JP2003201331A - Polyisocyanate derivative and active energy ray-curable resin composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel polyisocyanate derivative which is a self-emulsifying type and which has excellent storage stability of an emulsion, and which has excellent coating properties such as hardness, antistatic property and antifogging property. To provide an active energy ray-curable resin composition using an isocyanate-based derivative. SOLUTION: The isocyanate group in the polyisocyanate compound (a1) is a hydroxyl group and a hydroxyl group-containing (meth) of a polyalkylene glycol derivative (a2) having a specific structure.
A polyisocyanate-based derivative formed by forming a urethane bond with a hydroxyl group of an acrylate (a3), and an active energy ray-curable resin composition using the same.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polyisocyanate derivative, and more particularly to a polyisocyanate derivative having self-emulsifying property that is excellent in leaving stability when used as an emulsion. The present invention relates to an active energy ray-curable resin composition using an isocyanate derivative.

[0002]

Conventionally, urethane (meth) acrylates obtained by reacting diol compounds such as polyester diols and polyether diols, diisocyanate compounds such as isophorone diisocyanate and diphenylmethane diisocyanate, and hydroxyl group-containing (meth) acrylates such as hydroxyethyl acrylate have been used. , Is known as an active energy ray-curable resin, and is used for applications such as wood coatings.

Since such a urethane (meth) acrylate generally has a high viscosity, its viscosity is adjusted by diluting it with an organic solvent or a reactive diluent before use.
It is applied and UV-cured to form a coating film. However, in the case of diluting with an organic solvent, it has become a problem under the VOC regulation in recent years regarding air pollution, working environment, fire risk and the like. On the other hand, in the case of diluting with a reactive diluent, a large amount may be required for lowering the viscosity, and there are problems such as difficulty in obtaining sufficient coating film physical properties.

Under these circumstances, in recent years, there is an increasing demand for water-dispersion type water systems. For example, a photocurable resin composition (see Patent Document 1) containing a polyfunctional urethane acrylate having a carboxyl group neutralized with an oxyalkylene group and an amino compound, a photopolymerization initiator, and water, and a carboxyl group. Containing urethane (meta)
Aqueous solution in which an acrylate is produced in the presence of a water-soluble reactive diluent having a water mixing ratio of 100% by weight or more, and after the carboxyl group of the polyurethane (meth) acrylate is converted to an amine salt, water is further added to emulsify the aqueous solution. Active energy ray-curable resin compositions (see Patent Document 2) have been proposed.

Further, a water-dispersible curable resin composition obtained by dispersing at least one curable oligomer selected from urethane acrylate and epoxy acrylate in a water solvent in the presence of a reactive emulsifier (see Patent Document 3). .) Is also proposed.

[0006]

[Patent Document 1] Japanese Patent Laid-Open No. 11-209448

[Patent Document 2] Japanese Patent Laid-Open No. 11-279242

[Patent Document 3] Japanese Patent Laid-Open No. 2000-159847

[0007]

However, in the techniques disclosed in Patent Document 1 and Patent Document 2 described above, a carboxyl group is introduced into the skeleton of urethane acrylate,
It is necessary to neutralize the carboxylic acid in making it aqueous,
Further, in the technique disclosed in Patent Document 3 described above, an emulsifier is required for water dispersion, and the stability of the resulting emulsion is left unsatisfactory, and the physical properties of the coating film are still unsatisfactory.

Under these circumstances, the present invention provides a self-emulsifying polyisocyanate derivative having excellent stability of leaving an emulsion, hardness, antistatic property, antifogging property, and further a plastic substrate. It is an object of the present invention to provide an active energy ray-curable resin composition using the polyisocyanate derivative, which is excellent in coating film physical properties such as adhesion to.

[0009]

However, the present inventors have
As a result of intensive studies in view of such circumstances, the isocyanate group in the polyisocyanate compound (a1) has a hydroxyl group of the polyalkylene glycol derivative (a2) represented by the following general formula (1) and a hydroxyl group-containing (meth) acrylate ( The present invention has been completed by finding that the polyisocyanate-based derivative formed by forming a urethane bond with the hydroxyl group of a3) meets the above object.

[0010]

[Chemical 2] Here, X is an alkylene group, Y is an alkyl group, (meth)
It is any of an acryloyl group, an allyl group, and an acyl group, and n is an integer of 1 or more.

Furthermore, in the present invention, when the polyisocyanate derivative [A] and the photopolymerization initiator [B] are contained, the emulsion is excellent in leaving stability, hardness, antistatic property and antifogging property. It becomes an active energy ray-curable resin composition having excellent coating film physical properties such as, and further, by using an ethylenically unsaturated monomer [C] in combination, in addition to hardness, antistatic property, antifogging property, plastic substrate The resulting active energy ray-curable resin composition has excellent adhesiveness to.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
In the polyisocyanate derivative [A] of the present invention, the isocyanate group in the polyisocyanate compound (a1) is
A polyisocyanate-based derivative formed by forming a urethane bond with the hydroxyl group of the polyalkylene glycol derivative (a2) represented by the general formula (1) and the hydroxyl group of the hydroxyl group-containing (meth) acrylate (a3). Each component constituting the isocyanate derivative will be described.

The polyisocyanate compound (a1) is not particularly limited, and examples thereof include aromatic, aliphatic, and alicyclic polyisocyanates. Among them, tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated Diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3- Bis (isocyanatomethyl) cyclohexane, phenylene diisocyanate, lysine diisocyanate, Down triisocyanate, polyisocyanate or trimer compounds of these polyisocyanates, such as naphthalene diisocyanate, biuret type polyisocyanate, water-dispersible polyisocyanate (Nippon Polyurethane Industry Co., Ltd. of "AQUANATE 10
0 "," Aquanate 110 "," Aquanate 20 "
0 "," Aquanate 210 ", etc.), or reaction products of these polyisocyanates and polyols.

The polyol is not particularly limited and, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, 1,4- Butanediol, polybutylene glycol, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol, hydrogenated bisphenol A, polycaprolactone, trimethylolethane, trimethylolpropane,
Polytrimethylolpropane, pentaerythritol,
Polypentaerythritol, sorbitol, mannitol, glycerin, polyglycerin, polytetramethylene glycol and other polyhydric alcohols, and polyethylene oxide, polypropylene oxide, ethylene oxide / propylene oxide block or random copolymer having at least one structure Ether polyol, polyester polyol which is a condensate of polyhydric alcohol or polyether polyol and polybasic acid such as maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid and isophthalic acid, caprolactone modified Caprolactone-modified polyol such as polytetramethylene polyol, polyolefin-based polyol,
Examples thereof include polybutadiene-based polyols such as hydrogenated polybutadiene polyol.

Further, examples of the polyol include 2,2-bis (hydroxymethyl) butyric acid, tartaric acid,
2,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxyethyl) propionic acid, 2,2-bis (hydroxypropyl) propion Acid, dihydroxymethylacetic acid, bis (4-hydroxyphenyl) acetic acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid, carboxyl group-containing polyol such as homogentisic acid, sodium 1,4-butanediol sulfonate, etc. Examples also include sulfonic acid group- or sulfonate group-containing polyols.

When the reaction product of polyisocyanate and polyol is used, for example, it may be used as a polyisocyanate containing a terminal isocyanate group obtained by reacting the above polyol with the above polyisocyanate. In the reaction of such polyisocyanate and polyol, a metal catalyst such as dibutyltin dilaurate or 1,8-diazabicyclo [5.4.
It is also preferable to use an amine catalyst such as [0] undecene-7.

The polyalkylene glycol derivative (a2) which forms a urethane bond with the isocyanate group in the polyisocyanate compound (a1) may have the structure represented by the general formula (1). Hydrogen is substituted with any of an alkyl group, a (meth) acryloyl group, an allyl group and an acyl group.

Specific examples of the polyalkylene glycol derivative (a2) represented by the general formula (1) include [when Y is an alkyl group], for example, polyethylene glycol monomethyl ether, polyethylene glycol lauryl ether, polyethylene glycol cetyl ether, Polyethylene glycol stearyl ether, polyethylene glycol nonyl phenyl ether, polyethylene glycol tridecyl ether, polyethylene glycol oleyl ether, polyethylene glycol octyl phenyl ether, polyoxyethylene oleyl cetyl ether, polypropylene glycol monomethyl ether, etc.

[Y: (meth) acryloyl group] For example, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) mono (meth) acrylate, poly (ethylene glycol) -Tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate, etc.

[In the case of Y: allyl group] For example, polyethylene glycol monoallyl ether, polypropylene glycol monoallyl ether, poly (ethylene glycol-propylene glycol) monoallyl ether, etc.

