JP2002173516A - Actinic energy ray-curable aqueous emulsion composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an actinic energy ray-curable aqueous emulsion composition curing by irradiation with actinic energy ray to form coating film having excellent water resistance, antistatic property and adhesion to a base material. SOLUTION: An actinic energy ray-curable aqueous emulsion composition obtainable by emulsifying a radical-polymerizable monomer and/or oligomer (B) in water by using a polymer (A) having a quaternary ammonium salt group and a (meth)acryloyl group. As the polymer (A), a polymer having further an organopolysiloxane unit can be used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an active energy ray-curable aqueous emulsion composition which is cured by irradiation with an active energy ray to form a film having excellent water resistance, antistatic properties and adhesion to a substrate. About things. Furthermore, the present invention relates to an active energy ray-curable aqueous emulsion composition which forms a film having excellent slipperiness in addition to the above-mentioned properties.

[0002]

2. Description of the Related Art Active energy ray-curable resins are used in a wide range of fields because of their good productivity, low-temperature curability, low pollution due to no solvent or low solvent, and the like. However, even if these resins are used as a coating material, a large amount of a solvent is added for the purpose of viscosity adjustment or the like even though they are solventless and low solvent.

[0003] In recent years, problems of environmental pollution have been pointed out, and it has been increasingly required to further improve the working environment from the viewpoint of safety and health, and technology development has been carried out in consideration of minimizing the amount of organic solvents used. There is a need for a technology, and a shift to so-called aqueous conversion, which uses as little organic solvent as possible, has become a technical problem.

[0004] However, the conventional monomer / oligomer capable of radical polymerization has a problem that the emulsifiability is insufficient when used alone. Therefore, it is conceivable to perform emulsification using an emulsifier such as that used in general water-based paints, for example, polyoxyethylene alkyl phenyl ether, but such an emulsifier is used for polymerization by active energy ray irradiation. Because it does not participate, it is not taken into the polymerization chain of the cured product, it is simply dissolved or finely dispersed in the crosslinked coating film, and as a result, the intended cured product in terms of properties such as water resistance and solvent resistance is obtained. There is a problem that can not be.

[0005] Therefore, as a so-called reactive surfactant in which the emulsifier also has radical polymerizability, for example, a compound having an ethylenically unsaturated double bond and a sulfonate of an alkali metal (JP-A-4-108815; Kaihei 4-
114020) and specific urethane (meth) acrylic prepolymers (JP-A-7-292045, JP-A-8-3
11153), and a combination of polyoxyethylene alkyl phenyl ether (meth) acrylate and bis (polyoxyethylene polycyclic phenyl ether) (meth) acrylated sulfate ester salt (Japanese Patent Application Laid-Open No. 9-136981). ing. However, these conventional reactive surfactants are radically polymerizable monomers /
These are used merely for emulsifying oligomers, and these have not yet become active as a component of a film to impart a function to a cured film.

[0006]

Accordingly, the present invention provides not only a function as an emulsifier for radically polymerizable monomers and oligomers, but also an effect of using a specific polymer.
It is an object of the present invention to provide an active energy ray-curable aqueous emulsion composition in which the polymer itself has a more effective function as a component of the coating.

[0007]

As a result of intensive studies to solve these problems, the present inventors have found that a polymer (A) having a quaternary ammonium base and a (meth) acryloyl group can be used to form a radical An active energy ray-curable aqueous emulsion composition obtained by emulsifying and dispersing a polymerizable monomer and / or oligomer (B) in water is applied to a substrate, dried with moisture, and irradiated with active energy rays. The present inventors have found that a film having excellent water resistance, antistatic property, and adhesion to a substrate is formed, and have completed the present invention.
In the present specification, “(meth) acryloyl group” means “acryloyl group” or “methacryloyl group”. Similarly, “(meth) acrylate” refers to “acrylate” or “methacrylate” as “(meth) acrylate”.
“Acrylic” shall mean “acryl” or “methacryl”.

That is, the gist of the present invention is to provide a polymer (A) having a quaternary ammonium base and a (meth) acryloyl group, a radically polymerizable monomer and / or
Or an active energy ray-curable aqueous emulsion composition obtained by emulsifying and dispersing the oligomer (B) in water. Further, the polymer (A) may further have an organopolysiloxane unit in the molecule. Another gist of the present invention is that (1) a tertiary amine compound (a1) having one radically polymerizable group in one molecule and one radically polymerizable group in one molecule in the presence of an organic solvent. And a compound having a hydroxyl group (a2) are copolymerized into a polymer having a tertiary amine and a hydroxyl group (A1), and (2) the obtained polymer (A1)
To the compound (a3) having a (meth) acryloyl group and an isocyanate group in one molecule to obtain a polymer (A2) having a tertiary amine and a (meth) acryloyl group,
(3) A quaternizing agent (a4) is reacted with the obtained polymer (A2) to form a quaternary ammonium salt group, a solution of the polymer (A) in an organic solvent, a radical polymerizable monomer and / or
Alternatively, there is provided the method for producing an active energy ray-curable aqueous emulsion composition, wherein the organic solvent is distilled off from a mixture of the oligomer (B) and water. Furthermore, another gist of the present invention resides in a coating agent containing the active energy ray-curable aqueous emulsion composition and a photopolymerization initiator. Furthermore, another gist of the present invention resides in a resin film, a resin sheet or paper having a cured film formed by applying the active energy ray-curable aqueous emulsion composition and irradiating the active energy ray.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. First, each component constituting the active energy ray-curable aqueous emulsion composition of the present invention will be described, and then adjustment of the composition will be described.

