxyl group of the blocked polyoxyethylene glycol, the polyoxyethylene chain-containing monoisocyanate is synthesized by removing the unreacted diisocyanate, if necessary. Then, the polyoxyethylene chain-containing monoisocyanate and diisocyanate can be obtained by an allophanatization reaction.

  In the preparation of the polyoxyethylene side chain-containing polyisocyanate, the one-end blocked polyoxyethylene glycol is preferably methoxyethylene glycol, and the diisocyanate is preferably aliphatic diisocyanate (for example, HDI). .

  The polyoxyethylene side chain-containing polyisocyanate thus obtained has, for example, a urethane group and an allophanate group, and is represented by the following formula (2).

(Wherein, X ₁ and X ₄ are the same as or different from each other, a diisocyanate residue (a portion other than the isocyanate group of diisocyanate), X ₂ is an alkyl group having 1 to 20 carbon atoms, and n is 13 to 140. Indicates an integer.)
The blending ratio of the polyoxyethylene side chain-containing polyisocyanate is, for example, 5 to 40% by mass with respect to the total amount of raw water polyurethane resin (total amount charged).

  Further, in the polyoxyethylene side chain-containing active compound, the polyoxyethylene group is, for example, 50% by mass or more, preferably 60 to 90% by mass, and the number average molecular weight of the polyoxyethylene group is, for example, It is 600 to 6000, preferably 600 to 3000, and more preferably 800 to 2500.

  In the polyoxyethylene side chain-containing active compound, if the number average molecular weight of the polyoxyethylene group is less than the above lower limit, the water dispersibility of the aqueous polyurethane resin may be lowered. Of course, the water dispersibility of the aqueous polyurethane resin may be lowered.

  Then, a polyisocyanate, a polyol component (polyoxyethylene polyol is included as an essential component, and a high molecular weight polyol and a low molecular weight polyol are included as optional components) and a polyoxyethylene side chain-containing active compound are reacted. To obtain an isocyanate group-terminated prepolymer.

  In this reaction, the above components are blended in a proportion exceeding 1, preferably 1.1 to 10, in the equivalent ratio of isocyanate groups to hydroxyl groups (NCO / OH). And the said component is made to react by well-known polymerization methods, such as bulk polymerization and solution polymerization, Preferably, solution polymerization in which the adjustment of reactivity and a viscosity is easier.

  In bulk polymerization, for example, the above components are blended in a nitrogen atmosphere and reacted at a reaction temperature of 75 to 85 ° C. for about 1 to 20 hours.

  In solution polymerization, for example, the above components are blended in an organic solvent under a nitrogen atmosphere and reacted at a reaction temperature of 20 to 80 ° C. for about 1 to 20 hours.

  Examples of the organic solvent include acetone, methyl ethyl ketone, ethyl acetate, tetrahydrofuran, acetonitrile, and the like, which are inert to isocyanate groups and rich in hydrophilicity.

  In the above polymerization, if necessary, for example, a reaction catalyst such as amine, tin, or lead may be added, and unreacted polyisocyanate is obtained from the resulting isocyanate group-terminated prepolymer, for example, It can also be removed by a known method such as distillation or extraction.

  In order to obtain the aqueous polyurethane resin of the present invention, the isocyanate group-terminated prepolymer and the chain extender are then dispersed and reacted in, for example, water (dispersion medium).

  In the present invention, the chain extender contains water (including water as a dispersion medium) as an essential component, and can contain polyamine as an optional component if necessary.

  Examples of polyamines include polyamines, primary amino groups or alkoxysilyl compounds having primary amino groups and secondary amino groups (hereinafter referred to as amino group-containing alkoxysilyl compounds).

  Examples of polyamines include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,6-hexamethylenediamine, 1,4-cyclohexanediamine, and 3-aminomethyl-3,5,5-trimethyl. Cyclohexylamine (isophoronediamine), 4,4'-dicyclohexylmethanediamine, 2,5 (2,6) -bis (aminomethyl) bicyclo [2.2.1] heptane, 1,3-bis (aminomethyl) cyclohexane Diamines such as hydrazine, N- (2-aminoethyl) ethanolamine, N- (2-aminoethyl) isopropanolamine, for example, triamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, tetraamines and pentaamine Such as .

  Examples of the amino group-containing alkoxysilyl compound include alkoxysilyl group-containing monoamines such as γ-aminopropyltriethoxysilane and N-phenyl-γ-aminopropyltrimethoxysilane, and N-β (aminoethyl) γ-aminopropyl. Examples include trimethoxysilane and N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane.

  These polyamines can be used alone or in combination, and preferably include polyamines.

  Furthermore, a monoamine can be used in combination with the chain extender. By using a monoamine in combination, the viscosity of the resulting aqueous polyurethane resin can be lowered.

  Examples of the monoamine include alkylamines such as 2-ethylhexylamine and cyclohexylamine, dialkylamines such as diethylamine, dipropylamine, and dibutylamine, and monoamino alcohols such as monoethanolamine and diethanolamine.

  These monoamines can be used alone or in combination, and monoamino alcohols are preferable. The compounding ratio in the case of using monoamine in combination is, for example, 0.01 to 1% by mass with respect to the total amount of raw material of the aqueous polyurethane resin (total amount charged).

  Further, the above-described low molecular weight polyol can be used in combination with the chain extender. The low molecular weight polyol is used in an appropriate blending ratio depending on its purpose and application.

  In the present invention, in the reaction between the isocyanate group-terminated prepolymer and the chain extender, the isocyanate group in the isocyanate group-terminated prepolymer is 60 mol% or more, preferably 65 mol% or more, more preferably 70 mol%. The above is chain-extended with water.

  When the proportion of the isocyanate group chain-extended with water is less than the above lower limit, the water resistance of the resulting coating film may be lowered.

  In the case where the chain extender contains water and optional components (polyamine, monoamine, low molecular weight polyol, etc.), the active hydrogen group of the optional component is usually first relative to the isocyanate group of the isocyanate group-terminated prepolymer. Then, water (including water as a dispersion medium) reacts with the remaining isocyanate groups.

  That is, the ratio of the isocyanate group that is chain-extended with water can be determined as the ratio of the remaining isocyanate group after the active hydrogen group as an optional component reacts with the isocyanate group of the isocyanate group-terminated prepolymer.

  More specifically, for example, first, from the number of moles of isocyanate group of the isocyanate group-terminated prepolymer, the number of moles of isocyanate group chain-extended by an optional component (number of moles of active hydrogen contained in the optional component) is subtracted. Let the number of moles of the remaining isocyanate groups be the number of moles of isocyanate groups chain-extended with water. Thereby, the ratio of the isocyanate group which is chain-extended with water can be determined.

  In order to react the isocyanate group-terminated prepolymer and the chain extender in water, for example, first, water is added to the isocyanate group-terminated prepolymer to disperse the isocyanate group-terminated prepolymer in water, and then, optionally, optionally. The ingredients are added and the isocyanate-terminated prepolymer is chain extended with a chain extender.

  In order to disperse the isocyanate group-terminated prepolymer in water, water is added to the isocyanate group-terminated prepolymer with stirring at a ratio of 20 to 500 parts by mass of water with respect to 100 parts by mass of the isocyanate group-terminated prepolymer.

