KR20000020046A - Method for manufacturing cationic polyurethane prepolymer and water-dispersed polyurethane or polyurethane urea made from the prepolymer and their use. - Google Patents

Abstract

PURPOSE: A method for manufacturing cationic polyurethane prepolymer and water-dispersed polyurethane or polyurethane urea made from the prepolymer is provided by which products having good longitudinal strain, dispersity, resistance to abrasion, and resistance to chemical agent. CONSTITUTION: A polyurethane prepolymer is obtained by reacting: cationic diol which has at least one ammonium ion every two carbons in a principal chain; polyester polyol, polyether polyol, polylactone polyol, polycarbonate polyol, polythioether polyol, polyacetal polyol, aromatic polyol or their mixture; and diisocyanate, diisocyanate polymer or their mixture. A water-dispersed polyurethane or polyurethane urea is obtained by: manufacturing the polyurethane prepolymer; neutralizing the prepolymer by neutralization agent; dispersing the neutralized prepolymer in water; addition-reacting the dispersed prepolymer with branch-extension agent or mono alcohol, secondary amine, urea or their mixture and optionally hardening it by using UV or thermosetting agent.

Description

A process for preparing a cationic polyurethane prepolymer, a process for producing a water dispersible polyurethane or a polyurethane urea prepared from the prepolymer, and a use thereof.

The present invention relates to a process for producing a cationic polyurethane prepolymer, a process for producing a water dispersible polyurethane or polyurethane urea prepared from the prepolymer, and uses thereof.

Many methods for producing water dispersible polyurethanes or polyurethane ureas are known. The advantage of these dispersions is that they can be dispersed without the use of surfactants. This is because it contains a hydrophilic group capable of self-emulsifying in the molecule. These dispersions are largely divided into ionic and nonionic forms according to the presence or absence of ions in the chain, and the ionic form is further divided into cationic forms into which ammonium ions are introduced and anionic forms into which sulfonate groups or carboxylate groups are introduced.

Anionic water dispersible polyurethanes or polyurethane ureas are disclosed in U.S. Patent No. 4,250,077 (von Bonin et al.), U.S. Patent No. 4,365,024 (Frentzel), U.S. Patent No. 4,460,738 (Frentzel) And the like, and Korean Patent Application No. 95-52369 (US Patent Application No. 08 / 772,167) by the present inventors. In general, a carboxyl group generated by adding and reacting dimethylolpropionic acid (DMPA) or an acid anhydride derivative having a carboxyl group with a tri-functional polyol or trifunctional monomer having a small molecular weight in a 1: 1 molar ratio is introduced. The polyol of the present invention is mixed with diisocyanate or the like and then reacted to prepare a prepolymer having a terminal ending with an isocyanate group. After neutralizing it and dispersing it with water by the self-emulsification method, branch extension is performed with a branch extender to obtain a water dispersible polyurethane. In this method, many inventions have been proposed in introducing a hydrophilic group (for example, a carboxyl group) capable of self-emulsifying or self-emulsifying.

As shown in U.S. Patent Nos. 3,479,310, 4,238,378 and 4,293,474, conventionally, ammonium ions, which are cations, are located in the main chain or immediately adjacent to the prepolymer, or urethane or urea bonds are present in the ionic group, so that dispersion Disadvantages have been raised that are difficult and the particles are not uniform. To overcome this, a large amount of cationic group was introduced or a large amount of solvent (dimethylformamide (DMF), acetone, methyl ethyl ketone (MEK), N-methylpyrrolidone (NMP), etc.) was required. The dispersion thus synthesized became a factor that inhibited the inherent properties of urethane.

Accordingly, it is an object of the present invention to provide a method for producing a cationic polyurethane prepolymer which is easy to disperse and whose dispersion particles are the main raw material of a water dispersible polyurethane or polyurethane urea.

Another object of the present invention is to provide a method for producing a water-dispersible polyurethane or polyurethane urea having excellent dispersion stability and uniform dispersion particles.

In order to achieve the above object, there are two methods for producing a polyurethane prepolymer according to the present invention, a method for producing a polyurethane prepolymer not including a double bond and a polyurethane prepolymer including a double bond.

The first method comprises a cationic diol having at least one ammonium ion in the main chain at least 2 carbon atoms apart; Polyester polyols, polyether polyols, polylactone polyols, polycarbonate polyols, polythioether polyols, polyacetal polyols, aromatic polyols or mixtures thereof; The diisocyanate, diisocyanate polymer or a mixture thereof is reacted so that the content of isocyanate groups is 0.5 to 30%. The second method comprises a cationic diol having at least one ammonium ion in the main chain at least 2 carbon atoms apart; Diols, diamines, primary amines or mixtures thereof having a double bond; Polyester polyols, polyether polyols, polylactone polyols, polycarbonate polyols, polythioether polyols, polyacetal polyols, aromatic polyols or mixtures thereof; The diisocyanate, diisocyanate polymer or a mixture thereof is reacted so that the content of isocyanate groups is 0.5 to 30%.

In order to achieve the above another object, the first method for producing a water-dispersible polyurethane or polyurethane urea according to the present invention is first cationic diol having at least one ammonium ion in the main chain spaced apart by at least 2 carbon atoms; , Polyester polyols, polyether polyols, polylactone polyols, polycarbonate polyols, polythioether polyols, polyacetal polyols, aromatic polyols or mixtures thereof and diisocyanate, diisocyanate polymers or mixtures thereof, The method is prepared by neutralizing a polyurethane prepolymer having an isocyanate group content of 0.5 to 30% with a neutralizing agent, dispersing it in water, and then adding and reacting it with a branch extender. Another method is to place at least 2 carbon atoms apart from the main chain. Cationic with at least one ammonium ion Diols, polyester polyols, polyether polyols, polylactone polyols, polycarbonate polyols, polythioether polyols, polyacetal polyols, aromatic polyols or mixtures thereof and diols, diamines, primary amines having double bonds, or mixtures thereof It is prepared by reacting a mixture with a diisocyanate, a diisocyanate polymer or a mixture thereof, neutralizing a polyurethane prepolymer having an isocyanate group content of 0.5 to 30% with a neutralizing agent, dispersing it in water, and then adding and reacting with a branch extender. .