[0010] Quaternary ammonium base and (meth) acrylo
Polymer (A) having an yl group The polymer (A) is a monomer capable of radical polymerization and / or
Alternatively, the oligomer (B) is emulsified and dispersed in water, cured by irradiation with active energy rays, and at the same time, imparts antistatic properties and adhesion to a substrate to a formed film.

The polymer (A) has a quaternary ammonium base and a (meth) acryloyl group in a side chain bonded to the main chain of the polymer. The main chain of the polymer is formed by radical polymerization of a monomer having a carbon-carbon double bond such as a (meth) acryloyl group, a vinyl group, a styryl group, an allyl group, and a cinnamoyl group. The degree of polymerization of the main chain is as follows:
Has a molecular weight of usually 5000 to 1,000,000, preferably about 10,000 to 500,000. If the amount is less than the above, the properties as a polymer are poor, and the effect is merely a mere emulsifier, and cannot be involved in forming a good film. Further, the polymer (A) may further have an organopolysiloxane unit, an alkoxycarbonyl unit, a hydrocarbon residue and the like in the molecule.

The method for producing the polymer (A) is not limited, but the following method is preferred. That is, (1) a tertiary amine compound having one radical polymerizable group in one molecule (a
1) and a compound (a2) having one radical polymerizable group and a hydroxyl group in one molecule are copolymerized to obtain a polymer (A1) having a tertiary amine and a hydroxyl group. The compound (A3) having a (meth) acryloyl group and an isocyanate group in one molecule is added to the compound (A1) to obtain a polymer (A) having a tertiary amine and a (meth) acryloyl group.
(3) Polymer (A) obtained by reacting the obtained polymer (A2) with a quaternizing agent (a4) to form a quaternary ammonium base is preferred. Hereinafter, in the present invention, the above (1) is referred to as a copolymerization reaction, (2) as an addition reaction, and (3) as a quaternization reaction.

The copolymerization reaction of the above (1) is schematically shown as follows. (A1) is a first precursor of the polymer (A).

[0014]

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As the tertiary amine compound (a1) having one radical polymerizable group in one molecule, a compound having a structure represented by the following general formula (I) is preferable.

[0016]

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(In the formula (I), R ¹ is H or CH ₃ , R ²
And R ³ represent H or an alkyl group having 1 to 9 carbon atoms which may contain a substituent, and k represents an integer of 1 to 6. )

As (a1), for example, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate Examples thereof include N-dimethylaminobutyl (meth) acrylate, N, N-dipropylaminoethyl (meth) acrylate, and N, N-dibutylaminoethyl (meth) acrylate.

Examples of the compound (a2) having one radical polymerizable group and a hydroxyl group in one molecule include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( Examples thereof include (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, and 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalic acid.

When (a1) and (a2) are copolymerized, (a)
The amount of 1) is usually 25 to 99% by weight, preferably 3% by weight.
0 to 95% by weight. If the amount is less than 25% by weight, the resulting polymer (A) will have poor emulsifying and dispersing ability of radically polymerizable monomer / oligomer (B) in water and the antistatic property of the composition obtained by the present invention. The amount of compound (a2) to be used is generally 1 to 40% by weight, preferably 5 to 30% by weight. If the amount is less than 1% by weight, the amount of the (meth) acryloyl group introduced thereafter is reduced, and the curability of the active energy ray is reduced.

The copolymerization of (a1) and (a2) is usually carried out in an organic solvent using a radical polymerization initiator. Examples of the organic solvent include aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate, propyl acetate, butyl acetate and butyl butyrate; acetone, methyl ethyl ketone,
Ketones such as methyl isobutyl ketone and cyclohexanone; ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether and diethylene glycol dimethyl ether; 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 1-methoxy-2- Examples thereof include ether esters such as acetoxypropane, and these can be used as a mixture.

Examples of the radical polymerization initiator include peroxides such as benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, 2,2'-azobisisobutyronitrile, and 2,2'-azobis. −
Azo compounds such as (2,4-dimethylvaleronitrile) and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) are preferably used. The monomer concentration in the polymerization solution is usually 10 to 60% by weight, preferably 15 to 60% by weight.
50% by weight. The polymerization initiator is used in an amount of usually 0.1 to 10% by weight, preferably 0.3 to 2% by weight, based on the monomer mixture.
Used in weight%.

When copolymerizing (a1) and (a2), another polymerizable compound (a5) can be used in addition to these monomers. As such a polymerizable compound (a5),
(Meth) acrylic acid esters can be used. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, Benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, Examples thereof include ethyl carbitol (meth) acrylate, butoxyethyl (meth) acrylate, cyanoethyl (meth) acrylate, and glycidyl (meth) acrylate. Other than (meth) acrylic acid esters, styrene and the like can also be used.

As the other polymerizable compound (a5), an organopolysiloxane compound having one radical polymerizable group in one molecule can be used. In this case, a polymer having an organopolysiloxane unit in addition to a tertiary amino group and a hydroxyl group in the molecule of the polymer (A1) is obtained. Thereby, the slipperiness of the film can be improved. The organopolysiloxane unit preferably has a structure represented by the following general formula (II).