  When optional components are used in combination, the active components of the chain extender with respect to the isocyanate groups of the isocyanate group-terminated prepolymer (amino group and the isocyanate group-terminated prepolymer) are stirred with water in which the isocyanate group-terminated prepolymer is dispersed in water. The hydroxyl group is added dropwise such that the equivalent ratio (active hydrogen group / isocyanate group) is, for example, 0.4 or less, preferably 0.35 or less.

  Thereafter, the reaction is completed at room temperature, for example, with further stirring. Thereby, the aqueous polyurethane resin of the present invention is converted into an aqueous dispersion (the solid concentration is, for example, 10 to 60% by mass, preferably 15 to 50% by mass, more preferably 20 to 45% by mass). Aqueous dispersion).

  Contrary to the above, by adding an isocyanate group-terminated prepolymer to water, the isocyanate group-terminated prepolymer is dispersed in water, and then, if necessary, an optional component is added to chain-extend the isocyanate group-terminated prepolymer. The chain can be extended by an agent.

  In addition, after completion | finish of reaction, when the isocyanate group terminal prepolymer is obtained by solution polymerization, an organic solvent is removed by heating at appropriate temperature, for example under reduced pressure.

  In the aqueous polyurethane resin obtained by the above, in the aqueous polyurethane resin (that is, the solid content of the aqueous dispersion), the polyoxyethylene group is 50 to 90% by mass, preferably 50 to 85% by mass, and more preferably. Is contained in an amount of 55 to 85 mass%, more preferably 60 to 80 mass%. When the ratio of the polyoxyethylene group in the polyurethane resin is less than the above lower limit, the moisture permeability of the film may be reduced, and when the upper limit is exceeded, the strength of the film may be reduced.

  In the aqueous polyurethane resin thus obtained, the viscosity when prepared as an aqueous dispersion having a solid content concentration of 30% by mass is less than 5000 mPa · s, preferably less than 4500 mPa · s at 25 ° C. Preferably, it is less than 4000 mPa · s, usually 1000 or more.

  In addition, a viscosity can be measured based on JISK7117-1 (1999) using SB type | mold viscometer.

  And since all the polyoxyethylene polyol and the polyoxyethylene side chain containing active compound contained in the water-based polyurethane resin of this invention are nonionic, any resin of anionic resin, cationic resin, and nonionic resin Even if mixed, stable water dispersion can be ensured. Furthermore, the aqueous polyurethane resin of the present invention has a relatively low viscosity and can improve handling properties. Furthermore, since the water-based polyurethane resin of the present invention contains 50% by mass or more of a polyisocyanate containing no plural rings as a polyisocyanate, a soft texture can be obtained.

  Therefore, the aqueous polyurethane resin of the present invention exhibits excellent water swellability due to its high hydrophilicity, high stability, and excellent compatibility with other aqueous resins. And if this aqueous polyurethane resin is blended with other aqueous resins as a hydrophilic modifier, the hydrophilicity of the aqueous resin such as water permeability, moisture permeability, water retention, water swellability, antistatic property, etc. It can be significantly modified.

  Furthermore, in the polyurethane resin of the present invention, since 60 mol% or more of the isocyanate groups in the isocyanate group-terminated prepolymer are chain-extended with water, when such an aqueous polyurethane resin is blended with another aqueous resin, The aqueous resin can have excellent moisture permeability and water resistance even when the ethylene oxide content is high (such as 50% by mass or more).

  Therefore, this water-based polyurethane resin (hereinafter sometimes referred to as the first water-based resin in order to be distinguished from the second water-based resin described later) can be used as a hydrophilic resin excellent in moisture permeability and waterproofness.

  Moreover, other hydrophilic resin (henceforth a 2nd aqueous resin) of said aqueous polyurethane resin can be further mix | blended with such hydrophilic resin.

  Although it does not restrict | limit especially as 2nd aqueous resin, For example, it is prepared as an emulsion and aqueous solution of 2nd aqueous resin so that it can mix | blend in arbitrary ratios, Specifically, a vinyl acetate emulsion, an acrylic emulsion, polyurethane Examples thereof include aqueous emulsions such as emulsions, polyester emulsions, polyolefin emulsions, and other synthetic resin aqueous solutions such as aqueous polyvinyl alcohol, aqueous polyvinyl pyrrolidone, and aqueous polyvinyl acetal, for example, natural polymer aqueous solutions such as starch and gelatin.

  As the second aqueous resin, preferably, an aqueous polyurethane resin having a higher hydrophobicity than the first aqueous resin (hereinafter referred to as a second aqueous polyurethane resin) is used.

  Such a second aqueous polyurethane resin is prepared by, for example, synthesizing an isocyanate group-terminated prepolymer by reacting at least a polyisocyanate, a hydrophobic macropolyol, and a hydrophilic group-containing active compound as raw materials, It can be obtained by reacting the isocyanate group-terminated prepolymer with a chain extender.

  As the polyisocyanate, both the above-mentioned polycyclic-free polyisocyanate and multi-ring-containing polyisocyanate can be used without particular limitation. Preferably, multiple ring-containing polyisocyanate is used, and more preferably, multiple alicyclic ring-containing diisocyanates are used.

  Examples of the hydrophobic macropolyol include polyester polyol, polycarbonate polyol, and polyoxypolyalkylene polyol having 3 to 10 carbon atoms in the alkylene group.

  Polyester polyol is, for example, one or more of the above-described low molecular weight polyols and, for example, malonic acid, maleic acid, succinic acid, adipic acid, azelaic acid, tartaric acid, pimelic acid, sebacic acid, oxalic acid, terephthalic acid Polyester polyols produced by reaction with polycarboxylic acids such as isophthalic acid, maleic acid, maleic anhydride, fumaric acid, dimer acid, trimellitic acid or their derivatives, for example, ring-opening polymerization of ε-caprolactone, etc. And polycaprolactone polyol.

  Examples of the polycarbonate polyol include polycarbonate polyols produced by reacting one or more of the above-described low molecular weight polyols with carbonates such as dimethyl carbonate, diphenyl carbonate, ethylene carbonate, and phosgene. It is done.

  Examples of the polyoxyalkylene polyol having 3 to 10 carbon atoms of the alkylene group include ring-opening addition using, for example, cyclic ethers such as propylene oxide, oxetane, tetrahydrofuran, and tetrahydropyran, for example, using the above-described low molecular weight polyol as an initiator. The polyoxyalkylene polyol produced | generated by making it superpose | polymerize etc. are mentioned. Examples thereof include polyoxypropylene polyol and polytetramethylene ether polyol. Preferable examples include polyoxyalkylene polyols having 3 to 7 carbon atoms in the alkylene group, and more preferable examples include polyoxyalkylene polyols having 3 to 6 carbon atoms.

  Hydrophobic macropolyols can be used alone or in combination.

  The number average molecular weight of these hydrophobic macropolyols is, for example, 300 to 10,000, preferably 500 to 5,000.

  In addition, the hydrophobic macropolyol is preferably blended so as to be contained in an amount of 50% by mass or more, preferably 60% by mass or more based on the total amount of raw materials of the second aqueous polyurethane resin (total amount charged). By including 50% by mass or more of the hydrophobic macropolyol, the mechanical strength of the hydrophilic resin can be improved.

