JPH06306135A - Water-base polyurethane - Google Patents

Abstract

PURPOSE:To provide a water-base polyurethane excellent in storage stability, water resistance, pigment dispersion, and adhesion to various substrates. CONSTITUTION:A polyester obtd. by reacting an org. compd. having at least two hydroxyl groups, a cyclic acid anhydride, and a monomer having an epoxy group and a hydrocarbon group is reacted with a compd. having at least one ionic group and at least two isocyanate or isocyanate-reactive groups and an org. polyisocyanate to give a water-base polyurethane, which is widely usable for a printing ink, a coating material, an adhesive, a fiber-treating agent, a surface-treating agent, an emulsifier for resin-base or water-base polymn., etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous polyurethane useful as a paint, a printing ink, an adhesive, a fiber treating agent, a surface treating agent, a resin type or an emulsifying agent for an aqueous polymerization reaction.
More specifically, it relates to an aqueous polyurethane having excellent storage stability, water resistance, pigment dispersibility, and adhesion to various substrates.

[0002]

2. Description of the Related Art Conventionally, a resin is dispersed or dissolved in an aqueous medium by using a dispersant or an emulsifier, or a dispersible group, an emulsifiable group or a soluble group (ionic group and / or Alternatively, the latter self-emulsifying or self-dissolving resin has been found to be able to secure better performance. Aqueous dispersions or solutions of self-emulsifying or self-dissolving polyurethane containing only ionic groups have relatively good adhesion to the substrate and pigment dispersibility, but poor storage stability and water resistance. There is a drawback of. Therefore, a method has been proposed in which the resin contains only a nonionic group or both a nonionic group and an ionic group to compensate for these drawbacks.

On the other hand, regarding the adhesion to the substrate, an aqueous dispersion having superior performance to the conventional substrate has been obtained for a substrate such as paper having a porous surface and a non-smooth surface. Sufficiently satisfactory adhesion has not been obtained to a non-polar substrate such as a plastic film having a smooth surface. To improve the drawbacks of such an aqueous dispersion, a non-polar material such as a hydrocarbon compound is added to the aqueous dispersion or a hydrocarbon compound having a monovalent or divalent active hydrogen group is used as an organic diisocyanate. The method of reacting and introducing a hydrocarbon group into the terminal and / or the main chain is conventionally known. However, the aqueous polyurethane dispersions obtained by these methods have drawbacks such as not only poor water dispersibility and storage stability, but also reduced pigment dispersibility and adhesion to polar substrates.

[0004]

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted extensive studies to improve the above-mentioned drawbacks of an aqueous dispersion or aqueous solution of polyurethane, and as a result, have found that an aqueous dispersion of polyurethane having a hydrocarbon group in its side chain is obtained. The inventors have found that a liquid or an aqueous solution is excellent in storage stability, water resistance, pigment dispersibility, adhesion to various substrates, and particularly excellent adhesion to heteropolar substrates, and has reached the present invention. .

[0005]

The present invention provides an organic compound (A) having two or more hydroxyl groups, a cyclic acid anhydride (B), and
Of a polyester obtained by reacting one epoxy group with a monomer (C) having a hydrocarbon group, and a compound having at least one ionic group and at least two isocyanate groups or a group reactive with an isocyanate group ( An aqueous polyurethane obtained by reacting D) with an organic polyisocyanate (E). Hereinafter, the configuration of the present invention will be described in detail.

As the organic compound (A) having two or more hydroxyl groups, an aliphatic polyol, an alicyclic polyol, an aromatic polyol or a mixture thereof can be used. Examples of polyols include ethylene glycol,
Propylene glycol, 1,4-butylene glycol, 1,3-
Low molecular weight diols such as butylene glycol, butenediol, methyl-1,5-pentanediol, hexanediol, cyclohexanediol, cyclohexanedimethanol, bisphenol A, bisphenol F, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol ,
Other functional polyols such as dipentaerythritol, polyether polyols such as polyethylene-polypropylene glycol, polybutylene glycol, polytetramethylene glycol and known polyester polyols, 5-
Polyester polyols containing sodium sulfoisophthalate units, polycarbonate polyols, high molecular weight diols such as hydroxyethyl cellulose, nitrocellulose and the like. Of these, diols are preferably used when the aqueous polyurethane of the present invention is produced.