[Y: Acyl group] For example, polyethylene glycol monolaurate, polypropylene glycol monolaurate, poly (ethylene glycol-propylene glycol) monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, etc. Is mentioned. Among the above, polyethylene glycol derivatives are preferable, and the ethylene oxide addition mole number n is 5 to 500, particularly 5 to 100, and further preferably 6 to 50. Further, from the viewpoint of the hardness of the cured coating film, Y is preferably a (meth) acryloyl group, an allyl group or an acyl group.

The weight average molecular weight of the polyalkylene glycol derivative (a2) represented by the general formula (1) is preferably 100 to 20000, and particularly preferably 200 to 10
000, more preferably 400 to 4000. If the molecular weight is less than 100, self-emulsification becomes difficult, and 2000
If it exceeds 0, the water resistance of the cured coating film is remarkably deteriorated, which is not preferable.

Further, the hydroxyl value of the polyalkylene glycol derivative (a2) represented by the general formula (1) is 2 to
560 mg KOH / g is preferred, especially 5.5-28
0 mgKOH / g, further 14-145 mgKOH / g
Is preferred. When the hydroxyl value is less than 2 mgKOH / g, the water resistance of the cured coating film is remarkably poor and 560 mgKOH / g.
If it exceeds g, self-emulsification becomes difficult, which is not preferable.

The hydroxyl group-containing (meth) acrylate (a3) forming a urethane bond with the isocyanate group in the polyisocyanate compound (a1) is not particularly limited as long as it is an acrylic acid partial ester of a polyhydric alcohol. 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2
-Hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethylacryloyl phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2
-Hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol Examples include penta (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, ethylene oxide-modified dipentaerythritol penta (meth) acrylate, ethylene oxide-modified pentaerythritol tri (meth) acrylate, and the like.

The polyisocyanate derivative [A] of the present invention comprises a polyisocyanate compound (a1) and a polyalkylene glycol derivative (a) represented by the general formula (1).
2), the hydroxyl group-containing (meth) acrylate (a3) is reacted so that the isocyanate group in the polyisocyanate compound (a1) becomes a polyalkylene glycol derivative (a).
It is obtained by forming a urethane bond with the hydroxyl group of 2) and the hydroxyl group of the hydroxyl group-containing (meth) acrylate (a3).

For example, polyisocyanate compound (a
When 1) has two isocyanate groups, one isocyanate group forms a urethane bond with the hydroxyl group of the polyalkylene glycol derivative (a2), and the remaining one isocyanate group has a hydroxyl group-containing (meth) acrylate ( When the polyisocyanate derivative [A] has a urethane bond with a hydroxyl group of a3) and the polyisocyanate compound (a1) has three isocyanate groups, one isocyanate group is a polyalkylene glycol derivative (a2) ( Alternatively, a urethane bond is formed with the hydroxyl group of the hydroxyl group-containing (meth) acrylate (a3), and the remaining two isocyanate groups are combined with the hydroxyl group of the hydroxyl group-containing (meth) acrylate (a3) (or polyalkylene glycol derivative (a2)). Polyisocyanate based on urethane bond The body [A].

The reaction for forming the urethane bond is not particularly limited, and (a) the polyisocyanate compound (a1), the polyalkylene glycol derivative (a2) and the hydroxyl group-containing (meth) acrylate (a3) are collectively used. Method of charging reaction, (b) method of reacting polyisocyanate compound (a1) with hydroxyl group-containing (meth) acrylate (a3), and then reaction of polyalkylene glycol derivative (a2), (c) polyisocyanate compound (a1) ) And a polyalkylene glycol derivative (a2), and then a hydroxyl group-containing (meth) acrylate (a3) is reacted, but from the viewpoint of stability of reaction control and shortening of production time, Method) is preferred.

Further, in such a reaction, for the purpose of accelerating the reaction, a metal catalyst such as dibutyltin dilaurate or 1,8-diazabicyclo [5.4.0] undecene-
It is also preferable to use an amine-based catalyst such as No. 7, and the reaction temperature is preferably 30 to 90 ° C, particularly preferably 40 to 70 ° C.

Thus, the novel polyisocyanate derivative [A] of the present invention is obtained. The weight average molecular weight of the obtained polyisocyanate derivative [A] is 1,000.
˜100,000, more preferably 2,000
It is preferably ˜50,000. If the weight average molecular weight is less than 1000, the cured coating film becomes brittle,
When it exceeds 00, the viscosity becomes high and it is difficult to handle, and self-emulsification becomes difficult, which is not preferable.

The above-mentioned weight average molecular weight is a weight average molecular weight in terms of standard polystyrene molecular weight, and is measured by high performance liquid chromatography (Showa Denko KK, "Shode").
xGPC system-11 type "), column: Sh
odex GPC KF-806L (exclusion limit molecular weight:
2 × 10 ⁷ , separation range: 100 to 2 × 10 ⁷ , theoretical plate number: 10,000 plates / line, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 μm) It is measured by

The polyisocyanate derivative [A] thus obtained is a self-emulsifying type polyisocyanate derivative which is excellent in leaving stability when used as an emulsion. Next, an active energy ray-curable resin composition using the polyisocyanate derivative [A] will be described.

The active energy ray-curable resin composition of the present invention comprises the above polyisocyanate derivative [A] and a photopolymerization initiator [B].

The photopolymerization initiator [B] is not particularly limited as long as it can generate radicals by the action of light.
For example, 4-phenoxydichloroacetophenone, 4-
t-butyl-dichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylenephenyl) -2-hydroxy-2-methylpropan-1-one , 1- (4-dodecylphenyl) -2-hydroxy-
2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropane-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate,
4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2-
Methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, camphorquinone,
Dibenzosuberone, 2-ethylanthraquinone, 4 ',
4 ″ -diethylisophthalophenone, 3,3 ′, 4
4'-tetra (t-butylperoxycarbonyl) benzophenone, α-acyloxime ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, 4- (2-
Hydroxyethoxy) phenyl- (2-hydroxy-2
-Propyl) ketone and the like, among which benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoyl isopropyl ether, 4- (2-
Hydroxyethoxy) -phenyl (2-hydroxy-2
-Propyl) ketone, 2-hydroxy-2-methyl-1
-Phenylpropan-1-one is preferably used.

Further, triethanolamine, triisopropanolamine, 4,4 ', as an auxiliary agent for the photopolymerization initiator.
-Dimethylaminobenzophenone (Michler's ketone),
4,4′-Diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid (n-butoxy)
Ethyl, isoamyl 4-dimethylaminobenzoate, 4-
2-Ethylhexyl dimethylaminobenzoate, 2,4-
It is also possible to use diethylthioxanthone, 2,4-diisopropylthioxanthone and the like in combination.

In the present invention, in order to utilize the self-emulsifying property of the polyisocyanate derivative [A] to exert more functions as an aqueous dispersion composition, the water-soluble or It is desirable to use a photopolymerization initiator [B] having water dispersibility, for example, 2- (3-dimethylamino-2).
-Hydroxypropoxy) -3,4-dimethyl-9H-
Thioxanthone-9-onmethochloride ("Quantacure QTX", manufactured by Octel Chemicals)
Or 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1
It is preferable to use a water-soluble or water-dispersible photopolymerization initiator such as -ON (manufactured by Ciba Specialty Chemicals, "Irgacure 2959"). Among them, 1- [4-
(2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (manufactured by Ciba Specialty Chemicals, “Irgacure 295”
The water-soluble or water-dispersible photopolymerization initiator of 9 ") is suitable.

In the present invention, in addition to the polyisocyanate derivative [A] and the photopolymerization initiator [B], an ethylenically unsaturated monomer [C] is also contained to exert the effect of the present invention. Is preferable, and particularly preferable in terms of adhesion to a plastic substrate. The ethylenically unsaturated monomer [C] may be one having at least one ethylenically unsaturated group in one molecule, and examples thereof include monofunctional monomers, bifunctional monomers, and trifunctional or higher functional monomers.

Examples of the monofunctional monomer include styrene, vinyltoluene, chlorostyrene, α-methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, acrylonitrile, vinyl acetate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate , 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate Isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (Meth) acrylate, decyl (meth)
Acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, n-stearyl (meth) acrylate, benzyl (meth) acrylate, phenol ethylene oxide modified (n = 2) (meth) acrylate, nonylphenol propylene oxide modified (n
= 2.5) Half (meth) acrylate of phthalic acid derivative such as (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, furfuryl (meth) Acrylate, carbitol (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate, allyl (meth) acrylate, acryloylmorpholine, 2-hydroxyethylacrylamide, N-methylol (meth) acrylamide, N-vinylpyrrolidone , 2-vinylpyridine, polyoxyethylene secondary alkyl ether acrylate, and the like.

