TWI693263B - Active energy ray-curable resin composition, active energy ray-curable emulsion composition and coating agent composition - Google Patents

Abstract

式中，X為伸烷基，Y為氫原子、烷基、(甲基)丙烯醯基、烯丙基、醯基中之任一者，n為1以上之整數。The present invention provides an active energy ray-curable resin composition that is excellent in self-emulsifying property with respect to an aqueous medium, and is applied to a substrate and hardened to form a coating film that is excellent in hardness and temperature resistance and water resistance. This active energy ray-curable resin composition is characterized by containing an urethane (meth)acrylate compound (A) and ethylene oxide-modified trimethylolpropane tri(meth)acrylate (B ), the urethane (meth)acrylate-based compound (A) is the isocyanate group in the polyvalent isocyanate-based compound (a1) and the hydroxyl-containing (meth)acrylate-based compound (a2) The hydroxyl group and the hydroxyl group of the compound (a3) containing an oxyalkylene group represented by the following general formula (1) are formed by forming a urethane bond; [Chem 1]

In the formula, X is an alkylene group, Y is any one of a hydrogen atom, an alkyl group, a (meth)acryloyl group, an allyl group, and an acyl group, and n is an integer of 1 or more.

Description

Active energy ray-curable resin composition, active energy ray-curable emulsion composition and coating agent composition

The present invention relates to an active energy ray-curable resin composition, and more specifically relates to an active energy which is excellent in self-emulsifying property with respect to an aqueous medium and is applied to a substrate and cured after curing to obtain a coating film having excellent hardness and resistance to warm water. Radiation hardening resin composition. In addition, the present invention also relates to an active energy ray-curable emulsion composition formed by dispersing the active energy ray-curable resin composition in an aqueous medium, and a dispersion of the active energy ray curable resin composition in an aqueous medium. The coating agent composition.

Conventionally, a diol compound such as polyester diol or polyether diol is reacted with a diisocyanate compound such as isophorone diisocyanate, diphenylmethane diisocyanate, and a hydroxyl group-containing (meth)acrylate such as hydroxyethyl acrylate. The resulting urethane (meth)acrylate is known as an active energy ray-curable resin and is used in wood coatings or plastic coating agents.

Because urethane (meth)acrylate generally has a high viscosity, it will be diluted with an organic solvent or a reactive diluent to adjust the viscosity when used, and then coated and hardened with ultraviolet light to form a coating membrane. However, when diluting with an organic solvent, in recent years, it has become a problem under the regulations of VOCs such as air pollution, working environment, and the risk of fire. On the other hand, when diluting with a reactive diluent, a large amount of reactive diluent may be required for lowering the viscosity, and it may be difficult to obtain sufficient coating film physical properties.

Under such circumstances, in recent years, the demand for water systems such as water dispersion has increased. For example, it has been proposed to use polyfunctional urethane acrylate compounds for polyfunctional oligomers and ethyl carbamic acid having a hydrophilic group and a hydrophobic group for polyfunctional reactive surfactants. An ester acrylate-based compound is an active energy ray-curable emulsion composition composed of a polyfunctional oligomer dispersed in an aqueous medium in the presence of a polyfunctional reactive surfactant (for example, refer to Patent Document 1). ). In addition, in order to improve the temperature resistance of the cured coating film or to improve the whitening of the appearance of the coating film after immersion in warm water, it has also been proposed an active energy ray hardening emulsion composition, which contains a relatively high polarity introduced into the structure The urethane (meth)acrylate compound of the polyol (for example, refer to Patent Document 2.). [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Publication No. 2008-303258 [Patent Document 2] Japanese Patent Application Publication No. 2011-12120

[Problems to be Solved by the Invention] However, the technology disclosed in the above Patent Document 1 or Patent Document 2 is difficult to say that the adhesion to the coating film of the plastic substrate is usually satisfactory, and although it is not only usual, but also in warm water After the dipping, the appearance of the coating film does not change and it is judged to be good, but considering the point of practical use, there is a problem that the adhesiveness of the coating film is not satisfactory. Especially in the field of plastic coating, the appearance of the coating film does not change before and after the durability test is the basic required physical properties. Furthermore, when the adhesion of the coating film after the durability test is evaluated under the same evaluation conditions as usual, No change in coating adhesion is an important physical property index for practical use. In addition, in terms of general-purpose plastic substrates, in addition to ABS substrates, there are more heat-resistant polycarbonate substrates, and it is necessary for any of them to have coating film adhesion necessary for practical use. Active energy ray-curable resin composition.

Therefore, the object of the present invention is to provide active energy ray hardening which is excellent in self-emulsifying property for an aqueous medium and which can be applied to a substrate and hardened to obtain a coating film excellent in hardness and temperature resistance and water resistance after being hardened. Type resin composition, an active energy ray-curable emulsion composition formed by dispersing the active energy ray-curable resin composition in an aqueous medium, and a dispersion of the active energy ray curable resin composition in an aqueous medium Coating agent composition. [Means to solve the problem]

The inventors of the present case took the above situation as a reference to the results of in-depth research and found that by using an ethyl urethane (meth)acrylate compound having an oxyalkylene structure in combination with an ethylenically unsaturated monomer of a specific structure, An active energy ray-curable resin composition, which is excellent in self-emulsifying property for an aqueous medium, can be applied to a substrate and hardened to obtain high hardness, and is difficult to produce even after immersion in warm water The present invention has been completed by a hardened coating film in which the appearance of the coating film is deteriorated, such as whitening, or the adhesive performance is reduced.

That is, the gist of the present invention is an active energy ray-curable resin composition characterized by containing an urethane (meth)acrylate compound (A) and ethylene oxide-modified trimethylolpropane Tri(meth)acrylate (B); the urethane (meth)acrylate-based compound (A), the isocyanate group in the polyvalent isocyanate-based compound (a1) and the hydroxyl group-containing (methyl) ) The hydroxyl group of the acrylate compound (a2) and the hydroxyl group of the alkylene oxide-containing compound (a3) represented by the following general formula (1) are formed by forming an urethane bond.

式中，X為伸烷基，Y為氫原子、烷基、(甲基)丙烯醯基、烯丙基、醯基中之任一者， n為1以上之整數。【Chemistry 1】

In the formula, X is an alkylene group, Y is any one of a hydrogen atom, an alkyl group, a (meth)acryloyl group, an allyl group, and an acyl group, and n is an integer of 1 or more.

Furthermore, the present invention provides an active energy ray-curable emulsion composition formed by dispersing the active energy ray-curable resin composition in an aqueous medium, and a dispersion of the active energy ray curable resin composition in an aqueous medium The coating agent composition. [Effect of invention]

The active energy ray-curable resin composition of the present invention is excellent in self-emulsifying property for an aqueous medium, and a coating film excellent in hardness and resistance to warm water can be obtained after being applied to a substrate and cured, because even in warm water After immersion, it is difficult to cause deterioration of the appearance of the coating film such as whitening or the reduction of adhesion performance. As a variety of film forming materials, such as paints, adhesives, adhesives, adhesives, printing inks, protective coating agents, anchor coating agents ( anchor-coating agent), coating agent for hard coating, adhesive for magnetic powder coating, coating for sandblasting, plates, coating agent for top coat of optical film, metal evaporation or sputtering film, Coating agent for modified glass is very useful.

The present invention will be described in detail below. In the present invention, (meth)acrylic acid means acrylic acid or methacrylic acid, (meth)acrylic acid means acrylic acid or methacrylic acid, and (meth)acrylic acid means acrylic acid or methacrylic acid. Acrylate.

