JP2007023177A - Active energy ray-curing type aqueous urethane resin dispersion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new active energy ray-curing type aqueous urethane resin dispersion having excellent storage stability as an aqueous urethane resin dispersion and making a coating containing the resin dispersion form a film having excellent surface hardness and durability, especially alkali resistance by a drying step and an active energy ray irradiating step. <P>SOLUTION: The active energy ray-curing type aqueous urethane resin dispersion is obtained by reacting a polyalkylene ether chain-containing diol compound (A) with a polyol (B), a polyisocyanate (C) and a compound (D) having an α,β-unsaturated double bond and a hydroxy group in combination. The polyalkylene ether chain-containing diol compound (A) has a polyalkylene ether chain in a pendant form and two primary hydroxy groups. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention provides a polyalkylene ether chain-containing diol compound (A) having two primary hydroxyl groups having a polyalkylene ether chain in a pendant form, a polyol (B), a polyisocyanate (C), and α, β- The present invention relates to an active energy ray-curable aqueous urethane resin dispersion obtained by reacting a compound (D) having both an unsaturated double bond and a hydroxyl group.

  The active energy ray-curable resin composition is generally recognized as having excellent safety from the viewpoint of productivity and energy saving because it is excellent in safety because it does not contain a solvent and is excellent in curability. In view of such characteristics, the active energy ray-curable resin composition is employed as an active ingredient for various coatings and adhesives such as metal paints, various plastic film overcoat agents, woodwork paints, and printing inks.

  In the above applications, when it is necessary to reduce the viscosity of the product in spray coating, coating of several μm units with a roll coater, etc., a large amount of reactive diluent is usually used or an organic solvent is used in combination. Such a method is adopted. However, when a large amount of reactive diluent is used, problems such as skin irritation and curability deterioration are likely to occur, and when an organic solvent is used in combination, the risk of air pollution and fire increases.

  Therefore, in recent years, there has been an increasing demand for water-based compositions from the viewpoints of air pollution prevention, regulations under the Fire Service Act, occupational safety and health, and the like. Various water-based active energy ray-curable resin compositions have already been developed. As an anion type, a carboxylic acid salt or a sulfonic acid salt is generally introduced into the skeleton of polyurethane acrylate and dissolved or dispersed in water due to its hydrophilicity.

  The conventional active energy ray-curable aqueous urethane resin composition is composed of water and active energy ray-curable microgel particles dispersed in water, and the microgel particles have a urethane bond between the polyurethane resin skeleton and the skeleton. A gel-form film-forming polyurethane resin particle having a crosslinked structure crosslinked through a urea bond, wherein the polyurethane resin particle has an active energy ray-curable unsaturated double bond and a salt group An active energy ray-curable aqueous dispersion is known (see, for example, Patent Document 1). In this, it is described that the active energy ray-curable microgel particles improve the alkali resistance of the film cured with the active energy ray and improve the curability (wear resistance) of the film. In order to improve the alkali resistance in the presence of strong alkali in the formed film, it is necessary to reduce the amount of anionic functional groups in the active energy ray-curable microgel particles. However, the weight loss of the anionic functional group decreases the stability of the resin dispersion. Further, in order to increase the curability of the film, it is necessary to increase the amount of branched triisocyanate, but the stability of the resin solution is also lowered due to the cohesive strength of the resin.

  An active energy ray-curable water-containing resin composition using polyethylene glycol monoalkyl ethers containing one hydroxyl group has been proposed as a nonionic active energy ray-curable aqueous urethane resin composition (for example, Patent Documents). 2). However, when polyethylene glycol monoalkyl ethers containing one hydroxyl group are introduced by this proposed synthesis method, a polyethylene glycol chain is present at the end of the urethane resin, and a high molecular weight branched urethane resin is produced. In this case, the stability of the composition is poor.

JP-A-8-259888 Japanese Patent No. 2590682

  The subject of this invention is providing the novel active energy ray hardening-type water-based urethane resin dispersion which is excellent in storage stability with alkali resistance.

  As a result of intensive studies to solve the above problems, the present inventors have reacted a diol compound having a specific structure, a polyol, a polyisocyanate, and a compound having both an α, β-unsaturated double bond and a hydroxyl group. It was found that a novel active energy ray-curable aqueous urethane resin dispersion in which the polyalkylene ether chain thus obtained was introduced into the side chain of the polyurethane in a pendant manner could solve the above-mentioned problems, and the present invention was completed. It was.

  That is, the present invention provides a polyalkylene ether chain-containing diol compound (A) represented by the following general formula (1), polyol (B), polyisocyanate (C), and α, β-unsaturated double bond: Provided is an active energy ray-curable aqueous urethane resin dispersion obtained by reacting a compound (D) having both hydroxyl groups.

（式中、Ｒ１は、炭素数１〜９のアルキレン基又はジアルキレンエーテル基であり、Ｒ２は、炭素数１〜９のアルキル基であり、Ｒ３は、−ＣＯ−ＮＨ−Ｒ４−ＮＨ−ＣＯ−であり、Ｒ４は、炭素数２〜１８の有機基であり、Ａは、分子量２００〜１００００の２価のポリアルキレンエーテル基である。）

(In the formula, R 1 is an alkylene group or dialkylene ether group having 1 to 9 carbon atoms, R 2 is an alkyl group having 1 to 9 carbon atoms, and R 3 is —CO—NH—R 4 —NH—CO. R4 is an organic group having 2 to 18 carbon atoms, and A is a divalent polyalkylene ether group having a molecular weight of 200 to 10,000.

  The active energy ray-curable aqueous urethane resin composition using a polyalkylene ether chain-containing diol compound as a raw material of the present invention is extremely excellent in storage stability, and is hard and durable by drying and irradiation with active energy rays. In particular, a film having good alkali resistance can be formed.

  The present invention will be described in detail. First, the method for producing the polyalkylene ether chain-containing diol compound represented by the general formula (1) will be described.

  In the compound (I), R1 is an alkylene group or dialkylene ether group having 2 to 9 carbon atoms, R2 is an alkyl group having 1 to 9 carbon atoms, and A is a divalent polyvalent polymer having a molecular weight of 200 to 10,000. The primary amine, compound (II), which is an alkylene ether group, represents a monoacrylate having a hydroxyl group, wherein R1 is an alkyl group having 2 to 9 carbon atoms.

  The production method of the polyalkylene ether chain-containing diol compound is as follows. First, the compound (I) and the compound (II) are subjected to a so-called Michael addition reaction to obtain a secondary amine compound (III) having a primary hydroxyl group at the end of the molecule.

