JPH0753661A - Aqueous polyurethane and aqueous resin composition containing the same - Google Patents

Abstract

(57) [Summary] [Object] An object of the present invention is to provide an aqueous polyurethane excellent in storage stability, water resistance, adhesion to a substrate, and pigment dispersibility. [Structure] An aqueous polyurethane obtained by reacting an alkylene oxide addition polymer (A) represented by the following general formula with an organic diisocyanate compound (B). _{X- (O-C 2 H 4} ) m - (O-Y) n -OCH 2 CH
(OH) CH ₂ OH (In the formula, X represents a hydrocarbon group having 1 to 4 carbon atoms, Y represents a hydrocarbon group having 3 to 8 carbon atoms, m is an integer of 1 to 100, and n is Represents a non-negative integer no greater than m.) [Effect] The aqueous polyurethane of the present invention has various and wide-ranging uses that cannot be applied to conventional aqueous polyurethane dispersions, that is, printing inks, paints, adhesives, fiber treatment agents. ,
It can be used as a surface treating agent, an emulsifier for resin-based or water-based polymerization reactions, and the like.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an aqueous polyurethane useful as a constituent resin for paints, printing inks, adhesives, fiber treatment agents, surface treatment agents, etc., or as a high molecular weight emulsifier, and an essential resin component of said polyurethane. And an aqueous resin composition containing More specifically, it relates to an aqueous polyurethane having excellent storage stability, water resistance, adhesion to a substrate, and pigment dispersibility, and an aqueous resin composition containing the same.

[0002]

2. Description of the Related Art Conventionally, in paints, printing inks, adhesives and the like, it has been customary to dissolve a resin component or the like in an organic solvent or the like in order to ensure adaptability during processing such as painting and printing. However, in recent years, it has become an urgent need to make paints, printing inks, and the like water-based from the viewpoints of labor work environment, global environment conservation, and the like. On the other hand, polyurethane resins are used in various fields such as paints and printing inks, and attempts to use water-based polyurethane resins for paints, inks and the like have been actively made in such a social environment. Generally, when a polyurethane resin is made water-based, an ionic group represented by a carboxyl group or a tertiary amino group is introduced into the resin molecule, and these are neutralized with a volatile base or acid to form a salt. It imparts hydrophilicity. In this case, depending on the concentration of the ionic groups in the resin, the degree of neutralization, the hydrophilicity of the resin skeleton, and the like, the dispersion type or the dissolution type is adopted.

When an aqueous ionic functional group is used alone to obtain an aqueous polyurethane resin, its adhesion to a substrate and pigment dispersibility are relatively good, but its storage stability and water resistance are poor. Therefore, a method of compensating for these drawbacks by using a nonionic functional group alone or in combination with an ionic functional group has been proposed. For example, a method of reacting a polyethylene glycol or a polyethylene glycol monoalkyl ether with an organic diisocyanate to introduce a polyoxyethylene unit into the main chain or at the chain end is conventionally known. The water-based polyurethane obtained by this method has good storage stability and water resistance, but has a drawback that the adhesiveness to the substrate and the pigment dispersibility are insufficient and satisfactory performance cannot be obtained.

Further, JP-A-1-104612 and JP-A-1-10
Japanese Patent No. 4613 discloses a method of introducing a polyoxyethylene chain into a side chain. Specifically, the product obtained by reacting 1 mol of organic diisocyanate with about 1 mol of polyethylene glycol monoether and then reacting with about 1 mol of dialkanolamine is further reacted with organic diisocyanate. Introduced into the side chain. However, the aqueous dispersion of polyurethane obtained by this method has drawbacks such as unreacted organic diisocyanate remaining during the synthesis of the intermediate, resulting in a decrease in fluidity due to thickening and, in some cases, polyurethane gelation. Was.

[0005]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention The inventors of the present invention have conducted extensive studies to improve the above-mentioned drawbacks of the aqueous polyurethane resin, and as a result, by reacting a specific alkylene oxide addition polymer with a diisocyanate compound, storage The present inventors have found that a water-dispersible or water-soluble polyurethane having excellent stability, water resistance, adhesion to a substrate, and pigment dispersibility can be obtained, and the present invention has been completed. Further, it has been found that an aqueous dispersion containing the polyurethane as an essential component satisfies the above-mentioned various properties.