In addition, the second method for producing a polyurethane or polyurethane urea according to the present invention is capable of ultraviolet / thermosetting, firstly cationic diol having at least one ammonium ion in the main chain spaced at least by 2 carbon atoms, Prepared by reacting a polyester polyol, a polyether polyol, a polylactone polyol, a polycarbonate polyol, a polythioether polyol, a polyacetal polyol, an aromatic polyol or a mixture thereof with a diisocyanate, a diisocyanate polymer or a mixture thereof. UV or heat curable initiators are added to a polyurethane prepolymer having a content of 0.5 to 30% and then neutralized with a neutralizing agent and dispersed in water, followed by diols, diamines, primary amine monomers having double bonds as branch extenders or their It is a method of making the mixture by addition reaction. . Another method comprises cationic diols having at least one ammonium ion at least two carbon atoms in the main chain, diols having a double bond, diamines, primary amine monomers or mixtures thereof, polyester polyols, poly Prepared by reacting an ether polyol, a polylactone polyol, a polycarbonate polyol, a polythioether polyol, a polyacetal polyol, an aromatic polyol, or a mixture thereof with a diisocyanate, a diisocyanate polymer or a mixture thereof. UV- or heat-curable initiator is added to a polyurethane prepolymer having a double bond of 0.5 to 30%, neutralized with a neutralizing agent and dispersed in water, followed by an addition reaction with a branch extender, and a diol having a double bond as a branch extender. With diamines, primary amine monomers or mixtures thereof A method of producing by the reaction. Further alternative methods include cationic diols having at least one ammonium ion at least two carbon atoms apart from the main chain, polyester polyols, polyether polyols, polylactone polyols, polycarbonate polyols, polythioether polyols, Hydroxy vinyl monomers are prepared by reacting polyacetal polyols, aromatic polyols or mixtures thereof with diisocyanate, diisocyanate polymers or mixtures thereof and for polyurethane prepolymers having an isocyanate group content of 0.5 to 30%. And a UV- or thermosetting initiator, followed by neutralization with a neutralizing agent and dispersion in water, and a cationic diol having at least one ammonium ion in the main chain and separated by at least 2 carbon atoms, and a double bond. Diols, diamines, primary amine groups with Dimers or mixtures thereof, polyester polyols, polyether polyols, polylactone polyols, polycarbonate polyols, polythioether polyols, polyacetal polyols, aromatic polyols, or mixtures thereof, and diisocyanate, diisocyanate polymers, or mixtures thereof Prepared by reacting the mixture, the reaction of the hydroxy vinyl monomer to the polyurethane prepolymer having a double bond having an isocyanate group content of 0.5 to 30%, the addition of ultraviolet or heat curing initiator, neutralized with neutralizing agent and dispersed in water It is a method of manufacturing.

In order to achieve the above another object, the coating agent, the adhesive agent and the sizing agent according to the present invention contain a water dispersible polyurethane or a polyurethane urea produced by the above-mentioned first and second production methods.

Hereinafter, the present invention will be described in detail.

In the present invention, there is no urethane or urea bond in the ionic group, and at least one ammonium ion is introduced at a farther distance from the main chain of the prepolymer. The diol and polyol having such a cationic group were mixed with diisocyanate or the like to perform an addition reaction to prepare a prepolymer having a terminal ending with an isocyanate group. The prepolymer thus prepared is neutralized and dispersed in water by self-emulsification and branched with a branch extender to obtain a water dispersible polyurethane or polyurethane urea.

This method can easily and uniformly obtain a dispersion without the use of a small amount of cation groups and solvents, and the dispersion thus prepared has a great advantage that it is inferior to the solution type in many respects as well as physical properties. In particular, when a double bond is introduced, a small amount of a thermal curing initiator, an ultraviolet curing initiator, and a branch extender may be added to form a crosslinking or the like during curing, thereby producing a water-dispersible polyurethane or polyurethane urea having excellent physical properties. .

As used herein, the cationic diol having at least one ammonium ion far away from the main chain has a structure represented by the following formula (1).

here,

R ¹ is hydrogen or a hydrocarbon having 1 to 8 carbon atoms,

R ² is an aliphatic, cycloaliphatic, or aromatic hydrocarbon group, preferably CH ₂ CH ₂ or CH ₂ CH ₂ CH ₂ .

R ³ and R ⁴ are aliphatic, cycloaliphatic, or aromatic hydrocarbon groups, preferably CH ₃ or CH ₂ CH ₃ .

These are converted into a form in which some or all of the tertiary amine can be neutralized with an ionic group and dispersed in water by a general neutralizing agent (an inorganic or organic acid).

Preparation of Polyurethane Prepolymer

It is prepared by mixing a polyol with a diol monomer having one or more ammonium ions introduced therein, followed by reacting a diisocyanate or diisocyanate polymer under generally known reaction conditions.

The polyols are preferably polyether polyols, polyester polyols, polylactone polyols, polycarbonate polyols, polythioether polyols, polyacetal polyols, aromatic polyols, or mixtures thereof.

The polyether polyol is preferably a polyoxyalkylene polyol having a plurality of hydroxyl groups of 2 to 8 and a mixture thereof, and a molecular weight of 300 to 6,500 is preferred. Their preparation is by random or staged addition by the reaction of alkylene oxides with polyvalent initiators, which is a well known method. Alkylene oxides include ethylene oxide, propylene oxide, butylene oxide, amylene oxide and the like. Aralkylene oxides such as styrene oxide, halogenated alkylene oxides such as butylene chloride oxide, tetrahydrofuran, epichlorohydrin, or the like are also available. In particular, the polyether polyols handled in this patent include PP-750, PP-950, PP-1000, PP-2000, PP-3000, PP-4000, GP-400, GP-280, GP-1000, GP-3000, GP-4000, GL-3000, Polytetrahydrofuran 250, Polytetrahydrofuran 650, Polytetrahydrofuran 1000, Polytetrahydrofuran 2000, Polytetrahydrofuran 2900, Polytetrahydrofuran 4500 All are suitable for this invention.