As the cyclic acid anhydride (B), saturated or unsaturated aliphatic dicarboxylic acid anhydrides, aromatic dicarboxylic acid anhydrides, heterocyclic dicarboxylic acid anhydrides, and mixtures thereof can be used. The hydrogen atom of the hydrocarbon group or heterocyclic group of these dicarboxylic acid anhydrides is a saturated or unsaturated aliphatic hydrocarbon group, alicyclic group, aryl group,
It may be substituted with a heterocyclic group or a halogen atom.
These dicarboxylic acid anhydrides include, for example, maleic anhydride, phthalic anhydride, 1,2-cyclohexanedicarboxylic acid anhydride, cis-4-cyclohexene-1,2-dicarboxylic acid anhydride, itaconic anhydride, glutaric anhydride, Examples thereof include citraconic anhydride, succinic anhydride, methylhymic acid anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, dichlorophthalic anhydride and 4,5-dibromo-1,2-cyclohexanedicarboxylic acid.

The monomer (C) having one epoxy group and a hydrocarbon group (hereinafter referred to as epoxy monomer) is a saturated or unsaturated alkyl group which may be substituted with a halogen atom, an alicyclic alkyl group, Glycidyl ethers having an aryl group, a heterocyclic group or the like, or glycidyl esters having a substituent thereof, α
-Alkylene oxides such as monoepoxides of olefin oxides and polyenes, monoepoxides of unsaturated fatty acid esters, and monoepoxides of alicyclic unsaturated hydrocarbons. For example, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, dodecyl glycidyl ether, stearyl glycidyl ether, n-butylphenyl glycidyl ether, t-butylphenyl glycidyl ether, lauric acid glycidyl ester, sorbic acid glycidyl ester,
Examples include 1-octene oxide, 2-octene oxide, 1-tetradecene oxide, 1-octadecene oxide, cyclohexene oxide, butadiene monooxide, heptadiene monooxide, epoxy stearic acid ester, and epoxy oleic acid ester. Particularly preferred among these compounds are epoxy compounds having a hydrocarbon group having 5 or more carbon atoms.

The polyester having a hydrocarbon group in its side chain in the present invention can be produced by the method described in JP-A-61-47728. In general, an organic compound (A) having two or more hydroxyl groups is used as a reaction initiator,
It is considered that the ester compound is first produced by reacting with the cyclic acid anhydride (B), and then the polyester is produced by reacting the epoxy monomer (C) with the carboxyl group of the ester compound. In order to produce the polyester having a hydrocarbon group in the side chain according to the present invention, it is preferable to use the cyclic acid anhydride (B) and the epoxy monomer (c) in approximately equimolar amounts. Organic compound (A)
The use ratio of 0.1 to 0.5, preferably 0.2 to 0.5, relative to 1 mol of the cyclic acid anhydride (B) or the epoxy monomer (C).
It is 0.4 mol. This reaction can be carried out without solvent,
It is also possible to use an inert organic solvent which does not inhibit the reaction, for example, acetone, methyl ethyl ketone, ethyl acetate, dioxane, tetrahydrofuran or the like, in order to enhance the solubility. As for detailed manufacturing conditions, the conditions described in the above publication can be applied.

The aqueous polyurethane having a hydrocarbon group in the side chain of the present invention comprises a polyester (preferably a diol) having the above hydrocarbon group in the side chain, at least one ionic group and at least two isocyanate groups or It can be produced by reacting the compound (D) having an isocyanate group and a reactive group with the organic polyisocyanate (E). The reaction amount of the polyester having a hydrocarbon group in the side chain is not particularly limited as long as it does not impair water solubility, water dispersibility, and storage stability, but adhesion to non-polar substrates and water solubility, water dispersibility Considering the balance of storage stability, the range of 0.3 to 50% by weight is preferable.

