JPH08259888A - Active energy ray-curable aqueous dispersion - Google Patents

Abstract

PURPOSE: To obtain an active energy ray-curable aqueous dispersion used for coating compositions giving coating films excellent in adhesiveness and chemical resistance such as solvent and alkali resistances by dispersing the microgel particles of an active energy ray-curable polyurethane resin in water. CONSTITUTION: This dispersion is obtained by dispersing in water the coating film-forming polyurethane resin microgel particles having active energy ray- curable unsaturated double bonds and salt groups and comprising one or more kinds of polyurethane resin skeletons selected from among polyester-, polyether(polyester)-, and polycarbonate-polyurethane resin skeletons and a cross-linked structure wherein the skeletons are cross-linked to each other through urethane bonds or urea bonds.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to coating materials for wood building materials, coating agents for decorative paper for building materials, glossy varnish for paper, metal plates such as aluminum, iron, tin plate, galvanized sheet and other metal materials, packaging materials, cardboard. The present invention relates to an aqueous dispersion used for a coating composition such as an aqueous gravure ink for printing and a flexo ink. More specifically, the present invention has a short curing time, adhesion, excellent chemical resistance, odor, and water-dispersible active energy ray-curable building material paints having a low skin toxicity, paints for metals, luster varnishes, The present invention relates to an aqueous dispersion useful for coating compositions such as gravure ink and flexo ink.

[0002]

2. Description of the Related Art Paints for wood building materials, coating agents for decorative paper for building materials, gloss varnish for paper, metal plates such as aluminum, iron, tin plate, galvanized iron plate and other metal materials, corrugated board, various plastic films, etc. Active energy ray curing technology has been applied as a curing method in the fields of paints, coating agents, inks, etc. used for coating and printing of the above. However, in practical use, it is necessary to go through processes such as painting and printing, and it is necessary to dilute with a solvent or a monomer in order to obtain a coating viscosity suitable for these processes. It has been pointed out that solvent-based paints, coating agents, and inks that use organic solvents have problems in terms of safety and hygiene and the working environment.
Even in coating compositions such as coating agents and inks, there are problems with safety and hygiene as well as skin toxicity and odor of monomers. In addition, the solventless coating composition has a drawback in that the polymer raw material cannot be used due to the limitation of the coating viscosity, and therefore the chemical and physical performance of the coating film cannot be improved.

Water-soluble active energy ray-curable paints, coating agents, and inks developed to solve these problems have no problems in safety and hygiene and working environment, and polymer materials are applied. You can also do it. However, coating compositions such as water-soluble active energy ray-curable paints, coating agents, and inks also have the common problems of active energy ray-curable coating agents. That is, when the degree of cross-linking is increased, the adhesive strength is reduced by curing strain, and on the contrary, when the degree of cross-linking is decreased, the chemical resistance such as solvent resistance and alkali resistance is reduced, which is a contradictory problem. It cannot be solved by the method. JP-A-3
JP-A-166216 describes an aqueous polyurethane resin composition which is said to have improved chemical resistance, but when the concentration of acryloyl group is increased, the adhesiveness is lowered due to curing strain, and when the concentration of acryloyl group is decreased, the chemical resistance is reduced. descend. After all, chemical resistance and adhesion are not compatible.

[0004]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention As described above, the object of the present invention is to improve the adhesion of the coating film and the water-soluble property which is excellent in both chemical resistance such as solvent resistance and alkali resistance. It is to obtain an aqueous dispersion used in an active energy ray-curable coating composition.

[0005]

The present invention comprises water and active energy ray-curable microgel particles dispersed in water, wherein the microgel particles have a urethane bond or a urea bond between polyurethane resin skeletons. A gel-forming film-forming polyurethane resin particle comprising a crosslinked crosslinked structure, wherein the polyurethane resin particle has an active energy ray-curable unsaturated double bond and a salt group. Water dispersion.

The film-forming aqueous dispersion of the active energy ray-curable microgel particles of the present invention can be used in coating compositions such as paints, coating agents and inks, and these coating compositions are active energy rays. It is a curable type and has excellent coating properties that combine adhesiveness and chemical resistance.

The active energy ray-curable aqueous dispersion used in the present invention is a urethane polymer particle which is finely dispersed in an aqueous medium in a stable manner. And has the property of forming a film by applying itself. Further, it also has the property of forming a film by applying a mixture of other non-gel-state active energy ray-curable resin component dispersed in water.

The gel-forming film-forming polyurethane resin particles of the present invention include a compound having a known unsaturated double bond which is cured by active energy rays, a polymerization initiator for curing active energy rays, various resin compounds, It may contain various additives and auxiliaries such as aminoplast, diluent, plasticizer and wax. Therefore, it has a feature that a water-insoluble compound such as the known active energy ray-curable compound, which has been difficult to mix and use in the past, can be mixed and prepared as needed.

Further, the gel-forming film-forming polyurethane resin particles of the present invention have no environmental pollution and are excellent in safety and hygiene,
An active energy ray-curable water-dispersed polyurethane composition, the coating obtained by curing with active energy rays has flexibility and excellent adhesion peculiar to urethane resin, and especially chemical resistance such as solvent resistance and alkali resistance. It has excellent properties. Therefore, it has become possible to solve the above problems by applying the polyurethane resin particles of the present invention to an aqueous coating material, a coating agent, a printing ink and the like.

The active energy ray-curable aqueous dispersion of the present invention comprises water and microgel particles dispersed in water, wherein the microgel particles have an isocyanate group, an active energy ray-curable unsaturated double bond and a salt. It can be obtained by reacting a water-dispersible polyurethane resin skeleton (A) having a group of 1 with a cross-linking agent (B) that cross-links the skeletons by a urethane bond or a urea bond.

The microgel particles thus obtained have a film-forming property. In order to expect the effects of the present invention described above, the gel fraction of microgel particles (the measuring method will be described later)
Is preferably in the range of 10 to 90%. If it is less than 10%, the chemical resistance is poor, and if it exceeds 90%, the film forming property is lost. In order for the present invention to form a stable film when heated for the purpose of evaporating the water content of the film, it is desirable that the minimum film forming temperature is 25 ° C. or lower. Minimum film formation temperature is 25
If you try to form a coating under normal conditions if the temperature exceeds ℃,
Cracks and other defects can occur.

A typical method for producing the active energy ray-curable water dispersion is shown below. A water-dispersible polyurethane resin skeleton (A) having an isocyanate group, an active energy ray-curable unsaturated double bond and a salt group, which has been previously reacted in an organic solvent, is dispersed in water to prepare a solution. Then, a crosslinking agent (B) dissolved in water or an organic solvent is added to the solution to obtain an aqueous dispersion containing the organic solvent, and the solvent is desolvated.

