JP2005060690A - Polyurethane resin, aqueous polyurethane resin, hydrophilic modifier, moisture-permeable resin, and method for producing polyurethane resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyurethane resin, or a polyurethane thereof, which is water-soluble and has excellent compatibility and excellent water swellability after film formation, and can impart excellent hydrophilicity to an aqueous resin. To provide an aqueous polyurethane resin comprising a resin, a hydrophilic modifier containing the aqueous polyurethane resin, a moisture-permeable resin containing the polyurethane resin, and a method for producing the polyurethane resin.
A polyurethane resin is obtained by reacting at least a urethane prepolymer having an anionic group with a polyoxyethylene group-containing polyamine. A water-permeable resin can be obtained by dispersing and / or dissolving the polyurethane resin in water to obtain an aqueous polyurethane resin, and blending the hydrophilic modifier composed of the aqueous polyurethane resin into the aqueous resin. .
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Description

  The present invention relates to a polyurethane resin, a water-based polyurethane resin, a hydrophilic modifier, a moisture-permeable resin, and a method for producing the polyurethane resin, and in detail, blended with various water-based resins, water permeability, moisture permeability, water retention, Polyurethane resin suitable for modifying hydrophilic properties such as water swellability and antistatic property, or an aqueous polyurethane resin comprising the polyurethane resin, a hydrophilic modifier containing the aqueous polyurethane resin, and these The present invention relates to a moisture-permeable resin containing a polyurethane resin, and further to a method for producing the polyurethane resin.

Conventionally, a water-swellable polymer is also referred to as a water-absorbing polymer, and maintains high water retention due to the hydrophilicity and cross-linking network of the polymer itself, and can be used alone or in combination with other resins. It is used in various fields and applications that require hydrophilicity, such as moisture permeability, water retention, water swelling, and antistatic properties.
In recent years, it has been desired to reduce the use of organic solvents from the viewpoint of toxicity and air pollution. In various resin applications, from organic solvent-based resins that use organic solvents as solvents, water as dispersion media. The conversion to water-based resin using is being studied.

Therefore, a water-swellable polymer that can be easily blended into an aqueous resin and can impart high hydrophilicity is required.
In general, it is known that a water-swellable polymer introduces a hydrophilic group, particularly a polyoxyethylene group, in order to develop high water retention. In the water-swellable polymer, if the polyoxyethylene group content is increased, the hydrophilicity can be improved. On the other hand, if the polyoxyethylene group content is too high, the affinity for water is too strong. As a result, it becomes gelled or the aqueous resin finally obtained becomes unstable.

In order to maintain the mechanical strength at the time of water swelling, it is preferable to include cross-linking. However, if the cross-linking is included, the water swellability is inhibited, and as a result, compatibility with the aqueous resin is reduced. Cause a defect.
For example, JP-A-11-228808 (Patent Document 1) proposes an aqueous dispersion of crosslinked polyurethane particles containing a polyoxyethylene-containing polyamine and a water-dispersible polyisocyanate.

Conventionally, moisture-permeable and water-proofed fibers are obtained by applying a polyurethane resin dissolved in a mixture of water and an organic solvent to a fabric such as nylon and drying it. Therefore, a large amount of polar organic solvent is used, and it is necessary to remove it in the post-treatment.
For example, Japanese Examined Patent Publication No. 60-47954 (Patent Document 2) includes dimethylformamide, dimethyl sulfoxide, tetrahydrofuran and the like as polar organic solvents.
JP-A-11-228808 Japanese Patent Publication No. 60-47954

However, the aqueous dispersion described in Patent Document 1 has poor stability, and even when blended with an aqueous resin, the compatibility is poor, and even when a film is formed, a uniform hydrophilic film is formed. As a result, there is a problem that hydrophilicity cannot be substantially imparted.
Moreover, in the moisture-permeable waterproof processing method described in Patent Document 2, a large amount of polar organic solvent is used, which is not preferable from the viewpoints of toxicity, air pollution, and energy efficiency.

  An object of the present invention is a polyurethane resin that is water-soluble and can impart excellent hydrophilicity to an aqueous resin due to excellent compatibility and excellent water swellability after film formation, or It is to provide an aqueous polyurethane resin comprising the polyurethane resin, a hydrophilic modifier containing the aqueous polyurethane resin, a moisture-permeable resin containing the polyurethane resin, and a method for producing the polyurethane resin. .

In order to achieve the above object, the polyurethane resin of the present invention is characterized in that it is obtained by reacting at least a urethane prepolymer having an anionic group with a polyoxyethylene group-containing polyamine.
In the polyurethane resin of the present invention, it is preferable that the anionic group is contained in the urethane prepolymer in an amount of 5 to 200 milliequivalents per 100 g of the urethane prepolymer.

In the polyurethane resin of the present invention, it is preferable that the urethane prepolymer contains polyisocyanate and polyoxyalkylene polyol as raw materials.
In the polyurethane resin of the present invention, it is preferable that the polyoxyethylene group content in the urethane prepolymer is 40% by weight or more.

In the polyurethane resin of the present invention, it is preferable that the polyoxyethylene group content in the polyurethane resin is 40% by weight or more.
The polyurethane resin of the present invention preferably further contains a primary amino group or an alkoxysilyl compound having a primary amino group and a secondary amino group.

The aqueous 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 above-described polyurethane resin.
Moreover, the moisture-permeable resin of the present invention is characterized by containing the above-described hydrophilic modifier and an aqueous resin.