Polyester polyols are synthesized by reacting polycarboxylic acids with polyhydric alcohols. At this time, oxalic acid, malonic acid, rosinic acid, adipic acid, pimelic acid, subvertic acid, azeraic acid, sebacic acid, brasilic acid, tarpic acid, maleic acid, fmaric acid, glutamic acid as polycarboxylic acids Acids, α-hydromuconic acid, β-hydromuconic acid, isophthalic acid, terephthalic acid, hemimeltic acid, 1,4-cyclohexane-dicarbonylic acid or mixtures thereof are preferable, and as the polyhydric alcohol, Ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,4-pentanediol, 1,3-pentanediol, 1 , 6-hexanediol, 1,7-heptanediol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerol, 1,1,1-trimethyllopropane, 1,1,1-triethylethane, hexane- Preference is given to 1,2,6-triol, α-ethylglucoside, pentaneerythritiol, sorbitol or mixtures thereof.

The polylactone polyol is synthesized by reacting ε-carrolactone with a dihydric alcohol, and the molecular weight is generally 550, 1,000, 2,000, or the like.

The polycarbonate polyol is obtained by reacting diaryl carbonate, phosken, and diol.

Chain extenders used to control the properties of the polyurethane is as follows. Commonly used diols and polyols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, and 1,4-pentanediol , 1,3-pentanediol, 1,6-hexanediol, 1,7-heptanediol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerol, 1,1,1-trimethyllopropane, 1,1, 1-triethyl ethane, hexane-1,2,6-triol, α-ethylglucoside, pentaneerythritol, sorbitol and the like.

Diisocyanates include aromatic, cycloaliphatic and aliphatic diisocyanates.

Here, as the aliphatic or cycloaliphatic diisocyanate, hexamethylene diisocyanate, 4,4-dicyclohexylmethane diisocyanate, 1,4-tetramethylene diisocyanate, 1,10-decamethylene diisocyanate, isophorone diisocyanate, 1 , 4-cyclohexane diisocyanate, and the like, and aromatic diisocyanates include toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, 1,5-naphthalene diisocyanate, 4-methoxy-1,3 -Phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 2,4-dimethyl-1,3-phenylene diisocyanate, 4,4'- diisocyanate diphenyl ether, benzidine diisocyanate, 4 , 4'-diisocyanate dibenzyl and methylene-bis (4-phenyl isocyanate) -1,3-phenylene diisocyanate, or mixtures thereof.

In this reaction step, the ratio of the isocyanate group and the hydroxyl group of the reactant is preferably 0.5: 1 to 5: 1, more preferably 1.1: 1 to 2: 1. 25-150 degreeC is preferable and 25-100 degreeC of reaction temperature is more preferable.

In addition, to prepare a polyurethane prepolymer capable of UV / heat curing, a diol, diamine, primary amine monomer having a double bond is used in place of or in combination with the polyol. Where allylamine, allyl alcohol, 3-allyloxy-1,2-propanediol, trimethylolpropane allyl ether, diallylamine, N-ethyl-2- as a diol, diamine, or primary amine monomer having a double bond Methyl allylamine, hydroxypropyl acrylate or hydroxypropyl methacrylate are preferred, and when used in combination with a polyol, it is preferable to use from 0.1: 1 to 1: 0.1 molar ratio with respect to the polyol used, and 1: 0.2 to 1: 1 are more preferred.

Preparation of Water Dispersible Polyurethane or Polyurethane Urea

Water dispersible polyurethanes or polyurethane ureas can be readily prepared from the polyurethane prepolymers prepared above. This can be divided into a case of extending a branch again and a case of not.

In the case of branch extension, the tertiary amine of the prepolymer is first neutralized with a neutralizing agent and dispersed by addition of water. The dispersed prepolymer is branched with water or branched using an amine group having at least one activated hydrogen per nitrogen atom to prepare a water-dispersible polyurethane or polyurethane urea stable to water.

First, in the neutralization, it is possible to neutralize even a general neutralizing agent, but more preferable neutralizing agents are inorganic or organic acids, and mixtures thereof, soluble in water. The organic or inorganic acid may be hydrochloric acid, sulfuric acid, nitric acid, benzyl chloride, epichlorohydrin, glycolic acid, dimethyl sulfate, hydrobromic acid, trichloroacetic acid, trifluoroacetic acid, methane sulfonic acid, ethane sulfonic acid, benzene sulfonic acid, p-toluene Sulfonic acid, α-nitroacetic acid, acetic acid or formic acid. The addition amount of the neutralizing agent is most suitably an amount capable of neutralizing all tertiary amine groups included in the prepolymer, but can be dispersed even if only 50% of all tertiary amine groups are neutralized. That is, the molar ratio of the tertiary amine group to the neutralizing agent is preferably 1: 0.5 to 1: 1.2.

The amount of water used depends on the application in which such dispersions are used, but in general, it is preferred that the solids of the final dispersion be up to 80%. Therefore, UV or thermosetting water-dispersible polyurethanes or polyureas stable to water up to 80% of solids, that is, up to 80% by weight of solids, can be produced.

Branch extension is branch extension by adding a branch extender to an isocyanate-prepolymer which may be present in an aqueous solution for a certain time. The branch extender is a compound having two activated hydrogens and preferably has a molecular weight of 18 to 2,000. These are diols, triols, diamines, triamines, hydrazines, dihydrazines, or the like. Diamines include ethylene diamine, hexamethylene diamine, isophorone diamine, and the like. Diols include ethylene glycol, diethylene glycol, 1,4-butane diol, and the like, and triols such as glycerin. Triamines include melamine, diethylene triamine, and the like; triethylene tetramine, N-methyl-diethanolamine, N-butyl-diethanolamine, N-oleyl diethanolamine, N-chic Lohexyl-diethanolamine, N, N-dimethylhydrazine, N, N-dimethylethylenediamine or N, N-dimethyl-propylenediamine and the like are preferable.

In the case of not extending the branches, isocyanate groups at both ends of the polyurethane prepolymer prepared above are reacted with mono alcohol, mono secondary amine, mono amino alcohol or urea to prepare a polyurethane or polyurethane urea that is stable to water. Thereafter, the tertiary amine group is neutralized with a neutralizing agent and water is added to prepare a water dispersible polyurethane or polyurethane urea.

Reacting with the isocyanate groups at both ends of the prepared polyurethane prepolymer is a common mono alcohol, mono secondary amine, mono amino alcohol or urea.