The compound (E) having at least one ionic group and at least two isocyanate groups or groups reactive with an isocyanate group is, for example, JP-B-43-9076.
The compounds disclosed in the publication can be used. Examples of the ionic group include quaternary ammonium groups and tertiary
Examples include a primary amino group, a carboxylate group, a carboxyl group, a sulfonate group, a sulfonic acid group, a phosphonium group, a phosphonic acid group, and a sulfate ester group. Of these, functional groups such as a carboxyl group and a tertiary amino group, which are ion precursor groups, are converted into ionic groups by a simple reaction such as neutralization or quaternization with acetic acid, hydrochloric acid, ammonia or a tertiary amine. It can be easily converted.

Examples of the compound having at least one ionic group and at least two isocyanate groups include bis-chloromethyl-diphenylmethane-diisocyanate and 2,6-diisocyanate-benzyl chloride. The compound having at least one ionic group and at least two isocyanate group-reactive groups includes dimethylolpropionic acid, amino acids and aminosulfonic acids, and their oxyalkylation products and polyesterification products. Thing, diaminocarboxylic acid,
Examples thereof include sodium diaminobenzenesulfonate, glycerin monophosphate disodium salt, sodium hydroxyethylphosphonate, sodium dimethylolphosphinate, N-methylethanolamine, polyethylene glycol, polyoxyethylene-polyoxypropylene glycol and the like.

As the organic polyisocyanate (E), conventionally known tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, isophorone diisocyanate, dimeryl diisocyanate, lysine Diisocyanate, hydrogenation
Diisocyanates such as 4,4′-diphenylmethane diisocyanate and hydrogenated tolylene diisocyanate, isocyanate adducts with both ends thereof and glycols or diamines, or a mixture thereof are used. If necessary, triisocyanate or higher polyisocyanates such as triphenylmethane triisocyanate and polymethylene polyphenyl isocyanate can be mixed with the diisocyanates and used. Further, if necessary, monoisocyanates may be used as a molecular weight adjusting agent. In addition to these, commercially available polyisocyanate adducts such as Desmodur series (trade name, manufactured by Bayer, West Germany) can also be used.

Further, in the present invention, active hydrogen compounds such as polyhydroxy compounds and polyamine compounds which are generally used for producing polyurethane can be used. As the polyhydroxy compound, water, ethylene glycol, diethylene glycol, triethylene glycol,
Low molecular weight glycols such as butanediol, propanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol, triols such as trimethylolpropane and glycerin, and tetraols such as pentaerythritol. In addition to high molecular weight diols such as compounds, polyether diols, polyester diols, etc., bisphenols such as bisphenol A and bisphenol F, glycols obtained by adding alkylene oxides such as ethylene oxide and propylene oxide to bisphenol A and bisphenol F. Types can also be used.

Examples of the polyether diols include polymers, copolymers or graft copolymers of alkylene oxides such as tetrahydrofuran, ethylene oxide, propylene oxide, butylene oxide, hexanediol, methylhexanediol, heptanediol, There are polyether glycols by condensation of octane diol or mixtures thereof, propoxylated or ethoxylated polyether glycols. As polyester diols,
Ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, hexanediol, methyl-1,5-pentanediol, octanediol, cyclohexanediol, 2-ethyl-1,3- Polyester obtained by condensation reaction of saturated or unsaturated low molecular weight glycol such as hexanediol, bisphenol A, diethylene glycol, triethylene glycol, dipropylene glycol, and an aliphatic or aromatic dibasic acid or aromatic dibasic acid ester There are polyester polyols, polycarbonate polyols, silicone polyols and the like obtained by ring-opening polymerization of cyclic ester compounds such as polyols and ε-polycaprolactone, and powders obtained by the reaction of these with diisocyanate. Reaction products of hydroxyl group can also be used.