As the reverse procedure, an isocyanate group and an active energy ray obtained by previously reacting in an organic solvent in a solution prepared by dissolving the crosslinking agent (B) in water or a mixed liquid of water and an organic solvent. An aqueous dispersion containing an organic solvent is obtained by dispersing a polyurethane resin skeleton (A) having a curable unsaturated double bond and a salt group, and then produced by removing the solvent.

The active energy ray-curable aqueous dispersion, that is, the microgel particles, may contain other active energy ray-polymerizable compound therein. The preparation of microgel particles containing an active energy ray-polymerizable compound inside is shown below. Polyurethane resin skeleton (A)
Other active energy ray-curable compounds are added to the organic solvent solution of 1% to 50%, and water is further added to disperse the solution to prepare a cross-linking agent (B) dissolved in water or an organic solvent. Is added to obtain an aqueous dispersion containing an organic solvent. Then, the solvent is removed to prepare microgel particles containing an active energy ray-polymerizable compound inside.

Alternatively, the following method is also possible as the reverse procedure. That is, an organic solvent solution of a polyurethane resin skeleton (A) obtained by previously reacting in an organic solvent in a solution prepared by dissolving a crosslinking agent (B) in water or a mixed solution of water and an organic solvent, Active energy ray-curable compound of 1% to 50
% Of the added solution is dispersed to obtain an aqueous dispersion containing an organic solvent. Then, the solvent is removed to prepare microgel particles containing an active energy ray-polymerizable compound inside.

The above-mentioned polyurethane resin skeleton (A)
Is a bifunctional or higher polyisocyanate compound (A-1)
And a polyol having an average number of functional groups of 2 or more (A-2)
A compound having an active energy ray-curable unsaturated double bond and a hydroxyl group (A-3), and a compound having a salt group (A
-4) is reacted with to obtain a polyurethane resin skeleton (A) having a terminal isocyanate group.

The molar ratio of (A-1), (A-2), (A-3) and (A-4) is such that the isocyanate group content after the reaction is 1.0 to 20% by weight of solid content. Can be decided. However, when a trifunctional or higher functional polyol or polyisocyanate compound is used, it is desirable to adopt a compounding ratio and a synthesis method in consideration of preventing gelation during the synthesis reaction.

Generally, the particle size of the microgel is 20 to 20.
Although it is said to be 0 nm, the microgel particles of the present invention can contain other active energy ray-curable compounds and the like inside, and the particles at this time expand to around 500 nm and are stably dispersed. . Therefore, the particle size of the dispersion particles of the present invention is not limited to the general definition, as long as the particle size is stable without causing substantial precipitation.

The above polyisocyanate compound (A-
Specific examples of 1) include ethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,
2,4-trimethylhexamethylene diisocyanate,
Aliphatic diisocyanates such as 2,4,4-trimethylhexamethylene diisocyanate and lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, norbornane diisocyanatomethyl, isopropyldiamine Examples thereof include alicyclic diisocyanates such as lidenedicyclohexyl-4,4'-diisocyanate or diisocyanates such as aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate and tolylene diisocyanate. I can.

Further, the above-mentioned diisocyanate (A-
The polymer of 1) or an adduct of diisocyanate (A-1) and a polyol such as trimethylolpropane or ethylene glycol, or diisocyanate (A-
The modified urea of 1), the modified buret, the modified carbodiimide, the modified uretonimine, the modified alohanate and the like are applicable.

The above polyol component (A-2) comprises at least one polyol resin selected from the group consisting of polyester polyols, polyether polyols, polyester polyether polyols and polycarbonate polyols, and a polyol component consisting of other polyols. Become.

As typical examples of other polyols, first, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, a compound having an effect equivalent to that of a diol component,
2-methyl-1,3-propanediol, dipropylene glycol, 1,3-butylene glycol, 1,4 butylene glycol, neopentyl glycol, 1,6 hexanediol, 3-methyl-1,5-pentanediol, 2 -Ethyl-1,3-hexanediol, 2-butyl-2ethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, spiroglycols, monoglycidyl ethers, monoepoxides can be mentioned. .

Next, as the polyol component having a valence of 3 or more, polyhydric alcohols such as glycerin, trimethylolethane, trimethylolpropane and pentaerythritol, or compounds having an equivalent effect can be mentioned. Further, polybutadiene polyol, polypentadiene polyol, epoxy resin and the like are listed as the alcohol component or a component having an equivalent effect.

The above-mentioned polyester polyol can be obtained by various known methods, but typical methods are shown below. One method of obtaining a polyester polyol is by subjecting a polybasic acid or a compound having an effect equivalent thereto to dehydration or dealcoholization reaction or addition reaction of a polyhydric alcohol.

Further, starting from the above-mentioned polyols, polyhydroxy compounds, amines, etc. as starting materials, addition polymerization of lactone monomers such as ε-caprolactone, β-methyl-δ-valerolactone, etc. One kind of polylactone polyester polyol is obtained.

Typical of the above-mentioned polybasic acids are succinic acid,
Carbon number of succinic anhydride, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc.
Compounds having the same effect as dicarboxylic acid such as aliphatic dicarboxylic acid of 8 and dimethyl ester thereof, and fats such as hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, hexahydrophthalic acid, tetrahydrophthalic acid Aromatic dicarboxylic acids such as cyclic dicarboxylic acid, orthophthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, terephthalic acid dimethyl ester, etc., or compounds having the same effect, trimellitic acid, pyromellitic dianhydride, methyl maleated Examples thereof include cyclohexene tetrabasic acid anhydride (for example, manufactured by Dainippon Ink and Chemicals, Inc .: trade name Epiclon B4400).

As the polyhydric alcohol used as a raw material for the polyester polyol, among the polyols (A-2) listed above as representatives of other polyols, a diol or a compound having an effect equivalent to that of the diol, or a polyhydric alcohol is used. Examples thereof include compounds having the same effect as those of the class.

In the present invention, as the polyol component, α,
An unsaturated polyester polyol having a double bond at the β-position can be used. The α- and β-position double bonds are unsaturated dibasic acids having a double bond at the α- and β-positions such as maleic acid, fumaric acid, and itaconic acid as a part of the dibasic acid that constitutes the polyester component. Be introduced using.

To the polyester polyol, if necessary, a titanate ester such as tetraisopropyl titanate or tetrabutyl titanate or a tin-based catalyst such as dibutyltin oxide is added as an esterification catalyst, and dehydration is promoted. A solvent such as xylene, Solvesso 100, Solvesso 150, etc., and a known method such as addition of an additive such as triphenyl phosphite or trinonyl phenyl phosphite in order to prevent oxidative discoloration. Obtained by alcohol condensation. The average molecular weight of the polyol and the number of functional groups of the hydroxyl group can be determined by mixing the hydroxyl group equivalent of the alcohol component with the carboxyl group equivalent of these acid components at an arbitrary ratio of 1 equivalent or more. However, when using a trifunctional or higher functional acid or alcohol component or a component having an effect equivalent thereto, it is desirable to adopt a synthesis method in consideration of gelation prevention during synthesis.