[0006]

The present invention comprises an aqueous polyurethane obtained by reacting an alkylene oxide addition polymer (A) represented by the following general formula with an organic diisocyanate compound (B) and a polyurethane containing the same. The following aqueous resin composition is provided. Further, an alkylene oxide addition polymer (A), an organic diisocyanate compound (B),
Compound (C) having two or less active hydrogens reactive with an isocyanate group and a carboxyl group or a tertiary amino group
When a carboxyl group is present in the molecule of (C) in the aqueous polyurethane obtained by reacting with, it is essential that the active hydrogen coexisting in the molecule is more reactive with the isocyanate group than the carboxyl group. Provided are an aqueous polyurethane and an aqueous resin composition containing the polyurethane. _{X- (O-C 2 H 4} ) m - (O-Y) n -OCH 2 CH
(OH) CH ₂ OH (In the formula, X represents a hydrocarbon group having 1 to 4 carbon atoms, Y represents a hydrocarbon group having 3 to 8 carbon atoms, m is an integer of 1 to 100, and n is Represents a non-negative integer less than or equal to m.)

In the above general formula, when the hydrocarbon group represented by X has 5 or more carbon atoms, the hydrophilicity of the obtained polyurethane and the adhesion to the substrate may be impaired, which is not preferable. Further, the number m of the oxyethylene repeating units represented by (O—C ₂ H ₄ ) in the formula must be in the range of 1 to 100. When n exceeds 100, the water resistance and mechanical properties of the resulting polyurethane may be impaired, which is not preferable. Further, if the number of carbon atoms of the hydrocarbon group represented by Y is 9 or more, the hydrophilicity and mechanical properties of the resulting polyurethane may be impaired, which is not preferable. It is necessary that the number n of (O-Y) repeating units does not exceed m. When n exceeds m, the hydrophilicity of the obtained polyurethane may be insufficient, which is not preferable.

Although the (O—C ₂ H ₄ ) and (O—Y) repeating units are described as shown by the formula for the sake of convenience, they need not necessarily be distributed with blockiness. Specific examples of the alkylene oxide addition polymer (A) include:
Examples thereof include poly (oxyethylene) monomethyl ether glycidol adducts, poly (oxyethylene) monoethyl glycidyl ether hydrates, and poly (oxyethylene / oxypropylene / oxybutylene) monobutyl ether glycidol adducts.

Examples of the organic diisocyanate compound (B) include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, isophorone diisocyanate, dimeryl diisocyanate, lysine diisocyanate and water. Appendix 4,
Examples thereof include diisocyanates such as 4′-diphenylmethane diisocyanate and hydrogenated tolylene diisocyanate, or both-end isocyanate adducts of these with glycols or diamines. These conventionally known organic diisocyanates may be used alone or in combination of two or more. It can be used as a mixture.

Further, the aqueous polyurethane of the present invention has good water solubility and water dispersibility because it has a hydrophilic chain mainly composed of an ethylene oxide adduct in its side chain, but since it further improves hydrophilicity, Other than the above-mentioned polyalkylene oxide addition polymer (A), a compound (C) having two or less active hydrogens reactive with an isocyanate group and a carboxyl group or a tertiary amino group can be contained in the resin molecule. . When the active hydrogen compound (C) has a carboxyl group in the molecule, active hydrogen coexisting in the molecule needs to be more reactive than the carboxyl group with respect to the isocyanate group. When the active hydrogen is inferior to the carboxyl group in reactivity with the isocyanate group, the carboxyl group is not introduced into the obtained polyurethane resin, and the expected hydrophilicity may not be obtained depending on the method of using the aqueous polyurethane. .