  Further, in the moisture-permeable resin of the present invention, the above-mentioned aqueous resin is a polyurethane emulsion, and the above-mentioned polyurethane emulsion contains a macropolyol as a raw material, and the macropolyol has a carbon number of a polyester polyol, a polycarbonate polyol, and an alkylene group. Is at least one selected from the group consisting of 3 to 10 polyoxypolyalkylene polyols, and the macropolyol is preferably contained in an amount of 50% by weight or more based on the total amount of polyurethane raw materials of the polyurethane emulsion.

  In addition, the method for producing a polyurethane resin of the present invention is characterized in that at least a urethane prepolymer having an anionic group and a polyoxyethylene group-containing polyamine are reacted.

  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 further impart excellent hydrophilicity to the water-based resin. Can do. Therefore, the moisture-permeable resin of the present invention containing the hydrophilic modifier of the present invention and an aqueous resin forms a moisture-permeable and waterproof film on the base fabric by casting on the base fabric. Can be waterproof. As a result, it is effectively used for clothing and the like.

The polyurethane resin of the present invention can be obtained by reacting at least a urethane prepolymer having an anionic group with a polyoxyethylene group-containing polyamine.
In the present invention, the urethane prepolymer having an anionic group is, for example, a urethane prepolymer having an anionic group at the molecular side chain and a free isocyanate group at the molecular end, and a polyisocyanate, a polyol, It can be obtained by reacting with an active hydrogen group-containing compound having an anionic group.

The polyisocyanate is not particularly limited as long as it is usually used in the production of polyurethane resins, and examples thereof include aromatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and derivatives of these diisocyanates. Examples include modified products.
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- Examples include tolylene diisocyanate, 4,4′-toluidine diisocyanate, and 4,4′-diphenyl ether diisocyanate.

Examples of the araliphatic diisocyanate include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof.
Examples of the aliphatic diisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, and 1,3-butylene. Examples include diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate.

  Examples of the 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′-methylenebis (cyclohexyl isocyanate), 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, and the like.

Examples of the polyisocyanate derivatives include dimer, trimer, biuret, allophanate, carbodiimide, uretdione, oxadiazinetrione, polymethylene polyphenyl polyisocyanate (crude MDI, polymeric MDI), and crude TDI described above. Is mentioned.
Furthermore, as a modified polyisocyanate, for example, the above-described polyisocyanate or a polyisocyanate derivative and a polyol (described later) are reacted in an equivalent ratio in which the isocyanate group of the polyisocyanate is in excess of the hydroxyl group of the polyol. The polyol modified body obtained by this is mentioned.

  These polyisocyanates may be used alone or in combination of two or more. Of these polyisocyanates, aliphatic diisocyanates such as hexamethylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 4,4′- are preferable from the viewpoint of side reaction with water and weather resistance of the resin. Alicyclic diisocyanates such as methylene bis (cyclohexyl isocyanate) are used.

Although a polyol will not be restrict | limited especially if it is normally used for manufacture of a polyurethane resin, Preferably, a polyoxyalkylene polyol is used.
Examples of the polyoxyalkylene polyol include a block copolymer or a random copolymer obtained by addition reaction of alkylene oxide using a low molecular weight polyol as an initiator.

  Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,6-hexanediol, neopentyl glycol, alkane (carbon number). 7-22) Diol, diethylene glycol, triethylene glycol, dipropylene glycol, cyclohexanedimethanol, alkane-1,2-diol (carbon number 17-20), hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, Low molecular weight diols such as 2,6-dimethyl-1-octene-3,8-diol, bishydroxyethoxybenzene, xylene glycol, 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, 2,2-bis (hydroxymethyl) And low molecular weight triols such as -3-butanol.

Examples of the alkylene oxide include ethylene oxide and propylene oxide.
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, and specifically, for example, polyethylene glycol having a number average molecular weight of 500 to 3000 is preferably used.

In addition, polyoxyalkylene monools in which a part of the hydroxyl group is masked with a monoalcohol such as methanol or butanol can also be used as long as the chain elongation reaction described below is not inhibited.
Further, as the polyol, a high molecular weight polyol or a low molecular weight polyol other than the polyoxyalkylene polyol can be used. Examples of such a polyol include macropolyols such as polyester polyol, polycaprolactone polyol, and polycarbonate polyol as high molecular weight polyols, and those having a number average molecular weight of 500 to 4000 are preferable. Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,6-hexanediol, neopentyl glycol, alkane (carbon 7-22) Diol, diethylene glycol, triethylene glycol, dipropylene glycol, cyclohexanedimethanol, alkane-1,2-diol (carbon number 17-20), hydrogenated bisphenol A, 1,4-dihydroxy-2-butene 2,6-dimethyl-1-octene-3,8-diol, bishydroxyethoxybenzene, xylene glycol, bishydroxyethylene terephthalate and the like.

In addition, the active hydrogen group-containing compound having an anionic group has an anionic group such as a carboxyl group, a sulfonyl group, a phosphate group, a betaine structure-containing group such as sulfobetaine, and reacts with an isocyanate group. For example, it is a compound containing an active hydrogen group such as a hydroxyl group or an amino group.
Although it does not restrict | limit especially as an active hydrogen group containing compound which has such an anionic group, For example, the compound which has one anionic group and has two or more active hydrogen groups is mentioned. More specifically, examples of the active hydrogen group-containing compound having a carboxyl group include 2,2-dimethylol acetic acid, 2,2-dimethylol lactic acid, 2,2-dimethylol propionic acid, and 2,2-dimethylol butanoic acid. , 2,2-dimethylolbutyric acid, dihydroxycarboxylic acids such as 2,2-dimethylolvaleric acid, and diaminocarboxylic acids such as lysine and arginine.