As the polyether polyol, the above-mentioned polyols and 4,4-dihydroxydiphenyl-2,2-propane (bisphenol A), 4,4-
Examples thereof include polyhydroxy compounds such as dihydroxydiphenyl-2,2-methane, and polyether polyols obtained by addition-polymerizing ethylene oxide, propylene oxide, tetrahydrofuran or the like with an amine or the like as a starting material.

The polyester polyether polyol can be obtained by addition-polymerizing ethylene oxide, propylene oxide, tetrahydrofuran or the like with the above polyester polyol as a starting material. Alternatively, using the polyether polyol as a starting material, ε
It can also be obtained by addition-polymerizing a lactone monomer such as -caprolactone or β-methyl-δ-valerolactone.

Typical examples of the compound (A-3) having an active energy ray-curable unsaturated double bond and a hydroxyl group are 2-hydroxyethyl (meth) acrylate and 2-
Monohydroxymono (meth) acrylate such as hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate or glycerin di (meth) acrylate, Biscoat 214HP (manufactured by Osaka Organic Co., Ltd.)
Such as monohydroxydi (meth) acrylate, pentaerythritol triacrylate, etc., monohydroxytriacrylate, glycerin mono (meth) acrylate, etc., dihydroxymono (meth) acrylate, and ethylene oxide, propylene oxide, tetrahydrofuran addition polymerization thereof The compound etc. which were mentioned are mentioned. Further, a product obtained by reacting a half urethane obtained by reacting a diisocyanate having two isocyanate groups having different reactivity with monohydroxymonoacrylate, monohydroxydi (meth) acrylate, and dialkanolamine It can be given as a representative example of (A-3).

Representative examples of the above-mentioned diisocyanates having two isocyanate groups having different reactivities include isophorone diisocyanate and tolylene diisocyanate.

Representative examples of the above dialkanolamine include diethanolamine, diisopropanolamine,
Examples thereof include dipropanolamine and dibutanolamine.

A compound having an active energy ray-curable unsaturated double bond and a hydroxyl group (A-3) when the unsaturated polyester polyol having a double bond at the α and β positions is used as the polyol component (A-2). As the above), it is particularly preferable to use hydroxyvinyl ether such as hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, and cyclohexanedimethanol monovinyl ether in terms of high alternating copolymerizability. The unsaturated polyester polyol having a double bond at the α and β positions introduced by using an unsaturated dibasic acid having a double bond at the α and β positions is used as a polyol component (A
-2), the equivalent ratio of unsaturated groups of vinyl ether to 1 equivalent of unsaturated groups of the polyurethane resin skeleton (A) is preferably 0.2 to 5, and further prepared in the range of 0.5 to 2. Is more desirable. Similarly, when the polyurethane resin particles contain an active energy ray-polymerizable compound therein, the gel particle itself and the unsaturated double bond group of the compound contained therein are unsaturated. The equivalent ratio of the unsaturated group of vinyl ether to 1 equivalent of the unsaturated group introduced by using dibasic acid is preferably 0.2 to 5, and more preferably 0.5 to 2.

As the compound (A-4) having a salt group, the salt group may be any of a phosphoric acid ester group, a sulfonic acid group, a tertiary amino group, a carboxyl group, or a neutralization base thereof. Suitable are diols with and diamines. To give only representative examples as specific examples, polyoxyethylene glycol, polyoxyethylene diaminopropyl ether, trimethylolpropane monophosphate ester, trimethylolpropane monosulfate ester, and at least a part of the dibasic acid component are sodium sulfo amber. Acid or polyester diol which is sodium sulfoisophthalic acid, N-methyldiethanolamine, diaminocarboxylic acids such as lysine, cystine and 3,5-diaminocarboxylic acid, 2,6-dihydroxybenzoic acid and especially dihydroxyalkanoic acid such as 2,2 -Carboxyl group-containing polycaprolactone diol obtained by the reaction of dihydroxypropionic acid and 2,2-dihydroxypropionic acid with ε-caprolactone.

The required amount of these salt groups is introduced into the polyurethane resin skeleton (A), and the required amount is determined by the kind and combination of hydrophilic groups. Among the above-exemplified examples, the hydrophilic group is particularly preferably a carboxyl group or a sulfonate group in the molecule, or a mixture of two or more of them. In particular, introducing a carboxyl group is easy to balance and easy to operate in various respects.
In this case, the acid value of the solid content is preferably in the range of 10 to 80,
The range of 20 to 60 is more preferable.

The compound (A-3) having an active energy ray-curable unsaturated double bond and a hydroxyl group in the molecule is (A-
1) can react with (A-2) (A-4) as a polyol component, or with a part of the isocyanate group after the reaction of (A-1) (A-2) (A-4). The concentration of unsaturated groups in the active energy ray-curable aqueous dispersion is determined by the unsaturated groups of the active energy ray-curable unsaturated double bond contained in the polyurethane resin skeleton (A) and the film-forming polyurethane resin particles. The sum of the active energy ray-curable compound and the unsaturated group is 0.02 to 5 mmol / g, more preferably 0.05 to 2 mmol / g.

In the case where the polyurethane resin skeleton (A) is an active energy ray-curable water dispersion of an unsaturated polyester polyurethane resin skeleton, the unsaturated dibasic acid having a double bond at the α and β positions is similarly introduced. And the unsaturated group equivalent of the vinyl ether compound and the unsaturated group of the active energy ray-curable compound contained inside the film-forming polyurethane resin particles are preferably 0.02 to 5 mmol / g, more preferably Is adjusted to 0.05 to 2 mmol / g.

The reaction for producing the polyurethane resin skeleton (A) can be carried out in an organic solvent, and if desired, any known urethane catalyst and polymerization inhibitor can be added.

As the organic solvent, in consideration of the concentration in the final step, it is preferable to use acetone, methyl ethyl ketone, ethyl acetate, n-hexane or the like having a lower boiling point than water. Then, when an organic solvent having a boiling point lower than that of water is used, the dispersion can be obtained by substantially concentrating only water as a medium. Of course, using an organic solvent having a boiling point higher than that of water does not cause any problem as long as the dispersion stability is not impaired.

Examples of urethane catalysts include tin-based catalysts such as dibutyl tin laurate and stannous octylate,
Examples include amine catalysts such as triethylenediamine.

Typical examples of the polymerization inhibitor include tert-butyl hydroquinone and metoquinone.

In the present invention, the polyurethane resin skeleton (A) is usually produced in a state of being dissolved in an organic solvent, and known methods can be applied to disperse it in an aqueous medium.

For example, the polyurethane resin skeleton (A)
In the case of containing a carboxyl group as a hydrophilic group, it is dispersed in water together with a base for neutralizing a part or all of this, but the method is to gradually add this while stirring the water containing the base. A resin solution can be added and dispersed. On the contrary, it is also possible to gradually add water containing a base to this resin solution for phase inversion emulsification.

