CN1590429A - Polyurethane resin,water polyurethane resin,hydrophilic modifier,moisture resin and process for producing polyurethaneresin - Google Patents

Abstract

The invention provides a polyurethane resin, a water-based polyurethane resin, a hydrophilic modifier, a moisture-permeable resin and a method for producing the polyurethane resin. In order to provide a water-soluble polyurethane resin capable of imparting excellent hydrophilicity to the water-based resin due to excellent compatibility and excellent water-swellability after film formation, or a water-based polyurethane resin composed of the polyurethane resin and a water-based polyurethane resin containing the water-based A hydrophilic modifier for polyurethane resin, a moisture-permeable resin containing these polyurethane resins, and a method for producing the polyurethane resin. In the present invention, at least an anionic group-containing polyurethane prepolymer and a polyoxyethylene group-containing polymer Amines react to give polyurethane resins. A water-based polyurethane resin is obtained by dispersing and/or dissolving this polyurethane resin in water, and a moisture-permeable resin can be obtained by mixing a hydrophilic modifier composed of this water-based polyurethane resin with the water-based resin.

Description

Polyurethane resin, water-based polyurethane resin, hydrophilic modifier, moisture-permeable resin, and method for producing polyurethane resin

technical field

The present invention relates to polyurethane resins, water-based polyurethane resins, hydrophilic modifiers, moisture-permeable resins, and methods for producing the polyurethane resins. , moisture permeability, water retention, water swelling, antistatic properties, etc., modified polyurethane resin, or a water-based polyurethane resin composed of the polyurethane resin, and a hydrophilic modifier containing the water-based polyurethane resin , and a moisture-permeable resin containing these polyurethane resins, and a method for producing the polyurethane resin.

Background technique

So far, water-swellable polymers are also called water-absorbent polymers, which maintain high water retention by utilizing the hydrophilicity and cross-linked network of the polymer itself, and are used alone or in combination with other resins, where water permeability is required Or moisture permeability, water retention, water swelling, antistatic properties, etc., and various fields or applications of hydrophilicity.

In addition, in recent years, considering the toxicity of organic solvents and the pollution to the atmosphere, it is desired to reduce the use of organic solvents. People are studying how to use organic solvents as solvents in various resin applications. Water is used as a dispersion solvent for the conversion of water-based resins.

Therefore, a water-swellable polymer that can be easily compounded in an aqueous resin and that can impart high hydrophilicity is required.

In general, water-swellable polymers are known in which hydrophilic groups, particularly polyoxyethylene groups, are introduced in order to exhibit high hydrophilicity. In water-swellable polymers, if the polyoxyethylene group content is increased, the hydrophilicity can be improved, but on the other hand, if the polyoxyethylene group content is too high, the affinity with water is too strong, and condensation occurs. Gelling, or making the final water-based resin unstable.

In addition, in order to maintain the mechanical strength during water swelling, it is preferred to include crosslinks, but once the crosslinks are included, the water swelling property will be hindered, resulting in poor compatibility when blended with water-based resins.

For example, JP-A-11-228808 proposes an aqueous dispersion of crosslinked polyurethane particles containing polyoxyethylene-containing polyamine and water-dispersible polyisocyanate.

In addition, conventional moisture-permeable and waterproof fibers are obtained by coating a solution of polyurethane resin dissolved in a mixture of water and an organic solvent on a fabric such as nylon and drying it. Non-toxic organic solvents need to be removed in post-processing.

For example, in Japanese Patent Publication No. 60-47954, dimethylformamide, dimethylsulfoxide, tetrahydrofuran, and the like are listed as polar organic solvents.

However, the aqueous dispersion described in Japanese Unexamined Patent Publication No. 11-228808 has poor stability, and even if it is blended into a water-based resin, poor compatibility occurs, and a coating with uniform hydrophilicity cannot be obtained even if it is formed into a film. , As a result, hydrophilicity cannot be imparted substantially.

In addition, the moisture-permeable and water-repellent finishing method described in Japanese Patent Publication No. 60-47954 uses a large amount of polar organic solvents, which is undesirable in view of toxicity, air pollution, and energy efficiency.

Contents of the invention

The object of the present invention is to provide, have water-soluble, with its excellent compatibility and the excellent water-swellability after film-forming and can give water-based resin excellent hydrophilicity polyurethane resin, or the water-based polyurethane resin that is made of this polyurethane resin A polyurethane resin, a hydrophilic modifier comprising the water-based polyurethane resin, a moisture-permeable resin comprising the polyurethane resin, and a method for producing the polyurethane resin.

The polyurethane resin of the present invention is characterized in that it is obtained by reacting at least a polyurethane prepolymer having an anionic group with a polyoxyethylene group-containing polyamine.

In addition, the polyurethane resin of the present invention preferably contains 5 to 200 milliequivalents of the aforementioned anionic group per 100 g of the polyurethane prepolymer in the polyurethane prepolymer.

In addition, in the polyurethane resin of the present invention, it is suitable that the above-mentioned polyurethane prepolymer contains polyisocyanate and polyoxyalkylene polyol as raw materials.

Furthermore, in the polyurethane resin of the present invention, it is suitable that the polyoxyethylene group content in the above-mentioned polyurethane prepolymer is 40% by weight or more.

In addition, in the polyurethane resin of the present invention, it is suitable that the polyoxyethylene group content in the above-mentioned polyurethane resin is 40% by weight or more.

In addition, the polyurethane resin of the present invention is further preferably an alkoxysilyl compound containing a primary amine, or having a primary amine group and a secondary amine group.

In addition, the water-based polyurethane resin of the present invention is characterized in that the above-mentioned polyurethane resin is dispersed and/or dissolved in water.

The hydrophilic modifier of the present invention is characterized by containing the aforementioned polyurethane resin.

In addition, the moisture-permeable resin of the present invention is characterized by containing the above-mentioned hydrophilic modifier and an aqueous resin.

In addition, in the moisture-permeable resin of the present invention, the above-mentioned water-based resin is a polyurethane emulsion, and the above-mentioned polyurethane emulsion contains a macromolecular (macro) polyol as a raw material, and the macromolecular polyol is obtained from polyester polyol, polycarbonate polyol and alkyl At least one selected from the group consisting of polyoxyalkylene polyols having 3 to 10 carbon atoms in the group preferably contains 50% by weight or more of the macromolecular polyol relative to the total amount of polyurethane raw materials in the polyurethane emulsion.

The method for producing a polyurethane resin of the present invention is characterized by reacting at least a polyurethane prepolymer having an anionic group and a polyoxyethylene group-containing polyamine.