[0025]

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In the formula (II), R ⁴ and R ⁵ may be the same or different and each is a methyl group or a phenyl group, and n represents an integer of 5 or more, preferably 5 to 200.

Here, the organopolysiloxane compound having one radically polymerizable group in one molecule has a unit represented by the general formula (II) wherein (meth) acryloyl, styryl, cinnamoyl (cinnamate), vinyl And those having a structure bonded to allyl or the like. (A1) and (a)
Considering the easiness of copolymerization with 2), an organopolysiloxane compound having an acrylic group, a methacryl group, or a styryl group at the terminal is preferable.

As another polymerizable compound (a5), 1
Organopolysiloxane compounds having two mercapto groups in the molecule can be used. This allows
When (a1) and (a2) are polymerized, an organopolysiloxane unit can be introduced into the polymer (A1) via a sulfide bond by chain transfer.

In the present invention, (a5) is an optional component, and its use amount is usually 0 to
It is 40% by weight, preferably 0 to 30% by weight. By introducing a structural unit derived from (a5) into the polymer (A), the balance between hydrophilicity and hydrophobicity as an emulsifier and physical properties of a coating film can be adjusted. When an organopolysiloxane compound having one radical polymerizable group in one molecule or an organopolysiloxane compound having two mercapto groups in one molecule is used, usually 0.5
-30% by weight, preferably 1-20% by weight. If it is less than the above range, the effect of improving the slipperiness of the coating is not sufficient.

Next, in the addition reaction (2), the compound (a3) having a (meth) acryloyl group and an isocyanate group in one molecule is added to the polymer (A1) obtained in the step (1).
Is added to obtain a polymer (A2) having a tertiary amine and a (meth) acryloyl group.

The addition reaction of the above (2) is schematically shown as follows. (A2) is a second precursor of the polymer (A). n is an integer of 1 to 5.

[0032]

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Examples of (a3) include adducts of a compound having at least one (meth) acryloyl group and a hydroxyl group in one molecule and a diisocyanate compound in a molar ratio of 1: 1. Examples of the compound having at least one (meth) acryloyl group and a hydroxyl group in one molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth)
Examples thereof include (meth) acrylates having a hydroxyl group such as acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalic acid, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate. Among such (meth) acrylates, acrylates are preferable because they have higher reactivity to active energy rays than methacrylates and the curing rate of the finally formed polymer (A) is higher.

Further, as the diisocyanate compound,
Examples thereof include tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, trimethylhexamethylene diisocyanate, and methylcyclohexylene diisocyanate.

In order to produce the above adduct, both a compound having at least one (meth) acryloyl group and a hydroxyl group in one molecule and a diisocyanate compound are used.
First, they are mixed at a molar ratio of 1: 1. The reaction is preferably stirred at 60-110 ° C for 1-20 hours. In this addition reaction, for example, hydroquinone, hydroquinone monomethyl ether, catechol, pt-butyl catechol,
It is preferable to use a polymerization inhibitor such as phenothiazine. The amount of the polymerization inhibitor to be used is generally 0.01 to 1% by weight, preferably 0.05 to 0.5% by weight, based on the reaction mixture. In order to accelerate the addition reaction, a known reaction catalyst such as dibutyltin dilaurate or 1,4-diazabicyclo [2.2.2] octane may be added.

By adding (a3) to the polymer (A1), the hydroxyl group in (A1) has a structure in which all or a part of the hydroxyl group is bonded to a (meth) acryloyl group via a urethane bond. (A2). The polymer (A2) has a tertiary amine and (meth) in the side chain of the polymer.
It is characterized by having both acryloyl groups.

The polymer (A1) and the compound (a3) are represented by —O
H group / -NCO group ≧ 1, preferably 1 to 10 at a ratio. The following reaction is the same as that for producing the compound (a3), and it is preferable to stir at 60 to 110 ° C for 1 to 20 hours. The same applies to the case where a polymerization inhibitor or a reaction catalyst for accelerating the addition reaction can be added.

Next, in the quaternization reaction (3), the polymer (A2) obtained in the addition reaction (2) is reacted with a quaternizing agent (a4) to form a quaternary ammonium base. A polymer (A) having a quaternary ammonium base and a (meth) acryloyl group, which is an object of the present invention, is obtained.

The quaternization reaction of the above (3) is schematically shown as follows.

[0040]

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Examples of the quaternizing agent (a4) include halides such as methyl chloride, butyl chloride, methyl bromide, methylbenzyl chloride, benzyl chloride and methyl monochloroacetate; alkyl sulfates such as dimethyl sulfate, diethyl sulfate and dipropyl sulfate. And sulfonic acid esters such as methyl p-toluenesulfonate and methyl benzenesulfonate.

The reaction between the polymer (A2) and the quaternizing agent (a4) is performed by mixing the tertiary amine in the polymer (A2) and (a4) in an equimolar amount at 20 to 80 ° C. for 1 to 20 hours. It is preferable to carry out by stirring. In carrying out the quaternization reaction, alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol and isobutyl alcohol are used to increase the hydrophilicity of the solvent;
Ethers such as ethoxyethanol, 2-butoxyethanol and propylene glycol monomethyl ether;
It is desirable to add water; or a mixture thereof.