The compound having two or less active hydrogens and carboxyl groups reactive with an isocyanate group is
Dimethylolpropionic acid, amino acids and their oxyalkylation products and polyesterification products, diaminocarboxylic acids, dimethylethanolamine and the like can be mentioned. Examples of the compound having two or less active hydrogens reactive with an isocyanate group and a tertiary amino group include methyldiethanolamine and ethyldiethanolamine. These can be used alone or as a mixture of two or more kinds.

If desired, the aqueous polyurethane of the present invention may be obtained by using a compound other than the above-mentioned (A) and (C) in combination with a compound having two or less active hydrogens reactive with an isocyanate group. it can. Examples of such a compound include ethylene glycol, propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, butenediol, methyl-1,5-pentanediol, hexanediol, cyclohexanediol, cyclohexanedimethanol, Low molecular weight diols such as bisphenol A, bisphenol F, diethylene glycol and dipropylene glycol, polyethylene glycol, polyprorylene glycol, polyethylene-polypropylene glycol, polybutylene glycol, polyalkylene glycols such as polytetramethylene glycol, and known polyester polyols, 5- Polyester polyol containing sodium sulfoisophthalate unit, polycarbonate polyol, ethylenediamine, trimethylene Diamine, tetramethylenediamine, pentamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, xylylenediamine, 1,4-diaminocyclohexane, isophoronediamine, phenylenediamine and the like, but are not limited thereto. Not something. These compounds can be appropriately selected and used according to various properties of the polyurethane to be obtained and intended use.

The aqueous polyurethane of the present invention has the above-mentioned (A),
It can be obtained by reacting the components (B) and (C) according to a conventionally known polyurethane synthesis method. That is, a one-shot method in which all components are charged in a batch and reacted, or a prepolymer method in which a chain extender is used to increase the molecular weight after a terminal isocyanate prepolymer is generated can be used. The latter method is particularly preferable. In the prepolymer method, the polyalkylene oxide addition polymer (A) and the other active hydrogen compound (C) are added in excess of the organic diisocyanate (B).
And room temperature to 140 ° C., preferably 40
The reaction is carried out at -100 ° C to prepare a prepolymer having a terminal isocyanate group.

For the preparation of the prepolymer, if necessary, conventionally known urethanization catalysts such as dibutyltin dilaurate, tin octylate, triethylamine, N, N-dimethylbenzylamine, sodium hydroxide, diethylzinc tetra (n) are used. -Butoxy) Titanium or the like can be used. Furthermore, the preparation of the prepolymer can be carried out without solvent,
It is also possible to use an organic solvent which is inactive with respect to isocyanate groups in order to make the reaction uniform and adjust the viscosity. Specific examples of these organic solvents include acetone, methyl ethyl ketone, ethyl acetate, dioxane, acetonitrile, tetrahydrofuran and the like. If these organic solvents remain in the polyurethane or the aqueous resin composition without any problem, they can be left as they are, or they may be removed after the reaction is completed by a heating operation or a pressure reducing operation.

The aqueous polyurethane of the present invention can be produced by chain-extending the isocyanate-terminated polyurethane prepolymer with a so-called chain extender containing active hydrogen. At that time, after chain extension, it can be dispersed or dissolved in water by a conventionally known method, and the used organic solvent can be removed if necessary, or while the prepolymer is dispersed in water or after the chain is dispersed. The chain can be extended with an extender. Upon chain extension, the prepolymer solution may be added to water with stirring, or water may be added to the prepolymer solution with stirring. These reaction methods can be selected according to the purpose. When an ionic functional group such as a carboxyl group or a tertiary amino group is present in the prepolymer, the ionic functional group can be converted into a salt with an appropriate counter ion.

As the chain extender, ethylene glycol,
A polyol such as butanediol, an amino alcohol,
Primary or secondary aliphatic, alicyclic, aromatic, aralkyl or heterocyclic amines such as ethylenediamine, diaminodiphenylmethane, isophoronediamine and piperazine, especially hydrazine compounds such as diamine, hydrazine and adipic acid bishydrazide, water Etc. can be used alone or in combination of two or more.