As the polyamine compound, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, 1,7-diaminoheptane,
1,8-diaminooctane, xylylenediamine, 1,4-diaminocyclohexane, isophoronediamine, phenylenediamine, polyamidoamine, diamines such as dimerdiamine obtained by converting the carboxyl group of dimer acid into an amino group, triaminopropane, etc. Hydrazine compounds such as triamines, hydrazine, adipic acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide, carbodihydrazide and mixtures thereof, or terminal amino groups obtained by reaction of these with an organic polyisocyanate compound or polyepoxy compound or Reaction products of hydroxyl groups can be used.

In order to produce an aqueous polyurethane having a hydrocarbon group in its side chain, conventionally known methods for producing polyurethane can be applied. That is, a one-shot method in which the raw materials are charged in a batch and reacted, or a prepolymer method in which the terminal isocyanate prepolymer is generated and then the molecular weight is increased by a chain extender can be used. The latter method is particularly preferable.

In the present invention, the above-mentioned polyester having a hydrocarbon group in its side chain, a compound (D) having an ionic group,
An excess amount of the organic polyisocyanate (E) and, if necessary, an active hydrogen compound are added at room temperature to 140 ° C. according to a conventionally known method.
A prepolymer having a terminal isocyanate group is prepared by reacting at 0 ° C, preferably 40 to 100 ° C.
The equivalent ratio of isocyanate groups to active hydrogen is about 1.2: 1
A range of about 3: 1 is suitable, preferably within the range of 1.3: 1 to 2.2: 1. For the preparation of the prepolymer, conventionally known urethane-forming catalysts such as dibutyltin dilaurate, tin octylate, triethylamine, N, N-dimethylbenzylamine, sodium hydroxide, diethylzinc tetra (n-butoxy) are used, if necessary. Titanium or the like can be used.

Further, although the prepolymer can be prepared in the absence of a solvent, an organic solvent which is inert to isocyanate groups can be used 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, diglyme, dimethyl sulfoxide, N-methylpyrrolidone, and the like, and these solvents may be used alone or in a mixed system.

The aqueous polyurethane of the present invention can be produced by chain-extending a prepolymer having an isocyanate group at a terminal with a so-called chain extender containing active hydrogen. At that time, a solution obtained by diluting the chain extender with the inert organic solvent may be added dropwise to the prepolymer for reaction, or conversely, the prepolymer may be added dropwise for reaction with the chain extender solution. it can. After further chain extension, it can be dispersed in water by a conventionally known method and the organic solvent used can be removed if necessary, or the chain can be dispersed with a chain extender while dispersing the prepolymer in water or after the dispersion. It can be extended. In the 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. Conversion of any ionic groups in the prepolymer to ionic (salt) groups, eg carboxyl groups, may be carried out before the prepolymer is added to the water, or simultaneously with or after the addition. Ammonia or tertiary amines such as triethylamine, triethanolamine, N-methylmorpholine and the like are suitable as the agent used for the neutralization of the carboxyl group.

Examples of the chain extender containing active hydrogen used in the present invention include polyols such as ethylene glycol and butanediol selected from the above active hydrogen compounds, amino alcohols, ammonia, ethylenediamine, diaminodiphenylmethane and isophoronediamine. , Primary or secondary aliphatic, alicyclic, aromatic, aralkyl or heterocyclic amines such as piperazine, especially diamines, hydrazine compounds such as hydrazine or adipic acid bishydrazide, water etc. alone or in combination The above can be mixed and used.

The chain extender is preferably used in an amount of 0.7 to 1.1 with respect to 1 equivalent of free isocyanate groups in the prepolymer. Outside this range, adverse effects such as storage stability of the aqueous dispersion, film strength reduction, 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 in the range of room temperature to 95 ° C depending on the reactivity of active hydrogen and isocyanate, and particularly in the case of amine or hydrazine as the chain extender, it is preferably carried out at room temperature to 50 ° C. The aqueous polyurethane thus obtained can be used as it is after being dispersed in water, but usually, for the purpose of removing various organic solvents used in combination, a step of azeotropically removing with water by a heating operation and a depressurizing operation is adopted. Is common.