Examples of the active hydrogen group-containing compound having a sulfonyl group include N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid, 1,3-phenylenediamine-4,6-disulfonic acid, and diaminobutane. Examples include sulfonic acid, 3,6-diamino-2-toluenesulfonic acid, and 2,4-diamino-5-toluenesulfonic acid.
Examples of the active hydrogen group-containing compound having a phosphate group include 2,3-dihydroxypropylphenyl phosphate.

Examples of the active hydrogen group-containing compound having a betaine structure-containing group include a sulfobetaine group-containing compound obtained by reaction of a tertiary amine such as N-methyldiethanolamine with 1,3-propane sultone.
Furthermore, the alkylene oxide modified body obtained by adding alkylene oxides, such as ethylene oxide and a propylene oxide, to the active hydrogen group containing compound which has these anionic groups can also be mentioned.

These active hydrogen group-containing compounds having an anionic group may be used alone or in combination of two or more. Of these active hydrogen group-containing compounds having an anionic group, an active hydrogen group-containing compound having a carboxyl group is preferable.
Further, the active hydrogen group-containing compound having an anionic group is not particularly limited, but in such a ratio that the anionic group is 5 to 200 milliequivalents, more preferably 10 to 100 milliequivalents per 100 g of the urethane prepolymer. It is preferable to mix. By setting the anionic group to 5 milliequivalents or more per 100 g of the urethane prepolymer, the stability can be improved when the urethane prepolymer is dispersed in water. In addition, by making the anionic group 200 milliequivalent or less per 100 g of the urethane prepolymer, more economical production can be realized, and the hydrophilicity can be kept in a suitable range.

  The urethane prepolymer comprises the above-described polyisocyanate, the above-described polyol and the above-described active hydrogen group-containing compound having an anionic group, the active hydrogen group (hydroxyl group and amino group) of the active hydrogen group-containing compound having a polyol and an anionic group. The equivalent ratio of the isocyanate group of the polyisocyanate to the group) (NCO / active hydrogen group) is a ratio exceeding 1, preferably 1.1 to 20, for example, bulk polymerization or solution polymerization, It can be obtained by a known reaction method.

  Further, in this reaction, although not particularly limited, in the obtained urethane prepolymer, the polyoxyethylene group content is 40% by weight or more, further 45 to 95% by weight, and particularly 50 to 90% by weight. Thus, it is preferable to blend each component. If the polyoxyethylene group content in the urethane prepolymer is 40% by weight or more, a higher water swelling ratio can be obtained than in the case of less than 40% by weight, that is, higher hydrophilicity can be imparted. it can. Therefore, when a higher water swelling rate and hydrophilicity-imparting performance are required, the polyoxyethylene group content in the urethane prepolymer is preferably 40% by weight or more.

In bulk polymerization, for example, a polyisocyanate is stirred under a nitrogen stream, an active hydrogen group-containing compound having a polyol and an anionic group is added thereto, and the reaction is carried out at a reaction temperature of 75 to 85 ° C. for about 1 to several hours.
In solution polymerization, for example, a polyisocyanate is stirred in a reaction solvent under a nitrogen stream, and an active hydrogen group-containing compound having a polyol and an anionic group is added thereto, and the reaction temperature is 1 to below the boiling point of the reaction solvent. React for several hours. As the reaction solvent, a low-boiling solvent that is inactive with respect to isocyanate groups and active hydrogen groups, is rich in hydrophilicity, and easy to remove is used. Examples of such reaction solvents include acetone and methyl ethyl ketone. , Ethyl acetate, tetrahydrofuran, acetonitrile and the like.

In this reaction, if necessary, a reaction catalyst can be added, and the unreacted polyisocyanate monomer can be removed from the reaction system using a known means such as distillation or extraction. it can.
In this reaction, amines such as trimethylamine, triethylamine, tri-n-propylamine, tributylamine, triethanolamine, etc., for example, water, before the prepolymer reaction, after the reaction, or after the chain extension reaction described later. It is preferable to form a salt of an anionic group by adding a neutralizing agent selected from inorganic alkali salts such as potassium oxide and sodium hydroxide, and ammonia. The amount of neutralizing agent added is, for example, preferably 0.4 to 1.2 equivalents, and more preferably 0.6 to 1.0 equivalents per equivalent of anionic group. Furthermore, when the prepolymer is dispersed and / or dissolved in water and then subjected to the chain extension reaction described below, the prepolymer is dispersed and / or dissolved in water in order to improve the stability of the prepolymer in water. It is preferable to form a salt of an anionic group before.

The polyurethane resin of the present invention is obtained by reacting the urethane prepolymer having an anionic group thus obtained with a polyamine having a polyoxyethylene group as a chain extender to cause chain extension. Can be obtained.
The polyoxyethylene group-containing polyamine includes, for example, a polyoxyethylene ether diamine represented by the following structural formula (1), a polyoxyalkylene ether diamine represented by the following structural formula (2), and the following structural formula (3 ) And a polyamine represented by the following structural formula (4) are preferably used. The number average molecular weight of these polyoxyethylene ether diamines and polyoxyalkylene ether diamines is, for example, in the range of 100 to 20000, and more preferably in the range of 140 to 10,000. Fat and oil PEG # 1000 diamine (corresponding to structural formula (1)), Huntsman's Jeffamine ED-2003 (corresponding to structural formula (2)), EDR-148 (corresponding to structural formula (3)), XTJ-512 (structure) Formula (4) equivalent).