The amount of the chain extender used is preferably 0.7 to 1.1 with respect to 1 equivalent of free isocyanate groups in the prepolymer. Outside this range, adverse effects such as deterioration in storage stability and film strength of the resulting polyurethane and discoloration are observed. However, when the chain extender is water, it cannot be applied because it is in large excess with respect to the isocyanate. The chain extension reaction can be carried out at room temperature to 95 ° C. depending on the reactivity between active hydrogen and isocyanate. Particularly when the chain extender is amine or hydrazine, it is preferably carried out at room temperature to 50 ° C.

Although the aqueous polyurethane of the present invention can be used as it is after being dispersed in water or made water-soluble, it is usually azeotropically distilled with water by heating or depressurizing for the purpose of removing various organic solvents used together. It is common to employ a step of removing. The aqueous polyurethane of the present invention is
Even as it is, a resin film can be formed on any substrate such as wood, metal, glass, fiber, leather, plastic film and foam by a conventional method such as printing, coating, impregnation and spraying. The water-based polyurethane of the present invention can also be used as an emulsifier for resin-based or water-based polymerization reaction, or as an adhesive for polyethylene, polypropylene, polyester, nylon, polyurethane, leather and the like.

Further, the aqueous polyurethane of the present invention contains other conventional components such as organic solvents, coloring pigments, dyes, magnetic powders, fillers, emulsifiers, defoamers, surfactants, dispersion aids,
Thickener, heat stabilizer, leveling agent, anti-crater agent,
Anti-settling agent, UV absorber, antioxidant, flame retardant, etc., and other water-dispersible or water-soluble resin components are added, and as a water-based resin composition, printing ink, paint, adhesive, fiber treatment agent, surface It can be applied to treating agents and the like. Examples of the other water-dispersible or water-soluble resin component include aqueous polyester, aqueous acrylic resin, aqueous epoxy resin, aqueous melamine resin, acrylic aqueous dispersion, chlorinated polypropylene aqueous dispersion, and cellulose resin aqueous dispersion. be able to.

Further, by combining an ordinary crosslinking agent with the aqueous polyurethane of the present invention, a cured coating film having excellent film strength and chemical resistance can be formed. For example, when a carboxyl group is introduced into the aqueous polyurethane of the present invention, a polyaziridine compound, a polyepoxy compound, a polycarbodiimide compound, a metal chelate compound,
Polyoxazoline compounds, polyisocyanates, blocked polyisocyanates, partially or fully etherified amino resins and the like can be used as crosslinking agents. When an amino group or a hydrazine group is introduced into the terminal of the aqueous polyurethane of the present invention, polyacetoacetic acid ester or polycarbonyl compound can be used. Further, the reactive functional group of the cross-linking agent can be introduced into the resin of the present invention alone or in two or more kinds of resins, and the cross-linking reaction can be carried out by combining the two. These cross-linking reactions can take place at room temperature or can be accelerated by heating or addition of known reaction catalysts.

[0021]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples without departing from the technical idea of the present invention. In the example,
"Parts" means "parts by weight" and "%" means "% by weight". <Example 1> 100 parts of polyethylene glycol monomethyl ether (average molecular weight 1000) and 3 parts of potassium hydroxide were placed in a four-necked flask equipped with a thermometer, a stirrer and a reflux condenser, and heated to 120 ° C under reduced pressure. Dehydrate. afterwards,
Gradually add 7.4 parts of glycidol and react for about 3 hours.
After cooling, the added potassium hydroxide was neutralized with acetic acid, the resulting salt was filtered and the alkylene oxide addition polymer (m = 22, n =
I got 0). 400 parts of methyl ethyl ketone and 110 parts of polybutylene adipate (molecular weight 2000) are put into this, and heated to 80 ° C. under a nitrogen atmosphere while stirring. When the temperature stabilizes,
62 parts of isophorone diisocyanate was added dropwise and reacted at 80 ° C. for 3 hours to obtain an isocyanate-terminated prepolymer solution. The temperature of the reaction solution is further cooled to 30 ° C or lower, a mixed solution of 23 parts of isophoronediamine, 1 part of dibutylamine and 50 parts of methyl ethyl ketone is added dropwise over 1 hour, and then the temperature is raised to 50 ° C to end the chain extension reaction. did. Next, a mixture of 800 parts of water and 10 parts of dimethylethanolamine was added dropwise to obtain an aqueous dispersion of polyurethane. The resulting aqueous dispersion is under reduced pressure
The solvent was removed at 60 ° C to obtain a polyurethane water dispersion (a) having a polyoxyethylene unit in its side chain.
The nonvolatile content of the polyurethane water dispersion (a) is about 40%,
It contains about 35% of side chain type polyalkylene oxide units in the nonvolatile content.