[Active energy ray-curable resin composition] The active energy ray-curable resin composition of the present invention contains an urethane (meth)acrylate compound (A) and ethylene oxide-modified trimethylolpropane trioxide (Meth)acrylate (B).

The urethane (meth)acrylate compound (A) used in the present invention is composed of a polyvalent isocyanate compound (a1), a hydroxyl group-containing (meth)acrylate compound (a2) and the following general formula ( 1) The urethane (meth)acrylate compound composed of the alkylene oxide-containing compound (a3) represented is a polyvalent isocyanate-based compound (a1) with an isocyanate group and a hydroxyl group-containing (methyl ) The hydroxy group of the acrylate compound (a2) and the hydroxy group of the oxyalkylene group-containing compound (a3) represented by the following general formula (1) form an urethane bond (meth)acrylate obtained by forming an urethane bond Compound. Among them, the urethane (meth)acrylate compound (A) used in the present invention has the hydrophilicity derived from the compound (a3) containing an oxyalkylene group represented by the hydrophilic general formula (1) It is a structural unit and has a hydrophobic residue of a hydroxyl group-containing (meth)acrylate compound (a2), so it can function as a surfactant.

Examples of the polyvalent isocyanate-based compound (a1) include mesityl diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, and diisocyanate Aromatic polyisocyanates such as xylene dimethyl ester, tetramethyl xylene diisocyanate, phenyl diisocyanate, naphthyl diisocyanate; hexamethylene diisocyanate, diisocyanate Aliphatic polyisocyanates such as trimethylhexamethylene acid acid, urethane diisocyanate, urethane triisocyanate; hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane and other alicyclic polyisocyanates; or trimers of these polyisocyanates Compound or polymer compound, allophanate type polyisocyanate, biuret type polyisocyanate, water-dispersible type polyisocyanate (for example, ``AQUANATE 100'', ``AQUANATE'' manufactured by Tosoh Corporation) 110", "AQUANATE 200", "AQUANATE 210", etc.). These polyvalent isocyanate-based compounds (a1) can be used alone or in combination of two or more.

Among these, from the viewpoint of less yellowing of the cured coating film or the viewpoint of less curing shrinkage, alicyclic polyisocyanate is preferred, and isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, 1, 3-bis(isocyanatomethyl)cyclohexane.

Examples of the hydroxyl-containing (meth)acrylate-based compound (a2) include monofunctional hydroxyl-containing (meth)acrylate-based compounds and difunctional hydroxyl-containing (meth)acrylate-based compounds. , (Meth)acrylate-based compounds containing more than 3 functions of hydroxyl groups, (meth)acrylate-based compounds containing other hydroxyl groups. Examples of monofunctional hydroxyl-containing (meth)acrylate-based compounds include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 5-(meth)acrylic acid. Hydroxypentyl ester, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, (4-hydroxymethylcyclohexyl) (meth)acrylate ) Hydroxyalkyl (meth)acrylates such as methyl esters (meth)acrylates containing primary hydroxyl groups; 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (A ()) 2-hydroxy-3-phenoxypropyl acrylate and other (meth)acrylates containing secondary hydroxyl groups; 2,2-dimethyl-2-hydroxyethyl (meth)acrylate containing tertiary hydroxyl groups The (meth) acrylate and so on. Examples of the bifunctional hydroxyl-containing (meth)acrylate-based compounds include, for example, isocyanuric acid ethylene oxide modified di(meth)acrylate and glycerin epichlorohydrin modified 1,6 -Hexanediol di(meth)acrylate and the like. Examples of trifunctional or more hydroxyl-containing (meth)acrylate-based compounds include neopentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and caprolactone. Modified dipentaerythritol penta(meth)acrylate, caprolactone modified neopentaerythritol tri(meth)acrylate, ethylene oxide modified dipentaerythritol penta(meth)acrylate , Ethylene oxide modified neopentyl alcohol tri (meth) acrylate and so on. Examples of (meth)acrylate-based compounds containing other hydroxyl groups include 2-hydroxyethylacryloyl acetyl phosphate, 2-(meth)acryloyl oxyethyl-2-hydroxypropylbenzene di Formate, 2-hydroxy-3-(meth)acryloxypropyl (meth)acrylate, caprolactone modified 2-hydroxyethyl (meth)acrylate, etc. These hydroxyl-containing (meth)acrylate-based compounds (a2) can be used alone or in combination of two or more.

Among these, from the viewpoint of hardness or temperature resistance, it is preferably a polyfunctional hydroxyl group-containing (meth)acrylate-based compound, and particularly preferably a trifunctional or more hydroxyl group-containing (meth)acrylate-based compound, further It is preferably modified by pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, caprolactone modified dipentaerythritol penta(meth)acrylate, caprolactone modified Neopentaerythritol tri(meth)acrylate, ethylene oxide modified dipentaerythritol penta(meth)acrylate, ethylene oxide modified neopentaerythritol tri(meth)acrylate.

The alkylene oxide-containing compound (a3) is represented by the following general formula (1), and one type may be used alone or two or more types may be used in combination.

此處，X為伸烷基，Y為氫原子、烷基、(甲基)丙烯醯基、烯丙基、醯基中之任一者，n為1以上之整數。【Chemical 2】

Here, X is an alkylene group, Y is any one of a hydrogen atom, an alkyl group, a (meth)acryloyl group, an allyl group, and an acyl group, and n is an integer of 1 or more.

X in the above general formula (1) is an alkylene group. Among them, from the viewpoint of excellent hydrophilicity, it is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an ethylene group, an propyl group, and a tetramethylene group The alkylene group with the same carbon number of 1~4 is especially suitable for ethylidene group. In addition, when n is a polyoxyalkylene chain part of 2 or more, the oxyalkylene-containing compound (a3) may be a homopolymer of the same oxyalkylene chain, or may be a different oxyalkylene chain Chains are copolymerized into random or block-like ones.

As mentioned above, n in the general formula (1) is an integer of 1 or more, preferably 3 to 300, more preferably 5 to 200, further preferably 5 to 100, and particularly preferably 6 to 50. If the value of n is too large, the hardness of the coating film or the temperature resistance to water tends to decrease.

Any one of the Y series hydrogen atom, alkyl group, (meth)acryl acetyl group, allyl group, and acetyl group in the above general formula (1), among these, the balance between hydrophilicity and reactivity is excellent In view of this, a hydrogen atom, an alkyl group, and a (meth)acryloyl group are preferred, and a hydrogen atom is particularly preferred. As mentioned above, for the alkyl group, those having 1 to 20 carbon atoms are generally used, and those having 1 to 10 carbon atoms are preferably used. Among these, methyl and ethyl are particularly preferred. As for the above-mentioned acyl group, for example, an acetyl group, an acetylimidyl group, a thioethyl acetyl group, a benzene sulfonyl group, a phosphinonitride group, a phosphonoyl group, etc. Acetyl.

Specific examples of the alkylene oxide-containing compound (a3) include the following.