Generally, in order to easily obtain a stable resin dispersion having a fine particle size, water containing a base is gradually added dropwise to a well-stirred resin solution to carry out phase inversion emulsification. More preferably,

Typical examples of the basic substance applicable to neutralize and ionize the carboxyl group in the resin include lithium hydroxide, potassium hydroxide, sodium hydroxide, trimethylamine, triethylamine and tripropylamine. , Tertiary alkylamines such as morpholine, and tertiary alkanolamines such as dimethylethanolamine and diethylethanolamine. Among these bases, triethylamine and dimethylethanolamine are preferable because they have good dispersibility, high volatility, and hardly remain in the coating film. Moreover, you may use the said base individually or in combination of 2 or more types. The amount of base used is generally 0.
1 to 2.0 equivalents are preferable, and more preferably 0.3 to
1.2 equivalents.

Representative examples of the cross-linking agent (B) having an active hydrogen atom that reacts with an isocyanate group include ethylamine, propylamine, n-butylamine, hydrazine, ethylenediamine, and the like.
Aliphatic amines such as propylenediamine, butylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine, cyclohexylenediamine, isophoronediamine,
Alicyclic amines such as norbornanediaminomethyl, tolylenediamine, xylenediamine, phenylenediamine,
Aromatic amines such as tris (2-aminoethyl) amine and 2,6-diaminopyridine, γ-aminopropyltrimethoxysilane, γ-dibutylaminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-
Examples include aminosilanes such as β (aminoethyl) γ-aminopropyltrimethoxysilane and N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane.

The cross-linking agent (B) having an active hydrogen atom that reacts with an isocyanate group is suitable such that the ratio of the NCO group in the polyurethane skeleton (A) to the active hydrogen is approximately equivalent, and an excess of the active hydrogen. Atoms cause a Michael addition reaction with an acryloyl group, so the range of 0.7 to 2.0: 1.0 is preferable. Of course, if the residual concentration of the active energy ray-curable unsaturated group disappeared by the Michael addition reaction by the crosslinking agent (B) having an active hydrogen atom is in the range of 0.02 to 5 mmol / g, the crosslinking agent (B) May be added in excess.

The crosslinking reaction between the crosslinking agent (B) having an active hydrogen atom and the aqueous dispersion comprising the polyurethane resin skeleton (A) can be carried out at 5 ° C to 90 ° C.
Reaction temperatures in the range of 10 ° C to 45 ° C are preferred.

The microgel resin particles thus obtained are required to have a film-forming property. It is necessary to know the degree of gelation of the microgel resin particles as a factor affecting the film forming property. The degree of gelation, that is, the gel fraction is defined as follows. In the present invention, a soxhlet extraction apparatus using acetone as a solvent is used to detect the weight% of the acetone insoluble matter in the dry coating film, and this numerical value is defined as the gel fraction. When the gel fraction is 90% or more, the film forming property is lost, and when it is less than 10%, the effect of the present invention, that is, good chemical resistance is not exhibited. Therefore, in the present invention, it is necessary to adjust the above gel fraction within the range of 10 to 90%.

The other film-forming property is the minimum film-forming temperature, but it can be adjusted by using a known film-forming auxiliary.
When measured with an MFT tester (RIKEN SEIKI MFG. Co., Ltd.), it is preferably 25 ° C. or lower.

Representative examples of the active energy ray-curable compound contained in the film-forming polyurethane resin particles are ethyl (meth) acrylate, butyl (meth) acrylate, 2 ethylhexyl (meth) acrylate,
Alkyl (meth) such as lauryl (meth) acrylate
Acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, N, N-diethylaminoethyl methacrylate, 2-ethoxyethyl acrylate, caprolactone modified 2-hydroxyethyl (meth) acrylate, ethylene oxide modified phenoxy Phosphoric acid (meth) acrylate and other monoacrylates, N-vinylcaprolactam, octadecyl vinyl ether, cyclohexyl vinyl ether, phenyl vinyl ether and other monovinyl ethers, bis (acryloylethyl) hydroxyethyl isocyanurate, bis (acryloxy neopentyl glycol) adipate, Ethylene oxide modified bisphenol A di (meth) acrylate, dicyclopentanyl di (meth Acrylate, dipentaerythritol monohydroxy pentaacrylate, dipentaerythritol hexaacrylate, or the polyol component (A-2) in mentioned polyol and the (meth)
Examples thereof include acrylic acid ester. Furthermore, resinous acrylate oligomers such as epoxy acrylate, urethane acrylate, polyester acrylate, silicon acrylate, polyether acrylate, polybutadiene acrylate and the like can be mentioned.

When the polyurethane resin skeleton (A) is an unsaturated polyester resin skeleton, the active energy ray-curable compound contained in the film-forming polyurethane resin particles is preferably unsaturated polyester and vinyl esters. As a typical example, maleic acid, fumaric acid, itaconic acid or the like in a part or all of the dibasic acid of the polyester component, α introduced by using an unsaturated dibasic acid having a double bond at the β position, Unsaturated polyester having double bond at β-position, or ethyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether,
Examples thereof include monovinyl ethers such as phenyl vinyl ether, diethylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether and other divinyl ethers, and trimethylolpropane trivinyl ether and other polyvinyl ethers.

The active energy ray-curing reaction initiator may be contained in the film-forming polyurethane resin particles alone or in a mixture with an active energy ray-curable compound or the like. Typical examples of the initiator are as follows. 2-
Hydroxy-2-methyl-1-phenylpropane-1-
On, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylhexenyl Ketones, acetophenone compounds such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether,
Benzoin compounds such as benzyl methyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, hydroxybenzophenone, 4-benzoyl-4 ′
-Methyldiphenyl sulfide, benzophenone series such as 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-methylthioxanthone, 2,
4 dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone and other thioxanthone-based active energy ray initiators, Michler-ketone, 4,4′-diethylaminobenzophenone, 4-dimethylaminobenzoic acid methyl ester And the like.

Other substances that can be contained inside the film-forming polyurethane resin particles include non-reactive resins such as polyester resins and polyurethane resins, curing agents such as aminoplasts, diluents, plasticizers, waxes and the like. Various additives and colorants can be mentioned.

The active energy ray-curable aqueous dispersion of the present invention is the active energy ray-curable microgel particles alone or the non-gel state active energy ray-curable dispersion of the active energy ray-curable microgel particles and water. It can also be prepared from a resin. However, in order to exert the effect of the present invention, it is necessary to adjust the weight% of the active energy ray-curable microgel particles to 10 to 100% and the non-gel active energy ray-curable resin to 90 to 0%. .

Typical examples of the method for producing the non-gel active energy ray-curable resin include a polyisocyanate compound (A-1) having two or more functional groups, and a polyol (A) having an average number of functional groups of two or more groups. -2) and a compound having an active energy ray-curable unsaturated double bond and a hydroxyl group (A-
The reaction product obtained by reacting 3) with the compound (A-4) having a salt group is dispersed in water by an arbitrary known method, and concentrated.