<Example 2> 400 parts of methyl ethyl ketone, 200 parts of polybutylene adipate (molecular weight 2000) and dimethylol propion were added to the alkylene oxide addition polymer (m = 22, n = 0) obtained in the same manner as in Example 1. Add 6.7 parts of acid and heat to 80 ° C under nitrogen atmosphere with stirring. When the temperature became stable, 85 parts of isophorone diisocyanate was dropped and reacted at 80 ° C. for 3 hours to obtain an isocyanate-terminated prepolymer solution. The temperature of the reaction solution is further cooled to 30 ° C or lower, a mixed solution of 21 parts of isophoronediamine, 6 parts of dimethylethanolamine and 50 parts of methyl ethyl ketone is added dropwise over 1 hour, and then the temperature is raised to 50 ° C to carry out a chain extension reaction. finished. Next, 750 parts of water was added dropwise to obtain a polyurethane emulsion. The resulting emulsion was desolvated at 60 ° C. under reduced pressure to obtain a polyurethane aqueous solution (b) having a polyoxyethylene unit in its side chain. The non-volatile content of the aqueous polyurethane solution (b) is about 40%, and the non-volatile content contains about 25% of side chain type polyalkylene oxide units.

Example 3 20 parts of ethylene glycol monobutyl ether and 1 part of potassium hydroxide were placed in a pressure resistant reactor.
Add 120 parts and heat to 120 ℃, and dehydrate under reduced pressure with a slight flow of dry nitrogen gas. After that, 5 atmospheric pressure, 120 ℃
50 parts of ethylene oxide was gradually added while maintaining, and after reacting for about 30 minutes, a mixture of 50 parts of ethylene oxide and 100 parts of propylene oxide was gradually added, and then 50 parts of ethylene oxide was added, After reacting for about 2 hours, 12.5 parts of glycidol are added and further 2
After reacting for a period of time and cooling, the added potassium hydroxide was neutralized with acetic acid, and the formed salt was filtered to obtain a polyalkylene oxide addition polymer (m = 20, n = 0). 200 parts of polybutylene adipate glycol (molecular weight of about 2000), 21.5 parts of methyldiethanolamine and 300 parts of methyl ethyl ketone are put into this and heated to 80 ° C. under a nitrogen atmosphere while stirring.
After the temperature was stabilized, 150 parts of isophorone diisocyanate was added dropwise, and then a solution of 0.1 part of dibutyltin dilaurate and 10 parts of methyl ethyl ketone was added and reacted at the same temperature for 3 hours to obtain an isocyanate-terminated prepolymer solution. Further, the temperature of the reaction solution is cooled to 30 ° C or lower, a mixed solution of 35 parts of isophoronediamine, 5 parts of dibutylamine and 50 parts of methyl ethyl ketone is added dropwise over 1 hour, and then the temperature is raised to 50 ° C to end the chain extension reaction. did. Then after adding 11 parts of acetic acid,
1000 parts of water was added dropwise to obtain a polyurethane emulsion. By removing the solvent of the obtained emulsion at 60 ° C. under reduced pressure,
An aqueous polyurethane solution (c) having a polyalkylene oxide unit in its side chain was obtained. The non-volatile content of the aqueous polyurethane solution (c) is about 40%, and the non-volatile content contains about 40% of side chain type polyalkylene oxide units.

<Example 4> 250 parts of the polyurethane aqueous dispersion (a) obtained in Example 1 was mixed with an epoxy resin aqueous dispersion ("Aquatoto 3525" manufactured by Tohto Kasei Co., Ltd., nonvolatile content 55%).
50 parts were added to obtain an aqueous resin composition (d).

