JP6539463B2 - Active energy ray curable aqueous resin composition - Google Patents

Description

  The present invention relates to an active energy ray-curable aqueous resin composition. More specifically, the present invention relates to an active energy ray-curable aqueous resin composition useful as a raw material of, for example, a coating agent such as a paint, a printing ink, an adhesive, a resist agent, a molding material and the like.

  A compound having an ethylenically unsaturated group and a cyclic imide group as an aqueous emulsion which is excellent in curability by active energy rays, does not produce coloring and odor, and forms a cured film excellent in hardness, solvent resistance and water resistance There is proposed an emulsion in which a polymer as a constituent unit and a compound having two or more (meth) acryloyl groups are dispersed in an aqueous medium (see, for example, Patent Document 1).

  However, the emulsion is less likely to generate an odor because it is aqueous, but has the disadvantage of being inferior in dispersion stability and also inferior in film forming property.

  In recent years, it is excellent in dispersion stability and film-forming property, and further, it is excellent in the property (curling prevention property) which is hard to bend the resin film of a substrate when forming a film, and forms a film excellent in abrasion resistance and water resistance. It is desired to develop an active energy ray-curable aqueous resin composition.

JP 2000-234044 A

  The present invention has been made in view of the above-mentioned prior art, and is characterized by dispersion stability, film forming property, and a property (hereinafter referred to as anti-curling property) that makes it difficult to bend a resin film of a substrate when forming a film. It is an object of the present invention to provide an active energy ray-curable aqueous resin composition which forms a film excellent in abrasion resistance and water resistance.

  The present invention is an active energy ray-curable aqueous resin composition containing an emulsion particle comprising an (meth) acrylic polymer having an imide ring and an aqueous medium, wherein the emulsion particle contains a water-insoluble curable monomer. The present invention relates to an active energy ray-curable aqueous resin composition characterized by being emulsion particles.

  The active energy ray-curable aqueous resin composition of the present invention is excellent in dispersion stability, film-forming property and anti-curling property, and exhibits an excellent effect of forming a film excellent in abrasion resistance and water resistance.

  The active energy ray-curable aqueous resin composition of the present invention is, as described above, an active energy ray-curable aqueous resin composition containing an emulsion particle comprising an (meth) acrylic polymer having an imide ring and an aqueous medium. The emulsion particles are emulsion particles containing a water-insoluble curable monomer.

  In the active energy ray-curable aqueous resin composition of the present invention, the emulsion particles and the water-insoluble curable monomer are not merely dispersed in the aqueous medium, but the water-insoluble curable monomer is contained in the emulsion particles. Thus, it exhibits the excellent effect of forming a film excellent in dispersion stability, film-forming property and anti-curl property, and excellent in scratch resistance and water resistance.

  In the present invention, "(meth) acrylic" means acrylic or methacrylic. "(Meth) acrylate" means acrylate or methacrylate. "(Meth) acryloyl" means acryloyl or methacryloyl. Also, "(meth) acryloyloxy" means acryloyloxy or methacryloyloxy.

  The emulsion particles are composed of (meth) acrylic polymers having an imide ring. In the following, for convenience, a (meth) acrylic polymer having an imide ring is also simply referred to as a (meth) acrylic polymer.

  The emulsion particles can be obtained, for example, by polymerizing a monomer component having an imide ring and a monomer component containing a (meth) acrylic monomer by a polymerization method such as emulsion polymerization, but the present invention is only applicable to such a polymerization method. It is not limited to

  As an imide ring group which the monomer which has an imide ring has, for example, a formula (Ia):

(Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ² represents an alkyl group having 1 to 4 carbon atoms, and R ¹ and R ² may combine to form a ring) R ³ represents a direct bond or an alkylene group having 1 to 4 carbon atoms)
Cyclic imide group represented by formula (Ib):

(Wherein, R ^{1 to} R ³ are the same as above. R ⁴ and R ^{5 each} represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)
And a cyclic imide group represented by

In Formula (Ia) and Formula (Ib), when R ¹ and R ² are combined to form a ring, the group in which R ¹ and R ² are combined has, for example, 2 to 2 carbon atoms. 4 alkylene groups and the like. Among the alkylene groups, a propylene group and a butylene group are preferable from the viewpoint of the stability of the monomer having an imide ring. R ³ is a direct bond or an alkylene group having 1 to 4 carbon atoms, preferably a direct bond, an ethylene group or a propylene group.

  Examples of the polymerizable group of the monomer having an imide ring include, for example, ethylenic unsaturated groups such as vinyl group, allyl group, (meth) acryloyl group, (meth) acryloyloxy group, etc. It is not limited to the example only. Among these polymerizable groups, (meth) acryloyl group and (meth) acryloyloxy group are preferable, and (meth) acryloyloxy group is more preferable.

  Among monomers having an imide ring, from the viewpoint of obtaining an active energy ray-curable aqueous resin composition which forms a film excellent in dispersion stability, film-forming property and anti-curl property and excellent in scratch resistance and water resistance, A monomer having a cyclic imide group represented by the formula (Ia) and a (meth) acryloyloxy group, and a monomer having a cyclic imide group represented by the formula (Ib) and a (meth) acryloyloxy group are preferred, and the formula (IIa) :

(Wherein, R ³ is the same as above. R ⁶ is a hydrogen atom or a methyl group)
Maleimido (meth) acrylate represented by and Formula (IIb):

(Wherein, R ³ and R ⁶ are as defined above)
And maleimide (meth) acrylates of the formula (IIa) and the formula (IIb) in which R ³ is an ethylene group and R ⁶ is a hydrogen atom or a methyl group, and N is more preferably hexahydrophthalimide (meth) acrylate Further preferred is-(meth) acryloyloxyethyl hexahydrophthalimide.

  The content ratio of the monomer having an imide ring in the monomer component is an active energy ray-curable aqueous resin composition which forms a film excellent in dispersion stability, film forming property and anti-curling property and excellent in scratch resistance and water resistance. From the viewpoint of obtaining, it is preferably 3 to 95% by mass, more preferably 5 to 90% by mass, and still more preferably 5 to 80% by mass.

  Examples of (meth) acrylic monomers include (meth) acrylic acid, alkyl (meth) acrylates, hydroxyl group-containing (meth) acrylates, oxo group-containing (meth) acrylates, fluorine atom-containing (meth) acrylates, and epoxy group-containing Meta) acrylate, alkoxyalkyl (meth) acrylate, aralkyl (meth) acrylate, carbonyl group-containing (meth) acrylate, aziridinyl group-containing (meth) acrylate, nitrogen atom-containing (meth) acrylate, diene structure-containing (meth) acrylic acid compound And carboxyl group-terminated caprolactone modified (meth) acrylate and the like, but the present invention is not limited to such exemplification. These (meth) acrylic monomers may be used alone or in combination of two or more.

  Examples of the alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-Butyl (meth) acrylate, sec-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, tridecyl (meth) acrylate, n-lauryl (meth) acrylate, dodecyl (meth) Acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-methylcyclohexyl methyl (meth) acrylate, tert-butylcyclohexyl And C) an ester group such as acrylate and cyclododecyl (meth) acrylate having 1 to 18 carbon atoms, and alkyl (meth) acrylate which may have an alicyclic structure, and the like. It is not limited to only. These monomers may be used alone or in combination of two or more.

  As the hydroxyl group-containing (meth) acrylate, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy The hydroxyl group-containing (meth) acrylate having 1 to 18 carbon atoms of an ester group such as butyl (meth) acrylate, caprolactone modified hydroxy (meth) acrylate, etc. may be mentioned, but the present invention is limited to only such an example. Absent. These monomers may be used alone or in combination of two or more.

  As the oxo group-containing (meth) acrylate, for example, (di) ethylene glycol (methoxy) (ethylene glycol (meth) acrylate such as ethylene glycol (meth) acrylate, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, diethylene glycol methoxy (meth) acrylate) Although a meta) acrylate etc. are mentioned, this invention is not limited only to this illustration. These monomers may be used alone or in combination of two or more.

  As the fluorine atom-containing (meth) acrylate, for example, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorobutylethyl (meth) acrylate, perfluoroisononylethyl Although fluorine atom containing alkyl (meth) acrylate etc. which have a fluorine atom in ester groups, such as (meth) acrylate and perfluoro octyl ethyl (meth) acrylate, etc. are mentioned, this invention is not limited only to this illustration . These monomers may be used alone or in combination of two or more.

  Examples of epoxy group-containing (meth) acrylates include glycidyl (meth) acrylate, α-methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate and the like, but the present invention is not limited thereto. It is not limited to only. These monomers may be used alone or in combination of two or more.

  Examples of the alkoxyalkyl (meth) acrylate include 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, methoxyethyl (meth) acrylate, methoxybutyl (meth) acrylate, ethoxybutyl (meth) acrylate and trimethylolpropane Although tripropoxy (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, methyl (alpha) -allyloxy methyl acrylate etc. are mentioned, this invention is not limited only to this illustration. These monomers may be used alone or in combination of two or more.

  As the aralkyl (meth) acrylate, for example, an aralkyl having an aralkyl group having 7 to 18 carbon atoms, such as benzyl (meth) acrylate, phenylethyl (meth) acrylate, methyl benzyl (meth) acrylate and naphthylmethyl (meth) acrylate Although (meth) acrylate etc. are mentioned, this invention is not limited only to this illustration. These monomers may be used alone or in combination of two or more.

  Examples of the carbonyl group-containing (meth) acrylate include, but are not limited to, acetonyl (meth) acrylate, diacetone (meth) acrylate, 2- (acetoacetoxy) ethyl (meth) acrylate, oxocyclohexylmethyl (meth) acrylate and the like. The invention is not limited to such examples. These monomers may be used alone or in combination of two or more.

  As an aziridinyl group containing (meth) acrylate, although 2-aziridinyl ethyl (meth) acrylate etc. are mentioned, for example, this invention is not limited only to this illustration.

  Examples of nitrogen atom-containing (meth) acrylates include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, ethylene oxide addition (meth) acrylate of morpholine, and the like. It is not limited. These monomers may be used alone or in combination of two or more.