  In addition, in the synthesis | combination of 2nd water-based polyurethane resin, the above-mentioned hydrophilic macropolyol and low molecular weight polyol can also be used together as a raw material with hydrophobic macropolyol. When the hydrophilic macropolyol is used in combination, the blending ratio is, for example, 0.01 to 10% by mass with respect to the total raw material amount (total charged amount) of the second aqueous polyurethane resin. When using together, the compounding ratio is 0.01-5 mass% with respect to the raw material total amount (preparation total amount) of 2nd water-based polyurethane resin, for example.

  Examples of the hydrophilic group-containing active compound include nonionic group-containing active compounds and ionic group-containing active compounds.

  Examples of the nonionic group-containing active compound include polyoxyethylene glycol, one-end blocked polyoxyethylene glycol, and the above-described polyoxyethylene side chain-containing active compound. In addition, in a nonionic group containing active compound, the number average molecular weights of a nonionic group, ie, a polyoxyethylene group, are 600-6000, for example.

  The ionic group-containing active compound is, for example, a compound having both an anionic group such as a carboxylic acid, a cationic group such as a quaternary amine, and an active hydrogen group such as two or more hydroxyl groups or amino groups. Preferably, a compound having both an anionic group and two or more hydroxyl groups, more preferably a compound having both a carboxylic acid and two hydroxyl groups (carboxylic acid group-containing polyol).

  Examples of the carboxylic acid group-containing polyol include 2,2-dimethylolacetic acid, 2,2-dimethylollactic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, 2 , 2-hydroxylvaleric acid such as 2-dimethylolvaleric acid. Preferably, 2, 2- dimethylol propionic acid and 2, 2- dimethylol butanoic acid are mentioned.

  These hydrophilic group-containing active compounds can be used alone or in combination, preferably ionic group-containing active compounds, more preferably carboxylic acid group-containing polyols.

  If the hydrophilic group-containing active compound is a carboxylic acid group-containing polyol, a coating film excellent in water resistance can be obtained.

  The mixing ratio of the hydrophilic group-containing active compound is, for example, 5 to 25% by mass in the case of the nonionic group-containing active compound with respect to the total amount of raw material (total charged amount) of the second aqueous polyurethane resin, and is ionic. In the case of a group-containing active compound, it is 1.5 to 8% by mass.

  And in order to obtain an isocyanate group terminal prepolymer, the said component is mix | blended in the ratio exceeding 1 in the equivalent ratio (NCO / OH) of the isocyanate group with respect to a hydroxyl group, Preferably, it is a ratio of 1.05-4.0. The above components are reacted in the same manner as described above.

  When an ionic group-containing active compound is added, after the reaction, a neutralizing agent (for example, a tertiary amine such as triethylamine or triisopropanolamine in the case of an anionic group) is added, Neutralizes ionic groups.

  The isocyanate group-terminated prepolymer is prepared by reacting, for example, polyisocyanate, hydrophobic macropolyol, and, if necessary, low molecular weight polyol without adding a hydrophilic group-containing active compound, and then adding an emulsifier. Can also be prepared.

  Thereafter, the isocyanate group-terminated prepolymer and the chain extender are reacted in water by the same method as described above to obtain a second aqueous polyurethane resin.

  Examples of the chain extender include the same chain extenders as described above, and preferably include polyamines.

  Thus, the second aqueous polyurethane resin can be obtained as an aqueous dispersion (an aqueous dispersion having a solid content concentration of, for example, 10 to 60% by mass, preferably 20 to 50% by mass).

  In addition, the second aqueous resin has a tensile strength of, for example, 6 MPa or more, more preferably 8 MPa or more, especially as a mechanical strength when it is cast (for example, when cast with a width of 10 mm and a thickness of 0.1 mm). It is preferable that it is 10 MPa or more and the elongation is, for example, 200% or more, further 300% or more, and particularly 400% or more. Similarly, the water swelling rate when casting is preferably 20% or less, more preferably 10% or less, and particularly preferably 5% or less.

  And the hydrophilic resin which is excellent in moisture-permeable waterproofness and mechanical strength can be obtained by mix | blending the above-mentioned water-based polyurethane resin with such 2nd water-based resin as 1st water-based resin.

  The blend ratio of the first aqueous resin and the second aqueous resin is, for example, the first aqueous resin (solid content of the aqueous dispersion of the first aqueous resin) and the second aqueous resin (solid of the aqueous dispersion of the second aqueous resin). The first aqueous resin is, for example, 10 to 80% by mass, and preferably 15 to 70% by mass with respect to the total amount of (min). When the blending ratio of the first aqueous resin is less than 10% by mass, the moisture permeability of the film obtained by casting may be deteriorated. When it exceeds 80% by mass, the strength of the film obtained by casting is reduced. When it falls, it may be inferior to water resistance.

  Moreover, a curing agent can be further blended in the hydrophilic resin (including the first aqueous resin as an essential component and the second aqueous resin as an optional component).

  By adding a curing agent, the water resistance of the hydrophilic resin can be improved.

  Examples of the curing agent include an isocyanate curing agent, and more specifically, a water-dispersible blocked isocyanate curing agent and a water-dispersible non-blocked isocyanate curing agent. Preferably, a water-dispersible blocked isocyanate curing agent is used.

  Examples of the water-dispersible blocked isocyanate curing agent include, for example, a blocked isocyanate dispersed in water with an external emulsifier, and a block isocyanate capable of being internally emulsified. Preferably, a blocked isocyanate dispersed in water with an external emulsifier is used. Can be mentioned.

  Internally emulsifiable blocked isocyanate (for example, obtained by subjecting the above-mentioned one-end-capped polyoxyethylene glycol and isocyanate to a urethanization reaction in a proportion in which the isocyanate group of the isocyanate is excessive with respect to the hydroxyl group of the one-end-capped polyoxyethylene glycol. The obtained polyoxyethylene chain-containing monoisocyanate and / or polyoxyethylene chain-containing polyisocyanate may be inferior in the appearance of a coating film obtained by casting.

  On the other hand, according to the blocked isocyanate dispersed in water with an external emulsifier, the appearance of the coating film obtained by casting can be improved.

  In the blocked isocyanate dispersed in water by such an external emulsifier, examples of the isocyanate include polycyclic isocyanate, aliphatic diisocyanate, monoaromatic ring-containing diisocyanate, monoalicyclic ring-containing diisocyanate, and modified products thereof. Preferably, a monoaromatic ring-containing diisocyanate (polyisocyanate containing one aromatic ring) or a modified product thereof can be used.

  In the blocked isocyanate, if the isocyanate is a single aromatic ring-containing diisocyanate (polyisocyanate containing one aromatic ring) or a modified product thereof, the water resistance of the hydrophilic resin can be improved.

  In the blocked isocyanate, the blocking agent is not particularly limited as long as it is a blocking agent that dissociates from isocyanate by heat treatment. For example, alcohol compounds, phenol compounds, active methylene compounds, amine compounds, imine compounds Compounds, oxime compounds, carbamic acid compounds, urea compounds, acid amide (lactam) compounds, acid imide compounds, triazole compounds, pyrazole compounds, imidazole compounds, imidazoline compounds, mercaptan compounds, heavy compounds And sulfites.