When Y is a hydrogen atom, for example, at least one of polyethylene glycol, polypropylene glycol, polybutylene glycol, a block or random copolymer having ethylene oxide/propylene oxide/butylene oxide Structure of polyether polyol, polyoxytetramethylene glycol, polyethylene glycol-polypropylene glycol-polyethylene glycol (block copolymer), polypropylene glycol-polyethylene glycol-polypropylene glycol (block copolymerization) Products), polyethylene glycol-polypropylene glycol (random copolymer), polyoxytetramethylene glycol-polyethylene glycol-polyoxytetramethylene glycol (block copolymer), polyethylene Glycol-polyoxytetramethylene glycol (random copolymer), polypropylene glycol-polyoxytetramethylene glycol-polypropylene glycol (block copolymer), polyoxytetramethylene glycol -Polypropylene glycol-polyoxytetramethylene glycol (block copolymer), polypropylene glycol-polyoxytetramethylene glycol (random copolymer), etc.

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 nonylphenyl ether , Polyethylene glycol tridecyl ether, polyethylene glycol oleyl (oleyl) ether, polyethylene glycol octyl phenyl ether, polyoxyethylene oleyl hexadecyl ether and other polyethylene glycol derivatives ; Polypropylene glycol derivatives such as polypropylene glycol monomethyl ether.

When Y is a (meth)acryloyl group, for example, polyethylene glycol derivatives such as polyethylene glycol mono(meth)acrylate, polypropylene glycol derivatives such as polypropylene glycol mono(meth)acrylate, poly Ethylene glycol-polypropylene glycol-mono(meth)acrylate, poly(ethylene glycol-tetramethylene glycol) mono(meth)acrylate, poly(propylene glycol-tetramethylene glycol) mono(meth) Base) acrylate, etc.

When Y is an allyl group, polyethylene glycol derivatives such as polyethylene glycol monoallyl ether, polypropylene glycol derivatives such as polypropylene glycol monoallyl ether, and polyethylene glycol-polypropylene glycol-monoene Propyl ether and so on.

When Y is an acyl group, for example, polyethylene glycol derivatives such as polyethylene glycol monolaurate, polyethylene glycol monostearate, and polyethylene glycol monooleate can be cited.

Among the above, the compound (a3) containing an oxyethylidene group is preferably a polyethylene glycol derivative (a compound in which X in the formula (1) is an ethylidene group), and particularly preferably ethylene oxide plus Polyethylene glycol derivatives with a mole number (n value in formula (1)) of 5 to 200, further preferably an ethylene oxide addition mole number (n value in formula (1)) of 5 A polyethylene glycol derivative of ~100, especially a polyethylene glycol derivative with an ethylene oxide addition mole number (n value in formula (1)) of 6 to 50, with respect to a hydrophilic group and a hydrophobic group A well-balanced view is ideal. If the mole number n of addition of ethylene oxide is too small, it is difficult to obtain a stable emulsified dispersion liquid, and if it is too large, the hardness or temperature resistance at the time of curing the coating film tends to decrease. Further, from the viewpoint of affecting the hardenability, Y is preferably a hydrogen atom, an alkyl group, (meth)acryloyl group, and particularly preferably a hydrogen atom.

In addition, the weight average molecular weight of the alkylene oxide-containing compound (a3) represented by the above general formula (1) is usually preferably 100 to 10,000, particularly preferably 200 to 6,000, and further preferably 400 to 3,000. If the weight average molecular weight is too small, it may be difficult to obtain a stable emulsified dispersion liquid, and if it is too large, the temperature resistance water resistance at the time of becoming a cured coating film tends to decrease.

Further, as for the hydroxyl value of the compound (a3) containing an alkylene oxide oxide represented by the above general formula (1), it is usually preferably 2 to 560 mgKOH/g, particularly preferably 10 to 280 mgKOH/g, and further preferably 25~200mg KOH/g. If the hydroxyl value is too small, the temperature resistance of the cured coating film tends to decrease, and if it is too large, the emulsion stability tends to decrease.

The urethane (meth)acrylate-based compound (A) used in the present invention is composed of a polyvalent isocyanate-based compound (a1), a hydroxyl-containing (meth)acrylate-based compound (a2) and an The alkylene-extending compound (a3) reacts to allow the isocyanate group in the polyvalent isocyanate-based compound (a1) to react with the hydroxyl group of the (meth)acrylate-based compound (a2) containing a hydroxyl group and the compound containing an oxyalkylene group The hydroxyl group of (a3) is formed by forming a urethane bond.

For example, when the polyvalent isocyanate-based compound (a1) has two isocyanate groups, one isocyanate group and the hydroxyl group of the alkylene oxide-containing compound (a3) form an urethane bond, and the remaining one isocyanate group and the hydroxyl group-containing The hydroxyl group of the (meth)acrylate-based compound (a2) forms an urethane bond and becomes an urethane (meth)acrylate-based compound. In addition, when the polyvalent isocyanate-based compound (a1) has three isocyanate groups, one isocyanate group and the hydroxyl group of the alkylene oxide-containing compound (a3) (or hydroxyl-containing (meth)acrylate compound (a2)) The urethane bond is formed, and the remaining two isocyanate groups form the urethane bond with the hydroxyl group of the (meth)acrylate-based compound (a2) (or the alkylene oxide-containing compound (a3)) containing hydroxyl groups. Urethane (meth) acrylate compounds.

Examples of the reaction for forming the urethane bond described above include (a) a polyvalent isocyanate-based compound (a1), a hydroxyl-containing (meth)acrylate-based compound (a2), and an oxyalkylene group. The compound (a 3) is added together for the reaction method, (B) the polyvalent isocyanate-based compound (a1) and the hydroxyl-containing (meth)acrylate-based compound (a2) are reacted with the compound containing an alkylene oxide (a3) Reaction method, (C) After reacting the polyvalent isocyanate compound (a1) with the alkylene oxide-containing compound (a3), and reacting with the hydroxyl group-containing (meth)acrylate compound (a2) The method, considering the stability of reaction control and the viewpoint of shortening the manufacturing time, the method (B) above is ideal.

啉(N‐ethylmorph oline)等胺系觸媒；鉍系觸媒等。就鉍系觸媒而言，可舉例如硝酸鉍、溴化鉍、碘化鉍、硫化鉍等無機鉍化合物；二月桂酸二丁基鉍、二月桂酸二辛基鉍等有機鉍化合物；2-乙基己酸鉍鹽、環烷酸鉍鹽、異癸酸鉍鹽、新癸酸鉍鹽、月桂酸鉍鹽、馬來酸鉍鹽、硬脂酸鉍鹽、油酸鉍鹽、亞麻油酸(linoleic acid)鉍鹽、乙酸鉍鹽、雙新癸酸鉍、二水楊酸鉍鹽、二沒食子酸鉍鹽等有機酸鉍鹽等。此等之中，適宜為二月桂酸二丁基錫、1,8-二氮雜雙環[5,4,0]十一烯。In the production of the urethane (meth)acrylate compound (A), a catalyst is preferably used for the purpose of accelerating the reaction. Examples of the catalyst include dibutyltin dilaurate and trimethyltin hydroxide , Tetra-n-butyl tin and other organic metal compounds, tin octoate, zinc octoenoate, tin octoenoate, cobalt naphthenate, tin (II), tin (IV) and other metal salts; triethylamine, benzyl Diethylamine, 1,4-diazabicyclo[2,2,2]octane, 1,8-diazabicyclo[5,4,0]undecene, N,N,N',N' -Tetramethyl-1,3-butanediamine, N-ethyl

Amine catalysts such as N-ethylmorpholine; bismuth catalysts. Examples of bismuth catalysts include inorganic bismuth compounds such as bismuth nitrate, bismuth bromide, bismuth iodide, and bismuth sulfide; organic bismuth compounds such as dibutyl bismuth dilaurate and dioctyl bismuth dilaurate; 2 -Bismuth ethylhexanoate, bismuth naphthenate, bismuth isodecanoate, bismuth neodecanoate, bismuth laurate, bismuth maleate, bismuth stearate, bismuth oleate, linseed oil Bismuth salts of acid (linoleic acid), bismuth acetate, bismuth neodecanoate, bismuth disalicylate, bismuth digallate, and other organic acid bismuth salts. Among these, dibutyltin dilaurate and 1,8-diazabicyclo[5,4,0]undecene are suitable.