Typical examples of other active energy ray-curable aqueous resin compounds include polyester acrylate resins obtained by esterifying (meth) acrylic acid with the hydroxyl groups in the aqueous polyester resin.

The active energy ray-curable water dispersion comprising the active energy ray-curable microgel resin particles obtained according to the present invention may be diluted by adding water or an organic solvent such as alcohol. , Emulsifiers, surfactants, thickeners, heat stabilizers, defoamers, fillers, anti-settling agents, antioxidants, plasticizers, vinyl-based cross-linking agents, polymerization initiators for curing active energy rays, thermal decomposition Various water-soluble resins such as radical initiators, known polyester resins, polyamide resins, shellac or modified shellac, rosin derivatives, polyurethanes, acrylic copolymers, etc. A composition obtained by adding a resin or the like together with an emulsifier or an organic solvent may be used.

As the colorant, pigments and dyes may be used alone or in combination, for example, organic pigments such as soluble or insoluble azo type, phthalocyanine type, naphthol type, titanium oxide, rouge, carbon black, calcium carbonate, Examples thereof include inorganic pigments such as barium sulfate, and organic dyes such as metal complex salts, or a mixture thereof. The colorant may be a dry powder, but a press cake containing water may be used.

The water-based paint or printing ink of the present invention may be prepared by any method, for example, it can be prepared according to the following formulation. That is, the presscake or dry powder colorant is usually a mixture of some active energy ray-curable water dispersions and other aqueous resins, or other aqueous resin alone, and optionally a neutralizing agent, dispersion. It is kneaded and dispersed together with an auxiliary agent or a defoaming agent in a usual kneading machine such as a ball mill, a sand mill or another media mill to form a colorant base.
The colorant base is another resin component containing the remaining active energy ray-curable water-dispersed polyurethane compound, and
If necessary, it is mixed with water, a solvent, a neutralizing agent, a defoaming agent, and other additives, and finally prepared as an active energy ray-curable aqueous dispersion composition for the purpose of an aqueous paint or printing ink.

The active energy ray-curable aqueous dispersion of the present invention can be cured by a known method. For example, in the case of curing with an electron beam, after coating the adherend and evaporating and drying water and a small amount of an organic solvent when contained,
Acceleration voltage 20-2000 KeV, preferably 150-3
Using an electron beam irradiation device of 00 KeV, irradiation is carried out in an inert gas atmosphere containing or not containing a small amount of oxygen so that the total irradiation dose is 5 to 200 KGy, preferably 20 to 150 KGy to obtain a cured product. You can

Further, in the present invention, other curing means, for example, a method of curing in air or an inert gas atmosphere by ultraviolet rays obtained from a mercury lamp, a xenon lamp, etc., energy related to heat such as infrared rays, high frequency waves or microwaves There is a method of heat curing. In the case of using high-energy ionizing radiation having a function of absorbing a secondary electron by being absorbed by a substance such as the electron beam, X-ray, and gamma-ray, it is not necessary to add a polymerization initiator. When heat curing or ultraviolet curing is used, it is preferable to add a photopolymerization initiator or a thermal polymerization initiator. In addition, one kind selected from the above-mentioned curing method by ionizing radiation, curing method by ultraviolet ray, and curing method by heat can be used alone or in combination of two or more kinds, simultaneously or before and after each.

Examples of these heat or light polymerization initiators include 2,2'-azobisisobutyronitrile,
2,2'-azobis (2-methylbutyronitrile),
Azo initiators such as 2,2′-azobis (2,4-dimethylvaleronitrile) and 1,1′azobis (cyclohexane-1-carbonitrile), ketone peroxides such as methylethylketone peroxide and cyclohexanone peroxide , Cumene hydroperoxide, hydroperoxides such as tert-butyl peroxide, dialkyl tert-butyl peroxide, dialkyl peroxides such as dicumyl peroxide, tert-butyl peroxylaurylate, t
Examples thereof include peroxide initiators such as peroxyesters such as ert-butyl peroxybenzoate.

Further, as the photopolymerization initiator, for example, an intermolecular hydrogen abstraction type initiator such as benzyl, benzophenone, Michler's ketone, dibenzosuberone, 2-ethylanthraquinone, isobutylthioxanthone, benzoin ethyl ether, diethoxyacetophenone, Benzyl methyl ketal, 1-hydroxycyclohexyl phenyl ketone 4- (2-hydroxyethoxy) -phenl (2-hydroxy-2-propyl) ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one,
Acylphosphine oxide, 2-methyl-1- [4
A known and commonly used organic phase radical polymerization initiator such as an intramolecular bond cleavage type initiator such as-(methylthio) phenyl] -2-morpholinopropane-1 can be used. When these organic phase initiators are used, it is preferable to add them to the resin solution in advance before dispersing them in water.

On the other hand, examples of the initiator which can be added to the aqueous dispersion of the polymerizable unsaturated group-containing resin include potassium persulfate, ammonium persulfate, azobisbutyronitrile or its hydrochloride, and the like. Furthermore, if necessary, an organic peroxide such as cumene hydroperoxide or tert-butyl hydroperoxide can be used. In addition, a so-called redox system initiation is used in which these persulfates, peroxides and the like are used in combination with a metal ion such as iron ion or a reducing agent such as sodium sulfoxylate formaldehyde, sodium pyrosulfite or L-ascorbic acid. Agents can also be used.

The amount of the polymerization initiator used may be appropriately selected from the range of 0.2 to 20% based on the solid content excluding the colorant, but the range of 0.5 to 10% is particularly preferable.

The active energy ray-curable water-dispersed polyurethane composition of the present invention comprises wood, metal, glass, cloth, leather,
It can be applied to coated and printed materials including paper and plastic, and any coating method and printing method such as brush coating, spray coating, dip coating, vacuum coating, roll coating, or gravure printing and flexo printing can be applied. .

[0070]

EXAMPLES Next, the present invention will be described in more detail with reference to reference examples and examples. In the following, all parts and% represent weight ratios unless otherwise specified.

Preparation Example 1 MPD / IP was placed in a reactor equipped with a reflux condenser, a nitrogen inlet tube, and a thermometer and equipped with a stirrer.
32.84 parts of A500 (Kuraray Co., Ltd. molecular weight 500 polyester diol), dimethylol propionic acid 9.
53 parts, trimethylolpropane 0.39 parts, isophorone diisocyanate 3.04 parts, dicyclohexylmethane-4,4-diisocyanate 43.02 parts, dibutyltin laurylate 0.030 parts, methyl ethyl ketone 10
0.00 part was added and the temperature was raised to 70 ° C. in 0.5 hours with stirring and reacted at 70 to 75 ° C. for 5 hours, then tert-
Butylhydroquinone 0.05 part, viscoat # 214
11.19 parts of HP (Osaka Organic Chemical Co., Ltd.) and 0.030 part of dibutyltin laurate are added, the nitrogen introduction tube is replaced with an air introduction tube, and the mixture is allowed to react again at 70 to 75 ° C. for 6 hours to give poly. A solution of the (ester) urethane resin skeleton (a1) was obtained. After cooling to 50 ° C., 7.19 parts of triethylamine and 229.9 parts of pure water are gradually added to this solution,
Keep at 40 ℃, A-1130 (Nihon Unicar Co., Ltd.)
3) a solution prepared by diluting 1.60 parts of acetone with 8.0 parts of acetone.
It was dripped in 0 minutes. Surfynol AK02 (manufactured by Nissin Chemical Industry Co., Ltd.) (0.051 parts) was added, and the mixture was distilled under reduced pressure at 50 ° C. to remove methyl ethyl ketone to give a nonvolatile content of 29.
An active energy ray-curable aqueous dispersion (J1) having 1% and Gardner viscosity: WX was prepared.