Examples of the bifunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate. , Dipropylene glycol di (meth)
Acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
Ethylene oxide modified bisphenol A type di (meth)
Acrylate, propylene oxide-modified bisphenol A type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) Examples thereof include acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, hydroxypivalic acid-modified neopentyl glycol di (meth) acrylate, isocyanuric acid ethylene oxide-modified diacrylate, and the like.

Examples of the trifunctional or higher functional monomer include, for example,
Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (meth) acryloyloxyethoxy Trimethylolpropane, glycerin polyglycidyl ether poly (meth) acrylate, isocyanuric acid ethylene oxide modified triacrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate (Meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) Acrylate, ethylene oxide modified dipentaerythritol penta (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol tetra (meth) acrylate, ethoxylated Glycerin triacrylate etc. are mentioned.

Other examples include Michael adducts of acrylic acid or 2-acryloyloxyethyl dicarboxylic acid monoesters. Examples of Michael adducts of acrylic acid include acrylic acid dimers, methacrylic acid dimers, acrylic acid trimers, methacrylic acid trimers, and acrylic acids. Examples thereof include acid tetramers and methacrylic acid tetramers. Further, the 2-acryloyloxyethyl dicarboxylic acid monoester is a carboxylic acid having a specific substituent, for example, 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, 2-acryloyloxy. Examples thereof include ethyl phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, and 2-methacryloyloxyethyl hexahydrophthalic acid monoester. Further, other oligoester acrylates are also included.

Particularly in the present invention, the self-emulsifying property of the polyisocyanate derivative [A] is used to make the water-soluble dispersion liquid exhibit more functions in terms of use as a composition of an aqueous dispersion liquid. The use of an ethylenically unsaturated monomer [C] having water dispersibility is desirable, and among them, for example, acryloylmorpholine, 2-hydroxyethylacrylamide, polyethylene glycol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethylene oxide. Modified dipentaerythritol hexa (meth) acrylate, ethylene oxide modified pentaerythritol tetraacrylate, tri (meth) acryloyloxyethoxy trimethylolpropane, isocyanuric acid ethylene oxide modified diacry Water-soluble or water-dispersible of ethylene oxide, isocyanuric acid ethylene oxide-modified triacrylate, ethylene oxide-modified epoxy acrylate, polyoxyethylene secondary alkyl ether acrylate, ethoxylated glycerin triacrylate, and polyester acrylate containing polyethylene glycol as a main component. It is preferable to use the ethylenically unsaturated monomer. Among them, water-soluble or water-dispersible ethylenically unsaturated monomers such as acryloylmorpholine, polyethylene glycol diacrylate, isocyanuric acid ethylene oxide-modified diacrylate, isocyanuric acid ethylene oxide-modified triacrylate, and tri (meth) acryloyloxyethoxytrimethylolpropane. Is preferred. These ethylenically unsaturated monomers [C] may be used alone or in combination of two or more.

In the present invention, the above photopolymerization initiator [B]
The compounding amount is preferably 1 to 10 parts by weight, more preferably 1 to 8 parts by weight, particularly preferably 1 to 8 parts by weight, based on 100 parts by weight of the total amount of the polyisocyanate derivative [A] and the ethylenically unsaturated monomer [C]. It is preferably 1 to 5 parts by weight.
If the blending amount is less than 1 part by weight, the curing speed in the case of ultraviolet curing will be extremely slow, and if it exceeds 10 parts by weight, the curability will not be improved and it is wasteful.

The blending amount of the ethylenically unsaturated monomer [C] is preferably 0 to 500 parts by weight with respect to 100 parts by weight of the polyisocyanate derivative [A],
More preferably 0 to 200 parts by weight, particularly preferably 0 to
It is 100 parts by weight. If the blending amount exceeds 500 parts by weight, the cured coating film becomes brittle and self-emulsification becomes difficult, which is not preferable.

In addition to the polyisocyanate derivative [A], the photopolymerization initiator [B], and the ethylenically unsaturated monomer [C], fillers, dyes and pigments, oils, plasticizers, waxes, and drying agents. Agents, dispersants, wetting agents, emulsifiers, gelling agents, stabilizers, defoamers, leveling agents, thixotropic agents, antioxidants, flame retardants, antistatic agents, fillers, reinforcing agents, matting agents, It is also possible to add a crosslinking agent or the like.

Thus, an active energy ray-curable resin composition using the above polyisocyanate derivative [A] of the present invention is obtained. Such an active energy ray-curable resin composition has a self-emulsifying property and is a characteristic of the present invention to be a curable resin composition having excellent leaving stability of an emulsion.
The emulsified liquid is not limited to the use as it is, but it is also possible to mix it with an organic solvent and use it as a solution. As such an organic solvent,
Examples thereof include ethyl acetate, butyl acetate, toluene, xylene, methanol, ethanol, propanol, butanol, acetone, methyl isobutyl ketone, methyl ethyl ketone, cellosolves, diacetone alcohol and the like.

The active energy ray-curable resin composition of the present invention is cured by applying the active energy ray-curable resin composition to an object and irradiating it with an active energy ray. The object is not particularly limited, and examples thereof include polyolefin resins such as polyethylene, polypropylene and polycyclopentadiene, polycarbonate, polyester, ABS resin, acrylic resin and the like and molded products thereof (film, sheet, cup, etc.). ), Metal, glass and the like.

As the energy rays, far ultraviolet rays,
In addition to ultraviolet rays, near-ultraviolet rays, infrared rays, and other electromagnetic waves, X-rays, γ-rays, and other electromagnetic waves, electron rays, proton rays, neutron rays, etc. can be used, but the curing speed, availability of irradiation equipment, and price Curing by UV irradiation is advantageous. In addition, when electron beam irradiation is performed, it can be cured without using the photopolymerization initiator [B].

As a method of curing by ultraviolet irradiation
Is a high pressure mercury laser that emits light in the wavelength range of 150 to 450 nm.
Lamp, super high pressure mercury lamp, carbon arc lamp, metal hail
Drump, xenon lamp, chemical lamp, etc.
100-3000 mJ / cm ^TwoJust irradiate
Yes. After UV irradiation, heat as necessary to cure
It can be perfect.

Thus, in the polyisocyanate derivative [A] of the present invention, the isocyanate group in the polyisocyanate compound (a1) is a hydroxyl group of the polyalkylene glycol derivative (a2) represented by the general formula (1) and a hydroxyl group-containing ( Since a urethane bond is formed with each of the hydroxyl groups of the (meth) acrylate (a3), the polyisocyanate derivative has self-emulsifying property and is excellent in stability of leaving the emulsion, and further, the polyisocyanate derivative [ The active energy ray-curable resin composition containing A] is an active energy ray-curable resin composition having excellent stability in leaving an emulsion, and excellent coating film physical properties such as hardness, antistatic property and antifogging property. , Paint, adhesive, adhesive, adhesive, ink, protective coating, anchor coating, magnetic powder coating vine Over, for sandblasting film,
It is very useful as various film forming materials such as plate materials.

[0050]

EXAMPLES The present invention will be described in more detail below with reference to examples. In the examples, "%" and "parts" are based on weight unless otherwise specified.

Example 1 [Polyisocyanate derivative [A]] 4 equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port
In a three-necked flask, add 3 of hexamethylene diisocyanate.
Polymer (a1) (isocyanate group content 21.1%) 2
39.4 g (0.40 mol) and 2,6-di-tert-
2.0 g of butylcresol and 0.02 g of dibutyltin dilaurylate were charged, and pentaerythritol triacrylate (a3) (hydroxyl value 125.4 m
gKOH / g) (“Viscoat # 300” manufactured by Osaka Organic Chemical Industry Co., Ltd.) 358.6 g (0.80 mol) was added dropwise in about 1 hour and reacted at 60 ° C. for 4 hours to remove residual isocyanate groups. When it reaches 2.8%, cool to 50 ° C,
Furthermore, polyethylene glycol monomethyl ether (a
2) (weight average molecular weight 974.13, ethylene oxide addition mole number 22, hydroxyl value 57.6 mg KOH / g)
402.03 g (0.41 mol) was added dropwise at 55 ° C. in about 1 hour and reacted at 60 ° C. for 3 hours. When the residual isocyanate group became 0.1%, the reaction was terminated and polyisocyanate was added. A system derivative [A-1] was obtained (resin concentration 1
00%). Obtained polyisocyanate derivative [A-
1] had a weight average molecular weight of 4,500.

A chart of ¹ H-NMR (reference substance: tetramethylsilane, solvent: d6-DMSO) of the obtained polyisocyanate derivative [A-1] is shown in FIG.
A chart of ¹³ C-NMR (reference substance: tetramethylsilane, solvent: d6-DMSO) is shown in FIG. 2, and a chart of IR spectrum is shown in FIG. The main attributes of each chart are shown below. Incidentally, "270-30" manufactured by Hitachi Ltd. was used for IR measurement, and "AVANCE DPX400" manufactured by Bruker Japan Ltd. was used for NMR measurement.