As described above, the method for producing the polymer (A) in which (1) a copolymerization reaction → (2) an addition reaction → (3) a quaternization reaction is carried out in this order has been described. There may be other variations than the ones. For example, in the above-mentioned method, a method of exchanging the reaction of (2) and (3), a method of using a quaternary ammonium monomer instead of a tertiary amine monomer in (1), and the like can be mentioned.

As described in detail above, the polymer (A)
A polymer having a quaternary ammonium salt group and a (meth) acryloyl group, wherein the content of the quaternary ammonium salt group is usually 10 to 10 as a structural unit derived from the polymerizable monomer (a1).
It is 80% by weight, preferably 15 to 70% by weight. This numerical value is obtained by converting the content of the quaternary ammonium base present in the polymer (A) into the monomer (a1),
It is shown by. Further, the content of the (meth) acryloyl group is usually 0.5 to 40% by weight, preferably 1 to 30% by weight as a structural unit derived from the polymerizable monomer (a2). Similarly, this value indicates the content of the (meth) acryloyl group present in the polymer (A) as the monomer (a2)
And expressed in terms of% by weight. The polymer (A) further has an organopolysiloxane unit, if necessary. As a result, the polymer (A) has both self-emulsifiability and energy-ray curability, and gives excellent properties to the formed coating film.

Radical-polymerizable monomers and / or
Is an oligomer (B). The radically polymerizable monomer and / or oligomer constituting the active energy ray-curable aqueous emulsion composition of the present invention may be an aliphatic, alicyclic or aromatic mono- or polyalcohol and (meth) Ester-type (meth) acrylate obtained by a condensation reaction with acrylic acid, urethane (meth) acrylate obtained by a reaction between an isocyanate compound having two or more isocyanate groups in the molecule and a (meth) acrylate having a hydroxyl group, Compound having two or more epoxy groups in the molecule and (meth)
(Meth) such as epoxy (meth) acrylate obtained by glycidyl group ring-opening reaction with acrylic acid, polyester (meth) acrylate obtained by condensation reaction with saturated or unsaturated carboxylic acid, polyhydric alcohol and (meth) acrylic acid ) Acryloyl-functional monomers or oligomers thereof; vinyl compounds such as styrene, chlorostyrene, bromostyrene, dibromostyrene and divinylbenzene; diethylene glycol bisallyl carbonate;
(Meth) allyl compounds such as diallyl phthalate diallyl biphenylate and the like can be mentioned. Among them, ester acrylates, urethane acrylates, and epoxy acrylates having two or more acryloyl groups excellent in curability by active energy rays are preferable.

Preferred examples of the ester type acrylate include ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, propylene glycol diacrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate, and hydroxypivalin. Ester diacrylates having an aliphatic skeleton such as diacrylate of neopentyl glycol acid, 1,6-hexanediol diacrylate, and 1,9-nonanediol diacrylate; bis (4-acryloxycyclohexyl) methane, bis (4-acrylic) Roxyethoxycyclohexyl)
Alicyclic skeleton ester diacrylates such as methane, bis (4-acryloxycyclohexyl) propane, bis (4-acryloxyethoxycyclohexyl) propane, dicyclopentanediacrylate; bis (4-acryloxyethoxyphenyl) methane; Bis (4-acryloxydiethoxyphenyl) methane, 2,2-bis (4-
Acryloxyethoxyphenyl) propane, 2,2-bis (4-acryloxydiethoxyphenyl) propane,
Ester diacrylates having an aromatic skeleton such as bis (4-acryloxyethoxyphenyl) sulfone, bis (4-acryloxydiethoxyphenyl) sulfone; trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ditrimethylol Propane tetraacrylate, dipentaerythritol pentaacrylate,
Examples thereof include polyfunctional acrylates such as dipentaerythritol hexaacrylate and tris (acryloxyethyl) isocyanurate.

Preferred specific examples of urethane acrylate include isocyanate compounds such as tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and the like.
-Hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, caprolactone-modified 2-hydroxyethyl acrylate, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, pentaerythritol Examples thereof include urethane acrylate, which is a reaction product with an acrylate having a hydroxyl group such as triacrylate and dipentaerythritol pentaacrylate.

Preferred examples of the epoxy acrylate include 2,2-bis (4-glycidyloxycyclohexyl) propane, 2,2-bis (4-glycidyloxyphenyl) propane, bisphenol-A-diglycidyl ether, bisphenol- Epoxy acrylate, which is a reaction product of an epoxy compound such as F-diglycidyl ether and bisphenol-S-diglycidyl ether with acrylic acid, may be mentioned.

Optional Component (C) When ultraviolet rays are used as active energy rays for curing the active energy ray-curable aqueous emulsion composition of the present invention, the above polymer (A) and radically polymerizable monomers and / or oligomers (B) ), A photopolymerization initiator is used. As the photopolymerization initiator, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, diethoxyacetophenone, benzyl dimethyl ketal,
2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone, benzophenone, 2,4,6-trimethylbenzoindiphenylphosphine oxide, 2-methyl- [4- (methylthio)
Phenyl] -2-morpholino-1-propanone, 2-
Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, Michler's ketone,
Examples thereof include isoamyl N, N-dimethylaminobenzoate, 2-chlorothioxanthone, and 2,4-diethylthioxanthone, and two or more of these photopolymerization initiators can be used in combination as appropriate. The photopolymerization initiator can be generally added to the composition for forming a coating in an amount of 10% by weight or less, preferably 1 to 5% by weight.