  Examples of diene structure-containing (meth) acrylic acid compounds include 1,5-diene structure-containing (meth) acrylic acid compounds containing hetero atoms, and 1,6-diene structure-containing (meth) acrylic acid compounds containing hetero atoms These monomers may be used alone or in combination. Examples of 1,6-diene structure-containing (meth) acrylic acid compounds containing a hetero atom include α-allyloxymethyl (meth) acrylic acid, methyl α-allyloxymethyl (meth) acrylate, α-allyloxymethyl Ethyl (meth) acrylate, n-propyl α-allyloxymethyl (meth) acrylate, isopropyl α-allyloxymethyl (meth) acrylate, n-butyl α-allyloxymethyl (meth) acrylate, α-allyl Oxymethyl (meth) acrylate tert-butyl, α-allyloxymethyl (meth) acrylate phenoxyethyl, α-allyloxymethyl (meth) acrylate cyclohexyl, α-allyloxymethyl (meth) acrylate dicyclopentadi Enyl, α-allyloxymethyl (meth) acrylate isobornyl, α-α Examples include allyloxymethyl (meth) acrylates such as adamantyl oxymethyl (meth) acrylate, benzyl α-allyloxymethyl (meth) acrylate and tetrafurfuryl α-allyloxymethyl (meth) acrylate. The present invention is not limited to such examples. These diene structure-containing (meth) acrylates may be used alone or in combination of two or more.

  The content of the (meth) acrylic monomer in the monomer component is an active energy ray-curable aqueous resin composition which forms a film excellent in dispersion stability, film-forming property and anti-curl property and excellent in scratch resistance and water resistance. From a viewpoint of obtaining a thing, Preferably it is 5-97 mass%, More preferably, it is 10-95 mass%, More preferably, it is 20-95 mass%.

  The monomer component may contain an appropriate amount of a monomer having an imide ring and a monomer other than a (meth) acrylic monomer within a range not to impair the object of the present invention.

  Examples of the other monomer include aromatic monomers other than (meth) acrylic monomers, carboxyl group-containing aliphatic monomers other than (meth) acrylate monomers, nitrogen atom containing fats other than (meth) acrylate monomers Group monomers, silane group-containing aliphatic monomers, carbonyl group-containing aliphatic monomers other than (meth) acrylate monomers, aziridinyl group-containing aliphatic monomers other than (meth) acrylate monomers, olefin monomers, etc. However, the present invention is not limited to such examples. These monomers may be used alone or in combination of two or more.

  Examples of aromatic monomers other than (meth) acrylic monomers include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p -Ethylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-ethoxystyrene, m-ethoxystyrene, p-ethoxystyrene, o-fluorostyrene, m-fluorostyrene, p-fluorostyrene, o -Chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, o-acetoxystyrene, m-acetoxystyrene, p-acetoxystyrene, o-tert-butoxystyrene , M-tert-Butoxystyrene And p-tert-butoxystyrene, o-tert-butylstyrene, m-tert-butylstyrene, p-tert-butylstyrene, vinyl toluene and the like, but the present invention is not limited to such examples. Absent. These monomers may be used alone or in combination of two or more.

  Examples of the carboxyl group-containing aliphatic monomer other than the (meth) acrylate monomer include, for example, itaconic acid and the like, but the present invention is not limited to only this example.

  Examples of nitrogen atom-containing aliphatic monomers other than (meth) acrylate monomers include (meth) acrylamide, N-monomethyl (meth) acrylamide, N-monoethyl (meth) acrylamide, and N, N-dimethyl (meth) acrylamide. N-n-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, methylenebis (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, dimethylaminoethyl (meth) acrylamide, Acrylamide compounds such as N, N-dimethylaminopropyl acrylamide, diacetone acrylamide, N-vinyl pyrrolidone, N-vinyl pyridine, N-vinyl imidazole, N-vinyl pyrrole, N-vinyl oxazolate N-vinylsuccinimide, N-vinylmethylcarbamate, N, N-methylvinylacetamide, (meth) acryloyloxyethyltrimethylammonium chloride, 2-isopropenyl-2-oxazoline, 2-vinyl-2-oxazoline, Although meta) acrylonitrile, maleimide etc. are mentioned, this invention is not limited only to this illustration. These monomers may be used alone or in combination of two or more.

  Examples of silane group-containing aliphatic monomers include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (methoxyethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxysilane, 2-styrylethyltrimethoxysilane, vinyl Although trichlorosilane, (gamma)-(meth) acryloyl oxypropyl hydroxysilane, (gamma)-(meth) acryloyl oxypropyl methyl hydroxysilane etc. are mentioned, this invention is not limited only to this illustration. These monomers may be used alone or in combination of two or more.

  Examples of carbonyl group-containing aliphatic monomers other than (meth) acrylate monomers include, for example, acrolein, boromystylol, vinyl ethyl ketone, (meth) acryloyloxyalkylpropenal, 2-hydroxypropyl (meth) acrylate acetyl acetate, Although butanediol-1,4-acrylate acetyl acetate etc. are mentioned, this invention is not limited only to this illustration. These monomers may be used alone or in combination of two or more.

  Examples of the aziridinyl group-containing aliphatic monomer other than the (meth) acrylate monomer include, for example, (meth) acryloyl aziridine, but the present invention is not limited to such examples.

  As an olefin type monomer, although ethylene, propylene, 4-methyl- 1-pentene etc. are mentioned, for example, the present invention is not limited only to this illustration. These monomers may be used alone or in combination of two or more.

  Further, in the present invention, from the viewpoint of imparting UV stability and UV absorbability to the film to be formed, an appropriate amount of UV-stable monomer, UV-absorbing monomer, etc. as long as the object of the present invention is not inhibited. You may make it contain in a component.

  Examples of UV-stable monomers include 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4 -(Meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloyl-1-methoxy-2,2,6,6-tetramethylpiperidine, 4-cyano-4- 4- (Meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino -2,2,6,6-Tetramethylpiperidine, 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4- No-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4-cyano -4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, etc. may be mentioned, but the present invention Is not limited to such an example. These monomers may be used alone or in combination of two or more.

  Examples of the ultraviolet absorbing monomer include benzotriazole ultraviolet absorbing monomers and benzophenone ultraviolet absorbing monomers, but the present invention is not limited to such examples. These monomers may be used alone or in combination of two or more.

  As a benzotriazole type ultraviolet-ray absorbing monomer, for example, 2- [2'-hydroxy-5 '-(meth) acryloyloxymethylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(meth) ) Acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-5 '-(meth) acryloyloxymethylphenyl] -5-tert-butyl-2H-benzotriazole, 2- [2'-hydroxy -5 '-(Meth) acryloylaminomethyl-5'-tert-octylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(meth) acryloyloxypropylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(meth) acryloyloxy Cylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-tert-butyl-5 '-(meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-3' -Tert-Butyl-5 '-(meth) acryloyloxyethylphenyl] -5-chloro-2H-benzotriazole, 2- [2'-hydroxy-5'-tert-butyl-3'-(meth) acryloyloxyethyl Phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5 '-(meth) acryloyloxyethylphenyl] -5-chloro-2H-benzotriazole, 2- [2'-hydroxy-5'-(meth) ) Acryloyloxyethylphenyl] -5-cyano-2H-benzotriazole, 2- [2′-amino] Roxy-5 '-(meth) acryloyloxyethylphenyl] -5-tert-butyl-2H-benzotriazole, 2- [2'-hydroxy-5'-(β- (meth) acryloyloxyethoxy) -3'- Although tert-butylphenyl] -4-tert-butyl-2H-benzotriazole and the like can be mentioned, the present invention is not limited to such examples. These monomers may be used alone or in combination of two or more.

  Examples of benzophenone-based UV-absorbing monomers include 2-hydroxy-4- (meth) acryloyloxybenzophenone, 2-hydroxy-4- [2-hydroxy-3- (meth) acryloyloxy] propoxybenzophenone, 2-hydroxy- 4- [2- (Meth) acryloyloxy] ethoxybenzophenone, 2-hydroxy-4- [3- (meth) acryloyloxy-2-hydroxypropoxy] benzophenone, 2-hydroxy-3-tert-butyl-4- [2 Although-(meth) acryloyloxy] butoxy benzophenone etc. are mentioned, this invention is not limited only to this illustration. These monomers may be used alone or in combination of two or more.

  Examples of the polymerization method of the monomer component include a polymerization method such as an emulsion polymerization method, but the present invention is not limited to such an example. When the emulsion polymerization method is adopted as a polymerization method of the monomer component, an emulsion containing the emulsion particles and the aqueous medium used in the emulsion polymerization of the monomer component can be obtained. The emulsion has the advantage of being environmentally friendly as it does not require volatile organic solvents (VOCs).

  Below, the embodiment in the case of preparing an emulsion particle by emulsion-polymerizing a monomer component is described in detail.

  An aqueous medium can be used when the monomer component is emulsion polymerized. The aqueous medium means water or a mixed solvent of water and a hydrophilic organic solvent having a water content of 50% by mass or more. Examples of hydrophilic organic solvents include monohydric alcohols such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol and allyl alcohol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, dipropylene glycol Aliphatic organic acid alkyl esters such as polyhydric alcohols such as acetone, methyl ethyl ketone and methyl propyl ketone, methyl formate, ethyl formate, methyl acetate and methyl acetoacetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, Diethylene glycol diethyl ether, ethylene glycol monomethyl ether, ethylene glycol mono Chirueteru, although such polyhydric alkyl ethers of alcohols, such as dipropylene glycol monomethyl ether, the present invention is not limited those exemplified only. These hydrophilic organic solvents may be used alone or in combination of two or more. Among the aqueous media, water is preferred.

  As a method of emulsion-polymerizing a monomer component, for example, a surfactant is dissolved in an aqueous medium containing water and a water-soluble organic solvent such as a lower alcohol such as methanol and water, and the monomer component is stirred under stirring. And a method of dropping a polymerization initiator, a method of dropping a monomer component which has been emulsified in advance using a surfactant and water into an aqueous medium such as water, and the like. It is not limited. The amount of the aqueous medium may be appropriately set in consideration of the amount of non-volatile components contained in the obtained emulsion. The aqueous medium may be pre-charged to the reaction vessel or may be used as a pre-emulsion. In addition, the aqueous medium may be used when emulsion polymerization is carried out by emulsion polymerization of the monomer component, if necessary.

  In the emulsion polymerization of the monomer component, the emulsion polymerization may be carried out after mixing the monomer component, the surfactant and the aqueous medium, and the monomer component, the surfactant and the aqueous medium are emulsified by stirring and pre-emulsion The emulsion polymerization may be carried out after preparing the emulsion, or may be carried out by mixing at least one of the monomer component, the surfactant and the aqueous medium with the remaining pre-emulsion. The monomer component, the surfactant and the aqueous medium may be added all at once, may be added in portions, or may be dropped continuously.

  As surfactant, anionic surfactant, nonionic surfactant, cationic surfactant, amphoteric surfactant, polymeric surfactant etc. are mentioned, for example. These surfactants may be used alone or in combination of two or more.