  Examples of the alcohol compound include methanol, ethanol, 2-propanol, n-butanol, s-butanol, 2-ethylhexyl alcohol, 1- or 2-octanol, cyclohexyl alcohol, ethylene glycol, benzyl alcohol, 2,2 , 2-trifluoroethanol, 2,2,2-trichloroethanol, 2- (hydroxymethyl) furan, 2-methoxyethanol, methoxypropanol, 2-ethoxyethanol, n-propoxyethanol, 2-butoxyethanol, 2-ethoxy Ethoxyethanol, 2-ethoxybutoxyethanol, butoxyethoxyethanol, 2-ethylhexyloxyethanol, 2-butoxyethylethanol, 2-butoxyethoxyethanol, N, N-dibutyl-2 Hydroxyacetamide, N-hydroxysuccinimide, N-morpholine ethanol, 2,2-dimethyl-1,3-dioxolane-4-methanol, 3-oxazolidineethanol, 2-hydroxymethylpyridine, furfuryl alcohol, 12-hydroxystearic acid, Examples include triphenylsilanol and 2-hydroxyethyl methacrylate.

  Examples of phenolic compounds include phenol, cresol, ethylphenol, n-propylphenol, isopropylphenol, n-butylphenol, s-butylphenol, t-butylphenol, n-hexylphenol, 2-ethylhexylphenol, n-octylphenol, n -Nonylphenol, di-n-propylphenol, diisopropylphenol, isopropylcresol, di-n-butylphenol, di-s-butylphenol, di-t-butylphenol, di-n-octylphenol, di-2-ethylhexylphenol, di-n -Nonylphenol, nitrophenol, bromophenol, chlorophenol, fluorophenol, dimethylphenol, styrenated phenol, methyl salicyla , Methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 2-ethylhexyl hydroxybenzoate, 4-[(dimethylamino) methyl] phenol, 4-[(dimethylamino) methyl] nonylphenol, bis (4-hydroxy Phenyl) acetic acid, pyridinol, 2- or 8-hydroxyquinoline, 2-chloro-3-pyridinol, pyridine-2-thiol and the like.

  Examples of the active methylene compound include Meldrum's acid, dialkyl malonate (for example, dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-t-butyl malonate, di-2-ethylhexyl malonate, malonic acid. Methyl n-butyl, ethyl n-butyl malonate, methyl s-butyl malonate, ethyl s-butyl malonate, methyl t-butyl malonate, ethyl t-butyl malonate, diethyl methylmalonate, dibenzyl malonate, malon Diphenyl acid, benzyl methyl malonate, ethyl phenyl malonate, t-butylphenyl malonate, isopropylidene malonate, etc.), alkyl acetoacetate (eg methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate) , N-butyl acetoacetate, acetoacetic acid - butyl acetoacetate benzyl, phenyl acetoacetate, etc.), 2-acetoacetoxyethyl methacrylate, acetylacetone, and the like such as ethyl cyanoacetate.

  Examples of the amine compound include dibutylamine, diphenylamine, aniline, N-methylaniline, carbazole, bis (2,2,6,6-tetramethylpiperidinyl) amine, di-n-propylamine, diisopropylamine, Isopropylethylamine, 2,2,4- or 2,2,5-trimethylhexamethyleneamine, N-isopropylcyclohexylamine, dicyclohexylamine, bis (3,5,5-trimethylcyclohexyl) amine, piperidine, 2,6 -Dimethylpiperidine, 2,2,6,6-tetramethylpiperidine, (dimethylamino) -2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethyl-4-piperidine, 6- Examples include methyl-2-piperidine, 6-aminocaproic acid, etc. It is.

  Examples of the imine compound include ethyleneimine, polyethyleneimine, 1,4,5,6-tetrahydropyrimidine, guanidine and the like.

  Examples of oxime compounds include formaldehyde oxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime, diacetyl monooxime, benzophenoxime, 2,2,6,6-tetramethylcyclohexanone oxime, diisopropyl ketone oxime. , Methyl t-butyl ketone oxime, diisobutyl ketone oxime, methyl isobutyl ketone oxime, methyl isopropyl ketone oxime, methyl 2,4-dimethylpentyl ketone oxime, methyl 3-ethyl heptyl ketone oxime, methyl isoamyl ketone oxime, n-amyl ketone Oxime, 2,2,4,4-tetramethyl-1,3-cyclobutanedione monooxime, 4,4′-dimethoxybenzophenone oxime, 2-he Tanon'okishimu and the like.

  Examples of the carbamic acid compound include phenyl N-phenylcarbamate.

  Examples of the urea compound include urea, thiourea, and ethylene urea.

  Examples of acid amide (lactam) compounds include acetanilide, N-methylacetamide, acetic acid amide, ε-caprolactam, δ-valerolactam, γ-butyrolactam, pyrrolidone, 2,5-piperazinedione, laurolactam, and the like. It is done.

  Examples of the acid imide compound include succinimide, maleic imide, phthalimide, and the like.

  Examples of triazole compounds include 1,2,4-triazole and benzotriazole.

  Examples of the pyrazole compound include pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3, Examples include 5-dimethylpyrazole and 3-methyl-5-phenylpyrazole.

  Examples of the imidazole compound include imidazole, benzimidazole, 2-methylimidazole, 4-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2 -Phenylimidazole, 4-methyl-2-phenylimidazole and the like.

  Examples of the imidazoline-based compound include 2-methylimidazoline and 2-phenylimidazoline.

  Examples of mercaptan compounds include butyl mercaptan, dodecyl mercaptan, hexyl mercaptan, and the like.

  Examples of the bisulfite include sodium bisulfite.

  Moreover, as a blocking agent, it is not limited to the above, For example, other blocking agents, such as a benzoxazolone, an isatoic anhydride, tetrabutylphosphonium acetate, are mentioned.

  These blocking agents can be used alone or in combination of two or more.

  The blocking agent is preferably an oxime compound or a pyrazole compound, more preferably a pyrazole compound, and still more preferably 3,5-dimethylpyrazole.

  If the blocking agent is 3,5-dimethylpyrazole, the water resistance of the hydrophilic resin can be improved.

  Examples of the external emulsifier include surfactants such as polyoxyalkylene alkyl phenyl ether (eg, polyoxyethylene cumyl phenyl ether), alkyl sulfate metal salt, and linear alkylbenzene sulfonic acid metal salt.

  These external emulsifiers can be used alone or in combination of two or more.

  As the external emulsifier, preferably, polyoxyalkylene alkylphenyl ether is used.

  Such a water-dispersible isocyanate curing agent is prepared, for example, as a water dispersion by a known method and blended in a hydrophilic resin.

  The blending ratio of the water-dispersible isocyanate curing agent is such that the solid content of the aqueous resin in the hydrophilic resin (that is, the solid content of the aqueous dispersion of the first aqueous resin and the aqueous dispersion of the second aqueous resin blended as necessary). The solid dispersible isocyanate curing agent is, for example, 0.1 to 20 parts by mass, preferably 1 to 15 parts by mass in terms of solids with respect to 100 parts by mass in total.