<Example 5> 150 parts of isopropyl alcohol were placed in the same four-necked flask as in Example 1 and heated to 80 ° C under a nitrogen stream. 30 parts styrene, 75 parts ethyl acrylate, 2-hydroxyethyl acrylate from the dropping pipe
24 parts, acrylic acid 21 parts and azobisisobutyronitrile
3 parts of the mixture are added dropwise in about 2 hours. 1 after completion of dropping
0.5 parts of azobisisobutyronitrile is added 3 times every other time, and the reaction is continued for 1 hour. Thereafter, 27 parts of dimethylethanolamine and 600 parts of ion-exchanged water were added, and the solvent was removed under reduced pressure to obtain an acrylic resin aqueous solution having a nonvolatile content of about 40%. 750 parts of the polyurethane aqueous solution (b) obtained in Example 2 was put into this to obtain an aqueous resin composition (e).

<Example 6> To 250 parts of the aqueous polyurethane solution (c) obtained in Example 3, 25 parts of a water-soluble melamine resin ("Cymel-303" manufactured by Mitsui Cyanamid Co., Ltd.) was added to prepare an aqueous resin composition (f ) Got

Comparative Example 1 78.5 parts of polybutylene adipate glycol, 45.0 parts of polyethylene glycol and 90 parts of methyl ethyl ketone were charged in the same apparatus as in Example 1,
Heat to 80 ° C. under nitrogen atmosphere with stirring. After the temperature was stabilized, 20.6 parts of isophorone diisocyanate was added dropwise, and then a solution of 0.015 parts of dibutyltin dilaurate and 10 parts of methyl ethyl ketone was added and reacted at the same temperature for 3 hours to obtain an isocyanate-terminated prepolymer solution. Further, cool the reaction solution to a temperature of 30 ° C or lower, and add isophoronediamine 5.1
A mixture of 1 part, 0.8 part of dibutylamine and 200 parts of acetone was added dropwise over 1 hour, and then the temperature was raised to 50 ° C. to complete the chain extension reaction. Next, 350 parts of water was added dropwise to obtain an aqueous polyurethane dispersion. The obtained aqueous dispersion was desolvated under reduced pressure at 60 ° C. to obtain a polyurethane aqueous dispersion (g) having a nonvolatile content of 30.3% and a polyoxyethylene unit of 30% in the main chain.

Comparative Example 2 34.8 parts of tolylene diisocyanate (“TDI-80” manufactured by Nippon Polyurethane Industry Co., Ltd.) and 14.6 parts of methyl ethyl ketone were placed in the same apparatus as in Example 1, and the mixture was heated to 60 ° C. under a nitrogen atmosphere while stirring. Heat to add 402.4 parts of polyethylene glycol monomethyl ether (containing about 45 ethylene oxide units on average) to methyl ethyl ketone.
A solution previously dissolved in 100 parts was added dropwise over 1 hour. After reacting for 3 hours at a reaction temperature of 80 ° C., 10.5 parts of diethanolamine was added dropwise. Further, the mixture was reacted at the same temperature for 1 hour and cooled to obtain a diol solution having a polyoxyethylene unit having a nonvolatile content of 80.1%. Next, 72.7 parts of polybutylene adipate glycol, 65.1 parts of the diol solution, and 77 parts of methyl ethyl ketone were charged in the same apparatus as in Example 1,
Heat to 80 ° C. under nitrogen atmosphere with stirring. After the temperature became stable, 19.7 parts of isophorone diisocyanate was added dropwise, and then a solution of 0.015 parts of dibutyltin dilaurate and 10 parts of methyl ethyl ketone was added and reacted at the same temperature for 3 hours to obtain an isocyanate-terminated prepolymer solution. Further, cool the reaction solution to a temperature of 30 ° C or lower, and add isophoronediamine 4.9
A mixture of 1 part, 0.8 part of dibutylamine and 200 parts of acetone was added dropwise over 1 hour, and then the temperature was raised to 50 ° C. to complete the chain extension reaction. Next, 350 parts of water was added dropwise to obtain an aqueous polyurethane dispersion. The aqueous dispersion obtained was subjected to solvent removal under reduced pressure at 60 ° C. to obtain a polyurethane water dispersion (h) having a nonvolatile content of 30.3% and a polyoxyethylene unit of 30%.
However, an insoluble precipitate was observed. This is presumed to be a gelled product due to the incorporation of 2 molar equivalents of diethanolamine with respect to tolylene diisocyanate, which is a by-product contained in the diol solution. Therefore, a stable aqueous dispersion could not be obtained by this method.