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

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

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

(In the formula, m and n represent the degree of polymerization.)
In such a reaction, for example, a primary amino group or an alkoxysilyl compound having a primary amino group and a secondary amino group can be used in combination as a chain extender. Specifically, such alkoxysilyl compounds include alkoxysilyl group-containing monoamines such as γ-aminopropyltriethoxysilane and N-phenyl-γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ- Examples include alkoxysilyl group-containing diamines such as aminopropyltrimethoxysilane and N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane. A polyurethane resin obtained by using an alkoxysilyl compound in combination can have a crosslinkable functional group in the molecule, and a resin using the polyurethane resin can increase the molecular weight by crosslinking. For this reason, by controlling the use amount of the alkoxysilyl compound, a polyurethane resin having an arbitrary molecular weight can be obtained, and the solubility in water and the water swellability can be freely controlled.

  Furthermore, in addition to the polyoxyethylene group-containing polyamine and the alkoxysilyl compound, other amines can be used in combination as a chain extender. Examples of such amines include monoamines such as ethylamine, butylamine, isopropylamine, and dibutylamine, such as ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,6-hexamethylenediamine, 1,4-cyclohexanediamine, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophoronediamine), 4,4′-dicyclohexylmethanediamine, 2,5 (2,6) -bis (aminomethyl) Diamines such as bicyclo [2.2.1] heptane, 1,3-bis (aminomethyl) cyclohexane, hydrazine, for example, polyamines such as diethylenetriamine, triethylenetetramine, and tetraethylenepentamine, such as N- (2 -Aminoethyl) Examples include amino alcohols such as tanolamine. These amines used in combination as chain extenders may be used alone or in combination of two or more. As the amines, those in masked form such as ketimine, ketazine or amine salt can also be used.

In addition to the polyoxyethylene group-containing polyamine, in addition to the polyoxyethylene group-containing polyamine, the chain extender can be used in combination with the above-described alkoxysilyl compound and other amines. It is preferably blended so that it is contained in an amount of 40% by weight or more, more preferably 60% by weight or more.
And this reaction should just mix | blend an above-described chain extender, for example after mix | blending a urethane prepolymer and water. The amount of water blended is an amount in which the urethane prepolymer can be dissolved in water, for example, in the range of 20 to 500 parts by weight with respect to 100 parts by weight of the urethane prepolymer. Moreover, the compounding amount of the chain extender is such that the equivalent ratio of the isocyanate group of the urethane prepolymer to the amino group of the chain extender (isocyanate group / amino group) exceeds 1, preferably 1.1-20. Thus, it can be obtained by a known reaction method such as bulk polymerization or solution polymerization.

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

  In the above blending amount, this reaction is specifically performed by first slowly adding water to the urethane prepolymer while stirring or slowly stirring water while stirring the urethane prepolymer. And an urethane prepolymer are added to prepare an aqueous solution of the urethane prepolymer. The stirring is preferably performed using a homomixer or the like so that high shear is imparted.

Next, while stirring the aqueous solution of the urethane prepolymer, a chain extender is dripped quickly (that is, while the reaction between the isocyanate group and water does not proceed).
In this reaction, stirring is preferably performed using a homomixer or the like so as to obtain high shear. Moreover, in order to suppress reaction with the isocyanate group in a urethane prepolymer, and water, it is preferable to control reaction temperature at 5-30 degreeC, for example.

Moreover, after completion | finish of dripping of a chain extender, reaction is completed, for example at normal temperature, stirring further. Thereby, the polyurethane resin of the present invention can be prepared as an aqueous solution and obtained as an aqueous polyurethane resin. The pH of the aqueous polyurethane resin is usually about 7-9.
In addition, after completion | finish of reaction, when the urethane prepolymer is synthesize | combined by solution polymerization, what is necessary is just to remove an organic solvent by heating at appropriate temperature, for example under pressure reduction.

  The polyurethane resin of the present invention thus obtained can be prepared as an aqueous solution, and the aqueous polyurethane resin of the present invention prepared as an aqueous solution exhibits excellent water swellability due to its high hydrophilicity and high stability. Excellent compatibility with other aqueous resins such as aqueous emulsions. And if this water-based polyurethane resin is blended with other water-based resins as a hydrophilic modifier, the water-soluble, moisture-permeable, water-holding, water-swelling and antistatic properties of the water-based resin are remarkable. Therefore, the moisture-permeable resin of the present invention can be obtained by blending the hydrophilic modifier composed of the aqueous polyurethane resin and the aqueous resin.

  Although it does not restrict | limit especially as aqueous resin, As aqueous resin which can be mix | blended in arbitrary ratios, for example, other than aqueous emulsions, such as a vinyl acetate emulsion, an acrylic emulsion, a polyurethane emulsion, an ester emulsion, polyvinyl alcohol resin aqueous solution and polyvinylpyrrolidone resin Examples thereof include aqueous synthetic resin solutions such as aqueous solutions and polyvinyl acetal resin aqueous solutions, for example, natural polymer aqueous solutions such as starch and gelatin. Preferably, a polyurethane emulsion is used.

A polyurethane emulsion reacts an active hydrogen group-containing compound having at least two active hydrogen groups per molecule with an isocyanate group-containing compound having at least two isocyanate groups per molecule to disperse and / or dissolve in water. Can be obtained.
Preferred examples of the active hydrogen group-containing compound include polyester polyols, polycarbonate polyols, and macropolyols such as polyoxypolyalkylene polyols having 3 to 10 carbon atoms in the alkylene group.