  When the hydrophilic resin contains a water-dispersible isocyanate curing agent in the above proportion, water resistance and mechanical strength are improved.

  The hydrophilic resin may further contain a compatibilizing agent such as N-methylpyrrolidone or N, N-dimethylformamide.

  The hydrophilic resin of the present invention including the aqueous polyurethane resin of the present invention is excellent in mechanical properties, has a soft texture, and further obtains a film having both excellent moisture permeability and water resistance. Can do. Therefore, the hydrophilic resin of the present invention can be suitably used as a coating agent for moisture permeable and waterproof processing.

  And the hydrophilic resin of this invention can be obtained as a film which has the outstanding moisture-permeable waterproof performance by casting. The film can be cast as either a microporous film or a nonporous film.

  In particular, by laminating the film made of the hydrophilic resin of the present invention on the base fabric, the base fabric can be subjected to moisture-permeable waterproof processing, and for example, a moisture-permeable waterproof material used for clothing and the like can be obtained.

  Examples of the base fabric include woven fabrics, knitted fabrics, and nonwoven fabrics made of fibers such as polyester, nylon, and cotton.

  As a method for laminating a film made of a hydrophilic resin on a base fabric, for example, a method such as a laminating method or a direct coating method is used, and the method is appropriately selected depending on the application.

  In the laminating method, for example, there is a method in which a hydrophilic resin is applied to the surface of a release paper or the like and heat-treated to form a film, and then, for example, the release paper is peeled off from the film and laminated on a fabric via an adhesive or the like. Can be mentioned.

  In the direct coating method, a normal coating method, for example, a method of forming and laminating a film directly by using a normal coating method, for example, a knife coater or the like can be mentioned.

  Thus, the surface of the base fabric is covered with a moisture permeable and waterproof film made of a hydrophilic resin, whereby the surface of the base fabric is subjected to moisture permeable and waterproof processing. The moisture permeable and waterproof base fabric is used for clothing and the like as a moisture permeable waterproof material.

  The moisture-permeable waterproof property is the performance of the film that blocks rain and other water, but allows moisture (water vapor) to pass through. For example, in the case of moisture-permeable waterproof materials used in clothing, it is caused by sweating from the body. It is a performance that releases water vapor out of clothes and prevents rain from entering the clothes.

  In addition, the hydrophilic resin of the present invention needs to sufficiently ensure the following performance to the base fabric, the wear resistance, the tear resistance, and the like. Therefore, as the mechanical strength of the cast film of the hydrophilic resin of the present invention, the tensile strength is preferably 3 MPa or more, more preferably 4 MPa or more, and further preferably 6 MPa or more, and the elongation is, for example, 200 % Or more, further 300% or more, and more preferably 400% or more.

Furthermore, as the moisture permeability of the hydrophilic resin of the present invention, the moisture permeability in the moisture permeability test method A-1 (based on JIS L1099 (2006)) is 3000 ( g / m ² · 24 hrs) or more, preferably 4000 (g / m ² · 24 hrs) or more.

  The aqueous polyurethane resin, the second aqueous polyurethane resin, and the hydrophilic resin have a curing catalyst and various additives such as a plasticizer and an antifoaming agent as long as the excellent effects of the present invention are not impaired. , Leveling agent, fungicide, rust inhibitor, matting agent, flame retardant, thixotropic agent, tackifier, thickener, lubricant, antistatic agent, surfactant, reaction retarder, antioxidant, UV Absorbers, hydrolysis inhibitors, weathering stabilizers, dyes, inorganic pigments, organic pigments, extender pigments, tack inhibitors, and the like can be appropriately blended.

  Further, examples of the tack preventive agent include inorganic powder, and preferably silicon dioxide powder.

  The mixing ratio of various additives is appropriately selected depending on the purpose and application.

  Moreover, the water-based polyurethane resin and hydrophilic resin of the present invention can be widely used in various industrial fields such as automobiles, electronic devices, building materials, artificial leather, film processing, etc., not limited to the above-described clothing field.

  Hereinafter, the present invention will be described more specifically with reference to Preparation Examples, Synthesis Examples, Examples, and Comparative Examples, but these do not limit the present invention in any way. “Part” and “%” are based on mass unless otherwise specified. Moreover, the measuring method used for an Example etc. is shown below.

Preparation Example 1 (Synthesis of Polyoxyethylene Side Chain-Containing Polyol A)
Number average molecular weight heated to 507.1C by 627.1 parts of hexamethylene diisocyanate (Takenate 700, manufactured by Mitsui Chemicals) while introducing nitrogen gas in a reactor equipped with a thermometer, a nitrogen gas inlet tube and a stirrer 372.9 parts of 1000 methoxypolyethylene glycol (MPEG-1000, manufactured by Toho Chemical Co., Ltd.) was charged and reacted at 80 ° C. for 6 hours. After reaching a predetermined isocyanate group content, unreacted hexamethylene diisocyanate was removed with a Smith type thin film distiller to obtain polyoxyethylene chain-containing monoisocyanate. The calculated number average molecular weight of this polyoxyethylene chain-containing monoisocyanate was 1168.

  Next, 83.9 parts of diethanolamine was charged while introducing nitrogen gas at room temperature in a reactor equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer. While cooling, 916.1 parts of polyoxyethylene chain-containing monoisocyanate was added and reacted at 60 ° C. for 3 hours. Formation of urea bonds was confirmed by infrared spectrum, and polyoxyethylene side chain-containing polyol A was obtained. This polyoxyethylene side chain-containing polyol A contained 78.5% by mass of polyoxyethylene groups, and the calculated number average molecular weight was 1,275.

Example 1 (Synthesis of aqueous polyurethane resin A)
In a four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer, and a stirrer, 93.8 parts of 1,3- (bisisocyanatomethyl) cyclohexane (trade name: Takenate 600, manufactured by Mitsui Chemicals), In a nitrogen atmosphere, 357.8 parts of polyethylene glycol having a number average molecular weight of 1000 (trade name: PEG-1000, manufactured by Toho Chemical Co., Ltd.), 38.4 parts of polyoxyethylene side chain-containing polyol A, and 210 parts of acetonitrile are charged. The reaction temperature was adjusted to 73 to 77 ° C., and the reaction rate was reacted to 99% or more in 7 hours. Subsequently, this was cooled to 30 degreeC and the isocyanate terminal prepolymer was obtained.

  Next, while gradually adding 1041 parts of water adjusted in advance to 25 ° C. in this four-necked flask and stirring and mixing, the isocyanate group-terminated prepolymer was dispersed in water and stirred at 25-30 ° C. for 3 hours. The chain was elongated with water. Thereafter, an aqueous dispersion of the aqueous polyurethane resin A was prepared by removing a portion of acetonitrile and water under reduced pressure.

  About the obtained water-based polyurethane resin A, the ratio (mol%) of water elongation in the isocyanate group of the isocyanate group-terminated prepolymer, the solid content (mass%) of the aqueous dispersion, the viscosity (mPa · s / 25 ° C), and the formulation The calculated polyoxyethylene group content (EO content (mass%)) based on the formulation is shown in Table 1.