The aqueous dispersion of the aqueous polyurethane of the present invention comprises wood, metal, glass, fiber, leather, plastic,
A resin film can be formed on any base material including foam by a conventional method such as printing, coating, impregnation, spraying, paint, printing ink, adhesive, fiber treatment agent, surface treatment agent, resin system. Alternatively, it can be applied as an emulsifier for an aqueous polymerization reaction. In the aqueous dispersion, if necessary, other conventional components, such as organic solvents, color pigments, dyes, magnetic powders, fillers, emulsifiers, defoamers, surfactants, dispersion aids, thickeners, A heat stabilizer, a leveling agent, an anti-crater agent, an anti-settling agent, an ultraviolet absorber, an antioxidant, a flame retardant and the like can be added.
In addition, other water-based resins such as existing polyurethane, polyester, polyacrylate, polyvinyl acetate,
Polybutadiene, polyvinyl chloride, chlorinated polypropylene, polyethylene, polystyrene, polystyrene-acrylate copolymers, rosin derivatives, alcohol adducts of styrene-maleic anhydride copolymers, cellulosic resins and the like can also be used together.

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 as an ionic group, polyaziridine compound, polyepoxy compound, polycarbodiimide compound, metal chelate compound, polyoxazoline compound, polyisocyanate, blocked polyisocyanate, partial or complete An amino resin that has been etherified can be used as a crosslinking agent. When the terminal of the polyurethane of the present invention has an amino group or a hydrazine group, a polyacetoacetic acid ester or a polycarbonyl compound can be used as a crosslinking agent. further,
It is also possible to introduce these reactive groups into the resin of the present invention alone or in two or more kinds of resins, and to carry out the crosslinking reaction by a combination of both. These cross-linking reactions can take place at room temperature or can be accelerated by heating or addition of known reaction catalysts. Aqueous polyurethane of the present invention, polyethylene, polypropylene, polyester,
It can also be used as an adhesive for nylon, polyurethane, leather, etc.

[0025]

EXAMPLES The present invention will now be described in more detail by way of examples. In the examples, "parts" means "parts by weight" and "%" means "% by weight". <Production Example 1> In a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, 31 parts of ethylene glycol, 100 parts of succinic anhydride, decylglycidyl ether (epoxy equivalent)
254, hydrocarbon group content 71%) 254 parts and methyl ethyl ketone 42.8 parts were charged and dissolved by heating at 80 ° C., and stirred at the same temperature for 3 hours. Further, 2 parts of N, N-dimethylbenzylamine was added as a reaction catalyst and the reaction was carried out at the same temperature for 12 hours to give a polyester diol having a hydrocarbon group with an acid value of 10 or less in its side chain.
(a) A solution was obtained. The nonvolatile content of this solution was 90.2%, and the hydrocarbon group content of the obtained diol (a) was 37%.

<Production Example 2> In the same apparatus as in Production Example 1,
Ethylene glycol 18.6 parts, phthalic anhydride 148 parts, decyl glycidyl ether (epoxy equivalent 254, hydrocarbon group
(71%) 254 parts and methyl ethyl ketone 46.7 parts were charged and dissolved by heating at 80 ° C, followed by stirring at the same temperature for 3 hours. Further, 2 parts of N, N-dimethylbenzylamine was added as a reaction catalyst and reacted at the same temperature for 12 hours to obtain a polyester diol (b) having a side chain of a hydrocarbon group having an acid value of 10 or less. The nonvolatile content of this solution was 90.3%, and the hydrocarbon group content of the obtained diol (b) was 43%.

<Manufacturing Example 3> In the same apparatus as in Manufacturing Example 1,
45 parts of 1,4-butanediol, 154 parts of anhydrous 1,2-cyclohexanedicarboxylic acid, 378 parts of glycidyl stearate (epoxy equivalent: 378, 81% of hydrocarbon group), 378 parts of methyl ethyl ketone were charged and dissolved by heating at 80 ° C., The mixture was stirred at the same temperature for 3 hours. Furthermore, 2 parts of N, N-dimethylbenzylamine was added as a reaction catalyst and the reaction was carried out at the same temperature for 15 hours.
A polyester diol (c) having 10 or less hydrocarbon groups in the side chain was obtained. The nonvolatile content of this solution was 79.8%, and the hydrocarbon group content of the obtained diol (c) was 48%.