  Next, between 2 moles of the secondary amine compound (III) and 1 mole of the diisocyanate represented by (IV), the NH group and the NCO group of the diisocyanate are reacted leaving the hydroxyl group, and a polyalkylene ether chain-containing geopolymer. -The compound is produced.

  Examples of the primary amine having a polyalkylene ether group of Compound (I) include ethylene oxide (abbreviated as EO), 1,2- and 1,3, one end of which is blocked with an alkyloxy group such as a methoxy group ethoxy group. -Homopolymerization of intramolecular cyclic ether compounds such as propylene oxide (abbreviated as PO), 1,2-, 2,3- and 1,4-butylene oxide, alkyltetrahydrofuran or two or more types of random copolymerization and block copolymerization A polyalkylene oxide group having a number average molecular weight of 200 to 10,000, preferably 400 to 4,000, obtained by the above method is bonded to an amino group via an alkylene group or dialkylene ether group having 2 to 9 carbon atoms. A monoamine compound is mentioned.

  Examples of the monoacrylate having a hydroxyl group (II) include 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, hydroxypropyl acrylate, diethylene glycol monoacrylate, dipropylene glycol monoacrylate, triethylene glycol monoacrylate, and tripropylene. Examples include glycol monoacrylate.

  Diisocyanates are used for the purpose of reacting the secondary amino group of the secondary amine compound (III) with an isocyanate group and dimerizing the secondary amino compound (III) with a urea bond. Aromatic diisocyanates such as diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, phenylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate And aliphatic or alicyclic diisocyanates such as norbornene diisocyanate. However, aliphatic and alicyclic diisocyanates are preferable to highly reactive aromatic diisocyanates. Specifically, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate (TMDI), isophorone diisocyanate, dicyclohexylmethane diisocyanate (hydrogenated MDI) are preferred. More preferably used.

  Next, the polyalkylene ether chain-containing diol compound (A) of the general formula (1) is a polyol (B), a polyisocyanate (C), a compound having both an α, β-unsaturated double bond and a hydroxyl group (D The method for producing the active energy ray-curable aqueous urethane resin dispersion of the present invention is reacted.

  Examples of the polyol (B) that reacts with the polyisocyanate include polyols, low molecular polyols, and the like that are usually used as raw materials for polyurethane resins other than the polyalkylene ether chain-containing diol compound (A) of the general formula (1) of the present invention. Can be used.

  Examples of such polyols include polyesters, polycarbonates, polyester carbonates, polyethers, polyether carbonates, polyacrylates, polyolefin compounds, and polyester amides having a hydroxyl group at the terminal. Among these, polyesters, polycarbonates Polyethers, polyacrylates and polyolefin compounds are preferred.

  Examples of the polyester having a hydroxyl group at the terminal include a reaction product of a dihydric alcohol and a dibasic carboxylic acid. Instead of the free dicarboxylic acids, the corresponding anhydrides or diesters of lower alcohols or mixtures thereof can also be used for the production of the polyester.

  The dihydric alcohol is not particularly limited, but ethylene glycol, 1,3- and 1,2-propylene glycol, 1,4- and 1,3- and 2,3-butanediol, 1,6- Hexane glycol, 1,8-octanediol, neopentyl glycol, cyclohexanedimethanol, 1,4-bis- (hydroxymethyl) -cyclohexane, 2-methyl-1,3-propanediol, 2,2,4-trimethyl- Examples include 1,3-pentanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and dibutylene glycol.

  The dibasic carboxylic acid can be aliphatic, alicyclic, aromatic and / or heterocyclic and can be unsaturated or substituted with, for example, a halogen atom. Examples of these carboxylic acids include, but are not limited to, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimethic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahexan anhydride Examples include hydrophthalic acid, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic anhydride, maleic acid, fumaric acid, dimer fatty acid, dimethyl terephthalate and mixed terephthalate.

  These polyesters having hydroxyl groups at the ends can also have some of the carboxy end groups. For example, a lactone such as ε-caprolactone or a polyester of a hydroxycarboxylic acid such as ε-hydroxycaproic acid can be used.

  Examples of the polycarbonate having a hydroxyl group at the terminal include 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, polyethylene glycol, polypropylene glycol and / or polytetramethylene glycol. The reaction product of diol and phosgene, diallyl carbonate (for example, diphenyl carbonate) or cyclic carbonate (for example, propylene carbonate) can be mentioned.

  As the polyether having a hydroxyl group at the terminal, a starting compound having a reactive hydrogen atom and an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran, epichlorohydrin, or a mixture of these alkylene oxides are used. Reaction products are mentioned.

  Examples of such starting compounds having reactive hydrogen atoms include water, bisphenol A, and dihydric alcohols described above for producing polyester polyols.

  Examples of the low molecular weight polyol include the dihydric alcohols described above.

  A typical example of a polyacrylic ester having a hydroxy group at the terminal is α, ω-polyacrylic ester diol (for example, Tego Diol BD1000 manufactured by Tego Chemei).

  Examples of the polyolefin compound having a hydroxyl group at the terminal include hydroxyl group-terminated liquid polybutadiene, hydroxyl group-terminated polyolefin-based polyol (manufactured by Idemitsu Petrochemical Co., Ltd., Poly Bd R-15H, Epol).

  In the active energy ray-curable aqueous urethane resin dispersion of the present invention, the cohesive force can be increased by increasing the branching of the resin by setting the proportion of the triol or higher component in the polyol (B) to 10 to 40 mol%. In addition, by making the α, β-unsaturated double bond 1.0 to 6.0 mol / kg, the curability of the film is improved, and the alkali resistance and excellent wear resistance of the resin are improved. It is possible to obtain the film shown. Examples of the polyol more than triol include castor oil, trimethylolpropane, trimethylolpropane EO adduct, trimethylolethane, glycerin, pentaerythritol and the like.

  Further, in order to improve the storage stability of the resin solution, the compound (E) having both two or more hydroxyl groups and a group capable of forming a salt is used as a polyol, whereby the group capable of forming a salt is converted into a resin molecule. It can also be introduced inside.