  As an anionic surfactant, for example, alkyl sulfate salts such as ammonium dodecyl sulfate, sodium dodecyl sulfate; alkyl sulfonate salts such as ammonium dodecyl sulfonate, sodium dodecyl sulfonate, sodium alkyl diphenyl ether disulfonate; ammonium dodecyl benzene sulfonate, sodium dodecyl naphthalene Alkyl aryl sulfonate salt such as sulfonate; polyoxyethylene alkyl phenyl ether sulfate ester salt; polyoxyethylene alkyl sulfonate salt; polyoxyethylene alkyl sulfate salt; polyoxyethylene alkyl aryl sulfate salt; dialkyl sulfosuccinate salt; aryl sulfonic acid-formalin Condensate; Ammonium Fatty acid salts such as laurate, sodium stearylate; bis (polyoxyethylene polycyclic phenyl ether) methacrylate sulfonate salt, propenyl-alkyl sulfosuccinic acid ester salt, (meth) acrylic acid polyoxyethylene sulfonate, poly (meth) acrylic acid polyoxy acid Sulfuric acid ester having allyl group such as ethylene phosphate salt, sulfonate salt of allyloxymethyl alkyl oxypolyoxyethylene, or a salt thereof; sulfuric acid ester salt of allyloxymethyl alkoxyethyl polyoxyethylene, polyoxyalkylene alkenyl ether ammonium salt and the like However, the present invention is not limited to such examples.

  Examples of nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, condensate of polyethylene glycol and polypropylene glycol, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid monoglyceride, ethylene oxide and the like Examples thereof include condensates with aliphatic amines, allyloxymethylalkoxyethylhydroxypolyoxyethylene, polyoxyalkylene alkenyl ether and the like, but the present invention is not limited to such examples.

  Examples of the cationic surfactant include alkyl ammonium salts such as dodecyl ammonium chloride and the like, but the present invention is not limited to such examples.

  Examples of amphoteric surfactants include betaine ester surfactants and the like, but the present invention is not limited to such examples.

  Examples of the polymer surfactant include poly (meth) acrylates such as sodium polyacrylate; polyvinyl alcohol; polyvinyl pyrrolidone; polyhydroxy alkyl (meth) acrylates such as polyhydroxyethyl acrylate; and these polymers Although the copolymer etc. which make 1 or more types of monomers a copolymerization component are mentioned, this invention is not limited only to this illustration.

  Among surfactants, surfactants having a polymerizable group, that is, so-called reactive surfactants are preferable from the viewpoint of improving the water resistance of the film, and non-nonylphenyl type surfactants from the viewpoint of environmental protection. Agents are preferred.

  As a reactive surfactant, for example, propenyl-alkyl sulfosuccinic acid ester salt, (meth) acrylic acid polyoxyethylene sulfonate salt, (meth) acrylic acid polyoxyethylene phosphonate salt, polyoxyethylene alkyl propenyl phenyl ether sulfonate Salts, sulfonate salts of allyloxymethylalkyloxypolyoxyethylene, sulfonate salts of allyloxymethylnonylphenoxyethylhydroxypolyoxyethylene, allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate, bis (polyoxyethylene polycyclic phenyl ether ) Methacrylated sulfonate salt, allyloxymethylalkoxyethylhydroxypolyoxyethylene, polyoxyethylene alkyl propenyl group Vinyl ether, although such allyloxymethyl nonyl phenoxyethyl hydroxy polyoxyethylene and the like, and the present invention is not limited those exemplified only.

  The amount of surfactant per 100 parts by mass of the monomer component is preferably 0.01 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 1 part by mass or more from the viewpoint of improving the polymerization stability. From the viewpoint of improving the water resistance of the film, it is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, and still more preferably 5 parts by mass or less.

  As the polymerization initiator, for example, azobisisobutyronitrile, 2,2-azobis (2-methylbutyronitrile), 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis ( Azo compounds such as 2-diaminopropane) hydrochloride, 4, 4-azobis (4-cyanovaleric acid), 2, 2-azobis (2-methylpropionamidine); persulfates such as potassium persulfate; hydrogen peroxide And peroxides such as benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, ammonium peroxide and the like, but the present invention is not limited to such examples. These polymerization initiators may be used alone or in combination of two or more.

  The amount of the polymerization initiator per 100 parts by mass of the monomer component is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass from the viewpoint of increasing the polymerization rate and reducing the residual amount of the unreacted monomer component. The amount is more preferably 0.1 parts by mass or more, and preferably 20 parts by mass or less, more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less from the viewpoint of improving the water resistance of the film.

  The addition method of the polymerization initiator is not particularly limited. As an addition method of the addition method of a polymerization initiator, for example, batch charging, division charging, continuous dropping, etc. may be mentioned. Further, from the viewpoint of advancing the termination time of the polymerization reaction, a part of the polymerization initiator may be added before or after the termination of the addition of the monomer component into the reaction system.

  In order to accelerate the decomposition of the polymerization initiator, for example, a reducing agent such as sodium bisulfite, a decomposition agent of a polymerization initiator such as a transition metal salt such as ferrous sulfate, etc. It is also good.

  Moreover, in order to adjust the weight average molecular weight of the (meth) acrylic-type polymer which comprises emulsion particle | grains, a chain transfer agent can be used. As a chain transfer agent, for example, 2-ethylhexyl thioglycolate, tert-dodecyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, mercaptoacetic acid, mercaptopropionic acid, 2-mercaptoethanol, α-methylstyrene, α-methyl Although a styrene dimer etc. are mentioned, this invention is not limited only to this illustration. These chain transfer agents may be used alone or in combination of two or more. The amount of the chain transfer agent per 100 parts by mass of the monomer component is preferably 0.01 to 10 parts by mass from the viewpoint of appropriately adjusting the weight average molecular weight of the emulsion particles.

  If necessary, additives such as a pH buffer, a chelating agent and a coalescent may be added to the reaction system. The amount of additive can not be determined indiscriminately because it varies depending on the type. Usually, the amount of the additive per 100 parts by mass of the monomer component is preferably about 0.01 to 5 parts by mass, more preferably about 0.1 to 3 parts by mass.

  The atmosphere at which the monomer component is polymerized is not particularly limited, but is preferably an inert gas such as nitrogen gas from the viewpoint of enhancing the efficiency of the polymerization reaction.

  The polymerization temperature at the time of polymerizing the monomer component is not particularly limited, but is usually preferably 0 to 100 ° C, more preferably 40 to 95 ° C. The polymerization temperature may be constant or may be changed during the polymerization reaction.

  The polymerization time for polymerizing the monomer component is not particularly limited and may be appropriately set depending on the progress of the polymerization reaction, but is usually about 2 to 8 hours.

  When the monomer component is emulsion-polymerized, a part or all of the acidic groups of the (meth) acrylic polymer to be obtained may be neutralized by the neutralizing agent. The neutralizing agent may be used after adding the monomer component in the final stage, for example, it may be used between the first stage polymerization reaction and the second stage polymerization reaction, and the initial emulsion polymerization reaction May be used at the end of the

  As the neutralizing agent, for example, hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide; carbonates of alkali metals such as calcium carbonate or alkaline earth metals; organic amines such as ammonia, monomethylamine etc. Although an alkaline substance is mentioned, this invention is not limited only to this illustration. Among these neutralizing agents, from the viewpoint of improving the water resistance of the film, an alkaline substance having volatility such as ammonia is preferable.

The glass transition temperature of the (meth) acrylic polymer constituting the emulsion particles is the glass transition temperature (Tg) of the homopolymer comprising the monomer contained in the monomer component used as the raw material of the (meth) acrylic polymer From the temperature: K) and the mass fraction of the monomer, the formula:
1 / Tg = W ₁ / Tg ₁ + W ₂ / Tg ₂ + W ₃ / Tg ₃ +... + W _n / Tg _n
[Wherein, Tg is the glass transition temperature (K) of the polymer to be determined, W ₁ , W ₂ , W ₃ ... W _n is the mass fraction of each monomer, Tg ₁ , Tg ₂ , Tg ₃ ... Tg _n represents the glass transition temperature (K) of a homopolymer comprising a monomer corresponding to the mass fraction of each monomer.
It can be determined based on the expression of Fox. The glass transition temperature of the polymer can also be measured by DSC (differential scanning calorimetry device), DTA (differential thermal analysis device), TMA (thermomechanical measurement device) or the like.

  In the present invention, the glass transition temperature of the (meth) acrylic polymer means the glass transition temperature determined based on the equation of Fox.

  In addition, about the monomer whose glass transition temperature is unknown, such as a special monomer and a polyfunctional monomer, the glass transition temperature of a (meth) acrylic-type polymer is calculated | required using only the monomer in which the glass transition temperature is known.

  In view of the glass transition temperature of the (meth) acrylic polymer constituting the emulsion particle, the composition of the monomer component used as a raw material of the (meth) acrylic polymer constituting the emulsion particle can be determined .

  The glass transition temperatures of homopolymers are, for example, 105 ° C. for homopolymers of methyl methacrylate, 83 ° C. for homopolymers of cyclohexyl methacrylate, 100 ° C. for homopolymers of styrene, 84 ° C. for homopolymers of methyl α-allyloxymethyl acrylate. The homopolymer of 2- (2-vinyloxyethoxy) ethyl acrylate (VEEA) is -40 ° C, the homopolymer of acrylic acid is 95 ° C, and the homopolymer of 2-hydroxyethyl methacrylate is 55 ° C.

  The glass transition temperature of the (meth) acrylic polymer constituting the emulsion particles improves the dispersion stability of the active energy ray-curable aqueous resin composition, and forms a film excellent in anti-curling property, scratch resistance and water resistance. From the viewpoint of adhesion, preferably 30.degree. C. or higher, more preferably 40.degree. C. or higher, still more preferably 50.degree. C. or higher to improve the dispersion stability of the active energy ray-curable aqueous resin composition, to prevent curling and scratch resistance. And from the viewpoint of forming a film excellent in water resistance, preferably 120 ° C. or less.

  The (meth) acrylic polymer constituting the emulsion particles may have a crosslinked structure from the viewpoint of improving water resistance and storage stability. Examples of a method for providing a cross-linked structure to a (meth) acrylic polymer include a method in which a silane coupling agent and a polyfunctional monomer are contained in a monomer component, but the present invention is limited to only such an example. It is not a thing. Examples of the silane coupling agent include, for example, silane coupling agents having a polymerizable unsaturated bond such as (meth) acryloyl group, vinyl group, allyl group, propenyl group and the like, but the present invention is not limited thereto. It is not limited.