  Examples of the polyester polyol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 1,5-pentanediol, 1,4-butylene glycol, 1,6-hexanediol. , One or more of low molecular weight diols such as dipropylene glycol, tripropylene glycol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol and the like, for example, malonic acid, maleic acid, succinic acid, adipic acid, azelaic acid, Generated by reaction with polyvalent carboxylic acids such as tartaric acid, pimelic acid, sebacic acid, oxalic acid, terephthalic acid, isophthalic acid, maleic acid, maleic anhydride, fumaric acid, dimer acid, trimellitic acid or their derivatives And polyester polyols produced by ring-opening polymerization of ε-caprolactone and the like.

  Examples of the polycarbonate polyol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1, One or more diols such as 8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol-A, and, for example, dimethyl carbonate And those obtained by reacting with carbonates such as diphenyl carbonate, ethylene carbonate, and phosgene.

  Examples of the polyoxypolyalkylene polyol having 3 to 10 carbon atoms in the alkylene group include cyclic ethers such as oxetane, tetrahydrofuran, and tetrahydropyran, such as ethylene glycol, diethylene glycol, triethylene glycol, and 1,2-propylene glycol. Low molecular weight diols such as 1,3-butylene glycol, 1,5-pentanediol, 1,4-butylene glycol, 1,6-hexanediol, dipropylene glycol, tripropylene glycol, neopentyl glycol, Examples thereof include those obtained by ring-opening addition polymerization. A polyoxypolyalkylene polyol having 3 to 7 carbon atoms in the alkylene group is preferred, and a polyoxypolyalkylene polyol having 4 to 6 carbon atoms is more preferred.

The molecular weight (number average molecular weight) of these macropolyols is usually about 300 to 10,000, preferably about 500 to 5,000.
Moreover, it is preferable to use a macropolyol as a ratio which contains 50 weight% or more with respect to the total amount of a polyurethane raw material (namely, the raw material of the resin part in a polyurethane emulsion). By including 50% by weight or more of the macropolyol, the mechanical strength of the moisture-permeable resin can be further improved.

  In addition to the macro polyol, examples of the active hydrogen group-containing compound include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 1,5-pentanediol, 1,4 -Low molecular weight glycols such as butylene glycol, 1,6-hexanediol, dipropylene glycol, tripropylene glycol, neopentyl glycol, glycerin, trimethylo pullropane, ethylene oxide, propylene oxide, etc. You may use together the polyoxyalkylene polyol whose carbon number of the alkylene group which carried out addition polymerization is 2 or less.

As an isocyanate group containing compound, the thing similar to the polyisocyanate used for manufacture of a polyurethane resin can be used, Preferably an above-described aliphatic diisocyanate and an above-described alicyclic diisocyanate are mentioned.
In order to make an active hydrogen group containing compound and an isocyanate group containing compound react and to disperse and / or dissolve in water, an emulsifier is used, although not particularly limited. As the emulsifier, for example, in the reaction of an active hydrogen group-containing compound and an isocyanate group-containing compound, it reacts with an internal emulsifier that is reacted with them and modified into a molecular chain, or an active hydrogen group-containing compound or an isocyanate group-containing compound. Without using an external emulsifier, which is mixed separately.

Examples of the internal emulsifier include an active hydrogen group-containing compound having an anionic group, ethylene oxide repeating unit at least 3% by weight or more, and a polymer having at least one active hydrogen group in a molecular weight of 300 to 10,000. The nonionic group-containing compound can be preferably used.
As the external emulsifier, for example, a surfactant such as polyoxyalkylene alkylphenyl ether, alkylsulfuric acid metal salt, linear alkylbenzenesulfonic acid metal salt and the like can be suitably used.

  These emulsifiers are used in an amount of 15% by weight or less based on the polyurethane raw material, preferably an internal emulsifier, and more preferably an active hydrogen group-containing compound having an anionic group. The compounding ratio of the active hydrogen group-containing compound and the isocyanate group-containing compound is the equivalent ratio of the isocyanate group of the isocyanate group-containing compound to the active hydrogen group (hydroxyl group, amino group, etc.) of the active hydrogen group-containing compound (NCO / active hydrogen). Group) 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 1 or more, after the dispersion and / or dissolution in water, the chain is elongated using a chain extender such as amines. Also good. As the amines, the same amines used in the chain elongation of the polyurethane resin can be used. Preferably, monoamines such as ethylamine, butylamine, isopropylamine, dibutylamine, for example, ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,6-hexamethylenediamine, 1,4-cyclohexane Diamine, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophoronediamine), 4,4'-dicyclohexylmethanediamine, 2,5 (2,6) -bis (aminomethyl) bicyclo [2.2 .1] Diamines such as heptane, 1,3-bis (aminomethyl) cyclohexane, hydrazine, for example, polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, for example, N- (2-aminoethyl) ethanol Amine Any amino alcohols, alkoxysilyl group-containing monoamines such as γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N- Examples include alkoxysilyl group-containing diamines such as β (aminoethyl) γ-aminopropylmethyldimethoxysilane.

In addition, the aqueous resin has a tensile strength of 6 MPa or more, more preferably 8 MPa or more, and more preferably 10 MPa or more as a mechanical strength when cast (for example, when cast with a width of 10 mm and a thickness of 0.1 mm). The elongation is preferably 200% or more, more preferably 300% or more, and further preferably 400% or more.
The aqueous resin preferably has a water swelling rate of 20% or less when cast (for example, when cast at a width of 10 mm and a thickness of 0.1 mm), more preferably 10% or less. Furthermore, the thing of 5% or less is preferable.