<Example 1> 66 parts of polybutylene adipate glycol (hydroxyl value 56 mg KOH / g), 17.8 parts of polyester diol (a) solution, dimethylolpropionic acid 10.8
And 88 parts of methyl ethyl ketone are charged in the same apparatus as in Production Example 1 and heated to 80 ° C. under a nitrogen atmosphere while stirring.
After the temperature was stabilized, 44.6 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. Furthermore, the temperature of the reaction solution is cooled to 30 ° C or lower, and a mixed solution of 11.0 parts of isophoronediamine, 1.7 parts of dibutylamine and 200 parts of acetone is added dropwise over 1 hour, and then the temperature is raised to 50 ° C to carry out the chain extension reaction. finished. Then, a mixed solution of 5.5 parts of 25% aqueous ammonia and 345 parts of water was added dropwise to obtain an aqueous polyurethane dispersion. The resulting aqueous dispersion was desolvated under reduced pressure at 60 ° C. to obtain an aqueous dispersion of polyurethane (d) having a hydrocarbon group in its side chain. Polyurethane (d) contained 5% of hydrocarbon groups, had an acid value before neutralization of 30.2 mg KOH / g, and had an aqueous dispersion having a nonvolatile content of 30.3% and a pH of 7.1.

Example 2 Polybutylene adipate glycol (hydroxyl value 56 mg KOH / g) 67.7 parts, polyester diol (b) 19.3 parts, dimethylol propionic acid 10.8
And 88 parts of methyl ethyl ketone are charged in the same apparatus as in Production Example 1 and heated to 80 ° C. under a nitrogen atmosphere while stirring.
After the temperature was stabilized, 42.1 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, the temperature of the reaction solution is cooled to 30 ° C or lower, a mixed solution of 10.4 parts of isophoronediamine, 1.6 parts of dibutylamine and 200 parts of acetone is added dropwise over 1 hour, and then the temperature is raised to 50 ° C to end the chain extension reaction. did. Then, a mixed solution of 5.5 parts of 25% aqueous ammonia and 345 parts of water was added dropwise to obtain an aqueous polyurethane dispersion. The resulting aqueous dispersion is subjected to solvent removal under reduced pressure at 60 ° C to produce a polyurethane having a hydrocarbon group in its side chain.
An aqueous dispersion of (e) was obtained. Polyurethane (e) is a hydrocarbon group
It contained 5%, had an acid value before neutralization of 29.7 mg KOH / g, and had a nonvolatile content of 30.1% and a pH of 6.9 in the aqueous dispersion.

Example 3 47.9 parts of polytetramethylene glycol (hydroxyl value 58 mg KOH / g), 45.3 parts of polyester diol (c), 14.3 parts of dimethylolpropionic acid and 82 parts of methyl ethyl ketone were placed in the same apparatus as in Production Example 1. Charge and heat to 80 ° C under a nitrogen atmosphere with stirring. After the temperature became stable, 41.4 parts of tolylene diisocyanate (“TDI-80” manufactured by Nippon Polyurethane Industry Co., Ltd.) was added dropwise, then 0.015 parts of dibutyltin dilaurate and 10 parts of methyl ethyl ketone were added and reacted at the same temperature for 3 hours. An isocyanate-terminated prepolymer solution was obtained. Furthermore, the temperature of the reaction solution
After cooling to 30 ° C or lower, a mixed solution of 13.1 parts of isophoronediamine, 2.0 parts 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. Then, a mixed solution of 7.3 parts of 25% aqueous ammonia and 345 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 an aqueous dispersion of polyurethane (f) having a hydrocarbon group in its side chain. Polyurethane (f) contained 10% of hydrocarbon groups, had an acid value before neutralization of 39.7 mg KOH / g, and its aqueous dispersion had a nonvolatile content of 30.5% and a pH of 6.8.