  The average particle diameter of the emulsion particles is preferably 50 nm or more, more preferably 60 nm or more, still more preferably 70 nm or more from the viewpoint of improving the dispersion stability of the emulsion particles, and from the viewpoint of improving the surface smoothness of the film. Preferably it is 450 nm or less, More preferably, it is 400 nm or less, More preferably, it is 350 nm or less.

  The average particle size of the emulsion particles is as follows: Dilute the emulsion with distilled water, collect about 10 mL of the obtained diluted solution in a glass cell, and use this as a particle size distribution measuring device by dynamic light scattering method (Particle Sizing Systems (Particle Sizing Systems (Trade name: NICOM P Model 380) means volume average particle diameter measured using Windows based software [Windows (registered trademark) Based Software].

  The (meth) acrylic polymer constituting the emulsion particles preferably has a reactive functional group from the viewpoint of improving the scratch resistance of the formed film. Examples of reactive functional groups include, for example, hydroxyl group, carboxyl group, glycidyl group, vinyl group, vinyl ether group, allyl ether group, amino group, benzophenyl group, maleimide group, oxazoline group, etc. It is not limited to only this example. These reactive functional groups may be used alone or in combination. As a method of introducing a reactive functional group into a (meth) acrylic polymer, for example, an acrylic monomer having a desired reactive functional group, other (meth) acrylic monomers constituting emulsion particles, and acrylic resins other than acrylic monomers A method for introducing a desired reactive functional group into a (meth) acrylic polymer by polymerizing with a monomer of (1), after preparing a (meth) acrylic polymer having an appropriate functional group in advance, the (meth) acrylic polymer There is a method of introducing a desired reactive functional group into a (meth) acrylic polymer by reacting an acrylic monomer having a desired reactive functional group with a functional group of It is not limited to When using a (meth) acrylic polymer having a reactive functional group, a curable monomer and / or a curable oligomer having a functional group capable of reacting with the reactive functional group of the (meth) acrylic polymer, The abrasion resistance of the formed film can be improved by using a crosslinking agent having a functional group capable of reacting with the reactive functional group possessed by the acrylic polymer.

  The number of functional groups possessed by one (meth) acrylic polymer is preferably one or more, and more preferably two or more from the viewpoint of improving the scratch resistance of the film to be formed.

  When emulsion particles are prepared by emulsion polymerization of monomer components using an aqueous medium, an aqueous medium in which the emulsion particles are dispersed can be obtained.

  The content of the emulsion particles in the aqueous medium in which the emulsion particles are dispersed is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more from the viewpoint of improving the productivity. From the viewpoint, it is preferably 65% by mass or less, more preferably 60% by mass or less.

  The emulsion particles contain a water insoluble curable monomer. In the present invention, the non-water-soluble curable monomer is a concept including the non-water-soluble curable oligomer for convenience. Also, a monomer means a compound having a molecular weight of less than 1000, and an oligomer means a compound having a molecular weight of 1000 or more.

  In the present invention, since the water-insoluble curable monomer is contained in the emulsion particles, the active energy ray-curable aqueous resin composition of the present invention is excellent in the dispersion stability, the film forming property and the anti-curl property, It exhibits an excellent effect of forming a film excellent in scratch resistance and water resistance.

  The water-insoluble curable monomer is a compound having a group having an unsaturated double bond such as a (meth) acryloyl group, a vinyl group or a vinyl ether group, or a curable group having a cyclic ether group or a maleimide group. These curable groups may be used alone or in combination.

  Since the water-insoluble curable monomer has a curable group, it can form a film having excellent scratch resistance. The number of curable groups possessed by the water-insoluble curable monomer improves the dispersion stability of the active energy ray-curable aqueous resin composition, and forms a film excellent in anti-curling property, scratch resistance and water resistance. Preferably, it is 2 or more, More preferably, it is 3 or more.

  Further, the molecular weight / functional group number of the water-insoluble curable monomer is preferably 80 or more, more preferably 85 or more from the viewpoint of forming a film excellent in scratch resistance, and forms a film excellent in adhesion. From the viewpoint, it is preferably 160 or less, more preferably 150 or less, and still more preferably 140 or less. When two or more types of water-insoluble curable monomers are used in combination, the molecular weight / functional group number of the water-insoluble curable monomer is calculated by adding the product of the mass fraction of each water-insoluble curable monomer and the functional group number. Value.

  As the water-insoluble curable monomer, for example, pentaerythritol triacrylate (molecular weight: 298) [for example, Shin-Nakamura Chemical Co., Ltd. product, product number: A-TMM-3LM-N, etc.], pentaerythritol trimethacrylate, tri Methylolpropane triacrylate (molecular weight: 296) [for example, product made by Sartmar, product number: SR 351], trimethylolpropane trimethacrylate (molecular weight: 338) [for example, product made by Sartomer, product number: SR 350, etc.], tetraethylene glycol diacrylate Tetraethylene glycol dimethacrylate (molecular weight: 330) (eg, manufactured by Sartmar, product number: SR209 etc.), dipentaerythritol hexaacrylate (molecular weight: 578) [eg, manufactured by Sartomer, product number: DPHA, etc. ], Dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate (molecular weight: 525) (for example, Sartomer Co., product number: SR399 etc.), dipentaerythritol pentamethacrylate, ethoxylated (the number of ethoxy groups is shown below. The same]) pentaerythritol tetraacrylate (molecular weight: 528) [eg, Sartmar, product number: SR494, etc.], ethoxylated (4) pentaerythritol tetramethacrylate, xylylene bis oxetane, 3-ethyl-3-{[(3 -Ethyloxetan-3-yl) methoxy] methyl} oxetane, divinylbenzene, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, diethylene glycol monovinyl ether, N, N'-methylenebisamine Rylamide, 1,4-butanediol divinyl ether, cyclohexane dimethanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, molecular weight 290 to 2000, molecular weight / functional group number 80 to 160, (meth) acryloylyl Although urethane (meth) acrylate having two or more groups, a hyperbranched oligomer having a molecular weight of less than 10000, and the like can be mentioned, the present invention is not limited to such examples. These water-insoluble curable monomers may be used alone or in combination of two or more.

  Among the water-insoluble curable monomers, pentaerythritol tri (meth) acrylate and trimethylolpropane tri (meth) acrylate from the viewpoint of forming a film excellent in anti-curling property, dispersion stability, abrasion resistance and water resistance. Tetraethylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethoxylated (4) pentaerythritol tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate are preferred, and pentaerythritol tri (meth) acrylate , Trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethoxylated (4) pentaerythritol tetra (meth) acrylate and dipentaerythritol Penta (meth) acrylate are more preferred. These water-insoluble curable monomers may be used alone or in combination of two or more.

  A water-insoluble curable monomer is contained from the viewpoint of obtaining an active energy ray-curable aqueous resin composition which forms a film excellent in dispersion stability, film-forming property and anti-curl property and excellent in scratch resistance and water resistance. The lower limit of the content of the water-insoluble curable monomer in the emulsion particles is preferably 3% by mass or more, more preferably 5% by mass or more, and the upper limit thereof is preferably 90% by mass or less, more preferably It is 85 mass% or less.

In the present invention, the content of the water-insoluble curable monomer in the emulsion particles is determined by measuring the particle diameter of the emulsion particles before and after the water-insoluble curable monomer is contained in the following examples, and examining the particle size distribution. As a result, the peak based on the emulsion particle before incorporating the water-insoluble curable monomer and the peak based on the water-insoluble curable monomer disappear, and only the peak based on the emulsion particle containing the water-insoluble curable monomer Was detected as a single peak, so it was confirmed that the total amount of the water-insoluble curable monomer added to the emulsion particles was included, and the formula:
[Content (% by mass) of water-insoluble curable monomer in emulsion particles]
= [Addition amount of water-insoluble curable monomer (parts by mass)]
{{Addition amount of water-insoluble curable monomer (parts by mass) + [addition amount of emulsion particles (parts by mass)}
× 100
Is a value determined based on

  The non-volatile content in the active energy ray-curable aqueous resin composition of the present invention is preferably 10% by mass or more, more preferably 20% by mass or more from the viewpoint of improving the productivity, and from the viewpoint of improving the handleability. Preferably it is 65 mass% or less, More preferably, it is 60 mass% or less.

The content of non-volatile components in the active energy ray-curable aqueous resin composition was determined by weighing 1 g of the active energy ray-curable aqueous resin composition and drying it with a hot air dryer at 110 ° C. for 1 hour. Nonvolatile content, formula:
[Non-volatile content (% by mass) in active energy ray-curable aqueous resin composition]
= ([Mass of residue] ÷ [active energy ray-curable aqueous resin composition 1 g]) x 100
It means the value determined based on.

  The active energy ray-curable aqueous resin composition of the present invention may contain a suitable amount of a crosslinking agent from the viewpoint of improving the scratch resistance. When the active energy ray-curable aqueous resin composition of the present invention contains a crosslinking agent, the active energy ray-curable aqueous resin composition of the present invention for a resin film not only at room temperature but also at high temperatures. It is possible to improve the scratch resistance of a film formed of an object.

  As a crosslinking agent, for example, melamine type crosslinking agent, oxazoline type crosslinking agent, acrylamide type crosslinking agent, polyamide type crosslinking agent, epoxy type crosslinking agent, isocyanate type crosslinking agent, aziridine type crosslinking agent, titanate type crosslinking agent, urea type crosslinking agent Although an agent, an alkyl alcohol-ized urea type crosslinking agent, etc. are mentioned, this invention is not limited only to this illustration. These crosslinking agents may be used alone or in combination.

  Among the crosslinking agents, oxazoline-based crosslinking agents and melamine-based crosslinking agents are preferable from the viewpoint of improving the adhesion of the film formed of the active energy ray-curable aqueous resin composition of the present invention to the resin film.

  As an oxazoline type crosslinking agent, for example, 2,2′-bis (2-oxazoline), 1,2-bis (2-oxazolin-2-yl) ethane, 1,4-bis (2-oxazolin-2-yl) ) Butane, 1,8-bis (2-oxazolin-2-yl) butane, 1,4-bis (2-oxazolin-2-yl) cyclohexane, 1,2-bis (2-oxazolin-2-yl) benzene 1,3-bis (2-oxazoline-2-yl) benzene, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2 -Isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline and the like can be mentioned, but the present invention It is not limited only to hunt illustration. Each of these oxazoline crosslinking agents may be used alone or in combination.

  Examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxymethylmelamine, hexapentyloxymethylmelamine and the like, but the present invention is limited to only such examples. It is not a thing. These melamine crosslinking agents may be used alone or in combination.

  From the viewpoint of improving the reaction rate, the active energy ray-curable aqueous resin composition of the present invention may optionally contain a polymerization initiator in an appropriate amount.