  Moreover, the obtained aqueous polyurethane resin A was prepared as an aqueous dispersion having a solid content concentration of 30% by mass, and the viscosity at 25 ° C. was measured according to JIS K 7117-1 (1999) using an SB type viscometer. And measured. The values are also shown in Table 1.

Examples 2 to 6 and Comparative Examples 1 to 3 (Synthesis of aqueous polyurethane resins B to I)
Based on the formulation shown in Table 1 below, in the same manner as in Example 1, an aqueous dispersion of aqueous polyurethane resin B (Example 2), an aqueous dispersion of aqueous polyurethane resin C (Example 3), and aqueous An aqueous dispersion of polyurethane resin D (Example 4), an aqueous dispersion of aqueous polyurethane resin E (Example 5), an aqueous dispersion of aqueous polyurethane resin F (Example 6), an aqueous dispersion of aqueous polyurethane resin G (Example 6) Comparative Example 1), an aqueous dispersion of aqueous polyurethane resin H (Comparative Example 2), and an aqueous dispersion of aqueous polyurethane resin I (Comparative Example 3) were prepared.

  Further, in the same manner as in Example 1, for the obtained aqueous polyurethane resins B to I, the ratio of water elongation in the isocyanate group of the isocyanate group-terminated prepolymer (mol%), the solid content (mass%) of the aqueous dispersion, and the viscosity Table 1 shows the calculated polyoxyethylene group content (EO content (% by mass)) based on (mPa · s / 25 ° C.) and the formulation.

  Further, the obtained aqueous polyurethane resins B to I were prepared as an aqueous dispersion having a solid concentration of 30% by mass, and the viscosity at 25 ° C. was measured using a SB type viscometer according to JIS K 7171-1 (1999). Measured according to The values are also shown in Table 1.

  The aqueous dispersion of the aqueous polyurethane resin G (Comparative Example 1) had a very high viscosity and was difficult to handle when prepared as an aqueous dispersion having a solid content concentration of 30% by mass. The partial concentration was measured as 27.5% by mass.

The abbreviations in Table 1 are as follows.
H ₆ XDI: 1,3-bis (isocyanatomethyl) cyclohexane, trade name Takenate 600, IPDI made by Mitsui Chemicals, Inc .: isophorone diisocyanate, trade name VESTANAT IPDI made by Evonik H ₁₂ MDI: 4,4′-methylene bis (cyclohexyl isocyanate) ), Trade name Desmodur W, Bayer PEG-1000: polyethylene glycol with a number average molecular weight of 1000, Toho Chemical Co., Ltd. POE side chain polyol A: polyoxyethylene side chain-containing polyol A
Triethylene glycol: Wako Pure Chemical Industries, Ltd. Ethylenediamine: Wako Pure Chemical Industries, Ltd. Monoethanolamine: Wako Pure Chemical Industries, Ltd. Diethanolamine: Wako Pure Chemical Industries, Ltd. Aminoalcohol EA: N- (2-aminoethyl) ethanolamine, Nippon Emulsifier Co., Ltd. Production Synthesis Example 1 (Synthesis of second aqueous polyurethane resin A)
In a four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer, and a stirrer, 89.3 parts of 4,4′-methylenebis (cyclohexyl isocyanate) (trade name: Desmodur W, manufactured by Bayer), Number average molecular weight 2000 polytetramethylene ether glycol (trade name: PTHF-2000, manufactured by BASF Japan) 234.2 parts and dimethylol heptane (trade name: butylethylpropanediol, manufactured by Kyowa Hakko Chemical Co., Ltd.) 6.6 And 11.4 parts of dimethylolpropionic acid (trade name: Bis-MPA, manufactured by Perstorp) and 150 parts of acetonitrile were prepared, and the reaction temperature was adjusted to 73 to 77 ° C. under a nitrogen atmosphere. The reaction rate was reacted to 99% or more over time.

  Next, 200 parts of acetone was charged, cooled to 30 ° C. with stirring until uniform, 8.6 parts of triethylamine was added, and the mixture was sufficiently stirred and neutralized to obtain an isocyanate group-terminated prepolymer.

  Next, the isocyanate group-terminated prepolymer was dispersed in water in this four-necked flask while gradually adding 1099 parts of water adjusted to 25 ° C. in advance and stirring and mixing.

  Then, 16.2 parts of isophorone diamine was added and stirred at 25-30 ° C. for 3 hours. Thereafter, an aqueous dispersion of the second aqueous polyurethane resin A was prepared by removing a portion of acetonitrile, acetone, and water under reduced pressure.

  About the obtained water-based polyurethane resin A, solid content (mass%) of water dispersion, viscosity (mPa · s / 25 ° C.), and calculated polyoxyethylene group content (EO content (EO content ( Table 2 shows the mass%)).

Synthesis Examples 2 to 5 (Synthesis of second aqueous polyurethane resins B to E)
Based on the formulation shown in Table 2 below, an aqueous dispersion of the second aqueous polyurethane resin B (Synthesis Example 2) and an aqueous dispersion of the second aqueous polyurethane resin C (Synthesis Example) were prepared in the same manner as in Synthesis Example 1. 3) An aqueous dispersion of the second aqueous polyurethane resin D (Synthesis Example 4) and an aqueous dispersion of the second aqueous polyurethane resin E (Synthesis Example 5) were respectively prepared.

  Further, similarly to Synthesis Example 1, for the obtained second aqueous polyurethane resins B to E, calculation based on the solid content (mass%) of the aqueous dispersion, viscosity (mPa · s / 25 ° C.), and formulation The upper polyoxyethylene group content (EO content (mass%)) is shown in Table 2.

Synthesis Example 6 (Synthesis of second aqueous polyurethane resin F)
In a four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer, and a stirrer, 78.5 parts of 4,4′-methylenebis (cyclohexyl isocyanate) (trade name: Desmodur W, manufactured by Bayer), Number average molecular weight 2000 polytetramethylene ether glycol (trade name: PTHF-2000, manufactured by BASF Japan) 208.5 parts, ethylene glycol 4.9 parts, polyoxyethylene side chain-containing polyol A 33.1 parts, acetonitrile The reaction temperature was adjusted to 73 to 77 ° C. under a nitrogen atmosphere, and the reaction rate was reacted to 99% or more in 7 hours.

  Next, 186 parts of acetone was charged and cooled to 30 ° C. with stirring until uniform, to obtain an isocyanate group-terminated prepolymer.

  Next, 965 parts of water adjusted to 25 ° C. in advance was gradually added to this four-necked flask, and the isocyanate group-terminated prepolymer was dispersed in water while stirring and mixing.

  Then, 13.8 parts of isophorone diamine was added and stirred at 25-30 ° C. for 3 hours. Thereafter, acetonitrile, acetone, and a part of water were removed under reduced pressure to prepare an aqueous dispersion of the second aqueous polyurethane resin F.

  Further, in the same manner as in Synthesis Example 1, with respect to the obtained aqueous polyurethane resin F, the solid content (mass%) of the aqueous dispersion, the viscosity (mPa · s / 25 ° C.), and the calculated polyoxy based on the formulation Table 2 shows the ethylene group content (EO content (mass%)).