[0053] ^[1 H-NMR] (see FIG. _{1) 3.13ppm: -C H 2 -NHCO} -O- 3.38ppm: -O-C H 3 3.65~3.66ppm: -O-C H _{2 C H 2 -O- 4.24~4.30ppm: -NHCO} -O-C H 2 -
_{C- (C H 2 -O-CO} -CH = CH 2) 3 5.86~5.90ppm: -O-CO-CH = C H 2 6.39~6.44ppm: -O-CO-CH = _{C H 2 6.08~6.15ppm: -O-CO} -C H = CH 2

[^ThirteenC-NMR] (see FIG. 2) 40.75 ppm:-CH_Two-NHCO-O-, N-C
H_Two(CH_Two)₅-NHCO-O- 42.17 to 42.24 ppm:-C(CH_Two-O-
CO-CH = CH_Two) _Three 58.81 ppm: -O-CH_Three 62.48-62.65 ppm:-CH_Two-O-CO-
CH = CH_Two 63.56 to 70.65 ppm: -NHCO-O-CH
_Two-C (CH_Two-O-CO-CH = CH_Two)_Three, -NH
CO-O-CH_Two CH_Two-O-, -O-CH_Two CH_Two−
O- 71.81 ppm: -O-CH_Two CH_Two-O-CH_Three 127.62-128.08 ppm: -O-CO-CH
= CH_Two 131.22-131.65 ppm: -O-CO-CH
=CH_Two 148.92 ppm: N-CON (isocyanurate
Ring carbon) 155.83-156.41 ppm: -NHCOO-
(Carbon of urethane bond) 165.25-165.59 ppm: -O-CO-CH
= CH_Two

[IR] (See FIG. 3) 1685 cm ^-1 : C = O (isocyanurate ring) 1725 cm ^-1 : C = O (ester bond, urethane bond) 3350 cm ^-1 : NH (urethane bond) This polyisocyanate system The structure of the derivative [A-1] is as follows.

[0056]

[Chemical 3]

The polyisocyanate derivative [A-1] obtained above was evaluated as follows. (Emulsifying property) The above polyisocyanate derivative [A]
While maintaining the temperature at 0 ° C and stirring with a stirrer, add ion-exchanged water that had been preheated to 60 ° C dropwise to adjust the resin content to 3
When the content reached 5%, the dropping was terminated, and then the mixture was stirred for 10 minutes with a stirrer, and the state of the liquid was observed, and evaluated as follows. ○: An emulsion was obtained ×: Not emulsified

(Stability of emulsified liquid standing) The above polyisocyanate derivative [A] was kept at 60 ° C. and stirred with a stirrer, ion-exchanged water preheated to 60 ° C. was added dropwise to the resin component. When the concentration reached 35%, the dropping was finished, and then the mixture was stirred for 10 minutes with a stirrer to obtain an emulsion, and the obtained emulsion was allowed to stand at room temperature and 60 ° C until separation. The number of days was measured. (In the following,
When the emulsion was not obtained, the stability of leaving the emulsion was not evaluated. )

[Active energy ray-curable resin composition] 100 parts of an emulsion of polyisocyanate derivative [A-1] obtained in the same manner as the above-mentioned evaluation of emulsification property and stability of leaving emulsion solution (resin content 35 Part) as a photopolymerization initiator [B] 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1.
-On (Ciba Specialty Chemicals, "Irgacure 2959") (1.4 parts) was added and mixed to obtain an active energy ray-curable resin composition (resin concentration: 35).
%). The following evaluation was performed about the obtained active energy ray-curable resin composition.

(Coating hardness) The above active energy ray-curable resin composition was applied on a glass plate using a 150 μm applicator so that the film thickness after drying would be 30 μm, and dried at 60 ° C. for 5 minutes. After doing, high pressure mercury lamp 80
W, 1 light, from a height of 13 cm to 2.55 m / m
One pass of ultraviolet irradiation (integrated irradiation amount 582 mJ / cm ² ) was performed at a conveyor speed of in to form a cured coating film. The pencil hardness of the cured coating film was measured according to JIS K5400.

(Antistatic property) The above active energy ray-curable resin composition was applied onto a glass plate using a 150 μm applicator so that the film thickness after drying would be 30 μm, and dried at 60 ° C. for 5 minutes. After doing, high pressure mercury lamp 80
W, 1 light, from a height of 13 cm to 2.55 m / m
One pass of ultraviolet irradiation (integrated irradiation amount 582 mJ / cm ² ) was performed at a conveyor speed of in to form a cured coating film. About the cured coating film, the surface resistivity (Ω
/ □) was measured.

(Anti-fog property) The above active energy ray-curable resin composition was applied onto a glass plate using a 150 μm applicator so that the film thickness after drying would be 30 μm,
After drying for 5 minutes at 60 ℃, high pressure mercury lamp 80W,
2.55 m / min from a height of 13 cm using one light
UV irradiation of 1 pass at the conveyor speed of
² mJ / cm ² ) was performed to form a cured coating film. The cured coating film was allowed to stand in saturated steam at 60 ° C. for 10 minutes, and then allowed to stand under conditions of 23 ° C. and 50% RH, and the time (sec) until the haze disappeared was measured.

Example 2 [Polyisocyanate derivative [A]] The same polyisocyanate derivative [A-1] as in Example 1 was prepared (resin concentration 100%, weight average molecular weight 4500).

[Active energy ray-curable resin composition] 100 parts of an emulsion of the polyisocyanate derivative [A-1] obtained in the same manner as in the above-mentioned evaluation of emulsification property and stability of leaving the emulsion solution (resin content 35 Part), as a photopolymerization initiator [B], 2-hydroxy-2-methyl-1-phenyl-propan-1-one (manufactured by Ciba Specialty Chemicals, “Darocur 1173”) 1.2 parts, ethylenic As an unsaturated monomer [C], 5 parts of isocyanuric acid ethylene oxide-modified triacrylate ("Aronix M-315" manufactured by Toagosei Co., Ltd.) was added and mixed to obtain an active energy ray-curable resin composition (resin content Concentration 40
%). The same evaluation as in Example 1 was performed on the obtained active energy ray-curable resin composition.

Further, the adhesion of the obtained active energy ray-curable resin composition to a plastic substrate was evaluated as follows. (Adhesion to plastic substrate) The above active energy ray-curable resin composition was applied onto a polycarbonate panel using a bar coater No. 14 is used, the film thickness after drying is 10μ.
m, and dried at 60 ° C for 5 minutes, then, using one high-pressure mercury lamp 80W, one pass UV irradiation from a height of 13 cm at a conveyor speed of 2.55 m / min (accumulation: Irradiation dose of 582 mJ / cm ² ) was performed to form a cured coating film. According to JIS K 5400, 100 points of 2 mm grids are made on the cured coating film, an adhesion test is performed with cellophane tape, and the peeled state of the grids is observed.
The number of remaining squares was evaluated.

Example 3 [Polyisocyanate derivative [A]] The same polyisocyanate derivative [A-1] as in Example 1 was prepared (resin concentration 100%, weight average molecular weight 4500).

[Active energy ray-curable resin composition] 100 parts of an emulsion of polyisocyanate derivative [A-1] obtained in the same manner as the above-mentioned evaluation of emulsification property and leaving stability of emulsion liquid (resin content 35 Part), as a photopolymerization initiator [B], 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Ciba Specialty Chemicals, “Darocur 1173”) 1.4 parts, ethylenic Acryloylmorpholine 5 as unsaturated monomer [C]
Parts were added and mixed to obtain an active energy ray-curable resin composition (resin content concentration 40%). The obtained active energy ray-curable resin composition was evaluated in the same manner as in Example 1, and the adhesion to a plastic substrate was also evaluated in the same manner as in Example 2.

Example 4 [Polyisocyanate derivative [A]] 4 equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port
In a three-necked flask, add 3 of hexamethylene diisocyanate.
Polymer (a1) (isocyanate group content 21.1%) 2
86.5 g (0.48 mol) and 2,6-di-tert-
2.0 g of butylcresol and 0.02 g of dibutyltin dilaurylate were charged, and pentaerythritol triacrylate (a3) (hydroxyl value 125.4 m
429.2 g (0.96 mol) of gKOH / g) (“Biscoat # 300” manufactured by Osaka Organic Chemical Industry Co., Ltd.) was added dropwise in about 1 hour and reacted at 60 ° C. for 4 hours to remove residual isocyanate groups. When it reaches 2.8%, cool to 50 ° C,
Furthermore, polyethylene glycol monoacrylate (a2)
(Weight average molecular weight 575.5, ethylene oxide addition mole number 10, hydroxyl value 97.5 mg KOH / g) 28
4.3 g (0.49 mol) was added dropwise at 55 ° C. in about 1 hour and reacted at 60 ° C. for 3 hours. When the residual isocyanate group became 0.1%, the reaction was terminated and polyisocyanate was added. A system derivative [A-2] was obtained (resin concentration 100
%). Obtained polyisocyanate derivative [A-2]
Had a weight average molecular weight of 7,300.