  As a polymerization initiator, although a photoinitiator, a thermal polymerization initiator, etc. are mentioned, for example, this invention is not limited only to this illustration. These polymerization initiators may be used alone or in combination. Some of the photopolymerization initiators act as a thermal polymerization initiator, and some of the thermal polymerization initiators act as a photopolymerization initiator, so those having both properties are irradiated with light or heated. Thus, the active energy ray curable aqueous resin composition can be cured. Among the polymerization initiators, a photopolymerization initiator is preferable because it does not give a heat history to a formed coating film, a substrate to which an active energy ray-curable aqueous resin composition is applied, and the like.

  As a photopolymerization initiator, for example, benzophenone, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, oxyphenyl-acetic acid 2- [ 2-Oxo-2-phenylacetoxyethoxy] -ethyl ester, oxyphenylacetic acid 2- [2-hydroxyethoxy] -ethyl ester, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl-diphenyl-phos Fin oxide, bis (2,4,6-trimethyl benzoyl) -phenyl phosphine oxide, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) 2-hydroxy-2 -Methylpropan-1-one, 2-methyl- -[4- (Methylthio) phenyl] 2-morpholinopropan-1-one, 2-morpholinopropan-1-one, iodonium, sulfonium salt, diazonium salt, (4-methylphenyl [4- (2-methylpropyl) phenyl ]-Hexafluorophosphate, diethyl thioxanthone, isopropyl thioxanthone and the like, but the present invention is not limited to such examples. These photopolymerization initiators may be used alone or in combination of two or more.

  As a thermal polymerization initiator, for example, 2,2'-azobis- (2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4'-) Oil-soluble initiators such as dimethylvaleronitrile), benzoyl peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, tert-butylperoxy-2-ethylhexanoate, Persulfates such as potassium persulfate, ammonium persulfate, sodium persulfate; water-soluble peroxides such as hydrogen peroxide; water-soluble azo compounds such as 2,2'-azobis (2-amidinopropane) dihydrochloride; Although mentioned, the present invention is not limited to only this illustration. These thermal polymerization initiators may be used alone or in combination of two or more.

  The polymerization initiator may be added, for example, directly to the active energy ray-curable aqueous resin composition, or may be mixed with an emulsion containing emulsion particles.

  The amount of the polymerization initiator per 100 parts by mass of the water-insoluble curable monomer is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, from the viewpoint of promoting the curing of the water-insoluble curable monomer. The amount is preferably 2 parts by mass or more, and preferably 20 parts by mass or less, more preferably 10 parts by mass or less from the viewpoint of preventing coloring of the cured product and improving weather resistance.

  The active energy ray-curable aqueous resin composition of the present invention can be prepared by incorporating a water-insoluble curable monomer in emulsion particles.

  As a method of incorporating the water-insoluble curable monomer into the emulsion particle, for example, a method of incorporating the water-insoluble curable monomer into the emulsion particle by mixing the emulsion containing the emulsion particle and the water-insoluble curable monomer Etc.

  As a specific method of incorporating the water-insoluble curable monomer into the emulsion particles, for example, Journal of Dispersion Science & Technology, Volume 5, page 231 (1984) Method in which the water-insoluble curable monomer is contained in the emulsion particle by mixing the emulsion particle and the water-insoluble curable monomer on the basis of the method described in 1.), Macromolecular Chemistry (Makromolecule Chemistry), In the method of incorporating water-insoluble curable monomers into emulsion particles by the two-step swelling method described in Volume 180, p. 737 (1979), molecular diffusion method, dynamic swelling method, diffusion swelling method, etc. Ri, a water-insoluble curing monomers but like method of containing the emulsion particles, the present invention is not limited only to those exemplified.

  As a method of incorporating a suitable non-water-soluble curable monomer into emulsion particles, the non-water-soluble curable monomer is emulsified by mixing an aqueous dispersion of the non-water-soluble curable monomer with an emulsion containing emulsion particles. The method of making it contained in particle | grains etc. are mentioned. As a method of mixing an aqueous dispersion of a water-insoluble curable monomer with an emulsion containing emulsion particles, for example, a batch addition method of continuous addition of an emulsion containing emulsion particles in an aqueous dispersion of a water-insoluble curable monomer, Although the additive method, the intermittent addition method, the combination of these methods, etc. are mentioned, this invention is not limited only to this illustration.

  When the water-insoluble curable monomer is contained in the emulsion particles, the non-water-soluble curable monomer is dispersed in water beforehand with a dispersing agent such as an emulsifier, and the obtained aqueous dispersion is, for example, 0 in particle diameter with a homogenizer or the like. It is preferable to finely disperse the dispersion so as to be about 0.1 to 1 μm and add the obtained fine dispersion of the water-insoluble curable monomer to the emulsion. When preparing the fine dispersion liquid of the water-insoluble curable monomer, for example, a high-pressure homogenizer, an ultrasonic homogenizer, etc. can be used as a homogenizer.

  In addition, in order to efficiently contain the water-insoluble curable monomer in the emulsion particles, an absorption accelerator can be used. The absorption accelerator may be previously contained in the emulsion, or may be used in combination with the water-insoluble curable monomer. The amount of the absorption promoter per 100 parts by mass of the nonvolatile matter of the emulsion particles is preferably 100 parts by mass or less, more preferably 50 parts by mass or less. The absorption promoter is not particularly limited as long as it exhibits an absorption promoting effect. Examples of the absorption promoter include general organic solvents such as toluene and ethyl acetate, and film-forming assistants such as 2,2,2-trimethyl-1,3-pentanediol monoisobutyrate. When a compound having volatility is used as the absorption accelerator, after preparation of the active energy ray-curable aqueous resin composition, the compound having volatility is easily removed by a degassing step or the like, if necessary. be able to.

  The active energy ray-curable aqueous resin composition of the present invention obtained as described above contains emulsion particles and an aqueous medium, and the emulsion particles contain a water-insoluble curable monomer, If necessary, for example, various additives and the like may be contained within the scope of not inhibiting the object of the present invention.

  The active energy ray-curable aqueous resin composition of the present invention is excellent in dispersion stability, film-forming property and anti-curl property, and forms a film excellent in scratch resistance and water resistance. It can be suitably used as a raw material for printing inks, adhesives, resist agents, molding materials and the like.

  When the active energy ray-curable aqueous resin composition of the present invention is cured, the active energy ray-curable aqueous resin composition can be irradiated with active energy rays.

  Examples of the active energy ray include vacuum ultraviolet rays, ultraviolet rays, visible rays, heat rays (near infrared rays, infrared rays, far infrared rays and the like), microwaves, electron rays, β rays, γ rays and the like. It is not limited to only this example. Among these active energy rays, for example, ultraviolet rays and heat rays are preferable because they are widely used in the curing step and the heat drying step, and a control method has been established and the burden on equipment is small.

  Next, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Example 1
1040 parts (by mass, hereinafter the same) of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser. In addition, 290 parts of deionized water was added to the dropping funnel, and an anionic surfactant as an emulsifier (polyoxyethylene alkyl phenyl ether sulfate ester salt, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon (registered trademark) HS-10). Of 120 parts of a 25% aqueous solution of methyl methacrylate, 680 parts of methyl methacrylate, 100 parts of cyclohexyl methacrylate, 200 parts of a maleimido acrylate wherein R ³ is ethylene and R ⁶ is a hydrogen atom in formula (IIa) An emulsion was prepared, of which 85 parts, 6% by weight of the total of all monomer components, was added into the flask. Thereafter, the temperature was raised to 80 ° C. with stirring while gently bubbling nitrogen gas into the flask, and 43 parts of a 3.5% aqueous ammonium persulfate solution was added into the flask to start a polymerization reaction. After completion of the polymerization reaction, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium bisulfite solution were dropped uniformly into the flask over 240 minutes.

  After completion of the dropwise addition, the temperature in the flask was maintained at 80 ° C. for 60 minutes, 25% ammonia water was added to the flask, and the pH was adjusted to 9 to complete the polymerization reaction. By cooling the obtained reaction liquid to room temperature, a polymer dispersion liquid containing emulsion particles and having a non-volatile content of 40% was obtained. When the glass transition temperature of the resin which comprises the emulsion particle | grains contained in the obtained polymer dispersion liquid was calculated | required, the said glass transition temperature was 88 degreeC.

  Next, pentaerythritol triacrylate [Shin-Nakamura Chemical Co., Ltd. product number: A-TMM-3LM-N] as a curable monomer with respect to 1000 parts of non-volatile components contained in the polymer dispersion liquid obtained above. A mixed solution of 300 parts of a photopolymerization initiator [2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by BASF, trade name: Lucirin TPO] 30 parts as an ultrasonic homogenizer [Nippon Seiki Seisakusho Co., Ltd. No .: US-600S], the solution dispersed therein is shaken at 23 ° C. for 24 hours, and pentaerythritol triacrylate is contained in the emulsion particles to obtain an active energy ray-curable aqueous resin composition I got

  The active energy ray-curable aqueous resin composition obtained above is diluted with distilled water, and about 10 mL of the obtained diluted solution is collected in a glass cell, and this is used as a particle size distribution measuring apparatus by particle dynamic scattering [particle sizing The particle size distribution was examined using Windows Co., Ltd. software (Windows (registered trademark) Based Software) using a system (Particle Sizing Systems, product name: NICOM P Model 380), and it contained pentaerythritol triacrylate. The peak based on the emulsion particle before the reaction and the peak based on the pentaerythritol triacrylate disappear, and only the peak based on the emulsion particle containing the pentaerythritol triacrylate is detected in a single peak. From what has been, it was confirmed that contains pentaerythritol triacrylate emulsion particles. In addition, the content of pentaerythritol triacrylate in the emulsion particles was 23% by mass.

  Next, as physical properties of the active energy ray-curable aqueous resin composition obtained above, dispersion stability, film-forming property, anti-curling property, scratch resistance and water resistance were examined based on the following methods. The results are shown in Table 1.

1. Dispersion stability The active energy ray-curable aqueous resin composition was allowed to stand at room temperature (about 25 ° C.), and the change with time of the appearance was visually observed and evaluated based on the following evaluation criteria.

〔Evaluation criteria〕
Even after 20 weeks, no precipitate was formed in the active energy ray-curable aqueous resin composition and no change in the appearance was observed.
15: At 2 weeks, no change in appearance such as occurrence of sediment is observed, but by 3 weeks, sediment is observed.
Although no change in appearance such as the occurrence of sediment is observed after 10: 1 week, the sediment is observed by 2 weeks.
5: After 3 days, no change in appearance such as generation of sediment is observed, but sediment is observed until 1 week has passed.
0: The occurrence of sediment is observed after 3 days.