The polyurethane resin, water-based polyurethane resin and hydrophilic modifier of the present invention have excellent compatibility and excellent water-swellability after film formation, and can also impart excellent hydrophilicity to the water-based resin. Therefore, the moisture-permeable resin of the present invention, which contains the hydrophilic modifier of the present invention and the water-based resin, is coated on the base fabric by casting to form a moisture-permeable and waterproof film on the base fabric, and can realize moisture permeability. Water repellent finish. Therefore, it can be effectively used for clothing materials and the like.

Detailed ways

The polyurethane resin of the present invention can be obtained by reacting at least a polyurethane prepolymer having an anionic group and a polyoxyethylene group-containing polyamine.

In the present invention, the polyurethane prepolymer with anionic group, for example, has anionic group on the molecular side chain and a polyurethane prepolymer with free isocyanate group at the molecular end, through polyisocyanate and polyol and containing It can be obtained by reacting an anionic active hydrogen-based compound.

The polyisocyanate can be selected from the polyisocyanate commonly used in the manufacture of polyurethane resins without particular limitation, for example, aromatic diisocyanate, araliphatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate and these diisocyanates can be mentioned. Derivatives or modifications of isocyanates, etc.

Examples of the aromatic diisocyanate include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate , 2,4- or 2,6-toluene diisocyanate, 4,4'-toluene diisocyanate, 4,4'-diphenyl ether diisocyanate, etc.

Examples of the araliphatic diisocyanate include 1,3- or 1,4-xylene diisocyanate or a mixture thereof.

Examples of aliphatic diisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, and 1,2-butylene diisocyanate. , 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate hexanoic acid methyl wait.

Examples of alicyclic diisocyanate include 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl- 3,5,5-Trimethylcyclohexyl isocyanate (isophorone diisocyanate), 4,4'-methylene bis(cyclohexyl diisocyanate), methyl-2,4-cyclohexane Diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,4-bis(isocyanatomethyl)cyclohexane, 1,3-bis(isocyanatomethyl)cyclohexane, 2,5(2,6)-bis(isocyanatomethyl)bicyclo[2.2.1]heptane, etc.

In addition, examples of polyisocyanate derivatives include dimers, trimers, biurets, allophanates, carbodiimides, uretdiones, oxadiones, etc., of the above-mentioned polyisocyanates. Azitrione, polymethylene polyphenyl polyisocyanate (Kul-do MDI, Polymeric MDI), and Kru-do TDI, etc.

In addition, as a modified product of polyisocyanate, for example, the above-mentioned polyisocyanate or a derivative of polyisocyanate is reacted with a polyol (described later) under the condition that the equivalent of the isocyanate group of the polyisocyanate is more than the hydroxyl group of the polyol. And the obtained polyalcohol modification.

These polyisocyanates can be used alone or in combination of two or more. In addition, among these polyisocyanates, aliphatic diisocyanates such as hexamethylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexyl alicyclic diisocyanates such as alkane, 4,4'-methylenebis(cyclohexylisocyanate), etc.

The polyol is not particularly limited as long as it is commonly used in the production of polyurethane resins, but polyoxyalkylene polyols are preferably used.

Examples of polyoxyalkylene polyols include block copolymers or random copolymers obtained by addition reaction of ethylene oxide using low-molecular-weight polyols as initiators.

Examples of low molecular weight polyols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,6-hexanediol, neopentyl Diol, alkane (7-22 carbon atoms) diol, diethylene glycol, triethylene glycol, dipropylene glycol, cyclohexanedimethanol, alkane-1,2-diol (17-20 carbon atoms) , hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, dihydroxyethoxybenzene, xylene glycol (xyleneglycol), low molecular weight diols such as bishydroxyethylene terephthalate, such as glycerin, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxy Low molecular weight triols such as methylpentane, 1,2,6-hexanetriol, 1,1,1-tris(hydroxymethyl)propane, 2,2-bis(hydroxymethyl)-3-butanol, etc. .

As an epoxide, ethylene oxide, propylene oxide, etc. are mentioned, for example.

These polyoxyalkylene polyols may be used alone or in combination of two or more. A polyoxyalkylene polyol having a high polyoxyethylene group content is preferably used, specifically, polyethylene glycol having a number average molecular weight of 500 to 3,000 is preferably used.

In addition, a polyoxyalkylene monoalcohol in which a part of the hydroxyl group is masked by a monoalcohol such as methanol or butanol may be used as long as the chain extension reaction described later is not inhibited.

In addition, as the polyol, a high-molecular-weight polyol or a low-molecular-weight polyol other than polyoxyalkylene polyol can be used. Such polyols, as high molecular weight polyols, for example, polyester polyols, polycaprolactone polyols, polycarbonate polyols, etc. 4000 polyols. In addition, examples of low-molecular-weight polyhydric alcohols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,6-hexanediol, Neopentyl glycol, alkane (7 to 22 carbon atoms) diol, diethylene glycol, triethylene glycol, dipropylene glycol, cyclohexanedimethanol, alkane-1,2-diol (17 to 22 carbon atoms) 20), hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, dihydroxyethoxybenzene, xylene ethyl Diol (xyleneglycol), bishydroxyethylene terephthalate, etc.

In addition, the active hydrogen group-containing compound having an anionic group is, for example, an anionic group having a betaine structure-containing group such as a carboxyl group, a sulfonyl group, a phosphoric acid group, and a sulfobetaine, and reacting with an isocyanate group, for example Compounds containing active hydrogen groups such as hydroxyl and amino groups.

The active hydrogen group-containing compound having such an anionic group is not particularly limited, and examples thereof include compounds having one anionic group and two or more active hydrogen groups. More specifically, examples of active hydrogen group-containing compounds having a carboxyl group include 2,2-dimethylolacetic acid, 2,2-dimethylollactic acid, 2,2-dimethylolpropionic acid, 2 , Dihydroxycarboxylic acids such as 2-dimethylolbutyric acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolpentanoic acid, diaminocarboxylic acids such as lysine and arginine wait.

Examples of active hydrogen group-containing compounds having a sulfonyl group include N,N-bis(2-hydroxyethyl)-2-aminoethylsulfonic acid, 1,3-phenylenediamine-4,6-disulfonic acid, acid, diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, 2,4-diamino-5-toluenesulfonic acid, etc.

As an active hydrogen group containing compound which has a phosphoric acid group, 2, 3- dihydroxypropyl phenyl phosphate etc. are mentioned, for example.

Examples of the active hydrogen group-containing compound having a betaine structure-containing group include sulfobetaine-group-containing compounds obtained by reacting tertiary amines such as N-methyldiethanolamine with 1,3-propanesultone.

Furthermore, an alkylene oxide modified product obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to an active hydrogen group-containing compound having these anionic groups is also mentioned.