Wherein the mono alcohol is R ¹ OH (R ¹ is a hydrocarbon group, preferably methyl or ethyl group) and the mono secondary amine is R ¹ R ² NH (R ¹ , R ² is a hydrocarbon group, preferably methyl or ethyl group ) And the mono amino alcohol is HOR ¹ NR ² R ³ (R ¹ is a hydrocarbon group, preferably an ethylene group, R ² and R ³ are each a hydrocarbon group, preferably a methyl group or an ethyl group).

Other additives other than the neutralizer and eggplant extender used to make the water dispersible polyurethane or polyurethane urea include thickening agents, pH adjusting agents, antifoaming agents and the like. The use of thickeners (US Pat. No. 3,923,713, Hermann) is preferred when an appropriate viscosity is required for application to coatings or adhesives, which are methylcellulose, hydroxyethylcellulose, polyacrylic emulsions plus polyarylic emulsions. plus alkalis, gums, and the like are suitable. Such dispersions may also be used in admixture with other dispersions (US Pat. No. 4,238,378, Markusch et al.).

In addition, fillers, plasticizers, pigments, carbon black, silica sol, aluminum clay, asbestos dispersion (asbestos dispersion) and the like can also be dispersed and used in such a dispersion.

UV / Heat Curable Water Dispersible Polyurethane or Polyurethane Urea Resin

In the production of UV / heat curable water-dispersible polyurethane or polyurethane urea resin, it can be divided into the case of branch extension and the case of no branch extension. In the case of branch extension first, UV / heat curing including the double bond When using a polyurethane prepolymer that can be used, it can be prepared in the same manner as the above-described water-dispersible polyurethane or polyurethane urea resin manufacturing process. When using a polyurethane prepolymer that does not contain a double bond and cannot be UV / heat cured, the UV curable water dispersible polyurethane or polyurethane urea using a diol, diamine, or primary amine monomer having a double bond as a branch extender. Can be prepared. In the case where branch extension is not performed, a water-dispersible polyurethane urea capable of ultraviolet / heat curing by adding a hydroxy vinyl monomer to the polyurethane prepolymer including the double bond or the polyurethane prepolymer not including the double bond. Prepare a resin. In addition, a thermosetting initiator, an ultraviolet curing initiator, or a mixture thereof may be added at a stage prior to neutralization with a neutralizing agent, and, if necessary, a thermosetting branch extending agent or an ultraviolet curing branch extending agent may be added.

Among the diol, diamine or primary amine monomers having a double bond, allylamine, allyl alcohol, 3-allyloxy-1,2-propanediol, trimethylolpropane allyl ether, diallylamine, N-ethyl-2- Methyl allylamine, hydroxypropyl acrylate or hydroxypropyl methacrylate and the like are preferable.

As the hydroxy vinyl monomer, a monomer having the following structural formula is preferable.

Wherein, R is a hydrocarbon group, preferably CH ₂ or CH ₂ CH _2. Or propylene glycol monoacrylate, pentaerythritol triacrylate, or the like.

The thermally curable initiator is preferably an organic or inorganic peroxide, azo compound, peroxide, organometallic compound, or a mixture thereof and the like, which is initiated at 50 to 200 ° C, and the addition amount thereof is a diol, diamine, primary amine monomer having a double bond or these Preference is given to 0.01 to 1 mole%, based on the total moles of the mixture of and branched extension added.

UV initiators include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, and benzoin octyl ether, which are initiated in the wavelength range of 180 to 460 nm of ultraviolet rays, diethoxyacetophenone, 2, 2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, methyl adraquinone, acetophenone, benzo Carbonyl compounds such as phenone, methyl benzoyl formate, benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholino-propene-1, di Compounds such as phenyl disulfide and dithiocarbamate, naphthalene compounds such as alpha-methylnaphthalene, condensed aromatic hydrocarbons such as anthracene, metal salts such as iron chloride, and the like, and the addition amount thereof is diol having a double bond, Diamines, primary amine monomers or their Preferred is from about 0.01 to 20% by weight relative to the total weight of the mixture and the branch extender added as necessary. In addition, ultraviolet light sources capable of emitting ultraviolet rays of 180 to 460 nm include low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, xenon mercury lamps, ultraviolet fluorescent lamps, carbon arc lamps, and electrodeless microwave lamps. desirable.

As a thermosetting type | mold ultraviolet-ray type | mold extension agent, the monomer which has a double bond in 2 or more terminal is used. Such monomers include butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, trimethylol propane triacrylate, pentaerythritol triacrylate, glyceryl propoxylay Acrylate derivatives such as tide triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacetate, alkoxylated tetraacetate, ditrimethylol propane tetraacrylate, styrene, acrylonitrile, or mixtures thereof. have. The amount of the monomer used is 0.01 to 50% by weight of the total solid, excluding water, preferably 0.1 to 10% by weight.

Thickening agents, pH adjusting agents, antifoaming agents, thickeners, and the like may be added to the ultraviolet curable water-dispersible polyurethane or polyurethane urea resin, and other dispersion resins may also be mixed with other dispersion resins. . In addition, fillers, plasticizers, pigments, carbon black, silica sol, aluminum clay, asbestos dispersion (asbestos dispersion) and the like can also be dispersed and used in such a dispersion.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

Synthesis Example 1

Preparation of Polyurethane Prepolymer Using Diol Having Two Ammonium Groups

A four-necked flask was equipped with a stirrer, a dry nitrogen flow device and a reflux tube, in which dimethylaminopropyldipropanolamine (15 g) containing two ammonium ions and polyetherdiol (PTMG-2000 BASF, or PPG-2000). Polyol Korea 100g), and DMF (20g) solvent and the catalyst dibutyltin dilaurate (0.0226g) was added and mixed sufficiently while passing through dry nitrogen at 60 ℃. And dicyclohexyl methane-4,4'- diisocyanate (Desmodure W, German Bayer, 39g) was added to react at 75 ℃ for 2 hours to prepare a polyurethane prepolymer of less than the theoretical isocyanate content. .

Synthesis Example 2

Preparation of Polyurethane Prepolymers Having Double Bonds Using Diols Having Two Ammonium Groups

A four-necked flask was equipped with a stirrer, a dry nitrogen flow device, and a reflux tube, in which a dimethylaminopropyldipropanolamine (15 g) containing two ammonium ions and a diol having a double bond trimethylolpropane allyl ether (trimethylolpropane allyl) ether, 5g), polyetherdiol (PTMG 2000 BASF or PPG 2000 Korea Polyol 100g), and DMF (20g) solvent and dibutyltin dilaurate (0.0226g) were added and passed through dry nitrogen at 60 ℃. The mixture was mixed sufficiently while making it. And dicyclohexyl methane-4,4'- diisocyanate (Desmodur W, Bayer, Germany, 47g) was added to react at 75 ℃ for 2 hours to prepare a polyurethane prepolymer of less than the theoretical isocyanate content.