(Preparation Example 2) MPD / IP was added to a reactor equipped with a reflux condenser, a nitrogen inlet tube, and a thermometer equipped with a stirrer.
A500 (Kuraray Co., Ltd. molecular weight 500 polyester diol) 32.65 parts, dimethylol propionic acid 1
0.50 parts, Bremmer GLM (manufactured by NOF CORPORATION)
3.25 parts, trimethylolpropane 0.47 parts 1,3
-Bis (isocyanatomethyl) cyclohexane 41.2
2 parts, tert-butylhydroquinone 0.03 part, dibutyltin laurylate 0.03 part, and methyl ethyl ketone 122.2 parts were added, and the mixture was stirred at a temperature of 0.5 to 70 ° C.
After heating for 5 hours at 70 ° C, tert-butyl hydroquinone 0.02 parts, biscoat # 214HP
(Osaka Organic Chemical Co., Ltd.) (11.87 parts) was added, the nitrogen introduction tube was replaced with an air introduction tube, and the mixture was reacted again at 70 ° C. for 6 hours to obtain a solution of the polyester urethane resin skeleton (a2). . After cooling to 50 ° C., this solution was prepared in another reactor equipped with a reflux condenser, a nitrogen inlet tube, and a thermometer equipped with a stirrer.
Parts, pure water 241.1 parts, isophorone diamine 1.50
Part, and 7.5 parts of acetone, kept at 35 to 40 ° C., added while stirring for 30 minutes, and further added 0.051 part of Surfynol AK02 (manufactured by Nissin Chemical Industry Co., Ltd.) to add 50 parts. The mixture was distilled under reduced pressure at ℃ to remove methyl ethyl ketone to prepare an active energy ray-curable water dispersion (J2) having a nonvolatile content of 30.5% and a viscosity of VW.

Preparation Example 3 A reactor equipped with a reflux condenser, a nitrogen inlet tube, and a thermometer and equipped with a stirrer was charged with 30.04 parts of polyether diol BAP3 glycol (polyether diol manufactured by Nippon Emulsifier Co., Ltd.) and diester. 10.11 parts of methylolpropionic acid, 0.43 of trimethylolpropane
Parts, isophorone diisocyanate 16.76 parts, dicyclohexylmethane-4,4-diisocyanate 31.6
4 parts, dibutyltin laurylate 0.03 part, and methyl ethyl ketone 99.96 parts were added, and the temperature was raised to 70 ° C. in 0.5 hours while stirring and reacted at 70 ° C. for 5 hours.
rt-Butyl hydroquinone 0.03 parts, biscoat #
214 HP (Osaka Organic Chemical Co., Ltd.) 10.97 parts was added, the nitrogen introduction tube was replaced with an air introduction tube, and the reaction was carried out again at 70 ° C. for 6 hours to give a polyether urethane resin skeleton (a
A solution of 3) was obtained. After cooling to 50 ° C., gradually adding 7.63 parts of triethylamine and 231.4 parts of pure water to this solution, while maintaining at 35 to 40 ° C., SH6020 (manufactured by Toray Dow Silicone Co., Ltd.) 2. A solution prepared by diluting 41 parts with 12 parts of acetone was added dropwise over 30 minutes. Surfynol AK02 (manufactured by Nissin Chemical Industry Co., Ltd.) 0.051 parts was added and distilled under reduced pressure at 50 ° C. to remove methyl ethyl ketone to remove non-volatile matter: 30.2%, viscosity XY, active energy ray. A curable water dispersion (J3) was prepared.

(Comparative Preparation Example 1) 21.05 parts of Praxel L205AL (Lactone Polyesterdiol Daicel Chemical Industries Ltd.) and dimethylol were placed in a reactor equipped with a reflux condenser, an air inlet tube, and a thermometer. Propionic acid 11.28 parts, Bremmer GLM (manufactured by NOF CORPORATION) 3.49 parts, trimethylolpropane 2.2
6 parts, norbornane diisocyanatomethyl 47.69
Parts, 0.028 parts of dibutyltin laurylate, 107.2 parts of ethyl acetate, and 15.0 parts of N-methylpyrrolidone were added and the temperature was raised to 70 ° C. in 0.5 hours with stirring, and after reaction at 70 ° C. for 5 hours, Further, 14.23 parts of 2-hydroxypropyl acrylate was added and reacted at 70 ° C. for 6 hours.
Then, while cooling, triethylamine 8.
50 parts was added, 0.51 part of Surfynol AK02 (manufactured by Nisshin Chemical Industry Co., Ltd.) was added, and then pure water 210.0 was added.
Parts were added over 30 minutes. Further, it was distilled under reduced pressure at 50 ° C., ethyl acetate was removed, and non-volatile content: 29.2%, viscosity: + E, active energy ray-curable water dispersion (H1).
Was prepared.

Preparation Example 4 MPD / IP was placed in a reactor equipped with a reflux condenser, a nitrogen inlet tube, and a thermometer and equipped with a stirrer.
A (Kuraray Co., Ltd. molecular weight 500 polyester diol) 39.58 parts, dimethylol propionic acid 9.79
Parts, trimethylolpropane 0.44 parts, 1,3-bis (isocyanatomethyl) cyclohexane 38.44 parts,
Add 0.03 parts of dibutyltin laurylate and 122.2 parts of methyl ethyl ketone and stir up to 70 ° C. with stirring.
After heating for 5 hours and reacting at 70-75 ° C. for 5 hours, te
rt-Butyl hydroquinone 0.03 parts, biscoat #
214 HP (Osaka Organic Chemical Co., Ltd.) 11.75 parts was added, the nitrogen introduction pipe was replaced with an air introduction pipe, and 70 to 7 again.
The reaction was carried out at 5 ° C. for 6 hours to obtain a solution of poly (ester) urethane resin skeleton (a4). After cooling to 50 ° C., 5.09 parts of Lucilin TPO (manufactured by BASF) and 7.38 parts of triethylamine were added to and mixed with this solution, and 254.0 parts of pure water was gradually added to 35-40 ° C. While keeping the temperature, a solution prepared by diluting 1.78 parts of A-1130 (manufactured by Nippon Unicar Co., Ltd.) with 8.9 parts of acetone was added dropwise over 30 minutes. Surfynol AK02 (manufactured by Nissin Chemical Industry Co., Ltd.)
0.051 part was added and distilled under reduced pressure at 50 ° C. to remove methyl ethyl ketone, and non-volatile content: 30.4%, viscosity W−
An active energy ray-curable water dispersion (J4) of X was prepared.