In addition, the reaction temperature is usually 30 to 90°C, preferably 40 to 80°C, and the reaction time is usually 2 to 10 hours, preferably 3 to 8 hours.

The weight average molecular weight of the urethane (meth)acrylate compound (A) is usually 500 to 50,000, particularly preferably 750 to 20,000, and further preferably 1,000 to 10,000. If the weight average molecular weight is too small, the cured coating film tends to become brittle, and if it is too large, the viscosity becomes high and the operation is difficult, and the hardness of the cured coating film tends to decrease.

Among them, the weight average molecular weight is the weight average molecular weight converted from the standard polystyrene molecular weight, and it is connected to three columns in series by using a high-performance liquid chromatography (Showa Denko KK, "Shodex GPC system-11 type") : Shodex GPC KF-806L (exclude limit molecular weight: 2×10 ⁷ , separation range: 100~2×10 ⁷ , theoretical number of layers: 10,000 layers/branch, filler material: styrene-divinylbenzene copolymer, filled Agent particle size: 10 μm).

In addition, for the viscosity of the urethane (meth)acrylate compound (A), the viscosity at 60°C is preferably 200 to 20,000 mPa･s, especially preferably 350 to 5,000 mPa･s, and further preferably 500 to 3,000 mPa･s. If the viscosity is too high, it tends to be difficult to uniformly disperse into the aqueous medium, and if it is too low, the self-emulsifying performance is low, and the solution tends to separate easily. Among them, the viscosity is measured by an E-type viscometer.

The sum of the contents of the urethane (meth)acrylate-based compound (A) and ethylene oxide modified trimethylolpropane tri(meth)acrylate (B) (other than (B)) When the ethylenically unsaturated monomer (E) is the sum of the contents of (A), (B) and (E)), the content of ethyl urethane (meth)acrylate compound (A) is It is preferably 5 to 55% by weight, particularly preferably 15 to 50% by weight, and further preferably 23 to 45% by weight. If the content is too small, the stability of the emulsion tends to decrease, and if it is too large, the temperature resistance of the coating film tends to decrease.

For the ethylene oxide-modified trimethylolpropane tri(meth)acrylate (B) used in the present invention, for example, ethoxylated trimethylolpropane triacrylate can be used. For example, new Nakamura Chemical Industry Co., Ltd. "A-TMPT-3EO", "A-TMPT-9EO", "AT-20E", "AT-30E", BASF Japan Co., Ltd. "Laromer LR-8863", Sartomer "SR-454", "SR499", "SR502" and other commercially available products.

The content of ethylene oxide-modified trimethylolpropane tri(meth)acrylate (B) relative to 100 parts by weight of the urethane (meth)acrylate compound (A) is preferably 40 ~1,500 parts by weight, more preferably 50~1,300 parts by weight, further preferably 60~330 parts by weight, especially preferably 90~220 parts by weight. If the content is too small, the adhesion of the hardened coating film tends to decrease, and if it is too large, the coating film tends to become brittle.

It is preferable that the active energy ray-curable resin composition of the present invention contains a photopolymerization initiator (C) by which the active energy ray is irradiated to initiate polymerization, from the viewpoint of promoting curing when the active energy ray is irradiated. The time point of adding the photopolymerization initiator (C) is not particularly limited, and may be added before the active energy ray-curable resin composition is dispersed in water, or may be added after the active energy ray-curable resin composition is dispersed in water. .

啉基(4-硫代甲基苯基)丙烷-1-酮、2-芐基-2-二甲胺基-1-(4-

啉基苯基)丁酮、2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙酮寡聚物等苯乙酮類；安息香(benzoin)、安息香甲醚、安息香乙醚、安息香異丙醚、安息香異丁醚等安息香類；二苯基酮、鄰苯甲醯基安息香酸甲酯、4-苯基二苯基酮、4-苯甲醯基-4’-甲基-二苯基硫、3,3’,4,4’-四(第三丁基過氧羰基)二苯基酮、2,4,6-三甲基二苯基酮、4-苯甲醯基-N,N-二甲基-N-[2-(1-側氧基-2-丙烯氧基)乙基]苯甲基溴化銨、(4-苯甲醯基苄基)三甲基氯化銨等二苯基酮類；2-異丙基噻吨酮(thioxant hone)、4-異丙基噻吨酮、2,4-二乙基噻吨酮、2,4-二氯噻吨酮、1-氯-4-丙氧基噻吨酮、2-(3-二甲胺基-2-羥基)-3,4-二甲基-9H-噻吨酮-9-酮內消旋氯化物(meso chloride)等噻吨酮類；2,4,6-三甲基苯甲醯基-二苯基氧化膦、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基-戊基氧化膦、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦等醯基氧化膦類等。其中，此等光聚合起始劑(C)，可僅單獨使用1種，也可併用2種以上。Examples of the photopolymerization initiator (C) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal , 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-

Porphyrin (4-thiomethylphenyl) propane-1-one, 2-benzyl-2-dimethylamino-1-(4-

Phenylphenyl) butanone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl] acetone oligomers such as acetophenone; benzoin, benzoin A Ether, benzoin ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin; diphenyl ketone, o-benzoyl benzoic acid methyl ester, 4-phenyl diphenyl ketone, 4-benzoyl acetyl-4 '-Methyl-diphenyl sulfide, 3,3',4,4'-tetra (third butyl peroxycarbonyl) diphenyl ketone, 2,4,6-trimethyl diphenyl ketone, 4 -Benzyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl] benzyl ammonium bromide, (4-benzylbenzyl Base) trimethyl ammonium chloride and other diphenyl ketones; 2-isopropyl thioxant hone (thioxant hone), 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2, 4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl-9H-thioxanthone- 9-keto meso chloride and other thioxanthones; 2,4,6-trimethylbenzyl-diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl) (Acyl)-2,4,4-trimethyl-pentylphosphine oxide, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide, etc. Among them, these photopolymerization initiators (C) may be used alone or in combination of two or more.

Among these, acetophenones and diphenyl ketones are preferably used, especially benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoyl isopropyl ether, 4-(2 -Hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 2-hydroxy-2-methyl-1-phenylpropan-1-one.

In addition, for these additives, triethanolamine, triisopropanolamine, 4,4'-dimethylaminodiphenyl ketone (Michler's ketone), 4,4'-diethylamine can also be used in combination Diphenyl ketone, 2-dimethylaminoethyl benzoic acid, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid (n-butoxy) ethyl ester, 4-dimethylamine Isoamyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, etc.

In the present invention, from the viewpoint of further exerting a function as a composition of an aqueous dispersion liquid, it is also preferable to use a water-soluble or water-dispersible photopolymerization initiator (C), for example 2-(3-dimethylamino-2-hydroxypropoxy)-3,4-dimethyl-9H-thioxanthone-9-one methyl chloride (methochlorid e) (manufactured by Octel Chemicals, "Quantacure QTX"), or 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one (manufactured by BASF, "Irgacure 2959"), A mixture of 1-hydroxy-cyclohexyl-phenyl-ketone and diphenyl ketone ("Irgacure 500" manufactured by BASF), bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide (Manufactured by BASF, "Irgacure 819") and other photopolymerization initiators. Among them, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one (manufactured by BASF, "Irgacure 2959"), 1- A water-soluble or water-dispersible photopolymerization initiator for a mixture of hydroxy-cyclohexyl-phenyl-ketone and diphenyl ketone (manufactured by BASF, "Irgacure 500").