And the moisture-permeable resin of this invention can be obtained by mix | blending the above-mentioned hydrophilic modifier with such aqueous resin. Further, in the blending of the hydrophilic modifier and the aqueous resin, a compatibilizing agent such as N-methylpyrrolidone or N, N-dimethylformamide may be blended together with these.
The blending ratio of the hydrophilic modifier is, for example, 20 to 80% by weight based on the solid content of the moisture-permeable resin (the total of the resin component in the aqueous resin and the resin component in the hydrophilic modifier), Preferably, it is 30 to 70% by weight. If the blending ratio of the hydrophilic modifier is less than 20% by weight with respect to the solid content of the moisture-permeable resin, the moisture permeability of the film obtained by casting may be lowered, and if it exceeds 80% by weight. The resin strength of the film obtained by casting may be lowered.

The moisture-permeable resin of the present invention can be used to obtain a moisture-permeable and waterproof film by casting, and is used for, for example, clothing that has been moisture-permeable and waterproofed by casting on a base fabric. A moisture permeable waterproof material can be obtained.
In addition, although the film | membrane which has moisture-permeable waterproof property has a microporous thing and a nonporous thing, any thing may be sufficient as it.

Examples of the base fabric include woven fabrics, knitted fabrics, and nonwoven fabrics made of fibers such as polyester, nylon, and cotton.
Various methods are used for casting the moisture permeable resin on the base fabric, and there are a laminating method, a direct coating method, and the like, which can be appropriately selected depending on the application. For example, in the case of the laminating method, there is a method in which a moisture-permeable resin is applied to the surface of a release paper and heat-treated, and then the release paper is laminated on a fabric and heat-sealed. In the case of the direct coating method, a normal coating method, for example, a method of directly applying to the surface of the base fabric or the release paper using a knife coater or the like can be mentioned.

By such casting, the surface of the base fabric is covered with a moisture-permeable waterproof coating made of a moisture-permeable resin, whereby the surface of the base fabric is subjected to a waterproof treatment.
Thus, the moisture-permeable waterproof fabric is used for clothing as a moisture-permeable waterproof material as described above.
Moisture-permeable and waterproof is the performance that the film does not allow rain or other water to pass through, but allows moisture (water vapor) to pass through. For example, in clothing applications, water vapor from sweating from the body is released outside the clothing. And preventing rain from entering the clothes.

  Further, the moisture-permeable resin of the present invention needs to sufficiently ensure the follow-up performance to the base fabric, the wear resistance performance, the tear resistance performance, and the like. Therefore, the mechanical strength of the film formed by casting the moisture-permeable resin of the present invention is preferably a tensile strength of 3 MPa or more, more preferably 4 MPa or more, and further preferably 6 MPa or more, and an elongation rate of 200% or more, further 300%. In addition, 400% or more is preferable.

Furthermore, as the moisture permeability of the moisture permeable resin of the present invention, the moisture permeability in the moisture permeability test method B (conforming to JIS L1099) is 10,000 (g / m ² · 24 hrs) when the thickness of the cast film is 0.03 mm. ) Or more.
The polyurethane resin, water-based polyurethane resin, hydrophilic modifier, and moisture-permeable resin of the present invention include a curing catalyst and various additives such as a plasticizer within a range that does not impair the excellent effects of the present invention described above. Antifoaming agent, leveling agent, antifungal agent, rust inhibitor, matting agent, flame retardant, thixotropic agent, tackifier, thickener, lubricant, antistatic agent, surfactant, reaction retarder, oxidation An inhibitor, an ultraviolet absorber, a hydrolysis inhibitor, a weather resistance stabilizer, a dye, an inorganic pigment, an organic pigment, an extender pigment, a curing agent, an anti-tack agent, and the like can be appropriately blended.

The curing agent is not particularly limited as long as it is a commonly used curing agent, and examples thereof include an isocyanate curing agent having an isocyanate group. Preferably, for example, a water-dispersible polyisocyanate is used. System curing agents and the like.
Moreover, an inorganic powder is mentioned as an anti-tack agent, Preferably, a silicon dioxide powder etc. are mentioned, for example.

The mixing ratio of these various additives is appropriately selected depending on the purpose and application.
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 apparel applications, but for various applications such as automobiles, electronic devices, building materials, artificial leather, and film processing. Can also be used.

Hereinafter, the present invention will be described more specifically with reference to Examples, Comparative Examples, and Synthesis Examples, but these do not limit the scope of the present invention.
Example 1
(Preparation of urethane prepolymer)
In a stirred reactor, 1,3-bis (isocyanatomethyl) cyclohexane (trade name: Takenate 600, manufactured by Mitsui Takeda Chemical) 8.3 parts by weight, ethylene glycol 1.2 parts by weight, dimethylolpropion Acid (trade name: Nikkamer PA, manufactured by Nippon Kasei Co., Ltd.) 0.7 parts by weight and acetonitrile 2.5 parts by weight were charged, the reaction solution temperature was adjusted to 70 to 75 ° C., and the reaction rate was reacted to 99% or more. Thus, a urethane prepolymer having an anionic group at the molecular side chain and a free isocyanate group at the molecular end was obtained. The carboxylic acid per 100 g of this urethane prepolymer was 49 meq.