A ¹ H-NMR (reference substance: tetramethylsilane, solvent: d6-DMSO) chart of the obtained polyisocyanate derivative [A-2] is shown in FIG.
FIG. 5 shows a chart of ¹³ C-NMR (reference substance: tetramethylsilane, solvent: d6-DMSO), and FIG. 6 shows a chart of IR. The main attributes of each chart are shown below.

[0070] ^[1 H-NMR] (see FIG. _{4) 3.14~3.15ppm: -C H 2 -NHCO} -O- 3.60~3.70ppm: -O-C H 2 C H 2 -O
_{-, - O-C H 2} CH 2 -O-CO-CH = CH 2, -
_{NHCO-O-CH 2 C H} 2 -O- 4.20~4.30ppm: -O-CH 2 C H 2 -O-
_{CO-CH = CH 2, -NHCO} -O-C H 2 CH 2 -
_{O -, - NHCO-O-} C H 2 -C- (C H 2 -O-C
_{O-CH = CH 2) 3} 5.86~5.90ppm: -O-CO-CH = C H 2 6.39~6.44ppm: -O-CO-CH = C H 2 6.08~6. 15ppm: -O-CO-C H = CH 2

[[^ThirteenC-NMR] (see FIG. 5) 40.79 ppm:-CH_Two-NHCO-O-, N-C
H_Two(CH_Two)₅-NHCO-O- 42.18 to 42.25 ppm:-C(CH_Two-O-
CO-CH = CH_Two) _Three 62.61 to 62.68 ppm:-CH_Two-O-CO-
CH = CH_Two 63.48-63.62 ppm: -NHCO-O-CH
_Two-C (CH_Two-O-CO-CH = CH_Two)_Three, 66.41 ppm: -CH_Two CH_Two-O-CO-CH =
CH_Two 68.72 to 68.97 ppm:-CH_TwoCH_Two-O-
CO-CH = CH_Two 69.53 ppm: -NHCO-O-CH_TwoCH_Two-O
− 70.30-70.47 ppm: -NHCO-O-CH
_Two CH_Two-O-, -O-CH_Two CH_Two-O- 127.65 to 127.96 ppm: -C (CH_Two-O
-CO-CH = CH_Two)_Three 128.24-128.27 ppm: -CH_TwoCH_Two−
O-CO-CH = CH _Two 130.94 to 131.67 ppm: -C-CH_Two-O
-CO-CH =CH_Two, -CH_TwoCH_Two-O-CO-C
H =CH_Two 148.97 ppm: N-CON (isocyanurate
Ring carbon) 155.85-156.44 ppm: -NHCOO-
(Carbon of urethane bond) 165.32-165.92 ppm: -CH_Two-O-C
O-CH = CH_Two

[IR] (See FIG. 6) 1685 cm ^-1 : C = O (isocyanurate ring) 1730 cm ^-1 : C = O (ester bond, urethane bond) 3375 cm ^-1 : NH (urethane bond) This polyisocyanate system The structure of the derivative [A-6] is as follows.

[0073]

[Chemical 4]

The polyisocyanate derivative [A] obtained above was evaluated in the same manner as in Example 1.

[Active energy ray-curable resin composition] 100 parts of an emulsion of the polyisocyanate derivative [A-2] obtained in the same manner as the above-mentioned evaluation of emulsification property and stability of leaving the emulsion solution (resin content 35 Part) as a photopolymerization initiator [B], 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1.
-On (Ciba Specialty Chemicals, "Irgacure 2959") (1.4 parts) was added and mixed to obtain an active energy ray-curable resin composition (resin concentration: 35).
%). The same evaluation as in Example 1 was performed on the obtained active energy ray-curable resin composition.

Example 5 [Polyisocyanate derivative [A]] 4 equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port
In a one-necked flask, an isophorone diisocyanate trimer (a1) (manufactured by Degussa Huls, "VESTANAT"
T-1890 ") (isocyanate group content 17.3
%) 280.2 g (0.38 mol) and 2,6-di-te
2.0 g of rt-butylcresol and 0.02 g of dibutyltin dilaurate were charged, and pentaerythritol triacrylate (a3) (hydroxyl value 12
5.4 mg KOH / g) (Osaka Organic Chemical Industry Co., Ltd., "Viscoat # 300") 343.2 g (0.77)
Mol) in about 1 hour and reacted at 60 ° C. for 4 hours,
50 ° C when the residual isocyanate group reaches 2.5%
And then polyethylene glycol monoacrylate (a2) (weight average molecular weight 982, ethylene oxide addition mole number 20, hydroxyl value 57.1 mgKOH / g)
376.6 g (0.38 mol) was added dropwise at 60 ° C. in about 1 hour and reacted at 60 ° C. for 3 hours. When the residual isocyanate group became 0.1%, the reaction was terminated and polyisocyanate was added. A system derivative [A-3] was obtained (resin concentration 10
0%).

The obtained polyisocyanate derivative [A
-3] had a weight average molecular weight of 4,750. The polyisocyanate derivative [A] obtained above was evaluated in the same manner as in Example 1.

[Active energy ray-curable resin composition] 100 parts of an emulsion of polyisocyanate derivative [A-3] obtained in the same manner as in the above-mentioned evaluation of emulsification property and stability evaluation of leaving the emulsion (resin content 35 Part), as a photopolymerization initiator [B], 2-hydroxy-2-methyl-1-phenyl-propan-1-one (manufactured by Ciba Specialty Chemicals, “Darocur 1173”) 1.4 parts is added, An active energy ray-curable resin composition was obtained by mixing (resin concentration 35%). The same evaluation as in Example 1 was performed on the obtained active energy ray-curable resin composition.

Example 6 [Polyisocyanate derivative [A]] The same polyisocyanate derivative [A-2] as in Example 4 was prepared (resin content concentration 100%, weight average molecular weight 7300).

[Active energy ray-curable resin composition] 100 parts of an emulsion of the polyisocyanate derivative [A-2] obtained in the same manner as the above-mentioned evaluation of emulsification property and leaving stability of emulsion liquid (resin content 35 Part), as a photopolymerization initiator [B], 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Ciba Specialty Chemicals, "Darocur 1173") 1.2 parts, ethylenic As an unsaturated monomer [C], 5 parts of isocyanuric acid ethylene oxide-modified triacrylate ("Aronix M-315" manufactured by Toagosei Co., Ltd.) was added and mixed to obtain an active energy ray-curable resin composition (resin content Concentration 40
%). The obtained active energy ray-curable resin composition was evaluated in the same manner as in Example 1, and the adhesion to a plastic substrate was also evaluated in the same manner as in Example 2.

Example 7 [Polyisocyanate Derivative [A]] The same polyisocyanate derivative [A-2] as in Example 4 was prepared (resin concentration 100%, weight average molecular weight 7300).

[Active energy ray-curable resin composition] 100 parts of an emulsion of polyisocyanate derivative [A-2] obtained in the same manner as the above-mentioned evaluation of emulsification property and stability of standing of emulsion liquid (resin content 35 Part), as a photopolymerization initiator [B], 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Ciba Specialty Chemicals, “Darocur 1173”) 1.4 parts, ethylenic Acryloylmorpholine 5 as unsaturated monomer [C]
Parts were added and mixed to obtain an active energy ray-curable resin composition (resin content concentration 40%). The obtained active energy ray-curable resin composition was evaluated in the same manner as in Example 1, and the adhesion to a plastic substrate was also evaluated in the same manner as in Example 2.

Example 8 [Polyisocyanate derivative [A]] 4 equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port
In a three-necked flask, add 3 of hexamethylene diisocyanate.
Polymer (a1) (isocyanate group content 21.1%) 2
39.4 g (0.40 mol) and 2,6-di-tert-
3.7 g of butylcresol and 0.02 g of dibutyltin dilaurylate were charged, and dipentaerythritol pentaacrylate (0.80 mol) (a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value 46. 0
mgKOH / g) charged as 975.8 g) (a3)
Was dropped in about 1 hour, and the mixture was reacted at 60 ° C. for 4 hours, cooled to 50 ° C. when the residual isocyanate group reached 1.4%, and further polyethylene glycol monoallyl ether (a2) (weight average molecular weight 1562. 95, ethylene oxide addition mole number 34, hydroxyl value 35.9 mg KOH
/ G) 643.9 g (0.41 mol) at 55 ° C. of about 1
The mixture was added dropwise over a period of time and reacted at 60 ° C. for 3 hours. When the residual isocyanate group became 0.1%, the reaction was terminated to obtain a polyisocyanate derivative [A-4] (resin content concentration 100% ). The weight average molecular weight of the obtained polyisocyanate derivative [A-4] was 4070.