Example 1

Preparation of Water Dispersible Polyurethane or Polyurethane Urea Using Polyurethane Prepolymer of Synthesis Example 1

After adding acetic acid, a neutralizing agent, equivalent to the equivalent of the tertiary amine of the prepolymer obtained in Synthesis Example 1, it was sufficiently neutralized by stirring for about 10 minutes. And a constant amount of water was added at a constant speed while vigorously stirring at a stirring speed of 1,000-2,000 RPM to disperse the prepolymer. At this time, an appropriate amount of water was added to adjust the amount of water to 30% or 35% of the total solids of the final dispersion.

While continuously dispersing the prepolymer dispersed in this way, ethylene diamine, which is a branch extender, was mixed with water and slowly added dropwise for about 5 to 10 minutes, followed by continuous stirring for 2 hours or longer to extend branch. The amount of ethylene diamine added was added by the equivalent of theoretical free-isocyanate.

The dispersion thus obtained is transparent and has a particle radius of about 20 nm.

Example 2

Preparation of Water Dispersible Polyurethane or Polyurethane Urea Using Branch Extender UV Curable Using Polyurethane Prepolymer of Synthesis Example 1

After adding acetic acid, a neutralizing agent, equivalent to the equivalent of the tertiary amine of the prepolymer obtained in Synthesis Example 1, it was sufficiently neutralized by stirring for about 10 minutes. In addition, benzoylperoxide (benzoylperoxide) at the time of heat curing, benzophenone (benzophenone) at the time of ultraviolet curing was added by 1 wt% and sufficiently stirred, and then vigorously stirred at a stirring speed of 1,000-2,000 RPM to add a certain amount of water at a constant speed. The prepolymer was dispersed. At this time, an appropriate amount of water was added to adjust the amount of water to 40% or 50% of the total solids of the final dispersion.

While continuing stirring the dispersed prepolymer, diallylamine, which is a branching agent containing a double bond in a molecule, was mixed with water and slowly added dropwise for about 5 to 10 minutes, followed by stirring for 2 hours or longer to extend branching. The amount of diallylamine added was added by the equivalent of theoretical free-isocyanate.

The dispersion thus obtained is transparent and has a particle radius of about 35 nm.

Example 3

Preparation of Water Dispersible Polyurethane or Polyurethane Urea Using UV-curable Crosslinking Agent and Branch Extender Using Polyurethane Prepolymer of Synthesis Example 1

After adding acetic acid, a neutralizing agent, equivalent to the equivalent of the tertiary amine of the prepolymer obtained in Synthesis Example 1, it was sufficiently neutralized by stirring for about 10 minutes. And 10% by weight of trimethylolpropane triacrylate (TMPTA) as a crosslinking agent, benzoylperoxide (benzoylperoxide) at the time of heat curing, benzophenone (1% by weight) at the time of ultraviolet curing was sufficiently stirred and then stirred A constant amount of water was added at a constant rate while vigorously stirring at a stirring rate of 1,000-2,000 RPM to disperse the prepolymer. At this time, an appropriate amount of water was added to adjust the amount of water to 40% or 50% of the total solids of the final dispersion.

While continuing dispersing the prepolymer dispersed in this way, diarylamine, which is a branch extender, was mixed with water and slowly added dropwise for about 5 to 10 minutes, followed by stirring for 2 hours or more to extend branch extension. The addition amount of diarylamine was added by the equivalent of theoretical free-isocyanate.

The dispersion thus obtained is transparent and has a particle radius of about 120 nm.

Example 4

Preparation of Water Dispersible Polyurethane or Polyurethane Urea without Branch Extension after Reaction of Polyurethane Prepolymer of Synthesis Example 1 with HEMA

After reacting by adding HEMA to the equivalent amount of preisocyanate of the prepolymer obtained in Synthesis Example 1, the reaction mixture was neutralized by adding about 10 minutes of acetic acid, which is theoretically equivalent to the equivalent amount of tertiary amine. In addition, benzoylperoxide (benzoylperoxide) at the time of heat curing, benzophenone (benzophenone) at the time of ultraviolet curing was added by 1 wt% and sufficiently stirred, and then vigorously stirred at a stirring speed of 1,000-2,000 RPM to add a certain amount of water at a constant speed. The prepolymer was dispersed. At this time, an appropriate amount of water was added to adjust the amount of water to 40% or 50% of the total solids of the final dispersion.

The dispersion thus obtained is transparent and has a particle radius of about 45 nm.

Example 5

Preparation of Water Dispersible Polyurethane or Polyurethane Urea without Branch Extension by Using a UV-curable Crosslinking Agent After Reaction of the Polyurethane Prepolymer of Synthesis Example 1 with HEMA

After reacting by adding HEMA to the equivalent amount of preisocyanate of the prepolymer obtained in Synthesis Example 1, the reaction mixture was neutralized by adding about 10 minutes of acetic acid, which is theoretically equivalent to the equivalent amount of tertiary amine. And 10% by weight of trimethylolpropane triacrylate (TMPTA) as a crosslinking agent, benzoylperoxide (benzoylperoxide) at the time of thermal curing, benzophenone at the time of ultraviolet curing was added by 1wt% and stirred sufficiently at a stirring speed of 1,000-2,000 RPM A constant amount of water was added at a constant rate with vigorous stirring to disperse the prepolymer. At this time, an appropriate amount of water was added to adjust the amount of water to 40% or 50% of the total solids of the final dispersion.

The dispersion thus obtained is transparent and has a particle radius of about 60 nm.

Example 6

Preparation of Water Dispersible Polyurethane or Polyurethane Urea Using Polyurethane Prepolymer of Synthesis Example 2

After adding acetic acid which is a neutralizing agent by the equivalent of the tertiary amine theoretically possessed in Synthesis Example 2, it was sufficiently neutralized by stirring for about 10 minutes. And a constant amount of water was added at a constant speed while vigorously stirring at a stirring speed of 1,000-2,000 RPM to disperse the prepolymer. At this time, an appropriate amount of water was added to adjust the amount of water to 30% or 35% of the total solids of the final dispersion.