In addition, the symbol in Table 2 is as follows.
H ₁₂ MDI: 4,4′-methylenebis (cyclohexyl isocyanate), trade name Desmodur W, Bayer PTHF2000: polytetramethylene ether glycol having a number average molecular weight of 2000, BASF Japan dimethylolheptane: butylethylpropanediol, Sobamol 908 manufactured by Kyowa Hakko Chemical Co., Ltd .: hydrogenated dimer alcohol (dimer aliphatic alcohol obtained by reduction of dimer acid, neopentyl glycol manufactured by Cognis Japan Co., Ltd .: trimethylolpropane manufactured by Mitsubishi Gas Chemical Co., Ltd., ethylene glycol manufactured by Mitsubishi Gas Chemical Co., Inc .: 2,2-dimethylolpropionic acid manufactured by Wako Pure Chemical Industries, Ltd .: Bis-MPA, POE side chain polyol A manufactured by Perstorp, Inc .: Polyoxyethylene side chain-containing polyol A
Triethylamine: Wako Pure Chemical Industries, Ltd. Isophoronediamine: Wako Pure Chemical Industries, Ltd. 1,6-hexamethylenediamine: HMD (Hexamethylenediamine), Invista Japan, Inc. Preparation Example 2 (Preparation of Curing Agent A)
A four-necked flask equipped with a stirrer, thermometer and reflux condenser was replaced with nitrogen, and then Takenate D-110N (xylylene diisocyanate trimethylolpropane adduct, solid content 75% by mass, manufactured by Mitsui Chemicals) 341 parts; Then, 64.7 parts of methyl ethyl ketone was charged and stirred, and Takenate D-110N was dissolved in methyl ethyl ketone.

  Next, 94.3 parts of 3,5-dimethylpyrazole (manufactured by Otsuka Chemical Co., Ltd.) was added over 1 hour while maintaining the internal temperature at 50 to 60 ° C. and stirring.

  Then, after stirring for 1 hour at an internal temperature of 50 ° C. and confirming that the solid of 3,5-dimethylpyrazole was completely dissolved, absorption of the isocyanate group disappeared by FT-IR (Fourier transform infrared spectrophotometer). It was confirmed that a blocked isocyanate was obtained.

  While stirring 500 parts of this blocked isocyanate with a homomixer (rotation speed: 4000 rpm), 17.5 parts of Nonal 912A (polyoxyethylene cumylphenyl ether, solid content: 100% by mass, manufactured by Toho Chemical Co., Ltd.) was added over 30 minutes. Then, 70 parts of a 25% by weight aqueous solution of Emulgen A-500 (polyoxyethylene distyrenated phenyl ether, solid content 100% by weight, manufactured by Kao Corporation) was added over 30 minutes, and then LUNOX 100 (sodium alkylbenzene sulfonate, solids) 35.0 parts of an aqueous solution having a solid content of 10% by weight (60% by weight, manufactured by Toho Chemical Co., Ltd.) was added over 30 minutes, and then 666 parts of water was added over 30 minutes for emulsification.

  Thereafter, 0.2 part of an antifoaming agent (BYK-022, manufactured by BYK Chemie) was added and stirred for 1 hour at a rotational speed of 1000 rpm, and then solids were removed by removing a part of the organic solvent and water under reduced pressure. A curing agent A of 40% by mass was obtained.

Preparation Examples 3, 5-7 (Preparation of curing agents B, D, E, F)
Based on the formulation shown in Table 3 below, the curing agent B (Preparation Example 3), the curing agent D (Preparation Example 5), the curing agent E (Preparation Example 6) and the curing agent were carried out in the same manner as in Preparation Example 2. F (Preparation Example 7) was prepared as an aqueous dispersion having a solid content of 40% by mass.

Preparation Example 4 (Preparation of curing agent C)
A four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser was replaced with nitrogen, and then Takenate D-110N (xylylene diisocyanate trimethylolpropane adduct, solid content 75% by mass, manufactured by Mitsui Chemicals) 293.8 Part and 56.3 parts of polyethylene glycol monomethyl ether (trade name methoxy PEG-1000, manufactured by Toho Chemical Co., Ltd.) were allowed to react at 74 ° C. for 3 hours. Next, 76.5 parts of methyl ethyl ketone was charged and stirred, and while maintaining the internal temperature at 50 to 60 ° C., 73.4 parts of 3,5-dimethylpyrazole (manufactured by Otsuka Chemical Co., Ltd.) was added over 1 hour. .

  Then, after stirring for 1 hour at an internal temperature of 50 ° C. and confirming that the solid of 3,5-dimethylpyrazole was completely dissolved, absorption of the isocyanate group disappeared by FT-IR (Fourier transform infrared spectrophotometer). It was confirmed that a blocked isocyanate was obtained.

  While stirring 500 parts of this blocked isocyanate with a homomixer (rotational speed 4000 rpm), 650 parts of water was added over 30 minutes and emulsified.

  Thereafter, 0.2 part of an antifoaming agent (BYK-022, manufactured by BYK Chemie) was added and stirred for 1 hour at a rotational speed of 1000 rpm, and then solids were removed by removing a part of the organic solvent and water under reduced pressure. A curing agent C of 40% by mass was obtained.

In addition, the symbol in Table 3 is as follows.
D-110N: Trimethylolpropane adduct of xylylene diisocyanate, solid content 75% by mass, Mitsui Chemicals D-103H: Trimethylolpropane adduct of tolylene diisocyanate, solid content 75% by mass, D- 160N: trimethylolpropane adduct of hexamethylene diisocyanate, solid content 75% by mass, MEOPEG1000 manufactured by Mitsui Chemicals, Inc .: polyethylene glycol monomethyl ether, trade name methoxyPEG-1000, molecular weight 1000, 3,5-dimethylpyrazole manufactured by Toho Chemical Co., Ltd. Methyl ethyl ketoxime manufactured by Otsuka Chemical Co., Ltd .: methyl ethyl ketone oxime, Emulgen A-500 manufactured by Ube Industries, Ltd .: polyoxyethylene distyrenated phenyl ether, solid content concentration: 100% by mass, HLB: 18.0, Kao (In the examples, it was diluted 4 times and used as a 25 mass% aqueous solution.)
Nonal 912A: polyoxyethylene cumyl phenyl ether, solid content concentration: 100% by mass, HLB: 14.3, manufactured by Toho Chemical Industry Co., Ltd. Lunox 100: sodium alkylbenzenesulfonate, solid content concentration 60% by mass, manufactured by Toho Chemical Industry Co., Ltd. (In the examples, diluted 6-fold and used as a 10% by mass aqueous solution.)
Antifoaming agent: BYK-022, manufactured by Big Chemie Co., Ltd. Example 7 (Preparation of hydrophilic resin A)
In a container equipped with a homodisper capable of high-speed stirring, 34 parts of an aqueous dispersion of aqueous polyurethane resin A (solid content 35.1% by mass) and an aqueous dispersion of second aqueous polyurethane resin A (solid content 30.6% by mass) %)), And further, the curing agent A is blended at a ratio of 2.8 parts by mass with respect to the total amount (as an aqueous dispersion) of the aqueous polyurethane resin A and the second aqueous polyurethane resin A, and 2000 min ^- stirring mixture 1 at 10 minutes. Thereafter, defoaming was performed under reduced pressure to obtain an aqueous dispersion of hydrophilic resin A.