A ¹ H-NMR (reference substance: tetramethylsilane, solvent: d6-DMSO) chart of the obtained polyisocyanate derivative [A-4] is shown in FIG.
FIG. 8 shows a chart of ¹³ C-NMR (reference substance: tetramethylsilane, solvent: d6-DMSO), and FIG. 9 shows a chart of IR. The main attributes of each chart are shown below.

[0085] ^[1 H-NMR] (see FIG. _{7) 3.13~3.14ppm: -C H 2 -NHCO} -O- 3.46~3.50ppm: -O-CH 2 C H 2 -O-
_{CH 2 -CH = CH 2 3.60~3.70ppm:} -O-C H 2 C H 2 -O
_{-, - O-C H 2} CH 2 -O-CH 2 -CH = CH 2,
_{-NHCO-O-CH 2 C H} 2 -O- 4.15~4.30ppm: -NHCO-O-C H 2 C
_{H 2 -O -, - O-} C H 2 -C (C H 2 -O-CO-C
_{H = CH 2) 2 -CH 2} - 5.85~5.90ppm: -O-CO-CH = C H 2 6.37~6.42ppm: -O-CO-CH = C H 2 6.07~ 6.14ppm: -O-CO-C H = CH 2

[0086] ^[13 C-NMR] (see FIG. _{8) 40.88ppm: - C H 2} -NHCO-O-, N- C
_{H 2 (CH 2) 5 -NHCO} -O- 43.06~43.18ppm: - C (CH 2 -O-C
_{O-CH = CH 2) 2} -CH 2 - 62.51~63.07ppm: - C H 2 -O-CO-
_{CH = CH 2, -O- C H} 2 -C (CH 2 -O-CO-
_{CH = CH 2) 2 -CH 2} - 69.86ppm: -CH 2 - C H 2 -O-CH 2 -C
_{H = CH 2 70.27~70.52ppm: - C} H 2 CH 2 -O-
_{CH 2 -CH = CH 2, -O-} C H 2 C H 2 -O- 69.37~69.59ppm: -NHCO-O- C H
_{2 CH 2 -O -, - NHCO} -O-CH 2 C H 2 -O- 127.58~128.07ppm: -C (CH 2 -O
_{-CO- C H = CH 2) 2} -CH 2 - 131.01~131.76ppm: -C (CH 2 -O
_{-CO-CH = C H 2)} 2 -CH 2 - 134.75ppm: -CH 2 CH 2 -O-CH 2 - C
_{H = CH 2 148.92ppm: N- C} O-N ( isocyanurate ring carbon) 155.93~156.40ppm: -NH C O-O-
(Carbon atoms of the urethane bond) 165.37~165.71ppm: -O- C O-CH
= CH ₂

[IR] (See FIG. 9) 1685 cm ^-1 : C = O (isocyanurate ring) 1730 cm ^-1 : C = O (ester bond, urethane bond) 3375 cm ^-1 : NH (urethane bond) This polyisocyanate system The structure of the derivative [A-8] is as follows.

[0088]

[Chemical 5]

The polyisocyanate derivative [A] obtained above was evaluated in the same manner as in Example 1.

[Active energy ray-curable resin composition] 100 parts of an emulsion of polyisocyanate derivative [A-4] obtained in the same manner as the above-mentioned evaluation of emulsification property and stability of leaving the emulsion solution (resin content 35 Part) as a photopolymerization initiator [B] 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1.
-On (Ciba Specialty Chemicals, "Irgacure 2959") (1.4 parts) was added and mixed to obtain an active energy ray-curable resin composition (resin concentration: 35).
%). The same evaluation as in Example 1 was performed on the obtained active energy ray-curable resin composition.

Example 9 [Polyisocyanate derivative [A]] In the preparation of the polyisocyanate derivative [A-4] of Example 8, dipentaerythritol pentaacrylate (0.80 mol) (dipentaerythritol pentaacrylate and A mixture of dipentaerythritol hexaacrylate (a hydroxyl value of 46.0 mgKOH / g) is charged as 975.8 g) (a3) is mixed with pentaerythritol triacrylate (a3) (a hydroxyl value of 125.4 mgKOH / g).
(Osaka Organic Chemical Industry Co., Ltd., "Viscoat # 30"
0 ") 358.6 g (0.80 mol), except that the same procedure was carried out to obtain a polyisocyanate derivative [A-5] (resin concentration 100%). The weight average molecular weight of the obtained polyisocyanate derivative [A-5] was 4,400. The polyisocyanate derivative [A] obtained above was evaluated in the same manner as in Example 1.

[Active energy ray-curable resin composition] 100 parts of an emulsion of polyisocyanate derivative [A-5] obtained in the same manner as in the above-mentioned evaluation of emulsification property and stability evaluation of leaving the emulsion liquid (resin content 35 Part) as a photopolymerization initiator [B], 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1.
-On (Ciba Specialty Chemicals, "Irgacure 2959") (1.4 parts) was added and mixed to obtain an active energy ray-curable resin composition (resin concentration: 35).
%). The same evaluation as in Example 1 was performed on the obtained active energy ray-curable resin composition.

Example 10 [Polyisocyanate derivative [A]] 4 equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port
In a one-necked flask, an isophorone diisocyanate trimer (a1) (manufactured by Degussa Huls, "VESTANAT"
T-1890 ") (isocyanate group content 17.3
%) 280.2 g (0.38 mol) and 2,6-di-te
2.0 g of rt-butylcresol and 0.02 g of dibutyltin dilaurate were charged, and pentaerythritol triacrylate (a3) (hydroxyl value 12
5.4 mg KOH / g) (Osaka Organic Chemical Industry Co., Ltd., "Viscoat # 300") 343.2 g (0.77)
Mol) in about 1 hour and reacted at 60 ° C. for 4 hours,
50 ° C when the residual isocyanate group reaches 2.5%
Then, the polyethylene glycol monoallyl ether (a2) (weight average molecular weight 1020.18, ethylene oxide addition mole number 22, hydroxyl value 55.0 mgK
(OH / g) 408.1 g (0.40 mol) was added dropwise at 60 ° C. in about 1 hour and reacted at 60 ° C. for 3 hours, and the reaction was terminated when the residual isocyanate group became 0.1%. Then, a polyisocyanate derivative [A-6] was obtained (resin content concentration 100%).

The obtained polyisocyanate derivative [A
-6] had a weight average molecular weight of 4,800. The polyisocyanate derivative [A] obtained above was evaluated in the same manner as in Example 1.

[Active energy ray-curable resin composition] 100 parts of an emulsion of the polyisocyanate derivative [A-6] obtained in the same manner as the above-mentioned evaluation of emulsification property and stability of leaving the emulsion solution (resin content 35 Part), as a photopolymerization initiator [B], 2-hydroxy-2-methyl-1-phenyl-propan-1-one (manufactured by Ciba Specialty Chemicals, “Darocur 1173”) 1.4 parts is added, By mixing, an active energy ray-curable resin composition was obtained (resin concentration 35%). The same evaluation as in Example 1 was performed on the obtained active energy ray-curable resin composition.

Example 11 [Polyisocyanate derivative [A]] The same polyisocyanate derivative [A-4] as in Example 8 was prepared (resin concentration 100%, weight average molecular weight 4070).

[Active energy ray-curable resin composition] 100 parts of an emulsion of polyisocyanate derivative [A-4] obtained in the same manner as in the above-mentioned evaluation of emulsification property and stability of leaving emulsion solution (resin content 35 Part), as a photopolymerization initiator [B], 2-hydroxy-2-methyl-1-phenyl-propan-1-one (manufactured by Ciba Specialty Chemicals, “Darocur 1173”) 1.2 parts, ethylenic As the unsaturated monomer [C], 5 parts of isocyanuric acid ethylene oxide-modified triacrylate ("Aronix M-315" manufactured by Toagosei Co., Ltd.) was added and mixed to obtain an active energy ray-curable resin composition (resin content Concentration 40
%). The obtained active energy ray-curable resin composition was evaluated in the same manner as in Example 1, and the adhesion to a plastic substrate was also evaluated in the same manner as in Example 2.

Example 12 [Polyisocyanate derivative [A]] The same polyisocyanate derivative [A-4] as in Example 8 was prepared (resin concentration 100%, weight average molecular weight 4070).