While continuously dispersing the prepolymer dispersed in this way, ethylene diamine, which is a branch extender, was mixed with water and slowly added dropwise for about 5 to 10 minutes, followed by continuous stirring for 2 hours or longer to extend branch. The amount of ethylene diamine added was added by the equivalent of theoretical free-isocyanate.

The dispersion thus obtained is transparent and has a particle radius of about 25 nm.

Example 7

Preparation of Water Dispersible Polyurethane or Polyurethane Urea Using Polyurethane Prepolymer of Synthesis Example 2

After adding acetic acid which is a neutralizing agent by the equivalent of the tertiary amine theoretically possessed in Synthesis Example 2, it was sufficiently neutralized by stirring for about 10 minutes. In addition, the initiator is added by benzoylperoxide (benzoylperoxide) at the time of heat curing, benzophenone (uvphenone) at the time of ultraviolet curing by adding a sufficient amount of water at a constant rate while stirring vigorously at a stirring speed of 1,000-2,000 RPM Was added to disperse the prepolymer. At this time, an appropriate amount of water was added to adjust the amount of water to 30% or 35% of the total solids of the final dispersion.

While continuously dispersing the prepolymer dispersed in this way, ethylene diamine, which is a branch extender, was mixed with water and slowly added dropwise for about 5 to 10 minutes, followed by continuous stirring for 2 hours or longer to extend branch. The amount of ethylene diamine added was added by the equivalent of theoretical free-isocyanate.

The dispersion thus obtained is transparent and has a particle radius of about 30 nm.

Example 8

Preparation of Water Dispersible Polyurethane or Polyurethane Urea Using Branch Extension Agent UV Curable Using Polyurethane Prepolymer of Synthesis Example 2

After adding acetic acid which is a neutralizing agent by the equivalent of the tertiary amine theoretically possessed in Synthesis Example 2, it was sufficiently neutralized by stirring for about 10 minutes. In addition, the initiator is added by benzoylperoxide (benzoylperoxide) at the time of heat curing, benzophenone (uvphenone) at the time of ultraviolet curing by adding a sufficient amount of water at a constant rate while stirring vigorously at a stirring speed of 1,000-2,000 RPM Was added to disperse the prepolymer. At this time, an appropriate amount of water was added to adjust the amount of water to 40% or 50% of the total solids of the final dispersion.

While continuing stirring the dispersed prepolymer, diallylamine, which is a branching agent containing a double bond in a molecule, was mixed with water and slowly added dropwise for about 5 to 10 minutes, followed by stirring for 2 hours or longer to extend branching. The amount of diallylamine added was added by the equivalent of theoretical free-isocyanate.

The dispersion thus obtained is transparent and has a particle radius of about 40 nm.

Example 9

Preparation of Water Dispersible Polyurethane or Polyurethane Urea Using UV-curable Crosslinking Agent and Branch Extender Using Polyurethane Prepolymer of Synthesis Example 2

After adding acetic acid which is a neutralizing agent by the equivalent of the tertiary amine theoretically possessed in Synthesis Example 2, it was sufficiently neutralized by stirring for about 10 minutes. 10 wt% of trimethylolpropane triacrylate (TMPTA) as a crosslinking agent, and benzoylperoxide (benzoylperoxide) at the time of heat curing and benzophenone (1 wt%) at the time of ultraviolet curing, were sufficiently stirred, and then stirred. A constant amount of water was added at a constant rate while vigorously stirring at a stirring rate of 1,000-2,000 RPM to disperse the prepolymer. At this time, an appropriate amount of water was added to adjust the amount of water to 40% or 50% of the total solids of the final dispersion.

While continuing dispersing the prepolymer dispersed in this way, diarylamine, which is a branch extender, was mixed with water and slowly added dropwise for about 5 to 10 minutes, followed by stirring for 2 hours or more to extend branch extension. The addition amount of diarylamine was added by the equivalent of theoretical free-isocyanate.

The dispersion thus obtained is transparent and has a particle radius of about 130 nm.

Example 10

Preparation of Water Dispersible Polyurethane or Polyurethane Urea without Branch Extension after Reaction of Polyurethane Prepolymer of Synthesis Example 2 with HEMA

After reacting by adding HEMA to the equivalent amount of preisocyanate of the prepolymer obtained in Synthesis Example 2, the reaction mixture was neutralized by adding about 10 minutes of acetic acid, which is a neutralizing agent, equivalent to the equivalent amount of tertiary amine. In addition, the initiator is added by benzoylperoxide (benzoylperoxide) at the time of heat curing, benzophenone (uvphenone) at the time of ultraviolet curing by adding a sufficient amount of water at a constant rate while stirring vigorously at a stirring speed of 1,000-2,000 RPM Was added to disperse the prepolymer. At this time, an appropriate amount of water was added to adjust the amount of water to 40% or 50% of the total solids of the final dispersion.

The dispersion thus obtained is transparent and has a particle radius of about 55 nm.

Example 11

Preparation of Water Dispersible Polyurethane or Polyurethane Urea without Branch Extension by Using a UV-curable Crosslinking Agent After Reaction of the Polyurethane Prepolymer of Synthesis Example 2 with HEMA

After reacting by adding HEMA to the equivalent amount of preisocyanate of the prepolymer obtained in Synthesis Example 2, the reaction mixture was neutralized by adding about 10 minutes of acetic acid, which is a neutralizing agent, equivalent to the equivalent amount of tertiary amine. 10 wt% of trimethylolpropane triacrylate (TMPTA) as a crosslinking agent, and benzoylperoxide (benzoylperoxide) at the time of heat curing and benzophenone (1 wt%) at the time of ultraviolet curing, were sufficiently stirred, and then stirred. A constant amount of water was added at a constant rate while vigorously stirring at a stirring rate of 1,000-2,000 RPM to disperse the prepolymer. At this time, an appropriate amount of water was added to adjust the amount of water to 40% or 50% of the total solids of the final dispersion.

The dispersion thus obtained is transparent and has a particle radius of about 80 nm.