The active energy ray-curable aqueous emulsion composition of the present invention may contain an ultraviolet absorber (for example, a benzotriazole-based, benzophenone-based, salicylic acid-based, or cyanoacrylate-based ultraviolet absorber) for the purpose of improving the film properties. Compounded in this type of composition such as a stabilizer (for example, a hindered amine-based ultraviolet stabilizer), an antioxidant (for example, a phenol-based, sulfur-based, or phosphorus-based antioxidant), an anti-blocking agent, a slip agent, and a leveling agent Various additives in the composition for forming a film, respectively.
2% by weight can be blended.

Aqueous Emulsion Composition The active energy ray-curable aqueous emulsion composition of the present invention uses a polymer (A) having a quaternary ammonium base and a (meth) acryloyl group, and is a monomer and / or an oligomer capable of radical polymerization. It can be adjusted by emulsifying and dispersing (B) and, if necessary, a photopolymerization initiator and other optional components (C) in water. The amount of the polymer (A) used is usually 5 to 95% by weight,
Preferably it is 10 to 90% by weight. If it is less than 5% by weight, a stable emulsion cannot be obtained. If the content exceeds 95% by weight, the curability by irradiation with active energy rays tends to decrease.

Since the polymer (A) is usually synthesized in the presence of an organic solvent, it is obtained in the form of an organic solvent solution. For this purpose, a solution of the polymer (A) in an organic solvent and a radically polymerizable monomer and / or oligomer (B) are mixed and dissolved, and the solvent is distilled off.
Emulsion method using a homogenizer, a mixer, etc., an organic solvent solution of the polymer (A) and a radically polymerizable monomer and / or oligomer (B) are mixed and dissolved, water is added, and a high-speed disper, a homogenizer, a mixer, etc. And then distilling off the solvent, and mixing and dissolving an organic solvent solution of the polymer (A) with a radically polymerizable monomer and / or oligomer (B), and then adding water, followed by stirring. The aqueous emulsion composition can be adjusted by increasing the temperature and distilling off the solvent. By these methods,
An aqueous emulsion composition containing substantially no organic solvent can be prepared. If the organic solvent remains, there is a problem that the organic solvent is released to the environment in the coating film forming process,
Its content is preferably at most 3% by weight.

The proportions of the components (A), (B) and (C) in the aqueous emulsion composition are selected from the following ranges. That is, the polymer (A) having a quaternary ammonium base and a (meth) acryloyl group is usually 3 to 50% by weight, preferably 5 to 40% by weight, and the radically polymerizable monomer and / or oligomer (B) is Usually 1-4
0% by weight, preferably 2 to 30% by weight, optional component (C)
Is used in an amount of about 0 to 2% by weight depending on the purpose. If (A) is less than the above, it is difficult to obtain a stable emulsion, and if (B) is less than the above, the curability by active energy ray irradiation tends to decrease. The water constituting the remainder of the aqueous emulsion composition is usually 40 to 95% by weight, preferably 50 to 90% by weight. Water content is 40% by weight
If it is less than 95%, the resulting aqueous emulsion composition has too high a viscosity to apply, and if it exceeds 95% by weight, a large amount of energy is required when the aqueous emulsion composition is applied to a substrate and dried. .

The aqueous emulsion composition of the present invention can be applied to a substrate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, cellulose acetate, vinyl chloride resin, ABS resin, synthetic paper and paper by dipping, flow coating, or the like. Spray method, bar coating method,
And a coating method using a coating device such as a gravure coat, a roll coat, a blade coat, and an air knife coat, and the cured film has a thickness of 1 to 50 μm, preferably 1 to 50 μm.
Coating is performed so as to be 20 μm. Next, after drying the water, in order to cross-link and cure the applied coating composition layer,
UV rays emitted from a light source such as a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, a tungsten lamp, or
Irradiation with an active energy ray such as an electron beam, α-ray, β-ray, or γ-ray, which is usually taken out from an electron beam accelerator of 20 to 2000 kV, is cured to form a film.

[0055]

EXAMPLES The present invention will be described more specifically with reference to Synthesis Examples and Examples below. Components, ratios, procedures, and the like described in the following synthesis examples and examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited by the specific examples described below. Parts and% described in Synthesis Examples and Examples mean parts by weight and% by weight, respectively.

A quaternary ammonium base and an acryloyl group
Synthesis Example of Polymer (A) Having: (Synthesis Example 1) N, N-dimethylaminoethyl methacrylate 80 parts, 2-hydroxyethyl methacrylate 10
Part, 2-ethylhexyl methacrylate 10 parts and a mixture of 200 parts of methyl ethyl ketone were heated to 80 ° C., and 2 hours after the heating, 0.3 parts each of azobisisobutyronitrile was added. Then 8
The reaction was carried out at 0 ° C. for 8 hours to obtain a copolymer having a solid content of 33%. To this, 26 parts of an adduct obtained by reacting 17 parts of isophorone diisocyanate and 9 parts of 2-hydroxyethyl acrylate at 80 ° C. for 6 hours is added.
A time reaction (confirmed disappearance of isocyanate group absorption at 2250 cm ^{-1 in} infrared absorption spectrum) gave a copolymer solution having a tertiary amine and an acryloyl group and having a solid content of 39%. Next, after adding 200 parts of isopropyl alcohol to the obtained copolymer solution, methyl chloride was introduced into the reaction system and reacted at 50 ° C. for 6 hours, and a polymer having a quaternary ammonium base and an acryloyl group [ I] 548 parts (solid content 27%). The solid content of the polymer [I] is 148 parts. The content of the quaternary ammonium base in the polymer [I] is converted to the content of the monomer, N, N-dimethylaminoethyl methacrylate (a1), which is 54% by weight. . Similarly, the content of the acryloyl group is 7% by weight.