  Examples of the compounds having a salt group, that is, a group capable of forming a salt, include, for example, a phosphate group, a sulfonic acid group, a substituted amino group, a carboxyl group as a salt group; Suitable are diols and diamines having any of phosphoric acid ester groups, neutralized sulfonic acid groups, neutralized substituted amino groups, neutralized carboxyl groups, and the like. Specific examples include polyoxyethylene glycol, polyoxyethylene diaminopropyl ether, trimethylolpropane monophosphate ester, trimethylolpropane monosulfate ester, at least part of the dibasic acid component is sodium sulfosuccinic acid or sodium sulfoisophthalate. Polyester diols, N-methyldiethanolamine, diaminocarboxylic acids such as lysine, cystine and 3,5-diaminocarboxylic acid, 2,6-dihydroxybenzoic acid and 3,5 dihydroxybenzoic acid, 2,2-bis (hydroxy) Methyl) propionic acid, 2,2-bis (hydroxyethyl) propionic acid, 2,2-bis (hydroxypropyl) propionic acid, bis (hydroxymethyl) acetic acid, 2,2-bis (hydroxymethyl) buta Dihydroxyalkylalkanoic acids such as acids, bis (4-hydroxyphenyl) acetic acid, 2,2-bis (4-hydroxyphenyl) pentanoic acid, tartaric acid, N, N-dihydroxyethylglycine, N, N-bis (2-hydroxy) Ethyl) -3-carboxy-propionamide, or a carboxyl group-containing polycaprolactone diol obtained by adding a lactone compound such as ε-caprolactone to dihydroxyalkylalkanoic acid. In order to improve compatibility, polyethylene glycol having a hydrophilic molecular chain having 3 or more repeating units of oxyethylene can be used in combination with a compound having a salt group.

  The required amount of the above-mentioned salt group is determined depending on the type and combination. Among them, a particularly preferable group having a salt group is a group of a salt having a carboxyl group or a sulfonate group in the molecule and any one or two types and neutralized with an amine such as triethylamine, Or it is a mixture of these. In particular, the introduction of a neutralized carboxyl group is easy to balance and easy to operate in various respects. In this case, the solid content acid value is preferably in the range of 5 to 30 (KOH mg / g), more preferably in the range of 10 to 25 (KOH mg / g).

  The polyisocyanate (C) used in the present invention is not particularly limited, but tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, cyclohexane-1,3- and 1,4-diisocyanate, 1- Isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (= isophorone diisocyanate), bis- (4-isocyanatocyclohexyl) methane (= dicyclohexylmethane diisocyanate), 2- and 4-isocyanatocyclohexyl-2 ′ -Isocyanatocyclohexylmethane, 1,3- and 1,4-bis- (isocyanatomethyl) -cyclohexane, bis- (4-isocyanato-3-methylcyclohexyl) methane, 1,3- and 1,4- Tramethylxylidene diisocyanate, 2,4- and / or 2,6-diisocyanatotoluene, 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate , P- and m-phenylene diisocyanates, xylylene diisocyanates, diisocyanates such as diphenyl-4,4′-diisocyanate, and triisocyanates such as trimers of 1,6-hexamethylene diisocyanate.

  By using dicyclohexylmethane-4,4′-diisocyanate (hereinafter referred to as hydrogenated MDI) for part or all of the polyisocyanate compound, an aqueous polyurethane resin using hydrogenated MDI can be obtained. It is preferably used in terms of excellent properties. The blending ratio of hydrogenated MDI to the total polyisocyanate is preferably 25% by mass or more.

  The compound (D) having both an α, β-unsaturated double bond and a hydroxyl group preferably has 1 to 2 hydroxyl groups and one or more ethylenically unsaturated double bonds. Examples of this include monohydroxy mono (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyalkyl (meth) acrylamide, or glycerin di ( Monohydroxy acrylic methacrylates such as (meth) acrylate and light ester G-201P (manufactured by Kyoeisha Chemical), monohydroxy triacrylates such as pentaerythritol triacrylate, monohydroxypentaacrylates such as dipentaerythritol pentaacrylate, and glycerin mono (meta ) Dihydroxy mono (meth) acrylates such as acrylates, and ethylene oxide, propylene oxide, tetrahydrofuran or epsilon capro Compounds which lactone was added polymerization.

  Furthermore, polyfunctional acrylates such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and dialkanolamines such as diethanolamine, diisopropanolamine, dipropanolamine, dibutanolamine, or Products obtained by Michael addition reaction with monoalkylmonoalkanolamines such as methylethanolamine, ethylethanolamine and methylpropanolamine, or diisocyanates having two different isocyanate groups such as isophorone diisocyanate and tolylene diisocyanate , Half-urethane obtained by reaction with monohydroxy monoacrylate, monohydroxy di (meth) acrylate, etc. And Le isocyanate, the dialkanolamines or the monoalkyl alkanolamines and also can be given product obtained by reacting.

  The production conditions for the above active energy ray-curable aqueous urethane resin dispersion are not particularly limited, but as a typical production method thereof, first, a polyalkylene ether chain-containing diol compound (A) and a polyol (B) And polyisocyanate (C) are blended so that the isocyanate groups are excessive to obtain an isocyanate group-terminated polyurethane prepolymer. Next, this isocyanate group-terminated polyurethane prepolymer is reacted with a compound (D) having both an α, β-unsaturated double bond and a hydroxyl group, so that the terminal is an unsaturated double bond or an isocyanate group. A polyurethane prepolymer having a polymerizable unsaturated double bond can be obtained. Next, the polyurethane prepolymer having an ethylenically unsaturated double bond is dispersed in water to prepare a water / organic solvent mixed solution. Thereafter, if necessary, a crosslinking agent dissolved in water or an organic solvent is added at 40 ° C. or lower. As another method for crosslinking or chain extension using a crosslinking agent, a crosslinking agent is dissolved in an aqueous phase in advance, and then a prepolymer neutralized solution is dispersed in water to prepare a water / organic solvent mixed solution. Finally, the active energy ray-curable aqueous urethane resin dispersion of the present invention can be obtained by distilling off the solvent from the water / organic solvent mixed solution under reduced pressure.

  The production conditions for the active energy ray-curable aqueous urethane resin dispersion containing the compound (E) having both the above-mentioned two or more hydroxyl groups and a group capable of forming a salt are not particularly limited. As a production method, first, a polyalkylene ether chain-containing diol compound (A), a polyol (B), a bifunctional or higher polyisocyanate (C), a group capable of forming a salt with two or more hydroxyl groups are combined. An isocyanate group-terminated polyurethane prepolymer is obtained by blending with the compound (E) having an excess of isocyanate groups. Next, this isocyanate group-terminated polyurethane prepolymer is reacted with a compound (D) having both an α, β-unsaturated double bond and a hydroxyl group, so that the terminal is an unsaturated double bond or an isocyanate group. A polyurethane prepolymer having a polymerizable unsaturated double bond and a salt group can be obtained. Next, the salt group in the polyurethane prepolymer having the ethylenically unsaturated double bond and the salt group is neutralized at 50 ° C. or less, and the ionized neutralized solution is dispersed in water to obtain a water / organic solvent mixed solution. To prepare. Thereafter, if necessary, a crosslinking agent dissolved in water or an organic solvent is added at 40 ° C. or lower. As another method of crosslinking or chain extension using a crosslinking agent, a crosslinking agent is dissolved in an aqueous phase in advance, and then an ionized prepolymer neutralized solution is dispersed in water to prepare a water / organic solvent mixed solution. Finally, the active energy ray-curable aqueous urethane resin aqueous dispersion of the present invention can be obtained by distilling off the solvent from the water / organic solvent mixed solution under reduced pressure.