These active hydrogen group-containing compounds having an anionic group may be used alone or in combination of two or more. In addition, among these active hydrogen group-containing compounds having an anionic group, active hydrogen group-containing compounds having a carboxyl group are preferably selected.

In addition, the active hydrogen group-containing compound having an anionic group is not particularly limited, but the anionic group is preferably 5 to 200 milliequivalents, preferably 10 to 100 milliequivalents, per 100 g of polyurethane prepolymer. Match the ratio. When the anionic group content per 100 g of the polyurethane prepolymer is 5 milliequivalents or more, stability can be improved during water dispersion of the polyurethane prepolymer. In addition, by making the anionic group content per 100 g of the polyurethane prepolymer 20 milliequivalents or less, more economical production can be achieved, and water retention can be kept within an appropriate range.

Therefore, adjust the ratio of polyisocyanate, polyol and active hydrogen group-containing compound with anionic group, so that the equivalent ratio of the isocyanate group of polyisocyanate relative to polyol and active hydrogen group-containing compound with anionic group (NCO/active hydrogen group) is more than 1, preferably 1.1 to 20, so that, for example, a known reaction method such as bulk polymerization or solution polymerization can be used to obtain a polyurethane prepolymer.

In addition, in this reaction, although not particularly limited, each component is preferably blended so that the polyoxyethylene group content in the obtained polyurethane prepolymer is 40% by weight or more, further 45 to 95% by weight. % by weight, especially 50 to 90% by weight. When the polyoxyethylene group content in the polyurethane prepolymer is greater than or equal to 40% by weight, a higher water swelling rate can be obtained, that is, higher hydrophilicity can be imparted than when the polyoxyethylene group content is less than 40% by weight. Therefore, when a higher water swelling rate and hydrophilicity-imparting performance are required, it is preferable to make the polyoxyethylene group content in the polyurethane prepolymer 40% by weight or more.

In bulk polymerization, for example, polyisocyanate is stirred under nitrogen flow, polyhydric alcohol and active hydrogen group-containing compound having anionic group are added thereto, and the reaction is carried out at a reaction temperature of 75 to 85°C for about 1 to several hours.

In the solution polymerization, for example, under a nitrogen flow, the polyisocyanate is stirred in a reaction solvent, a polyol and an active hydrogen group-containing compound having an anionic group are added thereto, and the reaction temperature is lower than or equal to the boiling point of the reaction solvent. response in about an hour. As the reaction solvent, a low-boiling-point solvent that is inert to isocyanate groups and active hydrogen groups, is rich in hydrophilicity, and is easy to remove is used. As such a reaction solvent, acetone, methyl ethyl ketone, and , ethyl acetate, tetrahydrofuran, acetonitrile, etc.

In this reaction, a reaction catalyst may be added as necessary, and unreacted polyisocyanate monomers may be removed from the reaction system by known means such as distillation or extraction.

In addition, in this reaction, before the prepolymer reaction, after the reaction, or after the chain extension reaction described later, it is preferred to add, for example, trimethylamine, triethylamine, tri-n-propylamine, tributylamine, triethanolamine Amines such as potassium hydroxide, sodium hydroxide and other inorganic salts, as well as selected neutralizers such as ammonia, form an anionic salt. The addition amount of the neutralizing agent is, for example, 0.4 to 1.2 equivalents, more preferably 0.6 to 1.0 equivalents, per 1 equivalent of the anionic group. Moreover, after the prepolymer is dispersed and/or dissolved in water, when carrying out the chain extension reaction described later, in order to improve the stability of the prepolymer in water, it is preferable to disperse and/or dissolve the prepolymer in water, Make it form an anionic salt.

Therefore, the polyurethane resin of the present invention can be obtained by using a polyoxyethylene group-containing polyamine as a chain extension agent, reacting it with the polyurethane prepolymer having an anionic group thus obtained, and extending the chain.

Polyoxyethylene group-containing polyamines, for example, polyoxyethylene ether diamine represented by the following structural formula (1), polyoxyalkylene ether diamine represented by the following structural formula (2), and polyoxyalkylene ether diamine represented by the following structural formula (3) are preferably used. ) represented by polyoxyethylene ether diamine, polyamine represented by the following structural formula (4). The number average molecular weight of these polyoxyethylene ether diamines or polyoxyalkylene ether diamines is, for example, in the range of 100 to 2,000, more preferably in the range of 140 to 10,000. Specifically, such as NOF's PEG#1000 diamine (corresponding to structural formula (1)) or Handsman's Jeffamine ED-2003 (corresponding to structural formula (2)), EDR-148 (corresponding to structural formula (3) ), XTJ-512 (equivalent to structural formula (4)), etc.

H ₂ NCH ₂ CH ₂ CH ₂ O(CH ₂ CH ₂ O) _n CH ₂ CH ₂ CH ₂ NH ₂

.....(1)

(In the formula, n represents the degree of polymerization.)

(In the formula, n, m, and l represent the degree of polymerization.)

H ₂ N(CH ₂ CH ₂ O) _n CH ₂ CH ₂ NH ₂ .....(3)

(In the formula, n represents the degree of polymerization.)

H ₂ N [(CH ₂ CH ₂ O) _n CH ₂ CH ₂ NH] _m H .....(4)

(In the formula, m and n represent the degree of polymerization.)

In addition, in such a reaction, as a chain extending agent, for example, a primary amine or an alkoxysilyl compound having a primary amino group and a secondary amino group can be used in combination. Specific examples of such alkoxysilyl compounds include alkoxysilyl group-containing compounds such as γ-aminopropyltriethoxysilane and N-phenyl-γ-aminopropyltrimethoxysilane. Amines, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane and other alkoxysilyl groups Diamines. The polyurethane resin obtained by using the alkoxysilyl compound in combination may have a crosslinkable functional group in the molecule, and the resin using this polyurethane resin can increase the molecular weight by crosslinking. Therefore, by controlling the amount of the alkoxysilyl compound used, a polyurethane resin of any molecular weight can be obtained, and water solubility and water swelling property can be freely controlled.

In addition to the above-mentioned polyoxyethylene group-containing polyamine and alkoxysilyl compound, other amines may be used in combination as the chain extender. Such amines include, for example, monoamines such as ethylamine, butylamine, isopropylamine, and dibutylamine, such as ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, 1, 6-hexanediamine, 1,4-cyclohexanediamine, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophoronediamine), 4,4'- Dicyclohexylmethanediamine, 2,5(2,6)-bis(aminomethyl)bicyclo[2.2.1]heptane, 1,3-bis(aminomethyl)cyclohexane, hydrazine and other diamines , such as polyamines such as diethylenetriamine, triethylenetetramine, and tetraethylenepentamine, and aminoalcohols such as N-(2-aminoethyl)ethanolamine. It should be noted that the amines used in combination as these chain extenders may be used alone or in combination of two or more. In addition, amines may be used in a masked form such as ketimine, ketazine or amine salt.