(Synthesis Example 2) A mixture of 40 parts of N, N-dimethylaminoethyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate, 50 parts of methyl methacrylate and 200 parts of methyl ethyl ketone was heated to 80 ° C., and Two hours after the temperature was raised, 0.3 parts of azobisisobutyronitrile was added to each, and 80 ° C.
For 8 hours to obtain a copolymer having a solid content of 33%. A mixture of 22.2 parts of isophorone diisocyanate, pentaerythritol triacrylate and pentaerythritol tetraacrylate (trade name: Biscoat 300, manufactured by Osaka Organic Chemical Industry Co., Ltd., hydroxyl value 131 m)
gKOH / g) of 57.1 parts was reacted at 80 ° C. for 6 hours, and 79.3 parts of an adduct [M] was added, followed by a reaction at 80 ° C. for 6 hours (2250 cm ⁻¹ isocyanate at infrared absorption spectrum). The disappearance of group absorption was confirmed) to obtain a copolymer solution having a tertiary amine and an acryloyl group and having a solid content of 47%. Next, after adding 50 parts of isopropyl alcohol to the obtained copolymer solution, 37.3 parts of diethylsulfuric acid was added, and reacted at 50 ° C. for 6 hours to obtain a polymer having a quaternary ammonium base and an acryloyl group. [II] 471 parts (solid content 46%) were obtained.

(Synthesis Example 3) 60 parts of N, N-dimethylaminoethyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate, an organopolysiloxane compound having a methacryloyl group at one end (trade name: F manufactured by Chisso Corporation)
M0725, number average number molecular weight 10,000) 10 parts, 2
When a mixture of 20 parts of ethylhexyl methacrylate and 200 parts of methyl ethyl ketone was heated to 80 ° C. and 2 hours after the temperature was raised, 0.3 parts of azobisisobutyronitrile was added, and 8 ° C
After reacting for an hour, a copolymer having a solid content of 33% was obtained. To this, an adduct of isophorone diisocyanate obtained in the same manner as in Synthesis Example 2 and biscoat 300 [M] 79.3.
g at 80 ° C. for 6 hours (infrared absorption spectrum confirms disappearance of isocyanate group absorption at 2250 cm ⁻¹ ), and solid content of tertiary amine, acryloyl group and organopolysiloxane unit of 47% A copolymer solution was obtained. Next, 50 parts of isopropyl alcohol was added to the obtained copolymer solution, and then 55.9 of diethyl sulfuric acid was added.
The mixture was reacted at 50 ° C. for 6 hours to obtain 490 parts (solid content: 48%) of a polymer [III] having a quaternary ammonium base, an acryloyl group and an organopolysiloxane unit.

(Synthesis Example 4) N, N-dimethylaminoethyl methacrylate 40 parts, 2-hydroxyethyl methacrylate 10 parts, an organopolysiloxane compound having a mercapto group at both terminals (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)
X-22-167B, number average molecular weight 3,340) 10
Parts, a mixture of 40 parts of n-butyl acrylate and 200 parts of methyl ethyl ketone was heated to 80 ° C., and 2 hours after the temperature was raised, 0.3 parts each of azobisisobutyronitrile was added. The mixture was reacted at 80 ° C. for 8 hours to obtain a copolymer having a solid content of 33%. 79.3 g of an adduct [M] of isophorone diisocyanate and biscoat 300 obtained in the same manner as in Synthesis Example 2
At 80 ° C. for 6 hours (22 in the infrared absorption spectrum).
Confirmed disappearance of isocyanate group absorption at 50 cm ^-1 )
Thus, a copolymer solution having a solid content of 47% and having a tertiary amine, an acryloyl group and an organopolysiloxane unit was obtained. Next, after adding 50 parts of isopropyl alcohol to the obtained copolymer solution, 37.3 parts of diethylsulfuric acid was added and reacted at 50 ° C. for 6 hours, and a quaternary ammonium base was reacted with an acryloyl group and an organopolysiloxane. 471 parts (solid content 46%) of a polymer [IV] having units were obtained.

Having a quaternary ammonium base,
Polymerization without royl group or organopolysiloxane unit
Synthesis Example of Compound : (Synthesis Example 5) A mixture of 80 parts of N, N-dimethylaminoethyl methacrylate, 20 parts of 2-ethylhexyl methacrylate and 200 parts of methyl ethyl ketone was heated to 8 parts.
When the temperature was raised to 0 ° C., and two hours after the temperature was raised, 0.3 parts of azobisisobutyronitrile was added, and the mixture was reacted at 80 ° C. for 8 hours. A 33% copolymer solution was obtained. Next, after adding 100 parts of isopropyl alcohol to the obtained copolymer solution, methyl chloride was introduced into the reaction system, and the mixture was reacted at 50 ° C. for 6 hours, and a polymer [V] 422 containing a quaternary ammonium base was added.
(Solid content 29%).