Comparative Example 3 78.9 parts of polybutylene adipate glycol, 7.5 parts of polyethylene glycol, 10.8 parts of dimethylolpropionic acid, and 90 parts of methyl ethyl ketone were charged in the same apparatus as in Example 1 and stirred at 80 ° C. under a nitrogen atmosphere. Heat to. After the temperature became stable, 41.1 parts of isophorone diisocyanate was dropped, and then a solution of 0.015 parts of dibutyltin dilaurate and 10 parts of methyl ethyl ketone was added and reacted at the same temperature for 3 hours to obtain an isocyanate-terminated prepolymer solution. Further, cool the reaction solution to a temperature of 30 ° C or lower, and add 10.2 parts of isophoronediamine and dibutylamine.
A mixed solution of 1.6 parts and 200 parts of acetone was added dropwise over 1 hour, and then the temperature was raised to 50 ° C. to terminate the chain extension reaction. Next, a mixed solution of 4.6 parts of 25% aqueous ammonia and 345 parts of water was added dropwise to obtain a polyurethane emulsion. The resulting emulsion was desolvated at 60 ° C. under reduced pressure to obtain a polyurethane aqueous solution (i) having a nonvolatile content of 30.3% and a polyoxyethylene unit of 5% in the main chain.

<Comparative Example 4> In Comparative Example 3, 300 parts of the polyurethane aqueous solution (i) was added to the water-soluble melamine resin "Cymel-303" 25
Parts were added to obtain an aqueous resin composition (j).

<Comparative Example 5> 50 parts of n-butanol and 1 part of potassium hydroxide were placed in a pressure resistant reactor, heated to 120 ° C., and dehydrated under reduced pressure while slightly flowing dry nitrogen gas. Then, a mixture of 150 parts of ethylene oxide and 400 parts of propylene oxide was gradually added while maintaining 5 atm and 120 ° C., and the reaction was carried out for about 2 hours, then 50 parts of glycidol was added and the reaction was continued for another 2 hours, followed by cooling. rear,
The added potassium hydroxide was neutralized with acetic acid, and the resulting salt was filtered to obtain a polyalkylene oxide addition polymer (m = 5, n = 1
I got 0). A mixture of 30 parts of dimethylolpropionic acid and 100 parts of methyl ethyl ketone is added to this and heated to 80 ° C under a nitrogen atmosphere while stirring. After the temperature was stabilized, 250 parts of isophorone diisocyanate was added dropwise, and then a solution of 0.1 part of dibutyltin dilaurate and 10 parts of methyl ethyl ketone was added and reacted at the same temperature for 3 hours to obtain an isocyanate-terminated prepolymer solution. Further, cool the reaction solution to a temperature of 30 ° C or below, and add 20 parts of isophoronediamine and dibutylamine.
A mixed solution of 3 parts and 50 parts of methyl ethyl ketone was added dropwise over 1 hour, and then the temperature was raised to 50 ° C. to complete the chain extension reaction. Then after adding 20 parts of dimethyl ethanolamine,
1000 parts of water was dropped, and the solvent was removed under reduced pressure at 60 ° C.
Polyurethane having a polyalkylene oxide unit was separated and precipitated, and a stable aqueous dispersion could not be obtained.