Preparation Example 5 In a reactor equipped with a stirrer equipped with a reflux condenser, a nitrogen inlet tube and a thermometer, 222.2 parts of a solution of the poly (ester) urethane resin skeleton (a2) was added.
3.0 parts of benzophenone, methyl benzoylbenzoate,
After adding 2.0 parts and dissolving, triethylamine 7.
A-1122 (manufactured by Nippon Unicar Co., Ltd.) while gradually adding 2 parts and 256.1 parts of pure water and maintaining the temperature at 35 to 40 ° C.
A solution prepared by diluting 1.89 parts with 9.5 parts of acetone was added dropwise over 30 minutes. Surfynol AK02 (manufactured by Nissin Chemical Industry Co., Ltd.) (0.051 parts) was added, and the mixture was distilled under reduced pressure at 50 ° C. to remove methyl ethyl ketone to obtain a nonvolatile content: 30.5.
%, Viscosity-X, active energy ray-curable water dispersion (J
5) was prepared.

Preparation Example 6 A reactor equipped with a stirrer equipped with a reflux condenser, a nitrogen inlet tube, and a thermometer was added to 222.2 parts of the solution of the polyester urethane resin skeleton (a4), and Irgacure-907 (manufactured by Ciba Geigy). ) 6.12 parts was added and dissolved, and then 7.38 parts of triethylamine and 257 parts of pure water were gradually added to the solution while maintaining the temperature at 35 to 40 ° C.
A solution prepared by diluting 1.98 parts of -1122 (manufactured by Nippon Unicar Co., Ltd.) with 10.0 parts of acetone was added dropwise over 30 minutes.
Surfynol AK02 (manufactured by Nisshin Chemical Industry Co., Ltd.)
051 parts were added, and the mixture was distilled under reduced pressure at 50 ° C. to remove methyl ethyl ketone to obtain a nonvolatile content: 30.4%, viscosity W−X,
The active energy ray-curable water dispersion (J6) was prepared.

Preparation Example 7 A reactor equipped with a stirrer equipped with a reflux condenser, a nitrogen inlet tube, and a thermometer, 200 parts of a solution of the poly (ester) urethane resin skeleton (a1), and Decklite UE-8200 ( Dainippon Ink and Chemicals, Inc.
(Manufactured by Mitsui Chemicals Co., Ltd.) 10.2 parts and 30 parts of methyl ethyl ketone were added and dissolved, and 7.19 parts of triethylamine and 267 parts of pure water were gradually added to the mixture while maintaining at 35 to 40 ° C.
2 (manufactured by Nippon Unicar Co., Ltd.) with 1.78 parts of acetone 1
The solution diluted with 1.8 parts was added dropwise over 30 minutes. Surfynol AK02 (manufactured by Nisshin Chemical Industry Co., Ltd.) 0.056
Parts were added and distilled under reduced pressure at 50 ° C. to remove methyl ethyl ketone to prepare an active energy ray-curable aqueous dispersion (J7) having a nonvolatile content of 29.9% and a viscosity of YZ.

Preparation Example 8 In a reactor equipped with a reflux condenser, a nitrogen inlet tube, and a thermometer, equipped with a stirrer, 200 parts of a solution of the poly (ester) urethane resin skeleton (a1), and Lipoxy VR-90 (Showa) were used. Polymer (manufactured by Kogyo Co., Ltd.) 20.5 parts and methyl ethyl ketone 40.3 parts were added and dissolved, then 7.19 parts of triethylamine and 292 parts of pure water were gradually added,
While maintaining the temperature at 35 to 40 ° C., a solution prepared by diluting 1.78 parts of A-1122 (manufactured by Nippon Unicar Co., Ltd.) with 8.9 parts of acetone was added dropwise over 30 minutes. Surfynol AK02
(Manufactured by Nissin Chemical Industry Co., Ltd.)
Was distilled under reduced pressure to remove methyl ethyl ketone to prepare an active energy ray-curable water dispersion (J8) having a nonvolatile content of 30.4% and a viscosity of 138 mPas.

Preparation Example 9 A reactor equipped with a reflux condenser, a nitrogen inlet tube and a thermometer was equipped with a stirrer, 200 parts of a solution of the poly (ester) urethane resin skeleton (a1), Kayarad DPHA (Nippon Kagaku 20.5 parts, 40.3 parts of methyl ethyl ketone were added and dissolved, and 7.19 parts of triethylamine and 292 parts of pure water were gradually added to obtain 3
While maintaining the temperature at 5 to 40 ° C., a solution prepared by diluting 1.78 parts of A-1122 (manufactured by Nippon Unicar Co., Ltd.) with 8.9 parts of acetone was added dropwise over 30 minutes. Surfinol AK02 (manufactured by Nisshin Chemical Industry Co., Ltd.) (0.061 parts) was added, and the mixture was distilled under reduced pressure at 50 ° C. to remove methyl ethyl ketone to remove non-volatile components:
An active energy ray-curable aqueous dispersion (J9) having a viscosity of 30.4% and a viscosity of 700 mPas was prepared.

Preparation Example 10 Neopentyl glycol 1
60.8 parts, 2-methyl-1,3 propanediol 13
9.1 parts, adipic acid 159.4 parts, maleic anhydride 9
Polyester resin 45.07 consisting of 8 parts and having a hydroxyl value of 212.0 KOHmg / g and an acid value of 0.3 KOHmg / g
Parts, dimethylolpropionic acid 10.52 parts, trimethylolpropane 0.47 parts, 1,3-bis (isocyanatomethyl) cyclohexane 41.28 parts, dibutyltin laurylate 0.03 parts, methyl ethyl ketone 122.
2 parts was added and the temperature was raised to 70 ° C. in 0.5 hours with stirring, and after reacting at 70 to 75 ° C. for 5 hours, 0.03 part of tert-butylhydroquinone and butanediol monovinyl ether (manufactured by BASF) 2 0.66 parts was added, the nitrogen introduction tube was replaced with an air introduction tube, and the mixture was reacted again at 70 to 75 ° C. for 6 hours to obtain a solution of the polyester urethane resin skeleton (a5). After cooling to 50 ° C., 4.30 parts of Irgacure 651 (manufactured by Ciba-Geigy), 4.31 parts of dicyclohexanedimethanol divinyl ether and 8.6 parts of methyl ethyl ketone were mixed and dissolved, and then 7.23 parts of triethylamine were dissolved. , And then 266 parts of pure water are gradually added, while maintaining at 35 to 40 ° C., A-1120
(Manufactured by Nippon Unicar Co., Ltd.) 3.10 parts of acetone 15.
The solution diluted with 5 parts was added dropwise over 30 minutes. Surfinol AK02 (manufactured by Nisshin Chemical Industry Co., Ltd.) was added in an amount of 0.056 parts and distilled under reduced pressure at 50 ° C. to remove methyl ethyl ketone to remove non-volatile matter: 30.0%, viscosity-W, active energy ray curing. Aqueous water dispersion (J10) was prepared.