Acryloyl group and organopolysiloxane
Polymerization with units but without quaternary ammonium base
Synthesis Example of Compound: (Synthesis Example 6) N, N-dimethylaminoethyl methacrylate 60 parts, 2-hydroxyethyl methacrylate 10
Part, an organopolysiloxane compound having a methacryloyl group at one end (trade name: FM072, manufactured by Chisso Corporation)
5, a mixture of 10 parts of a number average number molecular weight of 10,000), 20 parts of 2-ethylhexyl methacrylate and 200 parts of methyl ethyl ketone was heated to 80 ° C., and two hours after the temperature was raised. 0.3 parts of isobutyronitrile was added and reacted at 80 ° C. for 8 hours to obtain a copolymer having a solid content of 33%. To this was added 79.3 g of an adduct [M] of isophorone diisocyanate and biscoat 300 obtained in the same manner as in Synthesis Example 2, and reacted at 80 ° C. for 6 hours (225 in the infrared absorption spectrum).
The disappearance of absorption of isocyanate groups at 0 cm ^-1 was confirmed)
381 parts (solid content 47%) of a polymer [VI] having an acryloyl group and an organopolysiloxane unit were obtained.

Polymers [I] to-produced in Synthesis Examples 1 to 6
Table 1 shows the composition of [VI] based on the structural units derived from each monomer.

[0063]

[Table 1]

(Notes in Table 1) 2EHMA: 2-ethylhexyl methacrylate MMA: methyl methacrylate BA: n-butyl acrylate DMMA: N, N-dimethylaminoethyl methacrylate

(Examples 1 to 8 and Comparative Examples 1 and 2)
After blending any one of the polymers [I] to [VI], a monomer / oligomer capable of radical polymerization, a photopolymerization initiator, and water in the proportions shown in Table 2, the mixture was stirred for 100 minutes.
The temperature was raised to 0 ° C, and the solvent (methyl ethyl ketone and isopropyl alcohol) was distilled off to prepare an active energy ray-curable aqueous emulsion composition having the properties shown in Table 3. Examples 1 to 8 and Comparative Example 1 could prepare emulsions, but Comparative Example 2 could not prepare emulsions. The viscosity of the emulsion was measured by B
Measured at 25 ° C. using an L-type viscometer, and the particle size distribution is
LDSA- made by Tohnichi Computer Applications
It measured using the 3400A type particle size distribution analyzer.

[0066]

[Table 2]

(Notes in Table 2) DPHA: dipentaerythritol hexaacrylate UA1: urethane acrylate obtained by reacting isophorone diisocyanate and 2-hydroxyethyl acrylate at a molar ratio of 1: 2 UA2: isophorone diisocyanate and pentaerythritol triacrylate in moles Urethane acrylate obtained by reacting at a ratio of 1: 2 # 184: 1-hydroxycyclohexyl phenyl ketone (a photopolymerization initiator manufactured by Ciba Geigy, trade name Irgacure 184)

[0068]

[Table 3]

The active energy ray-curable aqueous emulsion composition shown in Table 3 was dried on a transparent biaxially stretched polyethylene terephthalate film (T600E manufactured by Mitsubishi Chemical Polyester Film Co., Ltd .: T600E) having a thickness of 100 μm using a bar coater. Apply so that the coating thickness is 6 μm,
It was dried by heating at 0 ° C. for 2 minutes. This is output power density 12
Using a 0 w / cm high pressure mercury lamp, 600 mJ / cm ² ultraviolet irradiation was performed at a position 10 cm below the light source to form a coating film. Table 4 shows the evaluation results of the obtained coating films.

Each evaluation item shown in Table 4 was evaluated according to the following method. (Transparency of cured film) The transparency of each film was measured according to JIS K-
The haze value (H%) was evaluated according to 7105. In addition, the haze value of the polyethylene terephthalate film as the base material was 1.4%. (Antistatic property) After each coating film was left in a constant temperature room at 23 ° C. and a relative humidity of 60% for 24 hours, an applied voltage of 1 was measured using a surface resistance meter (manufactured by Takedariken: TR-8601 type).
The surface resistivity was measured at 00 V for 1 minute. The surface resistivity of the polyethylene terephthalate film as the substrate was> 10 ¹⁶ Ω.

(Adhesion) A cross cut reaching the substrate surface was made at 1 mm intervals on the cured coating film, and a 1 mm ²
Zero pieces were made, cellotape (made by Nichiban) was stuck thereon, peeled off sharply, and the number of grids remaining on the substrate surface was counted. (Slipperiness) Each of the coating film was kept at 23 ° C. and 60% relative humidity.
% For 24 hours, and the dynamic friction coefficient was measured using a slip tester according to JIS K-7125. The coefficient of kinetic friction of the polyethylene terephthalate film as the base material was 0.48. (Water resistance) After dipping in running water of 30 ° C. for 30 minutes, each coating film was left in a constant temperature room at 23 ° C. and a relative humidity of 60% for 24 hours, and then the transparency (haze value) and antistatic property were measured. .