2. Film forming property The thickness of the coating film after drying is 10 μm on a transparent transparent glass plate (length: 150 mm, width: 70 mm, thickness: 1.5 mm) having a smooth surface with an active energy ray-curable aqueous resin composition Thus, the coated film was coated with a bar coater, and the formed film was visually observed and observed with a 50 × loupe, and evaluated based on the following evaluation criteria.

〔Evaluation criteria〕
20: No turbidity or cracks are observed in the film even when the film is observed visually and with a loupe 50 times.
15: No change was observed in the film when observed visually, but several cracks were observed in the film when the film was observed with a loupe 50 times.
10: When the film was visually observed, no change was observed in the film, but when the film was observed with a loupe 50 times, many cracks were observed in the film.
5: When the film is visually observed, turbidity and numerous cracks are observed in the film.
0: When the film is visually observed, turbidity is observed in the film and no film is formed.

3. Anti-curl property Polyethylene terephthalate (hereinafter referred to as PET) film (made by Toyobo Co., Ltd., trade name: Cosmo Shine (registered trademark) A4300, thickness: 100 μm) so that the film thickness after drying becomes 10 μm Active energy After forming a film by applying a line-curable aqueous resin composition with a bar coater and removing an aqueous medium contained in the active energy ray-curable aqueous resin composition, the integrated quantity of ultraviolet light is 500 mJ / cm. By irradiating so as to be ² , a cured film was formed.

  The laminate of the cured film and the PET film obtained above is cut into a size of 50 mm long and 50 mm wide, and the obtained test piece is allowed to stand on a horizontal table having a smooth flat surface, and then the surface of the horizontal table The four points from the test piece to the four corners were measured, the average value was determined from those values, and the anti-curl property was evaluated based on the following evaluation criteria.

〔Evaluation criteria〕
20: Average value is 0 mm or more and less than 15 mm 15: Average value is 15 mm or more and less than 20 mm 10: Average value is 25 mm or more and less than 30 mm 5: Average value is 30 mm or more and less than 35 mm 0: Coating film is not formed or average value is 35 mm or more Or it can not measure the height due to curling.

4. Scratch resistance A laminate of the cured film and the PET film obtained in the above "3. anti-curl property" was used. The test piece was produced by cutting the said laminated body to a suitable magnitude | size. A specimen with a load of 150 g / cm ² applied to steel wool [Nippon Steel Wool Co., Ltd., count: # 0000] with a dyeing fastness tester [Suga Test Instruments Co., Ltd., product number: FR-II] The coated surface was rubbed back and forth 20 times, and the number of flaws generated on the coated surface of the test piece was counted and evaluated based on the following evaluation criteria.

〔Evaluation criteria〕
20: No scratch 15: Number of scratches is 1 to 5 10: Number of scratches is 6 to 10 5: Number of scratches is 11 to 15 0: Number of scratches is 16 or more

5. Water resistant Activated by PET film (Toyobo Co., Ltd., trade name: Cosmoshine (registered trademark) A4300, thickness: 100 μm) so that the thickness of the film after drying with a bar coater (No. 11) becomes 10 μm After forming a film by applying the energy ray-curable aqueous resin composition and removing the aqueous medium contained in the active energy ray-curable aqueous resin composition, the integrated quantity of ultraviolet light is 500 mJ / cm ² . The cured film was formed by irradiation so that it might become.

A sample is prepared by cutting the laminate obtained above into a size of 50 mm long and 50 mm wide, the sample is immersed in deionized water at 25 ° C., and after one week, the PET film is taken out of the water, Measure the mass of the sample, the formula:
[Water absorption rate (mass%)]
= {[Mass of sample after immersion-mass of sample before immersion]
[Weight of sample before immersion]} × 100
The water absorption rate was determined based on the above, and the water resistance was evaluated based on the following evaluation criteria.

〔Evaluation criteria〕
20: Water absorption rate is less than 0.5% by mass 15: Water absorption rate is 0.5% by mass or more and less than 1% by mass 10: Water absorption rate is 1% by mass or more and less than 3% by mass 5: Water absorption rate is 3% by mass or more and 5% Less than% 0: no coating film is formed, or the water absorption rate is 5% by mass or more

6. Comprehensive Evaluation A comprehensive evaluation was performed by summing up the scores of the respective physical properties. The highest score in the comprehensive evaluation is 100 points, and the lowest score is 0 points.

Example 2
An active energy ray-curable aqueous resin composition in the same manner as in Example 1 except that the amount of pentaerythritol triacrylate is changed to 600 parts and the amount of photopolymerization initiator is changed to 60 parts in Example 1. Was prepared. The glass transition temperature of the resin constituting the emulsion particles contained in the polymer dispersion obtained when preparing the active energy ray-curable aqueous resin composition was determined to be 88 ° C. Met.

  The particle size distribution of the active energy ray-curable aqueous resin composition obtained above was examined in the same manner as in Example 1. As a result, the peak based on emulsion particles before containing pentaerythritol triacrylate and that based on pentaerythritol triacrylate Since the peak disappeared and only the peak based on the emulsion particle containing pentaerythritol triacrylate was detected in a single peak, it was confirmed that the emulsion particle contains pentaerythritol triacrylate. In addition, the content of pentaerythritol triacrylate in the emulsion particles was 38% by mass.

  Next, the physical properties of the active energy ray-curable aqueous resin composition obtained above were examined in the same manner as in Example 1. The results are shown in Table 1.

Example 3
An active energy ray-curable aqueous resin composition in the same manner as in Example 1 except that the amount of pentaerythritol triacrylate was changed to 1000 parts and the amount of photopolymerization initiator was changed to 100 parts in Example 1. Was prepared. The glass transition temperature of the resin constituting the emulsion particles contained in the polymer dispersion obtained when preparing the active energy ray-curable aqueous resin composition was determined to be 88 ° C. Met.

  The particle size distribution of the active energy ray-curable aqueous resin composition obtained above was examined in the same manner as in Example 1. As a result, the peak based on emulsion particles before containing pentaerythritol triacrylate and that based on pentaerythritol triacrylate Since the peak disappeared and only the peak based on the emulsion particle containing pentaerythritol triacrylate was detected in a single peak, it was confirmed that the emulsion particle contains pentaerythritol triacrylate. In addition, the content of pentaerythritol triacrylate in the emulsion particles was 50% by mass.

  Next, the physical properties of the active energy ray-curable aqueous resin composition obtained above were examined in the same manner as in Example 1. The results are shown in Table 1.

Example 4
An active energy ray-curable aqueous resin composition in the same manner as in Example 1 except that the amount of pentaerythritol triacrylate is changed to 3000 parts and the amount of photopolymerization initiator is changed to 300 parts in Example 1. Was prepared. The glass transition temperature of the resin constituting the emulsion particles contained in the polymer dispersion obtained when preparing the active energy ray-curable aqueous resin composition was determined to be 88 ° C. Met.

  The particle size distribution of the active energy ray-curable aqueous resin composition obtained above was examined in the same manner as in Example 1. As a result, the peak based on emulsion particles before containing pentaerythritol triacrylate and that based on pentaerythritol triacrylate Since the peak disappeared and only the peak based on the emulsion particle containing pentaerythritol triacrylate was detected in a single peak, it was confirmed that the emulsion particle contains pentaerythritol triacrylate. In addition, the content of pentaerythritol triacrylate in the emulsion particles was 75% by mass.

  Next, the physical properties of the active energy ray-curable aqueous resin composition obtained above were examined in the same manner as in Example 1. The results are shown in Table 1.

Example 5
1040 parts of deionized water were charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser. In addition, 290 parts of deionized water was added to the dropping funnel, and an anionic surfactant as an emulsifier (polyoxyethylene alkyl phenyl ether sulfate ester salt, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon (registered trademark) HS-10). Of a 25% aqueous solution, 410 parts of methyl methacrylate, 100 parts of cyclohexyl methacrylate, 270 parts of butyl acrylate, 200 parts of a maleimide acrylate in which R ³ is ethylene and R ⁶ is a hydrogen atom in formula (IIa) and 20 parts of acrylic acid A dripping pre-emulsion was prepared, and 85 parts corresponding to 6% by mass of the total of all the monomer components was added to the flask. Thereafter, the temperature was raised to 80 ° C. with stirring while gently bubbling nitrogen gas into the flask, and 43 parts of a 3.5% aqueous ammonium persulfate solution was added into the flask to start a polymerization reaction. After completion of the polymerization reaction, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium bisulfite solution were dropped uniformly into the flask over 240 minutes.

  After completion of the dropwise addition, the temperature in the flask was maintained at 80 ° C. for 60 minutes, 25% ammonia water was added to the flask, and the pH was adjusted to 9 to complete the polymerization reaction. By cooling the obtained reaction liquid to room temperature, a polymer dispersion liquid containing emulsion particles and having a non-volatile content of 40% was obtained. When the glass transition temperature of resin which comprises the emulsion particle | grains contained in the obtained polymer dispersion liquid was calculated | required, the said glass transition temperature was 30 degreeC.

  Next, pentaerythritol triacrylate [Shin-Nakamura Chemical Co., Ltd. product number: A-TMM-3LM-N] as a curable monomer with respect to 1000 parts of non-volatile components contained in the polymer dispersion liquid obtained above. A mixed solution of 100 parts and 10 parts of a photopolymerization initiator [2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by BASF, trade name: Lucirin TPO], as an ultrasonic homogenizer [Nippon Seiki Co., Ltd.] No .: US-600S], the solution dispersed therein is shaken at 23 ° C. for 24 hours, and pentaerythritol triacrylate is contained in the emulsion particles to obtain an active energy ray-curable aqueous resin composition I got

  The particle size distribution of the active energy ray-curable aqueous resin composition obtained above was examined in the same manner as in Example 1. As a result, the peak based on emulsion particles before containing pentaerythritol triacrylate and that based on pentaerythritol triacrylate Since the peak disappeared and only the peak based on the emulsion particle containing pentaerythritol triacrylate was detected in a single peak, it was confirmed that the emulsion particle contains pentaerythritol triacrylate. In addition, the content of pentaerythritol triacrylate in the emulsion particles was 9% by mass.

  Next, the physical properties of the active energy ray-curable aqueous resin composition obtained above were examined in the same manner as in Example 1. The results are shown in Table 1.