(Clear Paint Test Example) Examples 1 to 11 and Comparative Example 1 The active energy ray-curable water dispersion (J
1 to J10, H1) were blended as shown in Tables 1 to 3 to prepare Example compositions 1 to 11 and Comparative example 1. An aluminum plate, a veneer plywood, and an art paper were coated with a bar coater so that the thickness of the dried coating film was 2 to 3 μm, and dried at 60 ° C. for 5 minutes with a blow dryer. Irradiation dose of 35 with 120W high pressure mercury lamp
Ultraviolet irradiation of 0 mJ / cm ² was performed. The coating film before and after the ultraviolet irradiation was subjected to a pencil hardness test, a MEK resistance test, a cellophane tape peeling test on an aluminum plate and a veneer plywood, and a MEK resistance test and a blocking test on an art paper. . Each test method is shown below, and the test results are shown in Tables 1-3.

(Pencil Hardness Test) A precision drawing pencil (manufactured by Uni-Mitsubishi Pencil Co., Ltd.) cut into a cylindrical shape is scratched at an angle of 45 degrees with respect to the coated surface. It is shown by the hardness of the hardest pencil that does not break the coating film 5 times repeated 2 times or more.

(MEK Rubbing Test) Methyl ethyl ketone (MEK) was added to absorbent cotton wrapped in gauze to give 2 kg.
Rubbing the coating film under a load of 1
It measures the number of rubbing until 0% exposure, D
It was measured using an IC type rubbing tester type I (manufactured by Riken Engineering Co., Ltd.).

(Cellotape Peeling Test) In one method of adhesion strength test, a cut line having a depth of reaching the base material is inserted in a vertical and horizontal crosswise pattern on the surface of a test piece, and a 24 mm wide cellophane tape (manufactured by Nichiban Co., Ltd.) is used. After pasting, quickly by hand 18
Peel at 0 degrees. The results of this adhesion strength test are shown by examining the state of the coating film remaining. When the film does not peel at all, it is indicated by ◯, when it peels slightly along the cross, it is indicated by Δ, and when it peels, it is indicated by x.

(Blocking resistance test) Each of the printing inks of Examples 1 to 7 and Comparative Examples 1 to 3 was applied to a surface-treated polyester film having a thickness of 12 μm by drawdown rod #.
4 was used for coating, and the coating was dried with a dryer for 30 seconds.
After leaving it for 1 day, the coated surfaces are piled up, the temperature is 60 ° C, and the load is 50
After press-bonding at 0 g / cm ² and a humidity of 75% for 3 hours, the blocking state of the sample surface was observed. The evaluation criteria are shown below. ○ ・ ・ ・ Not blocked △ ・ ・ ・ Slightly blocked × ・ ・ ・ Blocked

[0087]

[Table 1]

In the table, "Irgacure" means "Irgacure 1173", "hardness test" means "pencil hardness test",
"MEK resistance" represents "MEK resistance test" and "peeling test" represents "cellophane tape peeling test".

[0089]

[Table 2]

"Blocking" in the table means "blocking test".

[0091]

[Table 3]

[0092]

[Table 4]

[0093]

[Table 5]

[0094]

[Table 6]

(Printing ink test example) Inks having the compositions shown in Table 7 were prepared by a conventional method. The thickness of the dry coating is 1.2 ~
Apply a bar coater to 2 μm and apply at 100 ℃ for 2
After drying with a blower dryer for 20 minutes, an electron beam was irradiated with an electron beam of 20 KGy by an electron curtain type electron beam irradiation device (manufactured by ESI). In addition to the MEK resistance test and the blocking resistance test described above, an ink gloss test was also performed by the following method.

(Ink Gloss Test) Example 1 was applied to art paper.
Each of the printing inks of 2 to 15 and Comparative Example 2 was applied using drawdown rod # 4, dried with a dryer for 30 seconds, and then the gloss of the ink surface was measured. The gloss was measured by using a GLOSSMETER manufactured by Nippon Denshoku Industries Co., Ltd. and measuring reflected light at 60 degrees.

[0097]

[Table 7]

“Titanium oxide” in the table means “Taipaque CR
-58-2 (manufactured by Ishihara Sangyo Co., Ltd.) "is used.

[0099]

As is clear from the above results, the coating film obtained from the active energy ray-curable water dispersion composition of the present invention has little curing strain due to the polymerization of unsaturated groups, and has good adhesion to an adherend. It has excellent properties and adhesion, high safety and hygiene, and because it is pre-crosslinked, it has excellent curability and chemical resistance. The same effect can be obtained in a composition with a known active energy ray-curable water dispersion composition. Furthermore, since water-insoluble initiators, active energy ray-curable compositions, etc., which have been difficult to mix until now, can be contained in the gel particles, any water-insoluble compound can be contained within the scope of the present invention. The same excellent effects as the above results can be obtained.

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Claims (6)

[Claims] 1. A water-dispersible active energy ray-curable microgel particle, wherein the microgel particle has a polyurethane resin skeleton and a crosslinked structure in which the skeletons are crosslinked through urethane bonds or urea bonds. A film-forming polyurethane resin particle in the form of a gel, wherein the polyurethane resin particle has an active energy ray-curable unsaturated double bond and a salt group. 2. The polyurethane resin skeleton is at least one resin skeleton selected from the group consisting of a polyester polyurethane resin skeleton, a polyether polyurethane resin skeleton, a polyether polyester polyurethane resin skeleton and a polycarbonate polyurethane resin skeleton. The active energy ray-curable water dispersion described in. 3. The polyurethane resin skeleton has an isocyanate group, and the crosslinked structure is a crosslinked structure formed by a reaction between the isocyanate group and a crosslinking agent having an active hydrogen atom. Active energy ray curable water dispersion. 4. The gel fraction of the microgel particles is 10
The active energy ray-curable water dispersion according to claim 1, which is ˜90%. 5. The active energy ray-curable water dispersion according to claim 1, wherein the gel-state film-forming polyurethane resin particles contain an active energy ray-polymerizable compound therein. 6. An active energy ray-curable microgel particle dispersed in water and water, and an active energy ray-curable resin in a non-gel state dispersed in water, wherein the microgel particle comprises a polyurethane resin skeleton and the skeleton. Is a gel-forming film-forming polyurethane resin particle consisting of a crosslinked structure in which a space is crosslinked via a urethane bond or 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 water dispersion characterized by having.