[Active energy ray-curable resin composition] 100 parts of an emulsion of a polyisocyanate derivative [A-4] (resin content 35 Part), as a photopolymerization initiator [B], 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Ciba Specialty Chemicals, “Darocur 1173”) 1.4 parts, ethylenic Acryloylmorpholine 5 as unsaturated monomer [C]
Parts were added and mixed to obtain an active energy ray-curable resin composition (resin content concentration 40%). The obtained active energy ray-curable resin composition was evaluated in the same manner as in Example 1, and the adhesion to a plastic substrate was also evaluated in the same manner as in Example 2.

Example 13 [Polyisocyanate derivative [A]] 4 equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port
In a three-necked flask, add 3 of hexamethylene diisocyanate.
Polymer (a1) (isocyanate group content 21.1%) 2
39.4 g (0.40 mol) and 2,6-di-tert-
3.5 g of butylcresol and 0.02 g of dibutyltin dilaurylate were charged, and a mixture of dipentaerythritol pentaacrylate (0.80 mol) (dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value 46. 0
mgKOH / g) charged as 975.8 g) (a3)
Was added dropwise over about 1 hour, and the mixture was reacted at 60 ° C. for 4 hours, cooled to 50 ° C. when the residual isocyanate groups reached 1.4%, and polyethylene glycol monostearate (a
2) (weight average molecular weight 1289.89, ethylene oxide addition mole number 23, hydroxyl value 43.5 mg KOH /
g) 531.4 g (0.41 mol) was added dropwise at 55 ° C. in about 1 hour and reacted at 60 ° C. for 3 hours to terminate the reaction when the residual isocyanate group became 0.1%, A polyisocyanate derivative [A-7] was obtained (resin concentration 100%). Obtained polyisocyanate derivative [A
-7] had a weight average molecular weight of 3,700.

A chart of ¹ H-NMR (reference substance: tetramethylsilane, solvent: d6-DMSO) of the obtained polyisocyanate derivative [A-7] is shown in FIG.
^{To, 1} 3 C-NMR (standard substance: tetramethylsilane,
Solvent: d6-DMSO) in FIG. 11 and I
The R chart is shown in FIG. The main attributes of each chart are shown below.

[0102] ^[1 H-NMR] (see FIG. _{10) 0.86~0.90ppm: -CH 2 -CH 2} -C H 3 2.31~2.35ppm: -CH 2 -O-CO-C H
_{2 - 3.13~3.14ppm: -C H 2 -NHCO} -O- 3.60~3.72ppm: -O-C H 2 C H 2 -O
_{-, - NHCO-O-CH} 2 C H 2 -O- 3.85~4.20ppm: -NHCO-O-C H 2 C
_{H 2 -O -, - C H} 2 -O-CO-CH 2 - 4.21~4.30ppm: -O-C H 2 -C (C H 2
_{-O-CO-CH = CH 2} ) 2 -CH 2 - 5.82~5.90ppm: -O-CO-CH = C H 2 6.06~6.14ppm: -O-CO-C H = CH _{2 6.35~6.44ppm: -O-CO-CH} = C H 2

[0103] ^[13 C-NMR] (see FIG. _{11) 14.10ppm: -CH 2 -CH 2} - C H 3 34.10ppm: -CH 2 -O-CO- C H 2 - 40.80ppm: - C H ₂ -NHCO-O-, N- C
_{H 2 (CH 2) 5 -NHCO} -O- 62.58~63.28ppm: -O- C H 2 -C (C
_{H 2 -O-CO-CH =} CH 2) 2 -CH 2 - 62.84~63.28ppm: - C H 2 -O-CO-
_{CH 2 - 69.10ppm: -NHCO-O-} C H 2 C H 2 -O
_{- 69.90ppm: - C H 2 CH} 2 -O-CO-CH 2
_{- 69.94~70.50ppm: -O- C H 2 C} H 2 -
O- 127.61~128.08ppm: -C _(CH 2 -O
_{-CO- C H = CH 2) 2} -CH 2 - 130.99~131.71ppm: -C (CH 2 -O
_{-CO-CH = C H 2)} 2 -CH 2 - 148.93ppm: N- C O-N ( isocyanurate ring carbon) 155.95~156.41ppm: -NH C O-O-
(Carbon atoms of the urethane bond) 165.32~165.65ppm: -O- C O-CH
_{= CH 2 173.64ppm: -CH 2 CH} 2 -O- C O-CH
_2-

[IR] (See FIG. 12) 1685 cm ^-1 : C = O (isocyanurate ring) 1730 cm ^-1 : C = O (ester bond, urethane bond) 3375 cm ^-1 : NH (urethane bond) This polyisocyanate system The structure of the derivative [A-11] is as follows.

[0105]

[Chemical 6]

The polyisocyanate derivative [A] obtained above was evaluated in the same manner as in Example 1.

[Active energy ray-curable resin composition] 100 parts of an emulsion of the polyisocyanate derivative [A-7] obtained in the same manner as in the above-described evaluation of emulsification property and stability of leaving emulsion solution (resin content 35 Part) as a photopolymerization initiator [B], 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1.
-On (Ciba Specialty Chemicals, "Irgacure 2959") (1.4 parts) was added and mixed to obtain an active energy ray-curable resin composition (resin concentration: 35).
%). The same evaluation as in Example 1 was performed on the obtained active energy ray-curable resin composition.

Example 14 [Polyisocyanate derivative [A]] 4 equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port
In a three-necked flask, add 3 of hexamethylene diisocyanate.
Polymer (a1) (isocyanate group content 21.1%) 2
39.4 g (0.40 mol) and 2,6-di-tert-
Butylcresol (3.0 g) and dibutyltin dilaurylate (0.02 g) were charged, and pentaerythritol triacrylate (a3) (hydroxyl value: 125.4 m
gKOH / g) (“Viscoat # 300” manufactured by Osaka Organic Chemical Industry Co., Ltd.) 358.6 g (0.80 mol) was added dropwise in about 1 hour and reacted at 60 ° C. for 4 hours to remove residual isocyanate groups. When it reaches 2.8%, cool to 50 ° C,
Furthermore, polyethylene glycol monostearate (a2)
(Weight average molecular weight 2200.39, ethylene oxide addition mole number 44, hydroxyl value 25.5 mgKOH / g) 9
06.6 g (0.41 mol) was added dropwise at 55 ° C. in about 1 hour and reacted at 60 ° C. for 3 hours. When the residual isocyanate group became 0.1%, the reaction was terminated and polyisocyanate was added. A system derivative [A-8] was obtained (resin concentration 100
%).

The obtained polyisocyanate derivative [A
-8] had a weight average molecular weight of 4,200. The polyisocyanate derivative [A] obtained above was evaluated in the same manner as in Example 1.

[Active energy ray-curable resin composition] 100 parts of an emulsion of polyisocyanate derivative [A-8] obtained in the same manner as the above-mentioned evaluation of emulsification property and leaving stability of emulsion liquid (resin content 35 Part) as a photopolymerization initiator [B], 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1.
-On (Ciba Specialty Chemicals, "Irgacure 2959") (1.4 parts) was added and mixed to obtain an active energy ray-curable resin composition (resin concentration: 35).
%). The same evaluation as in Example 1 was performed on the obtained active energy ray-curable resin composition.

Example 15 [Polyisocyanate derivative [A]] A polyisocyanate derivative [A-8] similar to that in Example 14 was prepared (resin concentration 100%, weight average molecular weight 4200).

[Active energy ray-curable resin composition] 100 parts of an emulsion of the polyisocyanate derivative [A-8] obtained in the same manner as in the above-mentioned evaluation of emulsification property and stability of leaving of emulsion liquid (resin content 35 Part), as a photopolymerization initiator [B], 2-hydroxy-2-methyl-1-phenyl-propan-1-one (manufactured by Ciba Specialty Chemicals, “Darocur 1173”) 1.2 parts, ethylenic As the unsaturated monomer [C], 5 parts of isocyanuric acid ethylene oxide-modified triacrylate ("Aronix M-315" manufactured by Toagosei Co., Ltd.) was added and mixed to obtain an active energy ray-curable resin composition (resin content Concentration 40
%). The obtained active energy ray-curable resin composition was evaluated in the same manner as in Example 1, and the adhesion to a plastic substrate was also evaluated in the same manner as in Example 2.

Example 16 [Polyisocyanate derivative [A]] A polyisocyanate derivative [A-8] similar to that in Example 14 was prepared (resin concentration 100%, weight average molecular weight 4200).

[Active energy ray-curable resin composition] 100 parts of an emulsion of the polyisocyanate derivative [A-8] obtained in the same manner as the above-mentioned evaluation of emulsification property and stability of leaving stability of emulsion liquid (resin content 35 Part), as a photopolymerization initiator [B], 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Ciba Specialty Chemicals, “Darocur 1173”) 1.4 parts, ethylenic Acryloylmorpholine 5 as unsaturated monomer [C]
Parts were added and mixed to obtain an active energy ray-curable resin composition (resin content concentration 40%). The obtained active energy ray-curable resin composition was evaluated in the same manner as in Example 1, and the adhesion to a plastic substrate was also evaluated in the same manner as in Example 2.