100 parts by weight relative to the total of (A) and (B) components (total of (A), (B), (D) and (E) components when containing the following components (D) and (E)), The use amount of the photopolymerization initiator (C) is preferably 1 to 10 parts by weight, particularly preferably 1 to 8 parts by weight, and further preferably 2 to 6 parts by weight. If the amount is too small, the curing speed due to irradiation of active energy rays such as ultraviolet rays becomes extremely slow, and the intended cured coating film tends not to be obtained. If the amount is too large, the hardenability will not be improved, and it will become the cause of the yellowing of the cured coating film.

In addition, the active energy ray-curable resin composition of the present invention may contain ethyl urethane (meth)acrylate compound (A) other than ethyl urethane (meth)acrylate compound (A) within a range that does not impair the effects of the present invention ( Ethylene unsaturated monomer (E) other than meth)acrylate-based compound (D) and ethylene oxide-modified trimethylolpropane tri(meth)acrylate (B).

Examples of the urethane (meth)acrylate compound (D) other than the urethane (meth)acrylate compound (A) include the polyvalent isocyanate compound (d1) and Ethyl urethane (meth)acrylate compound (D1) obtained by reaction of (meth)acrylate compound (d2) of hydroxyl group, or polyvalent isocyanate compound (d1), ) The urethane (meth)acrylate compound (D2) obtained by reacting the acrylate compound (d2) and the polyol compound (d3). In the present invention, the viewpoint of improving the hardness of the coating film is not It is desirable to contain the urethane (meth)acrylate compound (D1) within the range that hinders the adhesion of the cured coating film. Among them, the urethane (meth)acrylate-based compound (D) may be used alone or in combination of two or more.

As for the polyvalent isocyanate-based compound (d1), the same as the above (a1) can be exemplified. From the viewpoint of less yellowing of the cured coating film or less curing shrinkage, it is preferable to use an alicyclic polyvalent isocyanate compound, especially Isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, and 1,3-bis(isocyanatomethyl)cyclohexane are suitable.

As for the above-mentioned hydroxyl group-containing (meth)acrylate-based compound (d2), the same ones as the above (a2) can be exemplified.

The above-mentioned polyol compound (d3) may be, for example, a compound containing two or more hydroxyl groups, and examples thereof include aliphatic polyols, alicyclic polyols, polyether polyols, and polyester polyols. Polycarbonate polyol, polyolefin polyol, polybutadiene polyol, polyisoprene polyol, (meth)acrylic polyol, polysiloxane polyol, etc.

Among these, from the viewpoint of cost, aliphatic polyols and alicyclic polyols are preferably used, and from the viewpoint of versatility, polyester polyols, polyether polyols, and polycarbonate polyols are preferably used.

The urethane (meth)acrylate-based compound (D) can be produced by reacting the components as described above by a conventional reaction method. Generally, in the case of the above-mentioned urethane (meth)acrylate-based compound (D1), the polyvalent isocyanate-based compound (d1) and the hydroxyl-containing (meth)acrylate-based compound (d2) may be used together or separately Don't add it to the reactor to carry out the urethane reaction by a conventional reaction method to produce ethyl urethane (meth)acrylate compound (D1). In addition, in the case of the above urethane (meth)acrylate-based compound (D2), it may be more than the polyvalent isocyanate-based compound (d1) and the hydroxyl-containing (meth)acrylate-based compound (d2). Polyol-based compound (d3) is added to the reactor together or separately, and the urethane (meth)acrylate-based compound (D2) is produced by performing a urethane reaction by a conventional reaction method. In the method of producing a reaction product obtained by reacting a polyol-based compound (d3) and a polyvalent isocyanate-based compound (d1) in advance, a (meth)acrylate-based compound (d2) containing a hydroxyl group, It is effective for the stability of the urethane reaction or the reduction of by-products.

In the above urethane reaction, by stopping the reaction when the content of the remaining isocyanate groups in the reaction system becomes 0.5% by weight or less, an urethane (meth)acrylate compound can be obtained (D).

In addition, in the above urethane reaction, it is preferable to use a catalyst for the purpose of promoting the reaction, and for the catalyst, it is preferable to use the catalyst used in the production of the above urethane (meth)acrylate (A) Those with the same catalyst.

In the urethane reaction, organic solvents that do not have functional groups that react with isocyanate groups can be used, such as ethyl acetate, butyl acetate and other esters, methyl ethyl ketone, methyl isobutyl ketone and other ketones; toluene, di Organic solvents such as aromatics such as toluene.

In addition, the reaction temperature is usually 30 to 90°C, preferably 40 to 80°C, and the reaction time is usually 2 to 10 hours, preferably 3 to 8 hours.

In the present invention, considering the viewpoint of high cross-linking density and higher hardness of the cured coating film, the urethane (meth)acrylate-based compound (D) preferably has 2 to 20 ethylenically unsaturated groups, and particularly preferably There are 3 to 18, further preferably 5 to 15. If the number of ethylenically unsaturated groups is too large, the cross-linking density after curing becomes too high, because the shrinkage of curing becomes large and the adhesiveness tends to decrease. If it is too small, sufficient cross-linking density cannot be obtained, and hard coating cannot be expected. The tendency of the hardness of the film to increase.

In the present invention, the weight average molecular weight of the urethane (meth)acrylate compound (D) is preferably 500 to 30,000, particularly preferably 1,000 to 20,000, and further preferably 1,500 to 10,000. Especially for the urethane (meth)acrylate compound (D), when the urethane (meth)acrylate compound (D1) is used, the weight average molecular weight is preferably 500 to 10,000 , More preferably 800~8,000, further preferably 1,000~5,000, especially preferably 1,200~3,500. If the weight average molecular weight is too high, the viscosity of the composition tends to be high, and water dispersion tends to be difficult. If the weight average molecular weight is too low, although the crosslink density becomes relatively high, the hardness of the cured coating film tends not to increase. .

However, the above-mentioned weight average molecular weight is a weight average molecular weight converted from the molecular weight of polystyrene, and can be measured by the same method as described above.

In the present invention, the viscosity of the urethane (meth)acrylate compound (D) at 60°C is preferably 200 to 30,000 mPa･s, and particularly preferably 500 to 15,000 mPa･s. When the viscosity is outside the above range, the dispersibility of the aqueous medium tends to decrease. Among them, the viscosity is measured by an E-type viscometer.

When the active energy ray-curable resin composition of the present invention contains the urethane (meth)acrylate-based compound (D), the weight of the urethane (meth)acrylate-based compound (A) is 100 weight Parts, the content of the urethane (meth)acrylate compound (D) is preferably 30 parts by weight or less, more preferably 25 parts by weight or less, further preferably 20 parts by weight or less, and particularly preferably 10 parts by weight or less. If the content is too large, it is difficult to emulsify and disperse, or the stability of the solution decreases, which tends to hinder the adhesion.

In the present invention, it may contain (B) in addition to ethylene oxide-modified trimethylolpropane tri(meth)acrylate (B) to the extent that it does not hinder the adhesion of the coating film or the stability of the solution of the aqueous solution. ) Other than ethylenically unsaturated monomer (E).