Example 6
1040 parts of deionized water were charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser. In addition, 290 parts of deionized water was added to the dropping funnel, and an anionic surfactant as an emulsifier (polyoxyethylene alkyl phenyl ether sulfate ester salt, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon (registered trademark) HS-10). Of an aqueous solution of 120 parts of a 25% aqueous solution of methyl methacrylate, 730 parts of methyl methacrylate, 50 parts of cyclohexyl methacrylate, and 200 parts of a maleimide acrylate in which R ³ is ethylene and R ⁶ is a hydrogen atom in formula (IIa) An emulsion was prepared, of which 85 parts, 6% by weight of the total of all monomer components, was added into the flask. Thereafter, the temperature was raised to 80 ° C. with stirring while gently bubbling nitrogen gas into the flask, and 43 parts of a 3.5% aqueous ammonium persulfate solution was added into the flask to start a polymerization reaction. After completion of the polymerization reaction, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium bisulfite solution were dropped uniformly into the flask over 240 minutes.

  After completion of the dropwise addition, the temperature in the flask was maintained at 80 ° C. for 60 minutes, 25% ammonia water was added to the flask, and the pH was adjusted to 9 to complete the polymerization reaction. By cooling the obtained reaction liquid to room temperature, a polymer dispersion liquid containing emulsion particles and having a non-volatile content of 40% was obtained. When the glass transition temperature of the resin which comprises the emulsion particle contained in the obtained polymer dispersion liquid was calculated | required, the said glass transition temperature was 89 degreeC.

  Next, pentaerythritol triacrylate [Shin-Nakamura Chemical Co., Ltd. product number: A-TMM-3LM-N] as a curable monomer with respect to 1000 parts of non-volatile components contained in the polymer dispersion liquid obtained above. A mixed solution of 4000 parts and 400 parts of a photopolymerization initiator [2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by BASF, trade name: Lucirin TPO], as an ultrasonic homogenizer [Nippon Seiki Co., Ltd. No .: US-600S], the solution dispersed therein is shaken at 23 ° C. for 24 hours, and pentaerythritol triacrylate is contained in the emulsion particles to obtain an active energy ray-curable aqueous resin composition I got

  The particle size distribution of the active energy ray-curable aqueous resin composition obtained above was examined in the same manner as in Example 1. As a result, the peak based on emulsion particles before containing pentaerythritol triacrylate and that based on pentaerythritol triacrylate Since the peak disappeared and only the peak based on the emulsion particle containing pentaerythritol triacrylate was detected in a single peak, it was confirmed that the emulsion particle contains pentaerythritol triacrylate. In addition, the content of pentaerythritol triacrylate in the emulsion particles was 80% by mass.

  Next, the physical properties of the active energy ray-curable aqueous resin composition obtained above were examined in the same manner as in Example 1. The results are shown in Table 1.

Example 7
In Example 1, 500 parts of trimethylolpropane trimethacrylate (manufactured by Sartomer, product number: SR 350) and 500 parts of tetraethylene glycol dimethacrylate (manufactured by Sartomer, product number: SR 209) as a curable monomer are used as photopolymerization initiators. An active energy ray-curable aqueous resin composition was prepared in the same manner as in Example 1 except that the amount was changed to 100 parts. The glass transition temperature of the resin constituting the emulsion particles contained in the polymer dispersion obtained when preparing the active energy ray-curable aqueous resin composition was determined to be 88 ° C. Met.

  The particle size distribution of the active energy ray-curable aqueous resin composition obtained above was examined in the same manner as in Example 1. As a result, a peak based on emulsion particles before containing trimethylolpropane trimethacrylate and tetraethylene glycol dimethacrylate was obtained. And the peaks based on trimethylolpropane trimethacrylate and tetraethylene glycol dimethacrylate disappeared, and only the peaks based on the emulsion particles containing trimethylolpropane trimethacrylate and tetraethylene glycol dimethacrylate were detected in a single peak. It was confirmed that the emulsion particles contained trimethylolpropane trimethacrylate and tetraethylene glycol dimethacrylate. In addition, the content of the water-insoluble curable monomer in the emulsion particles was 50% by mass.

  Next, the physical properties of the active energy ray-curable aqueous resin composition obtained above were examined in the same manner as in Example 1. The results are shown in Table 1.

Example 8
In Example 1, 500 parts of tetraethylene glycol dimethacrylate (Sartmar, product number: SR 209) and 500 parts of dipentaerythritol hexaacrylate (Sartmar, product number: DPHA) as curable monomers are used as photopolymerization initiators. An active energy ray-curable aqueous resin composition was prepared in the same manner as in Example 1 except that the amount was changed to 100 parts. The glass transition temperature of the resin constituting the emulsion particles contained in the polymer dispersion obtained when preparing the active energy ray-curable aqueous resin composition was determined to be 88 ° C. Met.

  The particle size distribution of the active energy ray-curable aqueous resin composition obtained above was examined in the same manner as in Example 1. As a result, a peak based on emulsion particles before containing tetraethylene glycol dimethacrylate and dipentaerythritol hexaacrylate was obtained. And the peaks based on tetraethylene glycol dimethacrylate and dipentaerythritol hexaacrylate disappeared, and only the peaks based on the emulsion particles containing tetraethylene glycol dimethacrylate and dipentaerythritol hexaacrylate were detected in a single peak. It was confirmed that the emulsion particles contained tetraethylene glycol dimethacrylate and dipentaerythritol hexaacrylate. In addition, the content of tetraethylene glycol dimethacrylate and dipentaerythritol hexaacrylate in the emulsion particles was 50% by mass.

  Next, the physical properties of the active energy ray-curable aqueous resin composition obtained above were examined in the same manner as in Example 1. The results are shown in Table 1.

Example 9
Example 1 except that in Example 1, 1000 parts of ethoxylated (4) pentaerythritol tetraacrylate (Sartmar, product number: SR 494) was used as a curable monomer, and the amount of the photopolymerization initiator was changed to 100 parts. An active energy ray-curable aqueous resin composition was prepared in the same manner as in 1. The glass transition temperature of the resin constituting the emulsion particles contained in the polymer dispersion obtained when preparing the active energy ray-curable aqueous resin composition was determined to be 88 ° C. Met.

  The particle size distribution of the active energy ray-curable aqueous resin composition obtained above was examined in the same manner as in Example 1. As a result, it was found that the peak based on emulsion particles and ethoxy before containing ethoxylated (4) pentaerythritol tetraacrylate Since the peak based on (4) pentaerythritol tetraacrylate disappears and only the peak based on the emulsion particle containing ethoxylated (4) pentaerythritol tetraacrylate is detected in a single peak, it is ethoxylated to emulsion particle (4) It was confirmed that pentaerythritol tetraacrylate was contained. Further, the content of the water-insoluble curable monomer in the emulsion particles was 50% by mass.

  Next, the physical properties of the active energy ray-curable aqueous resin composition obtained above were examined in the same manner as in Example 1. The results are shown in Table 1.

Example 10
In Example 1, 600 parts of tetraethylene glycol dimethacrylate (Sartmar, product number: SR 209) and 400 parts of dipentaerythritol pentaacrylate (Sartmar, product number: SR 399) as curable monomers are used as photopolymerization initiators. An active energy ray-curable aqueous resin composition was prepared in the same manner as in Example 1 except that the amount was changed to 100 parts. The glass transition temperature of the resin constituting the emulsion particles contained in the polymer dispersion obtained when preparing the active energy ray-curable aqueous resin composition was determined to be 88 ° C. Met.

  The particle size distribution of the active energy ray-curable aqueous resin composition obtained above was examined in the same manner as in Example 1. As a result, a peak based on emulsion particles before containing tetraethylene glycol dimethacrylate and dipentaerythritol pentaacrylate was obtained. And the peaks based on tetraethylene glycol dimethacrylate and dipentaerythritol pentaacrylate have disappeared, and only peaks based on emulsion particles containing tetraethylene glycol dimethacrylate and dipentaerythritol pentaacrylate have been detected in a single peak. It was confirmed that the emulsion particles contained tetraethylene glycol dimethacrylate and dipentaerythritol pentaacrylate. Further, the content of tetraethylene glycol dimethacrylate and dipentaerythritol pentaacrylate in the emulsion particles was 50% by mass.

  Next, the physical properties of the active energy ray-curable aqueous resin composition obtained above were examined in the same manner as in Example 1. The results are shown in Table 1.

Example 11
1040 parts of deionized water were charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser. In addition, 290 parts of deionized water was added to the dropping funnel, and an anionic surfactant as an emulsifier (polyoxyethylene alkyl phenyl ether sulfate ester salt, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon (registered trademark) HS-10). Of an aqueous solution of 120 parts of a 25% aqueous solution of methyl methacrylate, 680 parts of methyl methacrylate, 250 parts of cyclohexyl methacrylate, 50 parts of maleimide acrylate wherein R ³ is ethylene and R ⁶ is hydrogen in formula (IIa) An emulsion was prepared, of which 85 parts, 6% by weight of the total of all monomer components, was added into the flask. Thereafter, the temperature was raised to 80 ° C. with stirring while gently bubbling nitrogen gas into the flask, and 43 parts of a 3.5% aqueous ammonium persulfate solution was added into the flask to start a polymerization reaction. After completion of the polymerization reaction, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium bisulfite solution were dropped uniformly into the flask over 240 minutes.

  After completion of the dropwise addition, the temperature in the flask was maintained at 80 ° C. for 60 minutes, 25% ammonia water was added to the flask, and the pH was adjusted to 9 to complete the polymerization reaction. By cooling the obtained reaction liquid to room temperature, a polymer dispersion liquid containing emulsion particles and having a non-volatile content of 40% was obtained. When the glass transition temperature of the resin which comprises the emulsion particle contained in the obtained polymer dispersion liquid was calculated | required, the said glass transition temperature was 95 degreeC.

  Next, pentaerythritol triacrylate [Shin-Nakamura Chemical Co., Ltd. product number: A-TMM-3LM-N] as a curable monomer with respect to 1000 parts of non-volatile components contained in the polymer dispersion liquid obtained above. A mixed solution of 1000 parts and 100 parts of a photopolymerization initiator [2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by BASF, trade name: Lucirin TPO)] as an ultrasonic homogenizer [Nippon Seiki Seisakusho Co., Ltd. No .: US-600S], the solution dispersed therein is shaken at 23 ° C. for 24 hours, and pentaerythritol triacrylate is contained in the emulsion particles to obtain an active energy ray-curable aqueous resin composition I got

  The particle size distribution of the active energy ray-curable aqueous resin composition obtained above was examined in the same manner as in Example 1. As a result, the peak based on emulsion particles before containing pentaerythritol triacrylate and that based on pentaerythritol triacrylate Since the peak disappeared and only the peak based on the emulsion particle containing pentaerythritol triacrylate was detected in a single peak, it was confirmed that the emulsion particle contains pentaerythritol triacrylate. In addition, the content of pentaerythritol triacrylate in the emulsion particles was 50% by mass.