  For the obtained hydrophilic resin A, the calculated polyoxyethylene group content (EO content (% by mass)) based on the formulation, excluding the compounding amount of the curing agent, and the solid content (% by mass) of the aqueous dispersion ) And viscosity (mPa · s / 25 ° C.) are shown in Table 4.

Examples 8 to 28 and Comparative Examples 4 to 6 (hydrophilic resins B to Y)
Based on the formulation shown in Tables 4 to 7, aqueous dispersions of hydrophilic resins B to Y were prepared in the same manner as in Example 7. In Examples 8 to 15, 17 to 21, 23 to 27, and Comparative Example 5, water was blended. Examples 16 and 17 did not contain a curing agent, Example 28 did not contain a second aqueous polyurethane resin, and Comparative Example 6 did not contain an aqueous polyurethane resin.

  For the obtained hydrophilic resins B to Y, the calculated polyoxyethylene group content (EO content (% by mass)) based on the formulation, excluding the compounding amount of the curing agent, the solid content of the aqueous dispersion ( (Mass%) and a viscosity (mPa * s / 25 degreeC) are shown to Tables 4-7.

  In Tables 4 to 7, the formulation of the curing agent is dispersed in water with respect to a total amount of 100 parts by mass of the solid content in the aqueous dispersion of the aqueous polyurethane resin and the solid content in the aqueous dispersion of the second aqueous polyurethane resin. It is expressed as the amount of liquid blended (unit: parts by mass).

Appearance of Evaluation Film Aqueous dispersions of hydrophilic resins of Examples and Comparative Examples were cast and cured at 120 ° C. for 2 minutes and further at 170 ° C. for 2 minutes, and a dry transparent film having a thickness of 0.04 mm (Examples 7 and 16 were 0.02 mm dry transparent films). The appearance of this film was evaluated according to the following criteria. The results are shown in Tables 4-7.
(Evaluation criteria)
“◯”: A smooth and clean film was obtained “Δ”: A film with a uniformly rough surface was obtained “X”: A water film with a rough surface was obtained Water resistance Examples and each The aqueous dispersion of the hydrophilic resin of the comparative example was cast and cured at 120 ° C. for 2 minutes and further at 170 ° C. for 2 minutes, and a dry transparent film having a film thickness of 0.04 mm (Examples 7 and 16 have a thickness of 0.2 mm). 02 mm dry transparent film) was formed. Then, this film was immersed in water for 2 minutes, the color change was observed visually, and the water resistance was determined according to the following criteria. The results are shown in Tables 4-7.

The films obtained in Examples 16 and 17 were wrinkled on the film in the water resistance test (* 1).
(Evaluation criteria)
“◯”: The color remains almost unchanged while being transparent “Δ”: The film becomes bluish and cloudy “×”: The moisture permeability test that makes the film turbid and whitish (moisture permeability test A-1 method)
The aqueous dispersions of hydrophilic resins of each Example and each Comparative Example were cast and cured at 120 ° C. for 2 minutes and further at 170 ° C. for 2 minutes to form a dry transparent film having a thickness of 0.02 mm. Thereafter, the moisture permeability of this film was evaluated according to JIS L1099 (2006) A-1 method (calcium chloride method). The results are shown in Tables 4-7.
Mechanical Strength Test Aqueous dispersions of hydrophilic resins of each Example and each Comparative Example were cast and cured at 120 ° C. for 2 minutes and further at 170 ° C. for 2 minutes, and a dry transparent film having a thickness of 0.04 mm ( In Examples 7 and 16, a 0.02 mm dry transparent film was formed. Thereafter, this film was cut into 1 cm strips and subjected to a tensile test under the conditions of a tensile speed of 200 mm / min. Stress at break (breaking strength (MPa)), elongation rate (breaking elongation (%)) and 100% modulus. (MPa) was measured. The results are shown in Tables 4-7.

  In addition, the film obtained in Comparative Example 6 was broken immediately after the tension and could not be quantified (* 2).

Claims (18)

A polyisocyanate containing 50% by mass or more of a polycyclic-free polyisocyanate containing no aromatic ring and alicyclic ring, or containing one aromatic ring or alicyclic ring,
Polyoxyethylene polyol, and
A polyoxyethylene side chain-containing active compound having two or more hydroxyl groups or isocyanate groups at the molecular ends and having a polyoxyethylene group in the side chain;
An isocyanate group-terminated prepolymer obtained by reacting at least;
An aqueous polyurethane resin obtained by reaction with a chain extender containing water,
An aqueous polyurethane resin characterized in that 60 mol% or more of isocyanate groups in the isocyanate group-terminated prepolymer are chain-extended with water.   2. The aqueous polyurethane resin according to claim 1, wherein the viscosity of the aqueous dispersion having a solid content of 30% by mass is less than 5000 mPa · s.   The aqueous polyurethane resin according to claim 1, wherein the polyoxyethylene group is contained in an amount of 50 to 90% by mass.   The number average molecular weight of polyoxyethylene polyol is 600-6000, The aqueous polyurethane resin as described in any one of Claims 1-3 characterized by the above-mentioned.   In the polyoxyethylene side chain containing active compound, the number average molecular weight of a polyoxyethylene group is 600-6000, The aqueous polyurethane resin as described in any one of Claims 1-4 characterized by the above-mentioned.   The polyoxyethylene side chain-containing active compound has at least one chemical bond selected from a urea group, a urethane group and an allophanate group, according to any one of claims 1 to 5, The aqueous polyurethane resin described.   The aqueous polyurethane resin according to claim 1, wherein the aqueous polyurethane resin is a hydrophilic modifier.   A hydrophilic resin comprising the aqueous polyurethane resin according to any one of claims 1 to 7 as the first aqueous resin.   The hydrophilic resin according to claim 8, comprising a second aqueous resin.   The hydrophilic resin according to claim 8, comprising a water-dispersible isocyanate curing agent. The second aqueous resin contains, as a raw material, at least one hydrophobic macropolyol selected from the group consisting of a polyester polyol, a polycarbonate polyol, and a polyoxyalkylene polyol having 3 to 10 carbon atoms in an alkylene group,
The hydrophilic resin according to claim 9 or 10, wherein the hydrophobic macropolyol is contained in an amount of 50% by mass or more based on the total amount of raw materials of the second aqueous resin.   The hydrophilic resin according to claim 11, wherein the second aqueous resin further contains a carboxylic acid group-containing polyol as a raw material. Isocyanate curing agent
The hydrophilic resin according to claim 10, wherein the isocyanate is a blocked isocyanate blocked with a blocking agent.   The hydrophilic resin according to claim 13, wherein the blocked isocyanate is dispersed in water with an external emulsifier.   The hydrophilic resin according to claim 13 or 14, wherein in the blocked isocyanate, the isocyanate is a polyisocyanate containing one aromatic ring or a modified product thereof.   The hydrophilic resin according to any one of claims 13 to 15, wherein in the blocked isocyanate, the blocking agent is 3,5-dimethylpyrazole.   The hydrophilic resin according to any one of claims 8 to 16, wherein the hydrophilic resin is a coating agent for moisture permeation waterproofing.   A film obtained from the hydrophilic resin according to any one of claims 8 to 17.