Preparation of the Psalms and Their Properties

The dispersions obtained in Examples 1 and 6 were first poured into a polypropylene plate (PP plate) (10 × 20 cm) and left in a low temperature 50 ° C. heat chamber for 3 hours in order to obtain a clean film, followed by a 80 ° C. heat chamber. Left for 3 hours to obtain a fully cured film. Then, the film was separated from the plate and left for 24 hours in a 60 ° C./20 mmHg decompression heat chamber in order to completely remove residual moisture to obtain a film having a thickness of about 0.3 ± 0.05 mm.

Exterior Tensile strength at break (kg / cm ² ) Elongation at Break (%) 100% modulus (kg / cm ² ) Example 1 Transparency 203 1094 20 Example 6 Transparency 189 1100 15

The dispersions obtained in Examples 2, 3, 4, 5, 7, 8, 9, 10 and 11 were first poured into a polypropylene plate (PP plate) (10 × 20 cm) and then heated in a 50 ° C. chamber to sufficiently remove excess moisture. It was left for 4 hours, and in the case of thermal curing, the heat chamber temperature was raised to 85 ° C. and left for 3 hours to obtain a cured film. In the case of UV curing, the temperature was raised to 80 ° C. to further remove water for 5 hours, and then, by UV irradiation in that state, a cured film was obtained. In order to completely remove the residual moisture of the obtained film, it was left for 24 hours in a 60 ℃ / 20mmHg pressure-reduction heat chamber to obtain a film of about 0.3 ± 0.05mm thickness.

division Exterior Tensile strength at break (kg / cm ² ) Elongation at Break (%) 100% modulus (kg / cm ² ) Example 2 Transparency 210 950 25 Example 3 Transparency 230 740 34 Example 4 Transparency 245 650 40 Example 5 Transparency 260 600 55 Example 7 Transparency 215 870 30 Example 8 Transparency 223 750 35 Example 9 Transparency 245 550 48 Example 10 Transparency 290 420 65 Example 11 Transparency 330 310 80

The water-dispersible polyurethane or polyurethane urea prepared in the present invention is excellent in solvent resistance, abrasion resistance, hydrolysis resistance, toughness, elasticity, dispersibility, etc., impregnating agent, coating agent, adhesive and nonwoven fabric of artificial leather, plastic, wood, metal It is well suited for use as coatings and adhesives, and paper sizing agents. In particular, UV-curable water-dispersible polyurethane or polyurethane urea has extended properties or crosslinks during curing, so that its physical properties are greatly improved, which further improves solvent resistance, abrasion resistance, gloss, toughness, and the like. Very good as a coating agent.

Claims (24)