Comparative Example 6 100 parts of lauryl alcohol and 5 parts of potassium hydroxide were placed in a pressure resistant reactor, heated to 120 ° C., and dehydrated under reduced pressure while slightly flowing dry nitrogen gas. Then, while maintaining at 5 atm and 120 ° C, 400 parts of ethylene oxide was gradually added, and after reacting for about 1 hour, 340 parts of propylene oxide was gradually added,
After reacting for about 2 hours, 44 parts of glycidol was added and the reaction was continued for another 2 hours. After cooling, the added potassium hydroxide was neutralized with acetic acid, and the formed salt was filtered to obtain a polyalkylene oxide addition polymer ( m = 17, n = 11) was obtained. 40 parts of dimethylolpropionic acid is put into this, and it heats at 80 degreeC under nitrogen atmosphere, stirring. When the temperature stabilizes, 250 parts of isophorone diisocyanate and 100 parts of methyl ethyl ketone
After dropwise adding the mixture of parts, dibutyltin dilaurate 0.1
Solution of 10 parts of methyl ethyl ketone was added and reacted at the same temperature for 3 hours to obtain an isocyanate-terminated prepolymer solution. Further, the temperature of the reaction solution is cooled to 30 ° C or lower, and a mixed solution of 20 parts of isophoronediamine, 5 parts of dibutylamine and 50 parts of methyl ethyl ketone is added dropwise over 1 hour, and then 50 parts are added.
The temperature was raised to ° C and the chain extension reaction was completed. Next, after adding 27 parts of dimethylethanolamine, 1000 parts of water was dropped,
When the solvent was removed under reduced pressure at 60 ° C., polyurethane having a polyalkylene oxide unit was separated and precipitated, and a stable aqueous dispersion could not be obtained.

The appearance and storage stability of the aqueous polyurethane dispersions or aqueous polyurethane solutions obtained in Examples 1 to 3 and Comparative Examples 1 to 3 and the aqueous resin compositions obtained in Examples 4 to 6 and Comparative Example 4 were evaluated. The evaluation results are shown in Table 1. The storage stability was evaluated by visually observing changes in appearance and viscosity after storage at 40 ° C. for 2 weeks (∘: no change, ×: change). Each of them is diluted with water to a nonvolatile content of 30% and coated on a galvanized steel sheet with a bar coater to a dry coating thickness of 10 μm.
Table 1 shows the results of evaluating the adhesion of the test pieces obtained by the heat treatment for minutes. The adhesion was evaluated by performing a cross-cut cellophane peeling test and showing the number of squares remaining in the 100 squares of 1 mm × 1 mm after peeling the cellophane tape without peeling the film. As shown in Table 1, the aqueous polyurethane of the present invention and the aqueous resin composition containing the same have excellent storage stability and excellent adhesion.

[0034]

[Table 1]

[0035]

EFFECTS OF THE INVENTION The aqueous polyurethane of the present invention and the aqueous resin composition containing it as an essential component are excellent in storage stability, adhesion to a substrate and the like, and therefore, cannot be applied to conventional polyurethane aqueous dispersions. There was a wide variety of uses that did not exist, namely printing inks, paints, adhesives, fiber treatment agents,
It can be used as a surface treatment agent, an emulsifier for resin-based or water-based polymerization reaction, and the like.

Claims (3)

[Claims] 1. An alkylene oxide addition polymer (A) represented by the following general formula and an organic diisocyanate compound
Aqueous polyurethane obtained by reacting with (B). _{X- (O-C 2 H 4} ) m - (O-Y) n -OCH 2 CH
(OH) CH ₂ OH (In the formula, X represents a hydrocarbon group having 1 to 4 carbon atoms, Y represents a hydrocarbon group having 3 to 8 carbon atoms, m is an integer of 1 to 100, and n is Represents a non-negative integer less than or equal to m.) 2. An alkylene oxide addition polymer (A)
An organic diisocyanate compound (B) is reacted with a compound (C) having two or less active hydrogens reactive with an isocyanate group and a carboxyl group or a tertiary amino group, The aqueous polyurethane according to claim 1, wherein when a carboxyl group is present in the molecule, the active hydrogen coexisting in the molecule is more reactive with the isocyanate group than the carboxyl group. 3. An aqueous resin composition containing the aqueous polyurethane according to claim 1 or 2 as an essential component.