  In the above, in the reaction for introducing a polyurethane prepolymer with an ethylenically unsaturated double bond, and the reaction step after the introduction of the ethylenically unsaturated double bond, a polymerization inhibitor such as hydroquinone, tertiary butyl hydroquine, hydroquinone monomethyl ether, etc. It is desirable to use

  The reaction between the hydroxyl group and the isocyanate group can be carried out in the range of 20 to 120 ° C. without solvent or in an organic solvent that does not react with the isocyanate group. At this time, an appropriate amount of a known polymerization inhibitor and reaction catalyst can be arbitrarily added. After completion of the reaction between the hydroxyl group and the isocyanate group, known resin compounds, aminoplasts, diluents, surfactants, plasticizers, waxes, hydrolysis inhibitors, emulsifiers, leveling agents, antifoaming agents, and antioxidants as necessary. Various resins such as agents and antibacterial agents, additives, auxiliaries and the like can be mixed.

  In addition, the above-mentioned active energy ray-curing monomer and / or oligomer having 5 or more α, β-unsaturated double bonds per molecule, 5 to 40% by mass is introduced at a stage before phase inversion to water. Excellent wear resistance of the film can be obtained. In order to ensure the stability of the aqueous dispersion, it is desirable to introduce a group capable of forming a salt into the resin molecule by using a compound having both a hydroxyl group and a group capable of forming a salt as a polyol.

  Examples of the organic solvent for the urethanization reaction are preferably reacted in an organic solvent inert to the isocyanate group, for example, acetone, methyl ethyl ketone, ethyl acetate, dioxane, acetonitrile, tetrahydrofuran, benzene, toluene, xylene. , Monoglyme, diglyme, dimethyl sulfoxide, N-methylpyrrolidone and the like. These organic solvents may be used in the total amount at the beginning of the urethanization reaction, or may be partially divided and used during the reaction.

  Moreover, as a urethanization catalyst, dibutyltin diisocyanate, tin compounds such as stannous octylate, tertiary amines such as diazabicycloundecene, or carboxylates thereof can be used. 10 ppm to 1,000 ppm is appropriate based on the solid content.

  As the reaction retarder, an acid such as phosphoric acid is usually used. The amount used is suitably 10 ppm to 1,000 ppm with respect to the solid content of the urethane resin.

  According to said manufacturing method, although the number average molecular weight of the urethane resin obtained is not limited, As a preferable polyurethane resin, a number average molecular weight becomes like this. Preferably it is 5,000-500,000, More preferably, it is 5,000-10, 000. The urethane prepolymer preferably has a number average molecular weight of 1,000 to 2,000.

  On the other hand, in the present invention, an organic diamine is optionally used as a chain extender for the urethane prepolymer.

  These organic diamines are not particularly limited, for example, diaminoethane, 1,2- or 1,3-diaminopropane, 1,2- or 1,3- or 1,4-diaminobutane, 1,5-diaminopentane. 1,6-diaminohexane, piperazine, N, N′-bis- (2-aminoethyl) piperazine, 1-amino-3-aminomethyl-3,5,5-trimethyl-cyclohexane (= isophoronediamine), bis -(4-aminocyclohexyl) methane, bis- (4-amino-3-butylcyclohexyl) methane, 1,2-, 1,3- and 1,4-diaminocyclohexane, 1,3-diaminopropane, norbornene diisocyanate, etc. Hydrazine, amino acid hydrazide, hydrazide of semi-carbazide carboxylic acid, bis (hydrazide) and bis Semicarbazide), and the like can also be used. Preferably, secondary amines such as piperazine are used in order to prevent Michael addition reaction of α and β unsaturated double bonds and active hydrogen of amine. The chain extension reaction conditions using the organic diamine are not particularly limited, but are usually 80 ° C. or lower, preferably 0 to 70 ° C. under good stirring conditions.

  The polyalkylene ether chain-containing diol compound (A) of the general formula (1) in the active energy ray-curable aqueous urethane resin dispersion of the present invention is based on 100 parts of the urethane resin dispersion in consideration of stability in water. 1 to 50 parts is preferable, and 1 to 30 parts is more preferable.

  According to the present invention, a so-called comb-type urethane in which a polyalkylene ether chain is grafted onto a side chain of a urethane resin in a pendant form, that is, a urethane resin in which a polyalkylene ether chain is introduced into a side chain of a urethane resin in a comb-like shape is manufactured. it can. Furthermore, the polyalkylene ether chain introduced into the side chain in a pendant form has an effect of improving the function of the surface or interface of the urethane resin. For example, a urethane resin having a polyethylene glycol chain in the side chain is easy to orient the polyethylene glycol chain on the surface of the urethane resin particle in water, and the dispersion stability with respect to water is improved.

  By improving the dispersibility in water, it becomes possible to introduce a urethane resin branched with a polyol (B) having a high molecular cohesive force, which is greater than triol, and the alkali resistance and wear resistance of the cured film of the resin are improved. It will be. Moreover, the alkali dispersion and abrasion resistance of the cured film are improved by encapsulating the water dispersion with monomers and oligomers containing 3 or more α, β-unsaturated bonds per molecule in the water dispersion. In order to further improve the water dispersibility stability, it can be improved by having a compound having a salt group in the resin.

  In the active energy ray-curable aqueous coating composition according to the present invention, the curing reaction of the composition proceeds by active energy rays. Curing with an active energy ray can be performed by a known method, for example, a method of irradiating an energy ray such as ultraviolet ray, visible light, electron beam, X-ray or the like with a lamp or a device that generates each energy ray. Among these, in particular, the coating composition can be designed so that curing proceeds by irradiation with ultraviolet rays, which is relatively inexpensive in terms of equipment costs and running costs.

  For example, in the case of curing with an electron beam, a polymerization initiator is not particularly required, and an electron beam irradiation device with an acceleration voltage of 20 to 2000 KeV, preferably 150 to 300 KeV is used, and a small amount of oxygen is contained or an inert gas atmosphere Among them, a cured coating film can be obtained by irradiating so that the total irradiation amount is 5 to 200 kGy, preferably 10 to 100 kGy.