The chain extender, in addition to the polyoxyethylene-containing polyamine, can also use the above-mentioned alkoxysilyl compound or other amines in combination, but the total amount of the polyoxyethylene-containing polyamine in the chain extender is The amount is at least 10% by weight or more, more preferably 40% by weight or more, most preferably 60% by weight or more.

In addition, this reaction may include, for example, mixing the above-mentioned chain extender after mixing the polyurethane prepolymer with water. The amount of water is 20 to 500 parts by weight relative to the amount that the polyurethane prepolymer can be dissolved in water, for example, 100 parts by weight of the polyurethane prepolymer. In addition, the compounding amount of the chain extender is compounded in such a ratio that the equivalent ratio (isocyanate group/amino group) of the isocyanate group of the polyurethane prepolymer to the amino group of the chain extender exceeds 1, preferably 1.1 to 20. It can be obtained by a known reaction method such as bulk polymerization or solution polymerization.

In addition, in such compounding, it is preferable to compound each component so that in the obtained polyurethane resin (solid content), the polyoxyethylene group content is 40% by weight or more, further 45 to 95% by weight, especially It is 50 to 90% by weight. When the polyoxyethylene group content in the polyurethane resin is 40% by weight or more, a higher water swelling ratio can be obtained, that is, higher hydrophilicity can be imparted than when the polyoxyethylene group content is less than 40% by weight. Therefore, when a higher water swelling rate and hydrophilicity imparting performance are required, it is preferable to make the polyoxyethylene group content in the polyurethane resin 40% by weight or more.

In the above compounding amount, the reaction, specifically, first, slowly add water to the polyurethane prepolymer while stirring, or slowly add the polyurethane prepolymer to water while stirring the water, thereby preparing Aqueous solutions of polyurethane prepolymers. For stirring, it is preferable to impart high shear to the solution at the time of mixing using an ultra-high speed mixer or the like.

Next, a chain extender is dropped into the aqueous solution of the polyurethane prepolymer rapidly (that is, when the reaction between the isocyanate group and water is not proceeding) while stirring the aqueous solution.

In this reaction, for stirring, it is preferable to impart high shear to the solution at the time of mixing using an ultra-high speed mixer or the like. In addition, in order to suppress the reaction between the isocyanate group and water in the polyurethane prepolymer, for example, it is preferable to control the reaction temperature at 5 to 30°C.

In addition, after the dropping of the chain extender is completed, the reaction is completed at, for example, normal temperature while stirring. Thus, the polyurethane resin of the present invention can be prepared in the form of an aqueous solution to obtain an aqueous polyurethane resin. The pH of the water-based polyurethane resin is usually around 7-9.

After completion of the reaction, for the synthesis of the polyurethane prepolymer by solution polymerization, the organic solvent can be removed by heating at an appropriate temperature under reduced pressure, for example.

The polyurethane resin of the present invention obtained in this way can be prepared into an aqueous solution, and the water-based polyurethane resin of the present invention made into an aqueous solution exhibits excellent water-swellability because of its high hydrophilicity, high stability, and water-based Excellent compatibility with other water-based resins such as emulsions. Moreover, the water-based polyurethane resin is used as a hydrophilic modifier. If it is combined with other water-based resins, it can make the water-based resin water-permeable, moisture-permeable, water-retaining, water-swellable, antistatic and other hydrophilic properties. Since it is a remarkable improvement, the moisture-permeable resin of the present invention can be obtained by blending a hydrophilic modifier composed of the water-based polyurethane resin with an aqueous resin.

There are no particular limitations on the water-based resin. Examples of aqueous resins that can be blended in any ratio include aqueous emulsions such as vinyl acetate emulsions, acrylic emulsions, polyurethane emulsions, and ester emulsions, aqueous solutions of polyvinyl alcohol resins, aqueous solutions of polyvinylpyrrolidone resins, polyvinyl acetal Aqueous solutions of synthetic resins such as aqueous resin solutions, aqueous solutions of natural polymers such as starch and gelatin, etc. Preferable ones may be polyurethane emulsions.

The polyurethane emulsion can be formed by dispersing and/or dissolving in water by reacting an active hydrogen group-containing compound having at least 2 active hydrogen groups per molecule with an isocyanate group-containing compound having at least 2 isocyanate groups per molecule. get.

Preferable examples of the active hydrogen group-containing compound include macromolecular polyols such as polyester polyols, polycarbonate polyols, and polyoxyalkylene polyols having 3 to 10 carbon atoms in the alkylene group.

Examples of polyester polyols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,5-pentanediol, 1,4-butanediol Alcohol, 1,6-hexanediol, dipropylene glycol, tripropylene glycol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol and other low-molecular-weight diols or two or more kinds with malonic acid , maleic acid, succinic acid, adipic acid, azelaic acid, tartaric acid, pimelic acid, sebacic acid, oxalic acid, terephthalic acid, isophthalic acid, maleic anhydride, fumaric acid, dimer acid, Polyester polyols produced by the reaction of polycarboxylic acids such as trimellitic acid or derivatives thereof, polyester polyols produced by ring-opening polymerization of ε-caprolactone and the like, and the like.

Examples of polycarbonate polyols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9 -Diols such as nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A Polycarbonate polyols obtained by reacting one or two or more types of polycarbonate with carbonates such as dimethyl carbonate, diphenyl carbonate, ethylene carbonate, and phosgene.

Examples of polyoxyalkylene polyalkylene polyols having 3 to 10 carbon atoms in the alkylene group include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, and 1,3-butanediol. , 1,5-pentanediol, 1,4-butanediol, 1,6-hexanediol, dipropylene glycol, tripropylene glycol, neopentyl glycol, etc. A polyoxypolyalkylene polyol having an alkylene group having 3 to 10 carbon atoms obtained by ring-opening polymerization of cyclic ethers such as cyclobutane, tetrahydrofuran, and tetrahydropyran. Polyoxypolyalkylene polyols having 3 to 7 carbon atoms in the alkylene group are preferably selected, and polyoxypolyalkylene polyols having 4 to 6 carbon atoms are most preferably selected.

The molecular weight (number average molecular weight) of these macromolecular polyols is about 300-10000 normally, Preferably it is about 500-5000.

In addition, the content of the macropolyol is preferably 50% by weight or more relative to the total amount of the polyurethane raw material (ie, the raw material of the resin portion in the polyurethane emulsion). When the content of the macromolecular polyol is greater than or equal to 50% by weight, the mechanical strength of the moisture-permeable resin can be further improved.