啉、2-羥基乙基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-乙烯基吡咯啶酮、2-乙烯基吡啶、2-(甲基)丙烯醯氧基乙基酸式磷酸單酯等。Examples of the ethylenically unsaturated monomer (E) include monofunctional monomers, bifunctional monomers, and trifunctional or higher monomers. Examples of monofunctional monomers include styrene, vinyl toluene, chlorostyrene, α-methylstyrene, methyl (meth)acrylate, ethyl (meth)acrylate, and (meth)acrylic acid. Nitrile, vinyl acetate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, phenoxyethyl (meth)acrylate, (Meth)acrylic acid 2-phenoxy-2-hydroxypropyl ester, (meth)acrylic acid 2-hydroxy-3-phenoxypropyl ester, (meth)acrylic acid 3-chloro-2-hydroxypropyl ester, glycerin Mono(meth)acrylate, glycidyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tri (meth)acrylate Cyclodecyl, dicyclopentenyl (meth)acrylate, n-butyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, (meth) Based) nonyl acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, n-stearyl (meth)acrylate, benzyl (meth)acrylate, Phenol ethylene oxide modified (meth)acrylate, nonylphenol propylene oxide modified (meth)acrylate, 2-(meth)acryloxy-2-hydroxypropylphthalic acid Half esters of phthalic acid derivatives such as esters (meth)acrylate, furfuryl (meth)acrylate, carbitol (meth)acrylate, benzyl (meth)acrylate, butyl (meth)acrylate Oxyethyl, allyl (meth)acrylate, (meth)acryloyl

Porphyrin, 2-hydroxyethyl(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylpyrrolidone, 2-vinylpyridine, 2-(meth)acrylamide Oxyethyl ethyl phosphate monoester, etc.

In addition to the above, a Michael addition product of (meth)acrylic acid or a 2-(meth)acryloyloxyethyl dicarboxylic acid monoester may also be mentioned. Examples of the substance include acrylic acid dimer, methacrylic acid dimer, acrylic acid trimer, methacrylic acid trimer, acrylic acid tetramer, and methacrylic acid tetramer. In addition, examples of the 2-propenyl oxyethyl dicarboxylic acid monoester which is a carboxylic acid having a specific substituent include 2-propenyl oxyethyl succinic acid monoester, 2-methacrylic acid Acetyloxyethyl succinic acid monoester, 2-propenyl acetyl ethyl phthalate monoester, 2-methacrylic acetyl ethyl phthalate monoester, 2-propenyl acetyl ethyl Hexahydrophthalic acid monoester, 2-methacryloxyethyl hexahydrophthalic acid monoester, etc. Furthermore, oligoester acrylate is also mentioned.

Examples of bifunctional monomers include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and 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-hexane Glycol di(meth)acrylate, 1,6-hexanediol ethylene oxide-modified di(meth)acrylate, glycerol di(meth)acrylate, neopentaerythritol di(meth)acrylic acid Ester, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl phthalate di(meth)acrylate Base) acrylate, hydroxytrimethyl acetic acid modified neopentyl glycol di (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate, 2- (meth) acrylic Acetyloxyethyl acid phosphate diester, etc.

Examples of the trifunctional or higher monomers include trimethylolpropane tri(meth)acrylate, neopentyl tetraol (meth)acrylate, neopentyl tetraol (meth)acrylate, Dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri(meth)acryloyloxyethoxytrimethylolpropane, glycerol polyglycidyl Ether poly(meth)acrylate, isocyanuric acid ethylene oxide modified tri(meth)acrylate, ethylene oxide modified dipentaerythritol penta(meth)acrylate, ethylene oxide Alkyl modified dipentaerythritol hexa(meth)acrylate, ethylene oxide modified neopentaerythritol tri(meth)acrylate, ethylene oxide modified neopentaerythritol tetra(meth)acrylic acid Ester, caprolactone modified dipentaerythritol penta(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, caprolactone modified neopentaerythritol tri(meth) Base) acrylate, caprolactone modified neopentyl alcohol tetra (meth) acrylate, succinic acid modified neopentyl alcohol tri (meth) acrylate, etc.

These ethylenically unsaturated monomers (E) may be used alone or in combination of two or more. In addition, the ethylenically unsaturated monomer (E) may be additionally blended with the active energy ray-curable resin composition of the present invention, or it may be an urethane (meth)acrylate-based compound (A) or The raw material for manufacturing the urethane (meth) acrylate compound (D) partially remains in the system during manufacturing.

When the active energy ray-curable resin composition of the present invention contains an ethylenically unsaturated monomer (E), the ethylenically unsaturated monomer relative to 100 parts by weight of the urethane (meth)acrylate compound (A) The content of the body (E) is preferably 60 parts by weight or less, particularly preferably 55 parts by weight or less, and further preferably 50 parts by weight or less. If the content is too large, it is difficult to emulsify and disperse, and the stability of the solution tends to decrease.

In addition, in the active energy ray-curable resin composition of the present invention, an adhesion-imparting agent, a UV absorber, an organic filler plasticizer, an inorganic filler plasticizer, a preservative, an antifungal agent, and a dispersant can also be appropriately blended. , Wetting agent stabilizer, defoamer, leveling agent, shake-imparting agent, antioxidant, flame retardant, antistatic agent, strengthening agent, matting agent, crosslinking agent, rust inhibitor, freeze-thaw stabilizer, pigment , Colorants, tackifiers, etc.

Furthermore, conventionally known emulsifiers such as surfactants without a polymerizable unsaturated group and reactive surfactants with one polymerizable unsaturated group may be used in combination as appropriate.

By blending the above urethane (meth)acrylate compound (A) and ethylene oxide-modified trimethylolpropane tri(meth)acrylate (B) in this way, it is more preferable By blending the photopolymerization initiator (C), the active energy ray-curable resin composition of the present invention can be obtained.

[Active energy ray-curable emulsion composition] By containing the above-mentioned ethyl urethane (meth)acrylate-based compound (A) and ethylene oxide modified trimethylolpropane tri(meth)acrylic acid The active energy ray-curable resin composition of the ester (B) is dispersed in an aqueous medium to obtain the active energy ray-curable emulsion composition of the present invention, which can be used as the coating agent composition of the present invention.

For the aqueous medium, water can be used, and it can also be used in a mixed solvent in which lower alcohols and the like are mixed in water within a range that does not impair the form of the emulsion of the present invention.

Examples of the method for producing the active energy ray-curable emulsion composition of the present invention include the following methods (1) to (4). (1) Add ethyl urethane (meth)acrylate compound (A), ethylene oxide modified trimethylolpropane tri(meth)acrylate (B) and aqueous medium, and add them together as needed Photopolymerization initiator (C), urethane (meth)acrylate compound (D) or ethylenically unsaturated monomer (E), usually at 30~70℃, preferably 50~65℃ Stirring method; (2) After the urethane (meth)acrylate compound (A) and ethylene oxide modified trimethylolpropane tri(meth)acrylate (B) With photopolymerization initiator (C), urethane (meth)acrylate compound (D) or ethylenically unsaturated monomer (E) at 40~65℃, preferably 55~60℃ Method of mixing and adding aqueous medium dropwise with stirring; (3) Modification of trimethylolpropane tri(meth)acrylate (B) with ethylene oxide, more suitable for photopolymerization initiators as required ( C), urethane (meth)acrylate compound (D) or ethylenically unsaturated monomer (E), heated to usually 40 ~ 43 ℃, preferably 55 ~ 65 ℃, dropwise as interface activity The method of stirring the urethane (meth)acrylate compound (A) dispersed in water as an agent and stirring; (4) The urethane (meth)acrylate compound dispersed in water In (A), a method of adding ethylene oxide-modified trimethylolpropane tri(meth)acrylate (B) dropwise at room temperature and usually stirring at room temperature to 40°C. The method for producing the active energy ray-curable emulsion composition of the present invention is not limited to such methods. In addition, in any method, when the photopolymerization initiator (C) is used, it is preferable to perform the mixing operation under light shielding or a light source where the photopolymerization initiator does not cause cracking.