  Other curing means include, for example, a method of curing in air or an inert gas atmosphere with ultraviolet rays obtained from a mercury lamp, a xenon lamp, or the like, or a method of heat curing. In these cases, a photopolymerization initiator or Add thermal polymerization initiator. A known material can be arbitrarily selected as the type of the photopolymerization initiator or the thermal polymerization initiator. Although the addition amount can also be chosen arbitrarily, for example, it is about 0.2 to 20%, preferably 0.5 to 10% of the solid content of the coating composition.

  Next, the use of the active energy ray-curable aqueous urethane resin dispersion of the present invention will be described. For example, an active energy ray-curable aqueous urethane resin dispersion having a polyethylene glycol chain in the side chain can be used for water-dispersed and water-soluble types, and the environment of conventional solvent-type and solvent-free active energy ray-curable urethane resins. Use as a compatible product can be expected. Since the resin composition can be reduced in viscosity, it can be used in products such as spray coating, coating in units of several μm on a roll coater, such as metal coatings, various plastic film overcoat agents, wood coatings, and printing inks. It is useful as an active ingredient for various coatings and adhesives.

  Next, the polyalkylene ether chain-containing diol compound and the active energy ray-curable aqueous urethane resin dispersion of the present invention using the same will be described in more detail with reference to synthesis examples and application examples. The present invention is not limited to these synthesis examples and application examples. In the synthesis examples and application examples, “part” and “%” relate to mass unless otherwise specified. The molecular weight refers to the number average molecular weight calculated from the hydroxyl value.

[Preparation Example 1] A diol compound nitrogen inlet tube having a polyethylene glycol chain in a pendant shape, a condenser for cooling, a thermometer, a stirrer, and heated in advance to 50 ° C. to be melted. Methoxypolyoxyethylene-2-propylamine (molecular weight = 1000) and 500 g (0.5 mol) were added and stirred. Next, 58 g (0.5 mol) of 2-hydroxyethyl acrylate was added in about 30 minutes while maintaining the internal temperature at 45 to 50 ° C. Then, it stirred for 5 hours, keeping internal temperature at 30-40 degreeC. Next, 42 g (0.25 mol) of hexamethylene diisocyanate (HDI) was added over about 30 minutes while maintaining the internal temperature at 30 to 40 ° C. It stirred for 1 hour, keeping internal temperature at 30-40 degreeC after throwing in. An infrared spectrophotometer was used to confirm that there was no isocyanate group peak, and the sample was taken out. The obtained diol compound was almost colorless at 50 ° C. and solidified into a wax at room temperature. It was confirmed by high performance liquid chromatography (Tosoh 8020) that it had a single peak and was a high purity product. The measured value of the hydroxyl value was substantially equal to 46.9 with respect to the calculated value of the hydroxyl value of 46.8, and it was confirmed that the hydroxyl group and HDI did not react during the dimerization with HDI.
Measurement result of H-NMR using deuterated chloroform as solvent 3.4 ppm: —OCH ₃
3.7 ppm: (OCH ₂ CH ₂ ) n
5.8 ppm: urea bond (—NH—CO—N)
In addition, the acrylic double bond and the urethane bond were not detected by H-NMR.

[Preparation Example 2] A 1-liter four-necked round bottom flask equipped with a diol compound nitrogen introduction tube having a pendant EO / PO copolymer chain, a condenser for cooling, a thermometer, and a stirrer is heated to 50 ° C. in advance. Melted methoxypoly (oxyethylene / oxypropylene) -2-propylamine (EO / PO = 9/1 molar ratio, molecular weight = 1000) and 500 g (0.5 mol) were added and stirred. Then, 72 g (0.5 mol) of 4-hydroxybutyl acrylate was added in about 30 minutes while maintaining the internal temperature at 45 to 50 ° C. Then, it stirred for 5 hours, keeping internal temperature at 30-40 degreeC. Next, 65.5 g (0.25 mol) of hydrogenated MDI was added over about 30 minutes while maintaining the internal temperature at 30 to 40 ° C. After the addition, the mixture is stirred for 1 hour while maintaining the internal temperature at 30 to 40 ° C. An infrared spectrophotometer was used to confirm that there was no isocyanate group peak, and the sample was taken out. The obtained diol compound was almost colorless at 50 ° C. and solidified into a wax at room temperature. It was confirmed by high performance liquid chromatography (Tosoh 8020) that it had a single peak and was a high purity product. The measured value of the hydroxyl value is almost equal to 44.2 with respect to the calculated value of the hydroxyl value of 44.0, and it was confirmed that the hydroxyl group and the hydrogenated MDI did not react during the dimerization with the hydrogenated MDI. .
Measurement result of H-NMR using deuterated chloroform as solvent 3.4 ppm: —OCH ₃
3.7 ppm: EO / PO
5.8 ppm: urea bond (—NH—CO—N)
In addition, acrylic double bond and urethane bond were not detected by H-NMR.

[Example 1] Synthesis of an active energy ray-curable urethane resin having a polyethylene glycol chain in a pendant shape (a)
In a 1 liter four-necked round bottom flask equipped with a nitrogen inlet tube, a condenser for cooling, a thermometer, and a stirrer, 133 parts of polytetramethylene ether glycol (PTMG) having a molecular weight of 1000 and 53 parts of the diol compound obtained in Preparation Example 1 , 38 parts of trimethylolpropane, 717 parts of methyl ethyl ketone (MEK) as a solvent, and 392 parts of 4,4′-hydrogenated MDI were reacted at 70 to 75 ° C. for 2 hours, and then stannous octylate as a urethanization catalyst. 1.5 parts was added and the reaction was further continued for 2 hours. After all the hydroxyl groups in the reaction product have been replaced with NCO, the nitrogen inlet tube is replaced with an air inlet tube, 245 parts of light ester G-201P (manufactured by Kyoeisha Chemical), 460 parts of MEK, 0.42 part of methoxyquinone and tert- 0.42 part of butyl hydroquinone was added. After heating again to 70-75 degreeC and making it react for 1 hour, 1.5 parts of stannous octylates were added, and also it was made to react for 8 hours, and the polyurethane resin solution was obtained. To this solution, a solution consisting of 3005 parts of pure water and 39 parts of anhydrous piperazine was gradually added over 30 minutes, followed by stirring and mixing at 40 ° C. for 1 hour. After adding 2 parts of Surfinol AK02 (manufactured by Nissin Chemical Industry Co., Ltd.), methyl ethyl ketone was distilled off under reduced pressure at 50 ° C., and the nonvolatile content was 29.0%, the viscosity was 17 cps, and the unsaturated group concentration was 2. An aqueous dispersion (a) of an active energy ray-curable polyurethane resin having 0 equivalent / kg and a number average molecular weight of 5000 was obtained.