In addition, as active hydrogen group-containing compounds, in addition to macromolecular polyols, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,5-pentanediol Alcohol, 1,4-butanediol, 1,6-hexanediol, dipropylene glycol, tripropylene glycol, neopentyl glycol, glycerin, trimethylolpropane and other low molecular weight diols or ethylene glycol, glycerin, etc. A polyoxyalkylene polyol having an alkylene group having 2 or less carbon atoms obtained by addition-polymerizing ethylene oxide, propylene oxide, or the like may also be used.

As the isocyanate group-containing compound, the same isocyanate group-containing compound as the polyisocyanate used in the production of the polyurethane resin can be used, and the above-mentioned aliphatic diisocyanate or the above-mentioned alicyclic diisocyanate is preferably mentioned.

In order to react the active hydrogen group-containing compound and the isocyanate group-containing compound, they need to be dispersed and/or dissolved in water, although there is no particular limitation therefor, but an emulsifier can be used. As an emulsifier, for example, in the reaction of an active hydrogen group-containing compound and an isocyanate group-containing compound, an internal emulsifier that modifies the molecular chain while reacting these compounds or makes the active hydrogen group-containing compound or isocyanate group-containing compound not The external emulsifier reacts so that it is additionally mixed.

As an internal emulsifier, those suitable for use include at least 3% by weight or more of active hydrogen-containing compounds with anionic groups, repeating units of ethylene oxide, and contain at least one or more active hydrogen-containing compounds in the polymer. A compound containing a nonionic group whose hydrogen group has a molecular weight of 300 to 10,000.

As the external emulsifier, surfactants such as polyoxyalkylene alkylphenyl ether, metal alkylsulfate, metal linear alkylbenzenesulfonate and the like are suitably used.

These emulsifiers are used in an amount of 15% by weight or less relative to the polyurethane raw material, and an active hydrogen group-containing compound having an anionic group is most suitable for use as an internal emulsifier. In addition, the mixing ratio of the active hydrogen group-containing compound and the isocyanate group-containing compound, that is, the equivalent ratio of the isocyanate group of the isocyanate group-containing compound to the active hydrogen group (hydroxyl, amino group, etc.) of the active hydrogen group-containing compound (NCO/active hydrogen group) It is 0.5 to 4.0, preferably 1.05 to 2.5.

Furthermore, in the polyurethane emulsion, when the above-mentioned equivalent ratio (NCO/active hydrogen group) is greater than or equal to 1, the chain can be extended by using a chain extender such as amines after dispersing and/or dissolving in water. As the amines, the same amines as those used for chain extension of the polyurethane resin can be used. Preferred examples include monoamines such as ethylamine, butylamine, isopropylamine, and dibutylamine, such as ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, 1,6-hexamethylene diamine, 1,4-cyclohexanediamine, 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (isophoronediamine), 4,4′-bicyclo Hexylmethanediamine, 2,5(2,6)-bis(aminomethyl)bicyclo[2.2.1]heptane, 1,3-bis(aminomethyl)cyclohexane, hydrazine and other diamines, such as Diethylenetriamine, triethylenetetramine, tetraethylenepentamine and other polyamines, such as amino alcohols such as N-(2-aminoethyl)ethanolamine, γ-aminopropyltriethoxysilane, N-phenyl - γ-aminopropyltrimethoxysilane and other alkoxysilyl-containing monoamines, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ- Alkoxysilyl group-containing diamines such as aminopropylmethyltrimethoxysilane.

In addition, the mechanical strength of the water-based resin when it is cast (for example, when it is cast with a width of 10mm and a thickness of 0.1mm), its tensile strength is greater than or equal to 6MPa, preferably greater than or equal to 8MPa, more preferably greater than or equal to 10 MPa, the elongation is greater than or equal to 200%, preferably greater than or equal to 300%, more preferably greater than or equal to 400%.

In addition, the water swelling rate of the cast water-based resin is preferably less than or equal to 20%, more preferably less than or equal to 10%, and most preferably less than or equal to 10% when it is cast (for example, with a width of 10mm and a thickness of 0.1mm). Preferably less than or equal to 5%.

Then, the moisture-permeable resin of the present invention can be obtained by mixing the above-mentioned hydrophilic modifier with such an aqueous resin. In addition, when compounding the hydrophilic modifier and the water-based resin, a compatibilizing agent such as N-methylpyrrolidone or N,N-dimethylformamide may be compounded together with them.

The mixing ratio of the hydrophilic modifier is, for example, 20 to 80% by weight relative to the solid content of the moisture-permeable resin (the total of the resin component in the water-based resin and the resin component in the hydrophilic modifier), preferably 30 to 70% by weight. If the mixing ratio of the hydrophilic modifier is less than 20% by weight relative to the solid content of the moisture-permeable resin, the moisture permeability of the film obtained by casting tends to be lowered, and if it exceeds 80% by weight, the film obtained by casting The resin strength tends to be lower.

The moisture-permeable resin of the present invention can obtain a moisture-permeable and waterproof film by casting, and in particular, by casting on a base fabric, can obtain a moisture-permeable and waterproof material used in, for example, moisture-permeable and waterproof-finished clothing.

The membrane having moisture permeability and water repellency may be either a microporous membrane or a non-porous membrane.

Moreover, as a base fabric, the woven fabric which consists of fibers, such as polyester, nylon, and cotton, a knitted fabric, a nonwoven fabric, etc. are mentioned, for example.

For the casting of the base fabric of the moisture-permeable resin, various methods can be used, among which there are lamination method, direct coating method, etc., which can be appropriately selected according to the application. For example, in the case of using the lamination method, a method of applying a moisture-permeable resin to the surface of a release paper or the like, heat-treating it, and then laminating the release paper on a fabric and thermally fusing it can be used. Moreover, when using the direct coating method, the method of directly coating on the surface of a base fabric or the surface of a release paper using a normal coating method, such as a knife coater, is mentioned.

Then, by such casting, the surface of the base fabric is covered with a moisture-permeable and waterproof film made of a moisture-permeable resin, thereby completing the moisture-permeable and waterproof finish on the surface of the base fabric.

Such a moisture-permeable waterproof base fabric is used as a moisture-permeable waterproof material for clothing as described above.

The so-called moisture permeability and water resistance refer to the performance that rain or other water does not pass through the coating, but moisture (water vapor) passes through it. It also prevents rain from entering the clothes.

In addition, the moisture-permeable resin of the present invention needs to ensure sufficient performance of following the base fabric, abrasion resistance, damage resistance, and the like. For this reason, the tensile strength as the mechanical strength of the casting film of the moisture-permeable resin of the present invention is 3 MPa or more, more preferably 4 MPa or more, most preferably 6 MPa or more, and the elongation is 200 MPa or more. %, more preferably greater than or equal to 300%, most preferably greater than or equal to 400%.