From the viewpoint of the operability of coating, the concentration of nonvolatile components of the obtained active energy ray-curable emulsion composition is preferably 10 to 80% by weight, particularly preferably 15 to 70% by weight, and further preferably 20 to 65% by weight . If the concentration of the non-volatile component is too low, there is a tendency to cause eye holes in the substrate during coating, and if it is too high, the fluidity tends to be low, and the coating tends to be difficult.

For the particles of the active energy ray-curable emulsion composition obtained, the average particle size is preferably 1 to 1,000 nm, more preferably 10 to 800 nm, and further preferably 20 to 600 nm. If the average particle size is too small, the viscosity of the active energy ray-curable emulsion composition tends to increase and the operation becomes difficult, and if it is too large, aggregation tends to occur and the stability of the emulsion tends to decrease. Among them, the average particle diameter is obtained by the following method. 0.1g of the emulsion composition was added dropwise in 500g of water, stirred and dispersed to prepare a sample for evaluation, using "NICOMP380" manufactured by Particle Sizing Systems, and the average particle size at 23°C was determined by the Volume-Wt NICOMP DISTRIBUTI ON mode .

Further, in terms of the viscosity of the active energy ray-curable emulsion composition, it is preferably 1 to 5,000 mPa･s (20°C), particularly preferably 2 to 2,500 mPa･s (20°C), and further preferably 4 to 1,500 mPa･s(20℃). If the viscosity is too low, the film thickness tends to be difficult to control, and if it is too high, the operation becomes difficult, and the coating workability tends to decrease. However, the viscosity is measured by a B-type viscometer.

[Coating agent composition] In this way, the active energy ray-curable emulsion composition used in the present invention is obtained, and the emulsion composition is used for a curable resin composition for forming a coating film on various substrates ( The coating agent composition) can be effectively used as, for example, a coating agent for a top coat and an anchor coating agent for various substrates. For example, after the active energy ray-curable emulsion composition is applied to the substrate and dried, the coating film is cured by irradiating the active energy ray to form a cured coating film on the substrate. The coating method is not particularly limited, and examples thereof include wet coating methods such as spraying, showering, dipping, roll, rotary, and screen printing.

Examples of various substrates include moldings made of polyolefin resins such as polyethylene, polypropylene, and polycyclopentadiene, polycarbonate, polyester, ABS resin, acrylic resin, metal, glass, etc. Products (films, sheets, cups, etc.).

For active energy rays, for example, far-ultraviolet, ultraviolet, near-ultraviolet, and infrared rays, electromagnetic waves such as X-rays, and gamma rays, electron beams, proton rays, and neutron rays can also be used. The ease of obtaining the device, the price, etc., are more advantageous for curing by ultraviolet irradiation. Among them, when irradiated with electron beams, it can be hardened without using a photopolymerization initiator (C).

As a method of curing by ultraviolet irradiation, a light source that emits light in a wavelength range of 150 to 450 nm, such as a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a metal halogen lamp, a xenon lamp, and a chemical lamp, can be cited , LED lights, etc., usually irradiated at a level of 100~3,000mJ/cm ² . After ultraviolet irradiation, it can also be heated according to requirements to achieve complete hardening. [Example]

The present invention will be described in more detail below with reference to examples. The present invention is not limited to the following examples without exceeding the gist. Among them, "parts" and "%" in the examples are the meaning of weight basis unless otherwise specified.

[Manufacture of urethane (meth)acrylate compound (A)] In a 4-neck flask equipped with a thermometer, stirrer and water-cooled condenser, isophorone diisocyanate (a1) (isocyanate group content 37.8%) 94.1 was added g (0.42 mol) and 2,6-bis(tertiary butyl) cresol 2.0g, dibutyl tin dilaurate 0.02g, dipentaerythritol pentaacrylate is added dropwise at 60°C for about 2 hours (a2) (0.51 mol) (added as a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value 50.0 mgKOH/g) 569.8g), react at 60°C for 2 hours . At the time when the remaining isocyanate group became 2.1%, polyethylene glycol (a3) (weight average molecular weight 993.1, ethylene oxide addition mole number 22, hydroxyl value 113mgKOH/g) 336.2g was further added at 55°C ( 0.34 mol), react at 60°C for 4 hours, and stop the reaction when the remaining isocyanate group becomes 0.3% to obtain a resin composition containing urethane acrylate (A-1) (resin component concentration 100%) . The composition obtained by the above preparation contains ethyl urethane (A-1) 69.4%, ethylenically unsaturated monomer (E-1) (dipentaerythritol pentaacrylate and dipentaerythritol Hexaacrylate mixture) 30.6%, and the weight average molecular weight is 2,500.

For ethylene oxide modified trimethylolpropane tri(meth)acrylate (B), the following were prepared. ･(B-1) Ethoxylated trimethylolpropane triacrylate (manufactured by BASF Japan Co., Ltd., "Laromer LR-8863")

For the photopolymerization initiator (C), the following are prepared. ･(C-1) A mixture of 1-hydroxy-cyclohexyl-phenyl-ketone and diphenyl ketone (manufactured by BASF, "Irgacure 500")

<Example 1> Preparation of an active energy ray-curable resin composition comprising: a resin composition containing 144.1 parts of urethane acrylate (A-1) obtained in the above manner (urethane acrylate acrylic) 100 parts of ester (A-1), 44.1 parts of ethylenically unsaturated compound (E-1)), and 1296.8 parts of ethoxylated trimethylolpropane triacrylate (B-1). The active energy ray-curable resin composition prepared in the above manner was stirred and mixed at 60°C to form a uniform resin solution. While maintaining the state of continuous stirring at 60°C, 1440.9 parts of ion-exchanged water was added dropwise to obtain an emulsified dispersion. Return the obtained emulsified dispersion to room temperature, add 57.6 parts of the photopolymerization initiator (C-1) and leveling agent (produced by Kyoeisha Chemical Co., Ltd., "POLYFLOW KL260"), and uniformly mix them. An active energy ray-curable emulsion composition (nonvolatile component concentration 50%) was obtained.

<Examples 2 to 5> The blending amount of each component is the same as in Table 1, and an active energy ray-curable resin composition was prepared in the same manner as in Example 1, and an active energy ray-curable emulsion composition (non-volatile) was further obtained. Ingredient concentration 50%).

<Comparative Example 1> An active energy ray-curable type was prepared in the same manner as in Example 1 without containing ethoxylated trimethylolpropane triacrylate (B-1), and the blending amount of each component was the same as in Table 1. The resin composition further obtained an active energy ray-curable emulsion composition (nonvolatile content concentration 50%).