Cationic diols having at least one ammonium ion in the main chain at least two carbon atoms apart; Polyester polyols, polyether polyols, polylactone polyols, polycarbonate polyols, polythioether polyols, polyacetal polyols, aromatic polyols or mixtures thereof; And reacting a reactant comprising a diisocyanate, a diisocyanate polymer or a mixture thereof to produce a polyurethane prepolymer having an isocyanate group content of 0.5 to 30%. The method of claim 1, wherein the reactant further comprises a diol, a diamine, a primary amine monomer having a double bond, or a mixture thereof. The diol, diamine, or primary amine monomer having a double bond is selected from allylamine, allyl alcohol, 3-allyloxy-1,2-propanediol, trimethylolpropane allyl ether, diallylamine or N. A process for producing a polyurethane prepolymer having a double bond, which is -ethyl-2-methylallylamine. The method of claim 1, wherein the cationic diol has the following structural formula. Wherein R ¹ is hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, R ² , R ³ , and R ⁴ are each an aliphatic, cycloaliphatic or aromatic hydrocarbon group. 5. The method of claim 4, wherein R ¹ is hydrogen or a methyl group, R ² is an ethylene group or a propylene group, and R ³ and R ⁴ are a methyl group or an ethyl group, respectively. The method of claim 1, wherein the diisocyanate polymer is prepared by addition reaction of diisocyanate, polyester polyol, polyether polyol or a mixture thereof, the isocyanate content is 0.1 to 30%, the molecular weight is 200 to 8,000 Method of producing a polyurethane prepolymer. Cationic diols having at least one ammonium ion in the main chain at least two carbon atoms apart; Polyester polyols, polyether polyols, polylactone polyols, polycarbonate polyols, polythioether polyols, polyacetal polyols, aromatic polyols or mixtures thereof; And reacting a reactant comprising a diisocyanate, a diisocyanate polymer or a mixture thereof to prepare a polyurethane prepolymer having an isocyanate group content of 0.5 to 30%; Neutralizing the polyurethane prepolymer with a neutralizing agent; Dispersing said neutralized polyurethane prepolymer in water; And Water dispersible polyurethane or polyurethane stable to water up to 80% solids, comprising the step of adding the dispersed polyurethane prepolymer with a branch extender or addition reaction with mono alcohol, secondary amine, urea or mixtures thereof How to make urea. The method of claim 7, wherein the reactant further comprises a diol, a diamine, a primary amine monomer having a double bond, or a mixture thereof. 8. The method of claim 7, wherein the neutralizing agent is an inorganic acid, an organic acid, or a mixture thereof, which is dissolved in water, and is added so that the molar ratio of tertiary amine to neutralizing agent included in the prepolymer is 1: 0.5 to 1: 1.2. Process for producing water dispersible polyurethane or polyurethane urea. The method of claim 9, wherein the inorganic acid or organic acid is hydrochloric acid, sulfuric acid, nitric acid, benzyl chloride, epichlorohydrin, glycolic acid, dimethyl sulfate, hydrobromic acid, trichloroacetic acid, trifluoroacetic acid, methane sulfonic acid, ethane sulfonic acid, benzene sulfonic acid , p-toluene sulfonic acid, α-nitroacetic acid, acetic acid or formic acid, characterized in that the method for producing a water-dispersible polyethane or polyurethane urea. 8. A process according to claim 7, wherein said branch extender is a diol, triol or polyamine having two activated hydrogens and having a molecular weight of 18 to 2,000. The method of claim 7, wherein the mono alcohol is R ¹ OH (wherein R ¹ is a methyl group or an ethyl group), the secondary amine is R ¹ R ² NH (wherein R ¹ , R ² is a methyl group or ethyl group) , Mono amino alcohol is HOR ¹ NR ² R ³ (wherein R ¹ is an ethylene group, R ² and R ³ is a methyl group or an ethyl group, respectively) method of producing a water dispersible polyurethane or polyurethane urea. Cationic diols having at least one ammonium ion in the main chain at least two carbon atoms apart; Diols, diamines, primary amine monomers having a double bond or mixtures thereof; Polyester polyols, polyether polyols, polylactone polyols, polycarbonate polyols, polythioether polyols, polyacetal polyols, aromatic polyols, or mixtures thereof; And reacting the diisocyanate, diisocyanate polymer or a mixture thereof to prepare a polyurethane prepolymer having a double bond having an isocyanate group content of 0.5 to 30%; Neutralizing the polyurethane prepolymer with a neutralizing agent; Dispersing said neutralized polyurethane prepolymer in water; Addition reaction of the dispersed polyurethane prepolymer with a branch extender or addition reaction with mono alcohol, secondary amine, urea or a mixture thereof; And A method of making an ultraviolet or heat curable water dispersible polyurethane or polyurethane urea, which is stable to water up to 80% solids, comprising curing the result with an ultraviolet or heat curable initiator. The method according to claim 13, wherein the ultraviolet or thermosetting initiator is added to prepare the polyurethane prepolymer having the double bond to prepare the ultraviolet or heat curable water dispersible polyurethane or the polyurethane urea having the double bond. The method according to claim 13, wherein after producing the water-dispersible polyurethane or polyurethane urea having the double bond, the UV- or thermosetting initiator is added to produce an ultraviolet- or heat-curable water-dispersible polyurethane or polyurethane urea. The method of claim 13, wherein the UV-curable initiator is benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin octyl ether, benzyl, diacetyl, diethoxy acetophenone, 2,2-die Methoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, methylanthraquinone, acetophenone, benzophenone, benzoyl Methyl formate, benzyldimethyl ketal, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholino-propene-1, diphenyldisulfide, dithiocarbamate , Alpha-methylnaphthalene, anthracene or iron chloride, and water dispersible polyurethane, characterized in that 0.01 to 20 parts by weight based on 100 parts by weight of the diol, diamine, primary amine monomer having a double bond or a mixture thereof. How to make polyurethane urea. The method of claim 13, wherein the curing of the resultant with the UV curing initiator comprises: leaving the resultant in a heat chamber at 30 to 60 ° C. for about 3 hours to remove most of the water; And On the result of most of the water removed, low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, xenon mercury lamp, ultraviolet fluorescent lamp, carbon arc lamp or electrodeless microwave UV lamp which can emit ultraviolet light of 180 to 460 nm. Method of producing a water-dispersible polyurethane or polyurethane urea comprising the step of irradiating ultraviolet rays using. The method of claim 13, wherein the thermally curable initiator is an organic or inorganic peroxide, azo compound, hydrogen peroxide, organometallic compound or a mixture thereof, and 0.01 to the diol, diamine, primary amine monomer having a double bond or a mixture thereof. To 1 mol%, and the reaction temperature of the thermal curing initiator is 50 to 200 ℃ producing a water-dispersible polyurethane or polyurethane urea characterized in that. The method of claim 13, wherein the curing of the thermal curing initiator comprises: leaving the resultant in a heat chamber at 30 to 60 ° C. for about 3 hours to remove most of the water; And Method of producing a water-dispersible polyurethane or polyurethane urea comprising the step of leaving the result in a heat chamber of 50 to 200 ℃. Cationic diols having at least one ammonium ion in the main chain at least two carbon atoms apart; Diols, diamines, primary amine monomers having a double bond or mixtures thereof; Polyester polyols, polyether polyols, polylactone polyols, polycarbonate polyols, polythioether polyols, polyacetal polyols, aromatic polyols, or mixtures thereof; And reacting the diisocyanate, diisocyanate polymer or a mixture thereof to prepare a polyurethane prepolymer having a double bond having an isocyanate group content of 0.5 to 30%; Preparing a urethane acrylate prepolymer by adding a hydroxy vinyl monomer to the polyurethane prepolymer; Adding an ultraviolet ray or thermosetting initiator to the urethane acrylate prepolymer; Neutralizing the urethane acrylate prepolymer with a neutralizing agent; Dispersing the neutralized urethane acrylate prepolymer in water and curing the fruit with an ultraviolet or heat curable initiator, to a water content up to 80% solids, ultraviolet or heat curable water dispersible polyurethane or polyurethane urea How to manufacture. The ultraviolet or heat curable water dispersible polyurethane or polyurethane according to claim 20, further comprising adding a crosslinking agent having a double bond to two or more terminals in the step of adding the ultraviolet or thermosetting initiator to the urethane acrylate prepolymer. How to make urea. 21. The method of claim 20, wherein the hydroxyvinyl monomers include hydroxymethyl methacrylate, hydroxymethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxy butyl acrylate and hydroxyhexyl acrylate. And pentaerythritol tetraacrylate or a mixture thereof in a 1 to 1 equivalent reaction with respect to the NCO equivalent of the polyurethane prepolymer, wherein the ultraviolet or heat curable water-dispersible polyurethane or polyurethane urea is prepared. 22. The method of claim 21, wherein the crosslinking agent having a double bond at two or more terminals includes butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, trimethylol propane Acrylates such as triacrylate, pentaerythritol triacrylate, glyceryl propoxylated triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacetate, alkoxylated tetraacetate and ditrimethylol propane tetraacrylate A derivative, styrene, acrylonitrile, or a mixture thereof, the method for producing an ultraviolet or heat curable water-dispersible polyurethane or polyurethane urea, characterized by using 0.01 to 50% by weight of the total solids, excluding water. Cationic diols having at least one ammonium ion in the main chain at least two carbon atoms apart; Diols, diamines, primary amine monomers having a double bond or mixtures thereof; Polyester polyols, polyether polyols, polylactone polyols, polycarbonate polyols, polythioether polyols, polyacetal polyols, aromatic polyols, or mixtures thereof; And neutralizing a polyurethane prepolymer having a double bond having a content of 0.5 to 30% of isocyanate groups with a neutralizing agent and adding a branch extender and an ultraviolet or heat curable initiator A coating material containing ultraviolet or heat curable water-dispersible polyurethane or polyurethane urea that is stable in water to 80% of the solid content prepared by dispersing in water.