[Example 2] Synthesis of an active energy ray-curable urethane resin having a polyethylene glycol chain in a pendant shape (b)
In a 1 liter four-necked round bottom flask equipped with a nitrogen inlet tube, a condenser for cooling, a thermometer, and a stirrer, 135 parts of polytetramethylene ether glycol (PTMG) having a molecular weight of 1000 and 52 parts of the diol compound obtained in Preparation Example 1 , 34 parts of trimethylolpropane, 49 parts of 2,2-bis (hydroxymethyl) propionic acid, 726 parts of methyl ethyl ketone (MEK) as a solvent, 454 parts of 4,4′-hydrogenated MDI, and reacted at 70 to 75 ° C. for 2 hours Then, 1.5 parts of stannous octylate as a urethanization catalyst was added and reacted for another 3 hours. After all the hydroxyl groups in the reaction solution were replaced with NCO, the nitrogen introduction tube was replaced with an air introduction tube, 237 parts of light ester G-201P (manufactured by Kyoeisha Chemical Co., Ltd.), 451 parts of MEK, 0.42 part of methoxyquinone and tert- 0.42 part of butyl hydroquinone was added. After heating again to 70-75 degreeC and making it react for 1 hour, 1.5 parts of stannous octylates were added, and also it was made to react for 8 hours, and the polyurethane resin solution was obtained. To this solution, 34 parts of triethylamine was added for neutralization, and then a solution consisting of 2975 parts of pure water and 39 parts of anhydrous piperazine was gradually added over 30 minutes, followed by stirring and mixing at 40 ° C. for 1 hour. After adding 2 parts of Surfinol AK02 (manufactured by Nissin Chemical Industry Co., Ltd.), methyl ethyl ketone was distilled off under reduced pressure at 50 ° C., nonvolatile content: 29.3%, solid content acid value 24 (KOH mg / g), An aqueous dispersion ((b)) of an active energy ray-curable polyurethane resin having a viscosity of 19 cps, an unsaturated group concentration of 2.0 equivalent / kg, and a number average molecular weight of 5000 was obtained.

[Example 3] Synthesis of an active energy ray-curable urethane resin having a polyethylene glycol chain in a pendant shape (c)
In a 1 liter four-necked round bottom flask equipped with a nitrogen inlet tube, a condenser for cooling, a thermometer, and a stirrer, 135 parts of polytetramethylene ether glycol (PTMG) having a molecular weight of 1000 and 52 parts of the diol compound obtained in Preparation Example 2 , 34 parts of trimethylolpropane, 49 parts of 2,2-bis (hydroxymethyl) propionic acid, 726 parts of methyl ethyl ketone (MEK) as a solvent, 454 parts of 4,4′-hydrogenated MDI, and reacted at 70 to 75 ° C. for 2 hours Then, 1.5 parts of stannous octylate as a urethanization catalyst was added and reacted for another 3 hours. After all the hydroxyl groups in the reaction solution were replaced with NCO, the nitrogen introduction tube was replaced with an air introduction tube, 237 parts of light ester G-201P (manufactured by Kyoeisha Chemical Co., Ltd.), 451 parts of MEK, 0.42 part of methoxyquinone and tert- 0.42 part of butyl hydroquinone was added. The temperature was again raised to 70 to 75 ° C. and reacted for 1 hour, and then 1.5 parts of stannous octylate was added and reacted for 8 hours to obtain a polyurethane resin solution. To this solution, 34 parts of triethylamine was added for neutralization, and then a solution consisting of 2975 parts of pure water and 39 parts of anhydrous piperazine was gradually added over 30 minutes, followed by stirring and mixing at 40 ° C. for 1 hour. After adding 2 parts of Surfinol AK02 (manufactured by Nissin Chemical Industry Co., Ltd.), methyl ethyl ketone was distilled off under reduced pressure at 50 ° C., nonvolatile content: 28.5%, solid content acid value 23 (KOH mg / g), An aqueous dispersion (c) of an active energy ray-curable polyurethane resin having a viscosity of 19 cps, an unsaturated group concentration of 2.0 equivalent / kg, and a number average molecular weight of 5000 was obtained.

[Example 4] Synthesis of an active energy ray-curable urethane resin having a polyethylene glycol chain in a pendant shape (d)
In a 1 liter four-necked round bottom flask equipped with a nitrogen inlet tube, a condenser for cooling, a thermometer, and a stirrer, 53 parts of polytetramethylene ether glycol (PTMG) having a molecular weight of 1000 and 22 parts of the diol compound obtained in Preparation Example 2 , 23 parts of trimethylolpropane, 43 parts of 2,2-bis (hydroxymethyl) propionic acid, 726 parts of methyl ethyl ketone (MEK) as a solvent, 301 parts of 4,4′-hydrogenated MDI, and reacted at 70 to 75 ° C. for 2 hours Then, 1.5 parts of stannous octylate as a urethanization catalyst was added and reacted for another 3 hours. After all the hydroxyl groups in the reaction solution have been replaced with NCO, the nitrogen inlet tube is replaced with an air inlet tube, 436 parts pentaerythritol heptaacrylate, 451 parts MEK, 0.42 parts methoxyquinone and 0.42 parts tert-butyl hydroquinone Was added. The temperature was again raised to 70 to 75 ° C. and reacted for 1 hour, and then 1.5 parts of stannous octylate was added and reacted for 8 hours to obtain a polyurethane resin solution. After neutralizing this solution by adding 32 parts of triethylamine, a solution consisting of 2978 parts of pure water and 26 parts of anhydrous piperazine was gradually added over 30 minutes, followed by stirring and mixing at 40 ° C. for 1 hour. After adding 2 parts of Surfynol AK02 (manufactured by Nissin Chemical Industry Co., Ltd.), methyl ethyl ketone was distilled off under reduced pressure at 50 ° C., and the nonvolatile content was 29.5%, the solid content acid value was 18 (KOHmg / g), An aqueous dispersion (d) of an active energy ray-curable polyurethane resin having a viscosity of 18 cps, an unsaturated group concentration of 4.4 equivalent / kg, and a number average molecular weight of 5000 was obtained.