啉(KJ Chemicals Corporation製，「ACMO」) ･(E-3)乙氧基化甘油三丙烯酸酯(新中村化學工業(股)製，「A-GLY-20E」) ･(E-4)乙氧基化新戊四醇四丙烯酸酯(新中村化學工業(股)製，「ATM-35E」)<Comparative Examples 2 to 4> Does not contain ethoxylated trimethylolpropane triacrylate (B-1), and further contains the following hydrophilic monomers (E-2) to (E-4) in addition to An active energy ray-curable resin composition was prepared in the same manner as in Example 4 to obtain an active energy ray-curable emulsion composition (nonvolatile component concentration 50%). ･(E-2)Acryloyl

Porphyrin (manufactured by KJ Chemicals Corporation, "ACMO") ･ (E-3) ethoxylated glycerin triacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd., "A-GLY-20E") ･ (E-4) B Oxygenated neopentaerythritol tetraacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd., "ATM-35E")

【Table 1】

The active energy ray-curable emulsion composition obtained above was evaluated as follows. The evaluation results of Examples and Comparative Examples are shown in Table 2.

<Solution stability> The active energy ray-curable emulsion compositions (emulsion dispersions of active energy ray-curable resin compositions) of Examples 1 to 5 and Comparative Examples 1 to 4 obtained above are allowed to stand at room temperature. To visually confirm the appearance after 24 hours. (Evaluation criteria) ○... The separation of the dispersion liquid was not confirmed. ×... The dispersion is separated.

<Coating film adhesion> The active energy ray-curable emulsion composition obtained above was applied to a polycarbonate substrate (manufactured by Nippon Testpanel Co., Ltd.) so that the film thickness after drying would become 25 μm after drying. Standard test board), after drying at 60 ℃ for 10 minutes, using an 80W high-pressure mercury lamp, from the height of 18cm at a conveyor belt speed of 3.4m/min 2 pulses of ultraviolet radiation (cumulative exposure 800mJ/cm ² ) To form a hard coating. For the obtained cured coating film, the adhesion to the coating film of the substrate was evaluated by the checkerboard tape method in accordance with JIS K 5400 (1990 edition). In addition, the appearance of the coating film of the obtained cured coating film was visually observed. (Evaluation criteria) ○... is 100/100 (the coating film still adhered to the base material after the test), and the appearance of the coating film was visually observed to be transparent. △...100/100 (the coating film still adhered to the substrate after the test), but the appearance of the coating film was visually observed to be cloudy. ×...99/100~0/100 (after the test, part of the coating film ~ all peeled off from the substrate).

<Coating film hardness> With respect to the cured coating film obtained above, the pencil hardness was measured in accordance with JIS K 5600-5-4. (Evaluation Criteria) ○…HB or more ×…Not up to HB

<Temperature and water resistance> [Coating film adhesion] For the above-mentioned 100/100 in the evaluation of the usual coating film adhesion, after immersing in purified water kept at 80 ℃ for 1 hour, borrow in accordance with JIS K 5400 (1990 version) The adhesion of the coating film to the substrate was evaluated by the checkerboard tape method. Among them, the evaluation of the adhesion of the coating film after the immersion in warm water was carried out immediately after the cured coating film was taken out from the warm water and one hour after the removal. In addition, the appearance of the coating film after immersion in warm water was visually observed. (Evaluation criteria) ○... is 100/100 (the coating film still adhered to the base material after the test), and the appearance of the coating film was visually observed to be transparent. △...100/100 (the coating film still adhered to the substrate after the test), but the appearance of the coating film was visually observed to be cloudy. ×...99/100~0/100 (after the test, part of the coating film ~ all peeled from the substrate).

【Table 2】

啉、具有親水骨架之甘油三丙烯酸酯之環氧乙烷加成物、新戊四醇之環氧乙烷加成物來替代環氧乙烷改性三羥甲基丙烷三(甲基)丙烯酸酯(B)之比較例2~4的活性能量射線硬化型樹脂組成物構成之活性能量射線硬化型乳化液組成物，係溶液安定性、形成為硬化塗膜時之平時的塗膜黏合性、塗膜硬度、耐溫水性中之任一者為低劣，無法滿足全部要求者。 [產業上利用性]Based on the above results, the active energy ray-curable resin composition described in Examples 1 to 5 has a self-emulsifying composition, and the emulsion composition system has excellent stability of the solution, and the coating film hardness when formed into a cured coating film The better. In particular, in Examples 3 to 5, it was found that it was excellent in either of the coating film adhesion to the usual substrate and the temperature resistance (temperature of the coating film after immersion in warm water, coating film appearance). In addition, in Examples 1 and 2, although the appearance of the coating film after immersion in warm water was observed to be turbid, it is still known that it is excellent in the adhesion to the coating film of the usual substrate and the adhesion of the coating film after the immersion in warm water By. On the other hand, the active energy ray-curable resin of Comparative Example 1 modified by ethylene oxide that does not contain an ethylenically unsaturated compound having a specific structure (B) The active energy ray-curable emulsion resin composition composed of the composition is formed into a cured coating film, and the adhesiveness to the coating film of the base material cannot be obtained even at ordinary times. In addition, acryl groups containing monomers that are hydrophilic

Ethylene oxide adducts of glycerol triacrylate with hydrophilic skeleton and ethylene oxide adducts of neopentyl alcohol to replace ethylene oxide modified trimethylolpropane tri(meth)acrylic acid The active energy ray-curable emulsion composition composed of the active energy ray-curable resin composition of Comparative Examples 2 to 4 of the ester (B) is the stability of the solution, the usual coating film adhesion when formed into a cured coating film, Any one of coating film hardness and temperature resistance is inferior, and cannot meet all requirements. [Industry availability]

The active energy ray-curable resin composition of the present invention has excellent self-emulsifying property with respect to an aqueous medium, and has excellent solution stability when emulsified and dispersed in an aqueous medium. In addition, the coating film formed on the substrate and hardened is excellent in hardness and temperature resistance, because even after immersion in warm water, it is difficult to cause deterioration of the coating film appearance such as whitening or the reduction of adhesion performance. Coating materials, such as paints, adhesives, adhesives, adhesives, printing inks, protective coating agents, anchor coating agents, hard coating agents, magnetic powder coating adhesives, sandblasting coatings, plates , Coating agent for optical film surface coating, metal deposition or sputtering film, coating agent for glass modification, etc. are very useful.

Claims (3)

An active energy ray-curable resin composition characterized by containing an urethane (meth)acrylate compound (A) and ethylene oxide-modified trimethylolpropane tri(meth)acrylate ( B), and the ethylenically unsaturated monomer (E) other than the ethylene oxide-modified trimethylolpropane tri(meth)acrylate (B); relative to the urethane (meth)acrylic acid 100 parts by weight of the ester compound (A), the content of the ethylene oxide modified trimethylolpropane tri(meth)acrylate (B) is 40 to 1500 parts by weight, the ethylenically unsaturated monomer (E ) Is less than 60 parts by weight; the urethane (meth)acrylate compound (A) is a polyvalent isocyanate compound (a1), and the isocyanate group in the compound (a1) is different from the hydroxyl group-containing (meth)acrylic acid The hydroxyl group of the ester compound (a2) and the hydroxyl group of the compound (a3) containing an oxyalkylene group represented by the following general formula (1) are formed by forming an urethane bond;

In the formula, X is an alkylene group having 1 to 10 carbon atoms, Y is any one of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, (meth)acryloyl, allyl, and acyl, n It is an integer of 1 or more. An active energy ray-curable emulsion composition characterized by dispersing an active energy ray-curable resin composition as described in item 1 of a patent application in an aqueous medium. A coating agent composition characterized by dispersing an active energy ray-curable resin composition as described in item 1 of a patent application in an aqueous medium.