Furthermore, as the moisture permeability of the moisture-permeable resin of the present invention, when the thickness of the cast film is 0.03 mm, the moisture permeability in the moisture permeability test method B (JIS L1099 standard) is greater than or equal to 10000 (g/ m ² ·24h) is satisfactory.

Furthermore, in the polyurethane resin, water-based polyurethane resin, hydrophilic modifier, and moisture-permeable resin of the present invention, within the range that does not hinder the excellent effects of the present invention described above, a curing catalyst or various additives can be suitably blended, Such as plasticizers, defoamers, leveling agents, antifungal agents, rust inhibitors, matting agents, flame retardants, thixotropic agents, adhesion imparting agents, thickeners, smoothing agents, antistatic agents, surface active Agents, reaction delay agents, antioxidants, UV absorbers, anti-hydrolysis agents, weather-resistant stabilizers, dyes, inorganic pigments, organic pigments, primer pigments, curing agents, anti-sticking agents, etc.

The curing agent is not particularly limited if it is a commonly used curing agent, for example, an isocyanate-based curing agent having an isocyanate group, preferably a water-dispersible polyisocyanate-based curing agent.

Moreover, inorganic powder is mentioned as a release agent, Preferably, a silica powder etc. are mentioned, for example.

The compounding ratio of these various additives is suitably selected according to the purpose and use.

In addition, the polyurethane resin, water-based polyurethane resin, hydrophilic modifier, and moisture-permeable resin of the present invention are not limited to the above-mentioned clothing applications, but can also be used in various applications such as automobiles, electronic equipment, building materials, artificial leather, and film treatment. used in .

Hereinafter, the present invention will be described more specifically with reference to Examples, Comparative Examples, and Synthesis Examples, but the scope of the present invention is not limited.

Example 1

Preparation of polyurethane prepolymer

8.3 parts by weight of 1,3-bis(isocyanatomethyl)cyclohexane (1,3-bis(isocyanatomethyl)cyclohexane) (trade name: タケネ-ト 600, Mitsui Takeda) are charged into the stirred reactor. Chemikar Corporation), 1.2 parts by weight ethylene glycol, 0.7 parts by weight dimethylolpropionic acid (trade name: Nichikama-PA, manufactured by Nippon Chemical Corporation), 2.5 parts by weight acetonitrile, and the reaction temperature is adjusted at 70 to 75 °C, react until the reaction rate is greater than or equal to 99%, and obtain a polyurethane prepolymer having anionic groups in the molecular side chains and free isocyanate groups in the molecular terminals. The carboxylic acid was 49 milliequivalents per 100 g of the polyurethane prepolymer.

Preparation of waterborne polyurethane resin

The polyurethane prepolymer obtained above was cooled to 30° C., 0.5 parts by weight of triethylamine was added, and the mixture was sufficiently stirred for neutralization. Thereafter, 100 parts by weight of water at 25° C. was slowly added to form an aqueous solution of a polyurethane prepolymer, and polyoxyethylene group-containing diamine (trade name: PEG#1000 diamine, manufactured by NOF Corporation) was rapidly and sequentially dropped. ) 20% by weight aqueous solution of 70.5 parts by weight, and hydrazine 10% by weight aqueous solution of 3.0 parts by weight, for chain extension reaction. The temperature of the reaction solution at this time was adjusted at 25-30°C. Thereafter, after continuing to stir at 25-30° C. for 3 hours, at 40-50° C. under reduced pressure, acetonitrile and part of the water were removed to obtain a water-based polyurethane resin with a solid content of 20% by weight and a viscosity of 190 mPa·s.

Embodiment 2-5

According to the formula shown in Table 1, through the same operation as Example 1, waterborne polyurethane resin was obtained.

Comparative example 1

According to the formula shown in table 1, through the same operation as Example 1, water-based polyurethane resin was made, but gelation occurred eventually.

Comparative example 2

Press the formula shown in table 1, by the operation identical with embodiment 1, make waterborne polyurethane resin.

Comparative example 3

47.1 parts by weight of Takene-to WD-725 (manufactured by Mitsui Takeda Chemical Co., Ltd., water-dispersible polyisocyanate: isocyanate group content 15.8%) and 62 parts by weight of ion-exchanged water were placed in the stirred reactor to uniformly disperse them. Thereafter, while stirring the dispersion, slowly add polyoxyethylene-containing diamine (trade name PEG#1000 diamine, NOF Company system) 54.3 parts by weight. Thereafter, although the reaction was followed at 25°C, the stability gradually decreased as the reaction proceeded, and gelation finally occurred.

The abbreviated symbols and product names in Table 1 are as follows. In addition, the formulations in Table 1 are expressed in parts by weight.

H6XDI: 1,3-bis(isocyanatomethyl)cyclohexane, trade name Takene-to 600, manufactured by Mitsui Takeda Chemical Co., Ltd.

H12MDI: 4,4'-methylene bis(cyclohexyl isocyanate), trade name Desmojiru-W, manufactured by Bayer Corporation

WD-725: Water-dispersible polyisocyanate (15.8% isocyanate group content), trade name タケネ-トWID-725, manufactured by Mitsui Takeda Chemical Co., Ltd.

PEG1000: polyethylene glycol (OH value 112), manufactured by NOF Corporation

EG: ethylene glycol

DMPA: dimethylolpropionic acid, trade name Nitsukama-PA, manufactured by Nippon Chemical Co., Ltd.

MPEG diol: methoxy-modified polyethylene glycol branched diol (OH value 89), manufactured by Mitsui Takeda Chemical Co., Ltd.

TEA: Triethylamine

NaOH: sodium hydroxide

PEG#1000 diamine: polyoxyethylene diamine (amine value 101), manufactured by NOF Corporation

Jefamin ED-2003: polyoxyalkylene diamine (amine value 53.9), manufactured by Handsman Co., Ltd., EO/PO molar ratio = 38.7/6.0

KBM-602: N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane (amine value 544), manufactured by Shin-Etsu Chemical Co., Ltd.

evaluate

1) Water swelling test

The water-based polyurethane resin (solid content: 20% by weight) of each example and comparative example 2 was cast to form a dry transparent film with a film thickness of 1 mm. Thereafter, the film was cut and processed into a size of 10 cm×10 cm, which was used as a sample.

Casting is to apply a water-based polyurethane resin on the surface of the release paper with a doctor blade, and apply heat treatment at 130°C for 5 minutes to obtain a transparent film.

Each of the obtained samples was immersed in distilled water at 25°C for 12 hours, the lengths of the vertical and horizontal sides immediately after taking out were measured, and the average of the lengths of the vertical and horizontal sides was used as the water swelling rate. (By the way, the so-called water swelling rate of 100% means that the length and width of the sides are doubled.) The results are shown in Table 1.