Comparative Example 1 [Polyisocyanate derivative [A]] 4 equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port
In a three-necked flask, add 3 of hexamethylene diisocyanate.
Polymer (a1) (isocyanate group content 21.1%) 2
39.4 g (0.40 mol) and 2,6-di-tert-
2.0 g of butylcresol and 0.02 g of dibutyltin dilaurylate were charged, and pentaerythritol triacrylate (a3) (hydroxyl value 125.4 m
713.9 g (1.47 mol) of gKOH / g) (“Biscoat # 300” manufactured by Osaka Organic Chemical Industry Co., Ltd.) was added dropwise in about 1 hour and reacted at 60 ° C. for 8 hours to remove residual isocyanate groups. The reaction was terminated when the content reached 0.3%, and a polyisocyanate derivative [A′-1] was obtained (resin content concentration 100%).

The weight average molecular weight of the resulting polyisocyanate derivative [A'-1] was 6,800. The polyisocyanate derivative [A] obtained above was evaluated in the same manner as in Example 1.

[Active energy ray-curable resin composition] The polyisocyanate derivative [A'-1] obtained above.
To 100 parts (resin content 100 parts), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1 as a photopolymerization initiator [B]
-ON (Ciba Specialty Chemicals, "Irgacure 2959") 4 parts was added and mixed to obtain an active energy ray-curable resin composition (resin concentration 100
%). The same evaluation as in Example 1 was performed on the obtained active energy ray-curable resin composition.

Comparative Example 2 [Polyisocyanate Derivative [A]] A polyisocyanate derivative [A′-1] similar to Comparative Example 1 was prepared (resin content concentration 100%, weight average molecular weight 6800).
Next, 100 parts of deionized water and a nonionic emulsifier polyethylene glycol nonyl phenyl ether (“NONION NS-240” manufactured by NOF CORPORATION) were placed in a four-necked flask equipped with a thermometer, a reflux cooling device and a stirrer. 16 parts was added and heated to 50 ° C., 40 parts of the above polyisocyanate derivative [A′-1] heated to 50 ° C. under strong stirring was added thereto, and stirring was continued at 50 ° C. for 30 minutes, An emulsion (resin content 35%) was obtained. This emulsion was evaluated according to the same evaluation criteria as in Example 1.

[Active energy ray-curable resin composition] 100 parts of the emulsion (35 parts of resin) obtained above was mixed with 2-hydroxy-2-methyl-1 as a photopolymerization initiator [B].
-Phenyl-propan-1-one (Ciba Specialty Chemicals, "Darocur 1173") 1.4
Parts were added and mixed to obtain an active energy ray-curable resin composition (resin content concentration 35%). The same evaluation as in Example 1 was performed on the obtained active energy ray-curable resin composition. The evaluation results of Examples and Comparative Examples are shown in Tables 1-9.

[0120]

[Table 1] (when Y in the general formula (1) is an alkyl group)

[0121]

[Table 2] (when Y in the general formula (1) is an alkyl group)

[0122]

[Table 3] (when Y in the general formula (1) is a (meth) acryloyl group)

[0123]

[Table 4] (when Y in the general formula (1) is a (meth) acryloyl group)

[0124]

[Table 5] (when Y in the general formula (1) is an allyl group)

[0125]

[Table 6] (when Y in the general formula (1) is an allyl group)

[0126]

[Table 7] (when Y in the general formula (1) is an acyl group)

[0127]

[Table 8] (when Y in the general formula (1) is an acyl group)

[0128]

[Table 9]

[0129]

The novel polyisocyanate derivative [A] of the present invention has a polyisocyanate compound (a1) in which the isocyanate group is a hydroxyl group of the polyalkylene glycol derivative (a2) represented by the general formula (1), A polyisocyanate derivative formed by forming a urethane bond with each of the hydroxyl groups of the hydroxyl group-containing (meth) acrylate (a3), which is a self-emulsifying type and exhibits an excellent effect of leaving stability of an emulsion. An active energy ray-curable resin composition containing an isocyanate derivative [A] and a photopolymerization initiator [B] is excellent in leaving stability of an emulsion and further has hardness, antistatic property, antifogging property and the like. It has excellent effects on the physical properties of the coating film. Furthermore, by using the ethylenically unsaturated monomer [C] together, in addition to hardness, antistatic property, antifogging property, plasticity And exhibits excellent effect also in adhesion to a substrate, coating, adhesive, glue, adhesive, ink, protective coatings, anchor coating agents,
It is very useful as various film forming materials such as magnetic powder coating binders, sandblast coatings, and plate materials.

[Brief description of drawings]

FIG. 1 is a ¹ H-NMR chart of a polyisocyanate derivative [A-1] obtained in Example 1.

2 is a ¹³ C-NMR chart of the polyisocyanate derivative [A-1] obtained in Example 1. FIG.

3 is an IR chart of the polyisocyanate derivative [A-1] obtained in Example 1. FIG.

FIG. 4 is a ¹ H-NMR chart of a polyisocyanate derivative [A-2] obtained in Example 4.

5 is a ¹³ C-NMR chart of the polyisocyanate derivative [A-2] obtained in Example 4. FIG.

6 is an IR chart of the polyisocyanate derivative [A-2] obtained in Example 4. FIG.

7 is a ¹ H-NMR chart of the polyisocyanate derivative [A-4] obtained in Example 8. FIG.

FIG. 8 is a ¹³ C-NMR chart of polyisocyanate derivative [A-4] obtained in Example 8.

9 is an IR chart of the polyisocyanate derivative [A-4] obtained in Example 8. FIG.

FIG. 10: Polyisocyanate obtained in Example 13
Of system derivative [A-7] ¹It is an H-NMR chart.

FIG. 11: Polyisocyanate obtained in Example 13
Of system derivative [A-7] ^ThirteenIt is a C-NMR chart.

12 is an IR chart of the polyisocyanate derivative [A-7] obtained in Example 13. FIG.

Continued front page    (72) Inventor Mamoru Akiyama             2-13-1, Muroyama, Ibaraki City, Osaka Prefecture, Japan             Central Research Laboratory, Seisei Kogyo Co., Ltd. F-term (reference) 2H025 AB01 AD01 BC14 BC66                 4J027 AC01 AC06 AG04 AG09 AG24                       AG25 AG27 AG33 AJ01 AJ05                       BA05 BA07 BA08 BA09 BA12                       BA13 BA16 BA19 BA20 BA26                       CB10 CC03 CC04 CC05 CC06                       CC08 CD08                 4J034 CA02 CA04 CA05 CB03 CC02                       CC03 CC08 CC26 CC45 CC52                       CC54 CC61 CC67 DF01 DF12                       DG03 DG04 DG09 DG10 DH02                       DP18 DQ15 FA01 FA05 FB01                       FC01 GA02 GA06 GA23 HA07                       HC03 HC12 HC13 HC22 HC61                       HC64 HC65 HC67 HC71 HC73                       JA06 JA21 QA03 QA05 QC05                       RA07 RA08

Claims (7)

[Claims] 1. An isocyanate group in the polyisocyanate compound (a1) is a hydroxyl group of a polyalkylene glycol derivative (a2) represented by the following general formula (1) and a hydroxyl group of a hydroxyl group-containing (meth) acrylate (a3): Polyisocyanate-based derivatives, each of which is formed with a urethane bond. [Chemical 1] Here, X is an alkylene group, Y is an alkyl group, (meth)
It is any of an acryloyl group, an allyl group, and an acyl group, and n is an integer of 1 or more. 2. The polyalkylene glycol derivative (a2) represented by the general formula (1) is a polyethylene glycol derivative, and the ethylene oxide addition mole number n is 5
The polyisocyanate-based derivative according to claim 1, wherein the polyisocyanate-based derivative is about 500. 3. An active energy ray curable resin composition comprising the polyisocyanate derivative [A] according to claim 1 or 2 and a photopolymerization initiator [B]. 4. An ethylenically unsaturated monomer [C]
The active energy ray-curable resin composition according to claim 3, which comprises: 5. The photopolymerization initiator [B] is a water-soluble or water-dispersible photopolymerization initiator.
Alternatively, the active energy ray-curable resin composition according to item 4. 6. The active energy ray-curable type according to claim 3, 4 or 5, wherein the ethylenically unsaturated monomer [C] is a water-soluble or water-dispersible ethylenically unsaturated monomer. Resin composition. 7. The active energy ray-curable resin composition according to claim 3, which has a self-emulsifying property.