[Example 5] Synthesis of an active energy ray-curable urethane resin having a polyethylene glycol chain in a pendant shape and encapsulating an oligomer having 6 α, β-unsaturated double bond groups per molecule (e)
In a 1 liter four-necked round bottom flask equipped with a nitrogen inlet tube, a condenser for cooling, a thermometer, and a stirrer, 53 parts of polytetramethylene ether glycol (PTMG) having a molecular weight of 1000 and 22 parts of the diol compound obtained in Preparation Example 2 , 23 parts of trimethylolpropane, 43 parts of 2,2-bis (hydroxymethyl) propionic acid, 726 parts of methyl ethyl ketone (MEK) as a solvent, 301 parts of 4,4′-hydrogenated MDI, and reacted at 70 to 75 ° C. for 2 hours Then, 1.5 parts of stannous octylate was added as a urethanization catalyst and reacted for another 3 hours. After all the hydroxyl groups in the reaction solution have been replaced with NCO, the nitrogen inlet tube is replaced with an air inlet tube, 436 parts of dipentaerythritol heptaacrylate, 451 parts of MEK, 0.42 parts of methoxyquinone and 0.42 of tert-butylhydroquinone. Parts were added. The temperature was again raised to 70 to 75 ° C. and reacted for 1 hour, and then 1.5 parts of stannous octylate was added and reacted for 8 hours to obtain a polyurethane resin solution. To this solution, 100 parts of dipentaerythritol hexaacrylate was added, and after further neutralizing by adding 32 parts of triethylamine, a solution consisting of 3268 parts of pure water and 26 parts of anhydrous piperazine was gradually added over 30 minutes, and then at 40 ° C. for 1 hour. Stir and mix. After adding 2 parts of Surfinol AK02 (manufactured by Nissin Chemical Industry Co., Ltd.), methyl ethyl ketone was distilled off under reduced pressure at 50 ° C., nonvolatile content: 28.9%, solid content acid value 16 (KOHmg / g), An aqueous dispersion (e) of an active energy ray-curable polyurethane resin having a viscosity of 19 cps, an unsaturated group concentration of 5.1 equivalent / kg, and a number average molecular weight of 5000 was obtained.

[Comparative Example 1] Synthesis of active energy ray-curable urethane resin having polyethylene glycol chain in main chain (f)
In a 1-liter four-necked round bottom flask equipped with a nitrogen inlet tube, a condenser for cooling, a thermometer, and a stirrer, 124 parts of polytetramethylene ether glycol (PTMG) with a molecular weight of 1000, 52 parts of polyethylene glycol (PEG) with a molecular weight of 1000, 35 parts of trimethylolpropane, 50 parts of 2,2-bis (hydroxymethyl) propionic acid, 726 parts of methyl ethyl ketone (MEK) as a solvent, 465 parts of 4,4′-hydrogenated MDI were charged and reacted at 70 to 75 ° C. for 2 hours. After that, 1.5 parts of stannous octylate as a urethanization catalyst was added and reacted for another 3 hours. After all the hydroxyl groups in the reaction solution were replaced with NCO, the nitrogen introduction tube was replaced with an air introduction tube, 237 parts of light ester G-201P (manufactured by Kyoeisha Chemical Co., Ltd.), 451 parts of MEK, 0.42 part of methoxyquinone and tert- 0.42 part of butyl hydroquinone was added. After heating again to 70-75 degreeC and reacting for 1 hour, 1.5 parts of stannous octylates were added and made to react for 7 hours, and the polyurethane resin solution was obtained. To this solution, 34 parts of triethylamine was added for neutralization, and then a solution consisting of 2975 parts of pure water and 31 parts of anhydrous piperazine was gradually added over 30 minutes, followed by stirring and mixing at 40 ° C. for 1 hour. After adding 2 parts of Surfynol AK02 (manufactured by Nissin Chemical Industry Co., Ltd.), methyl ethyl ketone was distilled off under reduced pressure at 50 ° C., nonvolatile content: 28.8%, solid content acid value 23 (KOH mg / g), An aqueous dispersion (f) of an active energy ray-curable polyurethane resin having a viscosity of 20 cps, an unsaturated group concentration of 2.0 equivalent / kg, and a number average molecular weight of 5000 was obtained.

[Comparative Example 2] Synthesis of urethane resin introduced with monomethoxypolyethylene glycol (g)
In a 1-liter four-necked round bottom flask equipped with a nitrogen inlet tube, a condenser for cooling, a thermometer, and a stirrer, 136 parts of polytetramethylene ether glycol (PTMG) having a molecular weight of 1000, 35 parts of trimethylolpropane, and 2,2-bis First, 50 parts of (hydroxymethyl) propionic acid, 679 parts of methyl ethyl ketone (MEK) as a solvent, and 459 parts of 4,4′-hydrogenated MDI were reacted at 70 to 75 ° C. for 2 hours, and then octylic acid first as a urethanization catalyst. 1.5 parts of tin was added and reacted for another 2 hours. After all the hydroxyl groups in the reaction solution have been replaced with NCO, the nitrogen introduction tube is replaced with an air introduction tube, 239 parts of light ester G-201P (manufactured by Kyoeisha Chemical Co., Ltd.), 42 parts of monomethoxypolyethylene glycol having a molecular weight of 1000, and 495 parts of MEK. Then, 0.42 part of methoxyquinone and 0.42 part of tert-butylhydroquinone were added. The temperature was again raised to 70 to 75 ° C. and reacted for 1 hour, and then 1.5 parts of stannous octylate was added and reacted for 7 hours to obtain a polyurethane resin solution. To this solution, 34 parts of triethylamine was added for neutralization, and then a solution consisting of 2975 parts of pure water and 31 parts of anhydrous piperazine was gradually added over 30 minutes, followed by stirring and mixing at 40 ° C. for 1 hour. 2 parts of Surfynol AK02 (manufactured by Nissin Chemical Industry Co., Ltd.) was added, and methyl ethyl ketone was distilled off at 50 ° C. under reduced pressure to obtain a nonvolatile content of 29.6%, a solid content acid value of 23 (KOHmg / g), and a viscosity. : An aqueous dispersion (g) of an active energy ray-curable polyurethane resin having 18 cps, an unsaturated group concentration of 2.0 equivalent / kg, and a number average molecular weight of 5000 was obtained.