<Example 4> Phthalic acid type polyester glycol ("YG-226" manufactured by Asahi Denka Co., Ltd., hydroxyl value 64 mg K)
OH / g) 64.7 parts, polyester (a) 16.0 parts, dimethylolpropionic acid 10.8 parts, and methyl ethyl ketone 90 parts were charged in the same apparatus as in Production Example 1 and stirred under a nitrogen atmosphere.
Heat to 80 ° C. When the temperature has stabilized, add 45.9 parts of isophorone diisocyanate and then add dibutyltin dilaurate.
Add 0.015 parts and a solution of 10 parts methyl ethyl ketone,
The reaction was carried out at the same temperature for 3 hours to obtain an isocyanate-terminated prepolymer solution. Further, the temperature of the reaction solution was cooled to 30 ° C. or lower, a mixed solution of 12.7 parts of adipic acid dihydrazide 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, a mixed solution of 5.5 parts of 25% ammonia water and 345 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 an aqueous dispersion of polyurethane (g) having a hydrocarbon group in its side chain. The polyurethane (g) contained 5% of hydrocarbon groups and had an acid value before neutralization of 30.5 mg KOH / g, and the aqueous dispersion thereof had a nonvolatile content of 30.5% and a pH of 7.3.

<Comparative Example 1> 86.1 parts of polybutylene adipate glycol (hydroxyl value 56 mg KOH / g), 10.8 parts of dimethylolpropionic acid, and 90 parts of methyl ethyl ketone were charged in the same apparatus as in Production Example 1 and stirred under a nitrogen atmosphere. so
Heat to 80 ° C. When the temperature has stabilized, add 41.1 parts of isophorone diisocyanate and then add dibutyltin dilaurate.
Add a solution of 0.015 parts and 10 parts of methyl ethyl ketone,
The reaction was carried out at the same temperature for 3 hours to obtain an isocyanate-terminated prepolymer solution. The reaction solution was cooled to 30 ° C or lower, and a mixed solution of 10.2 parts of isophoronediamine and 150 parts of acetone was added dropwise over 1 hour. Then, a mixed solution of 1.9 parts of n-decylamine and 50 parts of acetone was added over 15 minutes. Dropped. afterwards
The temperature was raised to 50 ° C. to complete the chain extension reaction. Next, a mixture of 5.5 parts of 25% ammonia water and 345 parts of water was added dropwise to obtain an aqueous dispersion of polyurethane, and the solvent was removed at 60 ° C under reduced pressure to remove the polyurethane having a hydrocarbon group at the end.
An aqueous dispersion of (g) was obtained. The resulting polyurethane (g) contained a hydrocarbon group of 1.1%, had an acid value before neutralization of 29.5 mg KOH / g, and had an aqueous dispersion having a nonvolatile content of 30.3% and a pH of 6.9.

<Comparative Example 2> 59.9 parts of polybutylene adipate glycol (hydroxyl value 56 mg KOH / g), 10.8 parts of dimethylolpropionic acid, 9.3 parts of 1,10-decanediol and 90 parts of methyl ethyl ketone were used in the same apparatus as in Production Example 1. And heat to 80 ° C under a nitrogen atmosphere with stirring. After the temperature was stabilized, 54.5 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. Furthermore, cool the reaction solution to a temperature of 30 ° C or lower and use isophoronediamine.
A mixed solution of 13.5 parts, 2.1 parts 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, 5.5 parts of 25% ammonia water and water 3
After adding a mixed solution with 45 parts by drops to obtain an aqueous dispersion of polyurethane, the solvent is removed under reduced pressure at 60 ° C to obtain an aqueous dispersion of polyurethane (h) having a hydrocarbon group in the main chain. It was The obtained polyurethane (h) contained 5% of a hydrocarbon unit, had an acid value before neutralization of 30.4 mg KOH / g, and had an aqueous dispersion having a nonvolatile content of 29.7% and a pH of 7.0.

Table 1 shows Examples 1 to 4 and Comparative Examples 1 and 2.
The appearance and storage stability test results of the aqueous dispersion obtained in Step 1 are shown. Regarding the storage stability, changes in appearance and viscosity after storage for 1 month at 4 ° C. were visually evaluated (◯: no change, ×: change).