[0072]

[Table 4]

(Example 9) The active energy ray-curable aqueous emulsion composition prepared in Example 3 was treated with 130 μm
Thick discharge treated synthetic paper (Oji Yuka Synthetic Paper Co., Ltd .: G
F) The coating thickness after drying using a bar coater is 6 μm
And dried by heating at 80 ° C. for 2 minutes. Using a high-pressure mercury lamp having an output density of 120 w / cm, this was irradiated with 600 mJ / cm ² of ultraviolet light at a position 10 cm below the light source to form a coating film. As a result of evaluating the adhesion of the obtained coating film, the adhesion was 100/100 and the adhesion was good.

Example 10 A coating film was formed on synthetic paper in the same manner as in Example 9 except that the active energy ray-curable aqueous emulsion composition prepared in Example 7 was used.
As a result of evaluating the adhesion of the obtained coating film, the adhesion was 100 /
At 100, the adhesion was good.

[0075]

The active energy ray-curable aqueous emulsion composition of the present invention has low pollution and low toxicity because it does not require the use of a solvent, and has no adverse effect on the environment. A crosslinked cured film having excellent transparency, antistatic properties, and adhesion to a substrate, and having good water resistance is formed by forming a crosslinked cured film with active energy rays. In particular, when a polymer having an organopolysiloxane unit is used as the polymer (A), a film having excellent slipperiness can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 5/00 C09D 5/00 Z 157/00 157/00 163/10 163/10 167/04 167/04 F-term (reference) FA261 FA281 GA08 MA08 MA10 NA04 NA12 NA20 PA17 4J100 AB02R AL03R AL04R AL08P AL08Q AL08R AL09Q BA02Q BA03Q BA04R BA31P BA33H BA38H BA40R BC04R BC28R BC43Q BC43R BC53Q BC54R CA04 CA05 HA31 HA62 HC05 HC59 JA01

Claims (10)

[Claims] 1. An active energy ray-curable type obtained by emulsifying and dispersing a polymer (A) having a quaternary ammonium base and a (meth) acryloyl group, and a radically polymerizable monomer and / or oligomer (B) in water. Aqueous emulsion composition. 2. The content of the quaternary ammonium base in the polymer (A) is 10 to 10 as a structural unit derived from a polymerizable monomer.
The active energy ray-curable aqueous emulsion composition according to claim 1, which is 80% by weight. 3. The polymer (A) having a content of a (meth) acryloyl group of from 0.1 to 0.1 as a structural unit derived from a polymerizable monomer.
The active energy ray-curable aqueous emulsion composition according to claim 1, which is 5 to 40% by weight. 4. The active energy ray-curable aqueous emulsion composition according to claim 1, wherein the polymer (A) further has an organopolysiloxane unit. 5. A polymer (A) having a quaternary ammonium base and a (meth) acryloyl group in an amount of 3 to 50% by weight, a radically polymerizable monomer and / or oligomer (B) 1
The active energy ray-curable aqueous emulsion composition according to any one of claims 1 to 4, comprising from 40 to 95% by weight of water and from 40 to 95% by weight of water. 6. The polymer (A) is (1) a tertiary amine compound (a1) having one radically polymerizable group in one molecule.
And a compound (a2) having one radical polymerizable group and a hydroxyl group in one molecule to form a polymer (A1) having a tertiary amine and a hydroxyl group, and (2) the obtained polymer Compound (a3) having a (meth) acryloyl group and an isocyanate group in one molecule is added to (A1) to obtain a polymer (A) having a tertiary amine and a (meth) acryloyl group.
The active energy ray according to any one of claims 1 to 5, wherein (2) and (3) the obtained polymer (A2) is reacted with a quaternizing agent (a4) to form a quaternary ammonium base. Curable aqueous emulsion composition. 7. A tertiary amine compound (a1) having one radical polymerizable group in one molecule and a compound (a2) having one radical polymerizable group and a hydroxyl group in one molecule.
To form a polymer having a tertiary amine and a hydroxyl group (A
(1) 25-99% by weight of (a1), (a2)
The active energy ray-curable aqueous emulsion composition according to claim 6, wherein 1 to 40% by weight is used. 8. A tertiary amine compound (a1) having one radically polymerizable group in one molecule in the presence of an organic solvent.
And a compound (a2) having one radical polymerizable group and a hydroxyl group in one molecule to form a polymer (A1) having a tertiary amine and a hydroxyl group, and (2) the obtained polymer Compound (a3) having a (meth) acryloyl group and an isocyanate group in one molecule is added to (A1) to obtain a polymer (A) having a tertiary amine and a (meth) acryloyl group.
(2) and (3) an organic solvent solution of the polymer (A) obtained by reacting the obtained polymer (A2) with a quaternizing agent (a4) to form a quaternary ammonium base, and a monomer capable of radical polymerization. The organic solvent is distilled off from a mixture of and / or the oligomer (B) and water.
A method for producing the active energy ray-curable aqueous emulsion composition according to any one of the preceding claims. 9. A coating agent comprising the active energy ray-curable aqueous emulsion composition according to any one of claims 1 to 8 and a photopolymerization initiator. 10. A resin film, a resin sheet or a resin sheet having a cured film formed by applying the active energy ray-curable aqueous emulsion composition according to claim 1 and irradiating the composition with an active energy ray. paper.