2) Compatibility test

As the water-based resin, Takerac W-6010 (manufactured by Mitsui Takeda Chemical Co., Ltd., aqueous dispersion of polycarbonate-based polyurethane resin, solid content 30% by weight, 30 MPa·s) and W-6020 (manufactured by Mitsui Takeda Chemical Co., Ltd., polyether Be the aqueous dispersion of polyurethane resin, solid content 30% by weight, 20MPa s), relative to each 100 parts by weight of these aqueous dispersions, mix the aqueous polyurethane resin 150 parts by weight of embodiment 1～5, comparative example 2, order Visually confirm the stability of the mixture. The results are shown in Table 1. In Table 1, "◯" indicates a state of homogeneous mutual dissolution, and "×" indicates a state of phase separation.

3) Moisture permeability test method A

The water-based polyurethane resin (solid content: 20% by weight) of each example and comparative example 2 was cast to form a dry transparent film with a film thickness of 0.05 mm. Thereafter, the film was evaluated in accordance with JIS L1099-A1. The results are shown in Table 1.

In Comparative Example 2, since the compatibility was poor, a uniform coating was not obtained and measurement could not be performed.

Table 1 formula Example 1 Example 2 Example 3 Example 4 Example 5 Comparative example 1 Comparative example 2 Comparative example 3 Polyisocyanate H6XDI 8.3 - - - - - - - H12MDI - 6.2 8.0 5.5 6.6 4.9 9.8 - WD-725 - - - - - - - 47.1 Polyol PEG1000 - 12.0 12.5 10.8 12.9 6.8 15.2 - EG 2.5 - - - - - - - Compounds containing active hydrogen groups containing anionic groups DMPA 0.7 0.8 0.8 0.7 0.9 - 1.0 - MPEG diol - - - - - 7.8 - - solvent Acetonitrile 2.5 8.1 8.4 7.3 8.3 8.3 10.3 - Neutralizer TEA 0.5 0.8 0.6 0.6 - - 0.8 - NaOH - - - - 0.2 - - - chain extender PEG diamine #1000 14.1 5.4 4.5 - 4.2 5.5 - 16.3 Jefamin ED-2003 - - - 7.3 - - - - Hydrazine 0.3 - - - - - 0.3 - KBM602 - - 0.2 0.2 - - - - distilled water 100 100 100 100 100 100 100 100 Anionic group equivalent per 100g polyurethane prepolymer (milligram equivalent) 49 32 32 32 32 0 32 0 Polyoxyethylene content (weight%) Content in prepolymer 0 63.3 63.3 63.3 63.3 75.0 63.3 - Content in polyurethane resin 56.4 69.7 67.8 67.5 68.3 80.6 60.6 65.2 Properties of Polyurethane Resin Aqueous Solution Solid content (weight%) 20 20 20 20 20 20 20 20 Viscosity (mPa·s) 190 20000 16000 9000 21000 gelation 100000 gelation Water swelling rate (%) 90 130 120 122 150 - 65 - Compatibility W-6010 ○ ○ ○ ○ ○ - x - W-6020 ○ ○ ○ ○ ○ - x - Moisture permeability test method A (g/m ² ·24h) W-6010 5500 9400 8000 7700 9200 - - - W-6020 6000 9600 9000 7200 10000 - - -

Synthesis Example 1

Synthesis of Waterborne Resins

11.75 parts by weight of 4,4'-methylene bis(cyclohexyl isocyanate), 31.39 parts by weight of polyoxytetramethylene ethylene glycol with a molecular weight of 2000 (number average molecular weight) are charged into the stirred reactor. Diol (trade name: PTG2000SN, manufactured by Hodo Ke Valley Chemical Co.), 2.37 parts by weight dimethylol butyric acid (commodity name: ニッカマ-BA, manufactured by Nippon Chemical Corporation) and 20.4 parts by weight acetone, the temperature of the reaction solution is adjusted at 53 ~55°C, as a reaction catalyst, add a small amount of stannous octoate (trade name: スタノクト, manufactured by Co., Ltd. API コ-ポレ-ション), and the reaction is carried out until the reaction rate is greater than or equal to 99%. Polyurethane prepolymers with free isocyanate groups at molecular ends.

This polyurethane prepolymer was cooled to 30° C., 1.46 parts by weight of triethylamine (carboxylic acid neutralization ratio: 0.9) was added, and the mixture was sufficiently stirred for neutralization. Thereafter, this was slowly added to 100 parts by weight of water at 25° C. to form an aqueous solution of a polyurethane prepolymer, and then 1.96 parts by weight of isophoronediamine was dropped rapidly to perform a chain extension reaction. The temperature of the reaction solution at this time was adjusted at 25-30°C. Thereafter, stirring was continued at 25 to 30° C. for 3 hours, and acetone was removed under reduced pressure at 40 to 50° C. to obtain a polyurethane emulsion with a solid content of 33% by weight and a viscosity of 25 mPa·s.

Synthesis Examples 2 and 3

According to the formula shown in Table 2, the polyurethane emulsion was obtained through the same operation as in Synthesis Example 1.

The abbreviated symbols and product names in Table 2 are as follows. In addition, the formulations in Table 2 are expressed in parts by weight.

PTG-1: polyoxytetramethylene glycol with a number average molecular weight of 20,000, trade name PTG-2000SN, manufactured by Hodo Ketani Chemical Co., Ltd.

Ester-1: Polyester polyol with a number average molecular weight of 2000, trade name Takerak U-5620 manufactured by Mitsui Takeda Chemical Co., Ltd.

DMBA: dimethylolbutyric acid, trade name Nikama-BA, manufactured by Nippon Chemical Corporation

IPDA: Isophorone diamine, manufactured by Degusa-Hylus Co., Ltd.

evaluate

4) Mechanical strength test

The polyurethane emulsion (solid content: 33% by weight) of each synthesis example was cast to form a dry transparent film with a film thickness of 0.1 mm. Thereafter, the film was cut into 1 cm rectangles, and a tensile test was performed at a tensile speed of 200 mm/min to measure stress and elongation at breakage. The results are shown in Table 2.

Table 2 formula Synthesis Example 1 Synthesis example 2 Synthesis example 3 Compounds containing isocyanate groups H12MDI 11.75 11.78 11.83 Active Hydrogen Compounds PTG-1 31.97 33.59 Ester-1 33.72 Active Hydrogen Compounds Containing Anionic Groups DMPA 2.05 2.05 DMBA 2.37 solvent Acetonitrile 20.97 acetone 20.38 20.92 Neutralizer TEA 1.46 1.39 1.32 chain extender IPDA 1.96 Ethylenediamine 0.69 Hydrazine 0.58 distilled water 100 100 100 Polyoxyethylene content (weight%) Content in polyurethane resin 0 0 0 Properties of water-based resin Solid content (weight%) 33 33 33 Viscosity (mPa·s) 25 twenty two 14 Water swelling rate (%) 2 2 2 Mechanical strength Tensile strength (MPa) 18 14 19 Elongation (%) 480 580 510

Example 6

The water-based polyurethane resin obtained in Example 3 and the water-based resin obtained in Synthesis Example 1 were mixed at a weight ratio of 60:40 to obtain a moisture-permeable resin. The solid content at this time was 25.2% by weight.