[Table 1]

<Example 5> 50 parts of an aqueous dispersion of polyurethane (d) having a nonvolatile content of 30%, 15 parts of a phthalocyanine pigment ("Rionol Blue KLH" manufactured by Toyo Ink Mfg. Co.), and 30 parts of water.
Parts and 5 parts of isopropyl alcohol were mixed and stirred, and the mixture was further kneaded with a ball mill for 20 hours to prepare a blue paint. Next, the obtained aqueous paint was applied to a polyethylene terephthalate film (PET) having a film thickness of 125 μm by a bar coater so that the film thickness would be 5 μm, and dried at 70 ° C. for 2 minutes. Further, a dry coating film was formed on a corona discharge treated polypropylene film (OPP) having a film thickness of 100 μm and an aluminum plate by the same method and conditions.

<Example 6> A blue paint was prepared in the same manner as in Example 5 using an aqueous dispersion of polyurethane (e).
A dry coating film was formed on two kinds of films and an aluminum plate. <Example 7> 50 parts of an aqueous dispersion of polyurethane (f) having a non-volatile content of 30%, titanium oxide (manufactured by Ishihara Sangyo Co., Ltd.
30 ") 35 parts, 10 parts of water, and 5 parts of isopropyl alcohol were mixed and stirred, and further ground by a ball mill for 20 hours to prepare a white paint, and two kinds of films and an aluminum plate were prepared in the same manner as in Example 4. A dry coating film was formed. <Example 8> Using an aqueous dispersion of polyurethane (g), a blue paint was prepared in the same manner as in Example 5, and a dry coating film was formed on two kinds of films and an aluminum plate. <Comparative Examples 3 to 4> Polyurethane (h) having a hydrocarbon group at the end and polyurethane having a hydrocarbon unit in the main chain
Using the aqueous dispersion (i), blue paints were prepared in the same manner as in Example 5, and a dry coating film was formed on two kinds of films and an aluminum plate.

The water resistance, adhesion and gloss of the coating films obtained in Examples 5-8 and Comparative Examples 3-4 were evaluated. The results are shown in Table 2. The evaluation was performed by the following method. Water resistance test: The number of times of rubbing until the coating film comes off after the cotton swab is impregnated with water. Adhesion test: Remaining rate (%) of coating film in cross-cut cellophane tape peel test Gloss test: 60 degree reflected light measured with a gloss meter Strength of (%)

[0038]

[Table 2] As shown in Tables 1 and 2, it is understood that the aqueous dispersion of the aqueous polyurethane of the present invention is excellent in storage stability, water resistance, adhesion to various substrates, and gloss, that is, pigment dispersibility. In particular, it excels in achieving both good adhesion to polar substrates and non-polar substrates.

[0039]

The present invention provides an aqueous polyurethane having excellent storage stability, water resistance, pigment dispersibility, and adhesion to various substrates. The water-based polyurethane of the present invention is particularly excellent in adhesion to heteropolar substrates, and therefore cannot be applied to conventional water-based polyurethanes in a wide variety of applications, that is, paints, printing inks, adhesives, fiber treatment agents, surface treatment agents. ,
It can be used as an emulsifier for resin-based or water-based polymerization reactions.

Front page continuation (72) Inventor Koichi Iibuchi, Toyo Inki Manufacturing Co., Ltd., 2-3-13 Kyobashi, Chuo-ku, Tokyo

Claims (2)

[Claims] 1. An organic compound (A) having two or more hydroxyl groups.
A polyester obtained by reacting a cyclic acid anhydride (B) with a monomer (C) having one epoxy group and a hydrocarbon group, at least one ionic group and at least two isocyanate groups or A compound having an isocyanate group and a reactive group (D), and an organic polyisocyanate (E)
Aqueous polyurethane made by reacting with. 2. The aqueous polyurethane according to claim 1, which is obtained by further chain extension with a polyhydrazine compound (F).