(Preparation of aqueous polyurethane resin)
The urethane 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, this was gradually added to 100 parts by weight of water at 25 ° C. to obtain an aqueous solution of urethane prepolymer, and then immediately, a polyoxyethylene group-containing diamine (trade name: PEG # 1000 diamine, manufactured by NOF Corporation) ) 70.5 parts by weight of a 20% by weight aqueous solution and 3.0 parts by weight of a 10% by weight hydrazine aqueous solution were successively added dropwise to cause a chain extension reaction. In addition, the reaction liquid temperature at this time was adjusted to 25-30 degreeC. Thereafter, stirring was continued at 25-30 ° C. for 3 hours, and then acetonitrile and water were partially removed at 40-50 ° C. under reduced pressure to obtain an aqueous polyurethane having a solid content of 20% by weight and a viscosity of 190 mPa · s. A resin was obtained.

Examples 2-5
In the formulation shown in Table 1, an aqueous polyurethane resin was obtained by the same operation as in Example 1.
Comparative Example 1
In the formulation shown in Table 1, an aqueous polyurethane resin was prepared by the same operation as in Example 1, but finally gelled.

Comparative Example 2
In the formulation shown in Table 1, an aqueous polyurethane resin was obtained by the same operation as in Example 1.
Comparative Example 3
In a stirred reactor, 47.1 parts by weight of Takenate 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 added uniformly. Dispersed. Thereafter, while stirring the dispersion, a polyoxyethylene-containing diamine having an amine value of 101 (trade name: PEG # 1000) at a ratio of an equivalent ratio of isocyanate group to amino group (isocyanate group / amino group) of 1.0. 54.3 parts by weight of a 30% by weight aqueous solution (diamine, manufactured by NOF Corporation) was slowly added. Thereafter, the reaction was followed at 25 ° C., but the stability gradually decreased with the reaction and finally gelled.

The abbreviations and product names in Table 1 are as follows. The formulations in Table 1 are shown in parts by weight.
H6XDI: 1,3-bis (isocyanatomethyl) cyclohexane, trade name Takenate 600, H12MDI manufactured by Mitsui Takeda Chemical Co., Ltd .: 4,4′-methylenebis (cyclohexyl isocyanate), trade name Desmodur W, WD-725 manufactured by Bayer Water dispersible polyisocyanate (isocyanate group content 15.8%), trade name Takenate WD-725, Mitsui Takeda Chemical Co., Ltd. PEG1000: Polyethylene glycol (OH number 112), NOF Corporation EG: Ethylene glycol DMPA: dimethylolpropion Acid, trade name Nikkamer PA, Nippon Kasei Co., Ltd. MPEG diol: methoxy modified polyethylene glycol branched diol (OH number 89), Mitsui Takeda Chemical Co., Ltd. TEA: Triethylamine NaOH: Sodium hydroxide PEG # 1000 : Polyoxyethylene diamine (amine value 101), manufactured by NOF Corporation JEFFAMINE ED-2003: polyoxyalkylene diamine (amine value 53.9), Huntsman Corp., 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. Evaluation 1) Water swelling test Water-based polyurethane resin of each Example and Comparative Example 2 (solid content) 20% by weight) was cast to form a dry transparent film having a thickness of 1 mm. Then, this film was cut into 10 cm × 10 cm to obtain a sample.

For casting, an aqueous polyurethane resin was applied to the surface of the release paper using a knife coater, and a heat treatment was performed 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 taken as the water swelling rate. (By the way, a water swelling rate of 100% indicates that the length of the side has increased by a factor of 2 both vertically and horizontally.) The results are shown in Table 1.
2) Compatibility test Takelac W-6010 (manufactured by Mitsui Takeda Chemical Co., Ltd., water dispersion of polycarbonate polyurethane resin, solid content 30 wt%, 30 mPa · s) and W-6020 (Mitsui Takeda Chemical Co., Ltd.) as aqueous resins Manufactured, water dispersion of polyether-based polyurethane resin, solid content 30% by weight, 20 mPa · s), and 100 parts by weight of each of these water-based polyurethane resins of Examples 1 to 5 and Comparative Example 2 150 parts by weight were mixed, and the stability of the mixed solution was visually confirmed. The results are shown in Table 1. In Table 1, “◯” indicates a state in which the components are uniformly mixed, and “x” indicates a state in which the phases are separated.
3) Moisture permeability test method A The aqueous polyurethane resin (solid content 20% by weight) of each Example and Comparative Example 2 was cast to form a dry transparent film having a thickness of 0.05 mm. Then, the moisture permeability of this film was evaluated according to JIS L1099-A1 method. The results are shown in Table 1.

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

Synthesis example 1
(Synthesis of aqueous resin)
In a stirred reactor, 11.75 parts by weight of 4,4′-methylenebis (cyclohexyl isocyanate) and polyoxytetramethylene glycol having a molecular weight of 2000 (number average molecular weight) (trade name: PTG2000SN, manufactured by Hodogaya Chemical Co., Ltd.) 39 parts by weight, dimethylol butanoic acid (trade name: Nikkamer BA, Nippon Kasei Co., Ltd.) 2.37 parts by weight and acetone 20.4 parts by weight were charged, and the reaction solution temperature was adjusted to 53 to 55 ° C. Add a small amount of stannous octylate (trade name: Stanocto, manufactured by API Corporation) as a reaction catalyst, react to a reaction rate of 99% or more, have an anionic group in the molecular side chain, and free at the molecular end A urethane prepolymer having an isocyanate group was obtained.