Example 7

The water-based polyurethane resin obtained in Example 3 and silicon dioxide (trade name Cylicia 310P, release agent, manufactured by Fuji Silycia Co., Ltd.) as an additive were fully stirred and mixed at a weight ratio of 60:2, and then mixed in a ratio of 62:38 This compound and the water-based resin obtained in Synthesis Example 1 yielded a moisture-permeable resin. The solid content concentration at this time was 26.5% by weight.

Examples 8 and 9

According to the formulation in Table 3, a moisture-permeable resin was obtained through the same operations as in Example 7.

Example 10

The water-based polyurethane resin obtained in Example 3 and the water-based resin obtained in Synthesis Example 2 were mixed at a weight ratio of 55:43 to obtain a moisture-permeable resin. Further, WD-725 (curing agent (water-dispersible polyisocyanate: isocyanate group content 15.8%, manufactured by Mitsui Takeda Chemical Co., Ltd.)) was mixed as an additive 2 in this moisture-permeable resin at a weight ratio of 98:2.

evaluate

5) Compatibility test

The stability of the moisture-permeable resin of each Example was confirmed visually. The results are shown in Table 3. In Table 3, "◯" indicates a homogeneously dissolved state, and "×" indicates a phase-separated state.

6) Moisture permeability test method B

The moisture-permeable resins of the respective examples were cast to form dry transparent coatings with a film thickness of 0.03 mm. Thereafter, moisture permeability was evaluated in accordance with JIS L1099-B1. The results are shown in Table 3.

7) Mechanical strength

The moisture-permeable resins of the respective examples were cast to form dry transparent coatings with a film thickness of 0.03 mm. Thereafter, the same operation as the tensile test of the polyurethane emulsion was performed, and the stress and elongation at break were measured. The results are shown in Table 3.

Abbreviated symbols in Table 3 are as follows. In addition, the formulations in Table 3 are expressed in parts by weight.

Additive 1: Silica (Anti-sticking agent, trade name Cylicia 310P, manufactured by Fuji Silycia Co., Ltd.)

Additive 2: WD-725 (water-dispersible polyisocyanate with isocyanate group content of 15.8%, manufactured by Mitsui Takeda Chemical Co., Ltd.)

table 3 formula Example 6 Example 7 Example 8 Example 9 Example 10 Waterborne polyurethane resin type Example 3 Example 3 Example 3 Example 4 Example 3 parts by weight 60 60 55 55 55 water-based resin type Synthesis Example 1 Synthesis Example 1 Synthesis example 2 Synthesis example 3 Synthesis Example 1 parts by weight 40 38 43 43 43 additive type - Additive 1 Additive 1 Additive 1 Additive 2 parts by weight - 2 2 2 2 Solid content (weight%) 25.2 26.5 27.2 27.2 27.2 Compatibility ○ ○ ○ ○ ○ Moisture permeability test method B Film thickness (μm) 33 28 31 26 34 Moisture permeability (g/m ² ·24h) 140000 105000 110000 120000 19000 Mechanical strength Tensile strength (MPa) 4.2 6.4 5.7 6.2 13 Elongation (%) 620 420 550 480 240

The moisture-permeable resins obtained in Examples 6-9 have good compatibility, mechanical strength, and extremely good moisture-permeability. The moisture-permeable resin obtained in Example 10, by adding a curing agent, not only has strong mechanical strength, but also has good Moisture permeability, and suitable for use as a moisture-permeable and waterproof coating.

In addition, although the above-mentioned description was provided as an exemplary embodiment of the present invention, these are simply illustrations and should not be interpreted as a limitative one. Modifications of the present invention that can be recognized by those skilled in the art are included in the scope of the claims described later.

Claims (11)

1. A polyurethane resin obtained by reacting at least a polyurethane prepolymer having an anionic group and a polyoxyethylene group-containing polyamine. 2. The polyurethane resin according to claim 1, wherein the content of the anionic group in the polyurethane prepolymer is 5 to 200 milliequivalents of the anionic group per 100 g of the polyurethane prepolymer. 3. The polyurethane resin according to claim 1, wherein the polyurethane prepolymer contains polyisocyanate and polyoxyalkylene polyol as raw materials. 4. The polyurethane resin according to claim 1, wherein the polyoxyethylene group content in the polyurethane prepolymer is greater than or equal to 40% by weight. 5. The polyurethane resin according to claim 1, wherein the polyoxyethylene group content in the polyurethane resin is greater than or equal to 40% by weight. 6. The polyurethane resin according to claim 1, further comprising, as a raw material, an alkoxysilyl compound having a primary amino group, or a primary amino group and a secondary amino group. 7. A water-based polyurethane resin characterized in that a polyurethane resin obtained by reacting at least a polyurethane prepolymer having an anionic group and a polyoxyethylene group-containing polyamine is dispersed and/or dissolved in water. 8. The hydrophilic modifier is characterized in that it comprises a water-based polyurethane resin, and the water-based polyurethane resin is a polyurethane resin obtained by at least reacting a polyurethane prepolymer having an anionic group and a polyoxyethylene group-containing polyamine Dispersed and/or dissolved in water. 9. A moisture-permeable resin, characterized in that it contains a hydrophilic modifier and a water-based resin, and the hydrophilic modifier contains at least a polyurethane prepolymer having an anionic group and a polyamine containing a polyoxyethylene group. A water-based polyurethane resin in which the polyurethane resin obtained by the reaction is dispersed and/or dissolved in water. 10. The moisture-permeable resin according to claim 9, wherein: Above-mentioned aqueous resin is polyurethane resin emulsion, The above-mentioned polyurethane resin emulsion contains a macromolecular polyol as a raw material, The above-mentioned macromolecular polyols are at least one selected from the group consisting of polyester polyols, polycarbonate polyols, and polyoxyalkylene polyols with 3 to 10 carbon atoms in the alkylene group, Relative to the total amount of polyurethane raw materials in the above-mentioned polyurethane emulsion, the above-mentioned macromolecular polyol is contained in an amount greater than or equal to 50% by weight. 11. A method for producing a polyurethane resin, comprising reacting at least a polyurethane prepolymer having an anionic group and a polyoxyethylene group-containing polyamine.