  Next, the physical properties of the active energy ray-curable aqueous resin composition obtained above were examined in the same manner as in Example 1. The results are shown in Table 1.

Example 12
1040 parts of deionized water were charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser. In addition, 290 parts of deionized water was added to the dropping funnel, and an anionic surfactant as an emulsifier (polyoxyethylene alkyl phenyl ether sulfate ester salt, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon (registered trademark) HS-10). A dripping pre-emulsion comprising 500 parts of a maleimido acrylate in which R ³ is ethylene and R ⁶ is a hydrogen atom in the formula (IIa), 120 parts of a 25% aqueous solution of Among them, 85 parts corresponding to 6% by mass of the total amount of all monomer components was added into the flask. Thereafter, the temperature was raised to 80 ° C. with stirring while gently bubbling nitrogen gas into the flask, and 43 parts of a 3.5% aqueous ammonium persulfate solution was added into the flask to start a polymerization reaction. After completion of the polymerization reaction, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium bisulfite solution were dropped uniformly into the flask over 240 minutes.

  After completion of the dropwise addition, the temperature in the flask was maintained at 80 ° C. for 60 minutes, 25% ammonia water was added to the flask, and the pH was adjusted to 9 to complete the polymerization reaction. By cooling the obtained reaction liquid to room temperature, a polymer dispersion liquid containing emulsion particles and having a non-volatile content of 40% was obtained. When the glass transition temperature of the resin which comprises the emulsion particle | grains contained in the obtained polymer dispersion liquid was calculated | required, the said glass transition temperature was 70 degreeC.

  Next, pentaerythritol triacrylate [Shin-Nakamura Chemical Co., Ltd. product number: A-TMM-3LM-N] as a curable monomer with respect to 1000 parts of non-volatile components contained in the polymer dispersion liquid obtained above. A mixed solution of 1000 parts and 100 parts of a photopolymerization initiator [2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by BASF, trade name: Lucirin TPO)] as an ultrasonic homogenizer [Nippon Seiki Seisakusho Co., Ltd. No .: US-600S], the solution dispersed therein is shaken at 23 ° C. for 24 hours, and pentaerythritol triacrylate is contained in the emulsion particles to obtain an active energy ray-curable aqueous resin composition I got

  The particle size distribution of the active energy ray-curable aqueous resin composition obtained above was examined in the same manner as in Example 1. As a result, a peak based on emulsion particles before containing pentaerythritol triacrylate and a peak based on pentaerythritol triacrylate Disappeared, and only the peak based on the emulsion particle containing pentaerythritol triacrylate was detected in a single peak, which confirmed that the emulsion particle contained pentaerythritol triacrylate. In addition, the content of pentaerythritol triacrylate in the emulsion particles was 50% by mass.

  Next, the physical properties of the active energy ray-curable aqueous resin composition obtained above were examined in the same manner as in Example 1. The results are shown in Table 1.

Example 13
1040 parts of deionized water were charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser. In addition, 290 parts of deionized water was added to the dropping funnel, and an anionic surfactant as an emulsifier (polyoxyethylene alkyl phenyl ether sulfate ester salt, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon (registered trademark) HS-10). Of an aqueous 25% aqueous solution, 680 parts of methyl methacrylate, 100 parts of cyclohexyl methacrylate, 200 parts of N-acryloyloxyethyl hexahydrophthalimide (manufactured by Toagosei Co., Ltd., trade name: Alonix (registered trademark) M-140) and acrylic acid A dropping pre-emulsion consisting of 20 parts was prepared, of which 85 parts, corresponding to 6% by mass of the total of all the monomer components, was added into the flask. Thereafter, the temperature was raised to 80 ° C. with stirring while gently bubbling nitrogen gas into the flask, and 43 parts of a 3.5% aqueous ammonium persulfate solution was added into the flask to start a polymerization reaction. After completion of the polymerization reaction, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium bisulfite solution were dropped uniformly into the flask over 240 minutes.

  After completion of the dropwise addition, the temperature in the flask was maintained at 80 ° C. for 60 minutes, 25% ammonia water was added to the flask, and the pH was adjusted to 9 to complete the polymerization reaction. By cooling the obtained reaction liquid to room temperature, a polymer dispersion liquid containing emulsion particles and having a non-volatile content of 40% was obtained. When the glass transition temperature of the resin which comprises the emulsion particle | grains contained in the obtained polymer dispersion liquid was calculated | required, the said glass transition temperature was 92 degreeC.

  Next, 1200 parts of tetraethylene glycol dimethacrylate [Sartomer, product number: SR209] and 1000 parts of dipentaerythritol hexaacrylate [Sartomer as a curable monomer relative to 1000 parts of the non-volatile content contained in the polymer dispersion obtained above] A mixture solution of 2800 parts of a product number, DPHA !, and 400 parts of a photopolymerization initiator [2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by BASF, trade name: Lucirin TPO] is used as an ultrasonic homogenizer [ A solution dispersed using Nippon Seiki Seisakusho Co., Ltd., part number: US-600S] is added, shaken at 23 ° C. for 24 hours, and containing pentaerythritol triacrylate in the emulsion particles to obtain active energy Obtain a radiation curable aqueous resin composition .

  The particle size distribution of the active energy ray-curable aqueous resin composition obtained above was examined in the same manner as in Example 1. As a result, a peak based on emulsion particles before containing tetraethylene glycol dimethacrylate and dipentaerythritol hexaacrylate was obtained. And the peaks based on tetraethylene glycol dimethacrylate and dipentaerythritol hexaacrylate disappeared, and only the peaks based on the emulsion particles containing tetraethylene glycol dimethacrylate and dipentaerythritol hexaacrylate were detected in a single peak. It was confirmed that the emulsion particles contained tetraethylene glycol dimethacrylate and dipentaerythritol hexaacrylate. Further, the content of tetraethylene glycol dimethacrylate and dipentaerythritol hexaacrylate in the emulsion particles was 80% by mass.

  Next, the physical properties of the active energy ray-curable aqueous resin composition obtained above were examined in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1
An active energy ray-curable aqueous resin composition was obtained by performing the same operation as in Example 5 except that pentaerythritol triacrylate was not used as a curable monomer in Example 5. In addition, when the glass transition temperature of the resin which comprises the emulsion particle contained in the polymer dispersion liquid obtained when preparing an active energy ray-curable aqueous resin composition was calculated | required, the said glass transition temperature is 30 degreeC. Met.

  The physical properties of the active energy ray-curable aqueous resin composition obtained above were examined in the same manner as in Example 1. The results are shown in Table 1.

Comparative example 2
1040 parts of deionized water were charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser. In addition, 290 parts of deionized water was added to the dropping funnel, and an anionic surfactant as an emulsifier (polyoxyethylene alkyl phenyl ether sulfate ester salt, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon (registered trademark) HS-10). Of 120 parts of a 25% aqueous solution of methyl methacrylate, 680 parts of methyl methacrylate, 100 parts of cyclohexyl methacrylate, 200 parts of a maleimido acrylate wherein R ³ is ethylene and R ⁶ is a hydrogen atom in formula (IIa) An emulsion was prepared, of which 85 parts, 6% by weight of the total of all monomer components, was added into the flask. Thereafter, the temperature was raised to 80 ° C. with stirring while gently bubbling nitrogen gas into the flask, and 43 parts of a 3.5% aqueous ammonium persulfate solution was added into the flask to start a polymerization reaction. After completion of the polymerization reaction, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium bisulfite solution were dropped uniformly into the flask over 240 minutes.

  After completion of the dropwise addition, the temperature in the flask was maintained at 80 ° C. for 60 minutes, 25% ammonia water was added to the flask, and the pH was adjusted to 9 to complete the polymerization reaction. By cooling the obtained reaction liquid to room temperature, a polymer dispersion liquid containing emulsion particles and having a non-volatile content of 40% was obtained. When the glass transition temperature of the resin which comprises the emulsion particle | grains contained in the obtained polymer dispersion liquid was calculated | required, the said glass transition temperature was 88 degreeC.

  Next, pentaerythritol triacrylate [Shin-Nakamura Chemical Co., Ltd. product number: A-TMM-3LM-N] as a curable monomer with respect to 1000 parts of non-volatile components contained in the polymer dispersion liquid obtained above. Add 300 parts and 30 parts of a photopolymerization initiator [2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by BASF, trade name: Lucirin TPO], and stir with a stirring rod at 23 ° C. to obtain an emulsion An active energy ray-curable aqueous resin composition was obtained by dispersing the particles and pentaerythritol triacrylate.

  The particle size distribution of the active energy ray-curable aqueous resin composition obtained above was examined in the same manner as in Example 1. As a result, a peak based on the emulsion particle itself and a peak based on pentaerythritol triacrylate were detected, and pentaerythritol triacrylate was detected. Since no peak based on the acrylate particle containing emulsion particles was detected, it was confirmed that the emulsion particles did not contain pentaerythritol triacrylate.

  Next, the physical properties of the active energy ray-curable aqueous resin composition obtained above were examined in the same manner as in Example 1. The results are shown in Table 1.

  From the results shown in Table 1, the active energy ray-curable aqueous resin composition obtained in each example was dispersed and stabilized compared to the active energy ray-curable aqueous resin composition obtained in each comparative example. It can be seen that a film is formed which is excellent in the film forming property and the anti-curling property, and excellent in the abrasion resistance and the water resistance.

Claims (3)

  An active energy ray-curable aqueous resin composition comprising an emulsion particle comprising an (meth) acrylic polymer having an imide ring and an aqueous medium, wherein the emulsion particle is an emulsion particle comprising a water-insoluble curable monomer An active energy ray-curable aqueous resin composition characterized in that The monomer component used as a raw material of the (meth) acrylic polymer having an imide ring has the formula (Ib):

(In the formula, R ¹ Is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ² Represents an alkyl group having 1 to 4 carbon atoms, and R ¹ And R ² And may be combined to form a ring. R ³ Is a direct bond or an alkylene group having 1 to 4 carbon atoms, R ^Four And R ^Five Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)
The active energy ray-curable aqueous resin composition according to claim 1, which contains a monomer having a cyclic imide group represented by The method for producing an active energy ray-curable aqueous resin composition according to claim 1 or 2, wherein the particle diameter is mixed when mixing an aqueous dispersion of a water-insoluble curable monomer with an emulsion containing emulsion particles. A fine dispersion of a water-insoluble curable monomer, in which the water-insoluble curable monomer is finely dispersed to 0.01 to 1 μm, is added to the emulsion, and the water-insoluble curable monomer is contained in the emulsion particles. A method of producing an active energy ray-curable aqueous resin composition characterized in that