[Comparative Example 3] Synthesis of urethane resin dispersed only with carboxyl group (h)
In a 1 liter four-necked round bottom flask equipped with a nitrogen inlet tube, a condenser for cooling, a thermometer, and a stirrer, 327 parts of polytetramethylene ether glycol (PTMG) having a molecular weight of 500 and 2,2-bis (hydroxymethyl) propionic acid 105 parts, 33 parts of light ester G-201P (manufactured by Kyoeisha Chemical Co., Ltd.), 5 parts of trimethylolpropane, 412 parts of 1,3-bis (isocyanatomethyl) cyclohexane, 0.3 part of tert-butylhydroquinone, stannous octylate 0.3 parts and 1222 parts of methyl ethyl ketone were added and heated to 70 ° C. with stirring for 0.5 hours. After reacting at 70 ° C. for 5 hours, 0.2 parts of tert-butylhydroquinone, biscoat # 214HP (Osaka Organic) 119 parts, manufactured by Chemical Co., Ltd.), and the nitrogen inlet tube is replaced with an air inlet tube, again at 70 ° C. By time reaction to obtain a solution of polyester urethane resin skeleton (a2). After cooling to 50 ° C., this solution was prepared in another reactor equipped with a stirrer equipped with a reflux condenser, a nitrogen inlet, and a thermometer prepared in advance, 72 parts triethylamine, 2411 parts pure water, isophoronediamine 15 Part of the solution and 75 parts of acetone were added over 30 minutes while maintaining the liquid temperature at 35 to 40 ° C. After adding 2 parts of Surfynol AK02 (manufactured by Nissin Chemical Industry Co., Ltd.), methyl ethyl ketone was distilled off at 50 ° C. under reduced pressure to remove nonvolatile content: 30.5%, solid content acid value 44 (KOHmg / g ), An aqueous dispersion (h) of an active energy ray-curable water polyurethane resin having a viscosity of 100 cps and an unsaturated group concentration of 2.4 equivalent / kg was prepared.

About the active energy ray hardening-type aqueous | water-based urethane resin dispersion made as an experiment in Examples 1-5 and Comparative Examples 1-3, the average particle diameter and the viscosity were measured with the following method.
(Measuring method of average particle diameter): It measured using the particle diameter measuring device SALD-2000 of Shimadzu Corporation.
(Measurement method of viscosity): Measured using a rotational viscosity type (BII type) manufactured by Toki Sangyo.
(Stability of resin dispersion): The state of the dispersion after standing at room temperature for 72 hours was visually observed.
The viscosity measurement results and stability evaluation results of the dispersion are shown in Table 1.

[Application Example 1] 4 parts of Irgacure 184 (manufactured by Ciba Specialty Chemicals) and 4 parts of ethanol are added to 100 parts of the solid content of the active energy ray-curable aqueous urethane resin dispersion produced in Example 1 and stirred until uniform. Mixed. The mixed solution was applied on each substrate (PET plate, glass plate, aluminum plate) to a film thickness of about 5 μm with a # 14 bar coater and dried with hot air at 80 ° C. for 5 minutes (PET only 60). C.) was irradiated with ultraviolet rays by an ultraviolet irradiation device (F-600) manufactured by FUSION, and a 240 W / cm H lamp. The irradiation energy amount was 500 mJ / cm ² .

  [Application Examples 2 to 8] Using the active energy ray-curable aqueous urethane resin dispersions prototyped in Examples 1 to 5 and Comparative Examples 1 to 3, preparation of a paint and preparation of a coated plate in the same manner as in Application Example 1 Went. Note that suffixes -1, -2, and -3 in the application examples represent a test base PET plate, a glass plate, and an aluminum plate, respectively.

About the coated board obtained by each application example, the pencil hardness of the cured film, solvent resistance, water resistance, alkali resistance, and abrasion resistance were evaluated by the following methods.
(Pencil hardness): According to JIS-K-5400.
(Solvent resistance): The rubbing tester (500 g load using MEK) was rubbed 10 times, and the appearance change was observed visually.
(Water resistance): After immersion in ion-exchanged water for 24 hours, change in appearance is visually observed.
(Alkali resistance): 1.5 cc of 5% NaOH water was dropped on the cured film, and after standing for 24 hr, the appearance change was visually observed.
(Abrasion resistance): A steel wool of # 0000 was slid back and forth 10 times under the condition of 100 g load / cm ² and the appearance of the film was visually observed.

  Tables 2 to 4 show the results of measurement and evaluation of the cured coating film.

  As shown in Tables 1 to 4, when the urethane resin having the polyethylene glycol chain of the present invention introduced into the side chain was dispersed in water, a stable aqueous dispersion having a small particle size was obtained. Moreover, the favorable result was obtained also about the alkali resistance and abrasion resistance of the coating film hardened | cured with the active energy ray.

The active energy ray-curable aqueous urethane resin dispersion using the polyalkylene ether chain-containing diol compound of the present invention as a raw material is extremely excellent in storage stability, and by drying and active energy ray irradiation, hardness, durability, In particular, a film having good alkali resistance can be formed. Therefore, it is extremely useful as a material for environment-friendly metal paints, various plastic film overcoat agents, woodwork paints, printing inks and the like.

Claims (6)

Polyalkylene ether chain-containing diol compound (A) represented by the following general formula (1), polyol (B), polyisocyanate (C), and an α, β-unsaturated double bond and a hydroxyl group. An active energy ray-curable aqueous urethane resin dispersion obtained by reacting the compound (D).

(In the formula, R 1 is an alkylene group or dialkylene ether group having 1 to 9 carbon atoms, R 2 is an alkyl group having 1 to 9 carbon atoms, and R 3 is —CO—NH—R 4 —NH—CO. R4 is an organic group having 2 to 18 carbon atoms, and A is a divalent polyalkylene ether group having a molecular weight of 200 to 10,000. The active energy ray-curable aqueous urethane resin dispersion according to claim 1, wherein R4 in the general formula (1) is a diisocyanate residue containing any one of an alkylene group, a phenylene group, a cyclohexylene group, and a biphenylene group. The active energy ray-curable aqueous urethane resin dispersion according to claim 1 or 2, wherein A in the general formula (1) is a repeating unit of the following formula, or a combination thereof.

(In the formula, m is an integer of 2 to 4.) The active energy ray-curable aqueous urethane according to any one of claims 1 to 3, wherein the polyol (B) contains a compound (E) having both two or more hydroxyl groups and a group capable of forming a salt. Resin dispersion. The polyol (B) described above contains 10 to 40 mol% of a triol or higher component, the α, β-unsaturated double bond amount is 1.0 to 6.0 mol / kg, and the number average molecular weight is The active energy ray-curable aqueous urethane resin dispersion according to any one of claims 1 to 4, wherein the dispersion is 5000 or more. The active energy ray-curable aqueous urethane according to any one of claims 1 to 6, wherein 5 to 40% by mass of a monomer and / or oligomer (F) having 3 or more α, β-unsaturated double bonds per molecule is encapsulated. Resin dispersion.