  The urethane prepolymer was cooled to 30 ° C., 1.46 parts by weight of triethylamine (carboxylic acid neutralization ratio of 0.9) was added, and the mixture was sufficiently stirred for neutralization. Thereafter, this was gradually added to 100 parts by weight of water at 25 ° C. to obtain an aqueous solution of a urethane prepolymer, and then 1.96 parts by weight of isophoronediamine was quickly added dropwise to cause a chain extension reaction. In addition, the reaction liquid temperature at this time was adjusted to 25-30 degreeC. Then, after continuing stirring at 25-30 degreeC for 3 hours, the polyurethane emulsion of 33 weight% of solid content and a viscosity of 25 mPa * s was obtained by removing acetone under 40-50 degreeC and pressure reduction.

Synthesis Examples 2 and 3
In the formulation shown in Table 2, a polyurethane emulsion was obtained in the same manner as in Synthesis Example 1.
The abbreviations and product names in Table 2 are as follows. The formulations in Table 2 are shown in parts by weight.

PTG-1: Polyoxytetramethylene glycol having a number average molecular weight of 2000, trade name PTG-2000SN, Ester-1 manufactured by Hodogaya Chemical Co., Ltd. Polyester polyol having a number average molecular weight of 2000, trade name Takelac U-5620, DMBA manufactured by Mitsui Takeda Chemical Co., Ltd. : Dimethylol butanoic acid, trade name Nikkamer BA, Nippon Kasei Co., Ltd. IPDA: isophorone diamine, Degussa Huls Co., Ltd. Evaluation 4) Mechanical strength test Polyurethane emulsion of each synthesis example (solid content 33% by weight) was cast, A dry transparent film having a thickness of 0.1 mm was formed. Then, this film was cut into 1 cm strips and subjected to a tensile test under the condition of a pulling speed of 200 mm / min, and the stress and elongation at break were measured. The results are shown in Table 2.

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 aqueous polyurethane resin obtained in Example 3 and silicon dioxide (trade name: Silicia 310P, anti-tacking agent, manufactured by Fuji Silysia) as additive 1 were sufficiently stirred and mixed at a weight ratio of 60: 2, followed by The mixture and the aqueous resin obtained in Synthesis Example 1 were mixed at 62:38 to obtain a moisture-permeable resin. The solid content concentration at this time was 26.5% by weight.

Examples 8 and 9
In the formulation shown in Table 3, a moisture-permeable resin was obtained by the same operation as in Example 7.
Example 10
The aqueous polyurethane resin obtained in Example 3 and the aqueous 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.)) as additive 2 was mixed with this moisture-permeable resin at a weight ratio of 98: 2. did.

Evaluation 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 state in which the components are uniformly mixed, and “x” indicates a state in which the phases are separated.

6) Moisture permeability test method B The moisture permeable resin of each example was cast to form a dry transparent film having a thickness of 0.03 mm. Then, the moisture permeability of this film was evaluated according to JIS L1099-B1 method. The results are shown in Table 3.
7) Mechanical strength The moisture-permeable resin of each Example was cast to form a dry transparent film having a thickness of 0.03 mm. Thereafter, the same operation as in 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.

In addition, the symbol in Table 3 is as follows. The formulations in Table 3 are shown in parts by weight.
Additive 1: Silicon dioxide (Anti-tacking agent, trade name: Cicilia 310P, manufactured by Fuji Silysia)
Additive 2: WD-725 (Water-dispersible polyisocyanate: isocyanate group content 15.8%, manufactured by Mitsui Takeda Chemical Co., Ltd.)

  The moisture-permeable resin obtained in Examples 6 to 9 has good compatibility, mechanical strength, and extremely good moisture permeability, and the moisture-permeable resin obtained in Example 10 contains a curing agent. It can be seen that, while having a tough mechanical strength, it has good moisture permeability and is suitable for use as a moisture-permeable and waterproof coating.

Claims (11)

A polyurethane resin obtained by reacting at least a urethane prepolymer having an anionic group with a polyoxyethylene group-containing polyamine. The polyurethane resin according to claim 1, wherein the anionic group is contained in the urethane prepolymer in an amount of 5 to 200 milliequivalents per 100 g of the urethane prepolymer. The polyurethane resin according to claim 1 or 2, wherein the urethane prepolymer contains polyisocyanate and polyoxyalkylene polyol as raw materials. The polyurethane resin according to any one of claims 1 to 3, wherein a content of polyoxyethylene groups in the urethane prepolymer is 40% by weight or more. The polyurethane resin according to claim 1, wherein the polyurethane resin has a polyoxyethylene group content of 40% by weight or more. The raw material further contains a primary amino group or an alkoxysilyl compound having a primary amino group and a secondary amino group, according to any one of claims 1 to 5. Polyurethane resin. An aqueous polyurethane resin, wherein the polyurethane resin according to any one of claims 1 to 6 is dispersed and / or dissolved in water. A hydrophilic modifier comprising the aqueous polyurethane resin according to claim 7. A moisture-permeable resin comprising the hydrophilic modifier according to claim 8 and an aqueous resin. The aqueous resin is a polyurethane emulsion;
The polyurethane emulsion contains a macropolyol as a raw material,
The macro polyol is at least one selected from the group consisting of a polyester polyol, a polycarbonate polyol, and a polyoxypolyalkylene polyol having 3 to 10 carbon atoms in an alkylene group,
10. The moisture-permeable resin according to claim 9, wherein the macropolyol is contained in an amount of 50% by weight or more based on a total amount of polyurethane raw materials of the polyurethane emulsion. A method for producing a polyurethane resin, comprising reacting at least a urethane prepolymer having an anionic group and a polyoxyethylene group-containing polyamine.