JP2018193485A - Active energy ray-curable composition and method for producing the same - Google Patents

Abstract

To provide an active energy ray-curable composition which has good coatability on a metal substrate and gives a coating film having excellent adhesion to a metal substrate and high rust prevention performance.SOLUTION: The active energy ray-curable composition is provided which contains: (A) a bisphenol type epoxy (meth)acrylate compound; (B) one or more monofunctional (meth)acrylate compounds selected from the group consisting of monofunctional (meth)acrylate compounds having both a carboxyl group and a cyclic skeleton and monofunctional (meth)acrylate compounds having both a hydroxyl group and a cyclic skeleton; (C) a monofunctional (meth)acrylate compound having a cyclic skeleton other than the compound (B); (D) a (meth)acrylate compound having a phosphate group; (E) a photopolymerization initiator; and (F) a modified siloxane compound.SELECTED DRAWING: None

Description

The present invention relates to an active energy ray-curable composition.

For example, in Patent Document 1, (Component A) 10 to 70% by weight of epoxy (meth) acrylate, (Component B) having 2 or more ethylenically unsaturated groups and 3 compounds other than Component A are included. ˜40 wt%, (Component C) 27 to 75 wt% of the compound having an aromatic group and one ethylenically unsaturated group, and (Component D) 0 to the ethylenically unsaturated compound other than components A to C An active energy ray-curable composition containing ˜30% by weight is described. And the coating film by this curable composition is said to show the effect that it is excellent in adhesiveness with a metal base material, is further excellent in flexibility, and is excellent in solvent resistance.

Patent Document 2 discloses that (Component A) 10 to 80% by weight of epoxy (meth) acrylate and (Component B) 20 to 90% by weight of a compound having an aromatic group and one ethylenically unsaturated group. And optionally (component C) having 2 or more ethylenically unsaturated groups and 0 to 40% by weight of compounds other than component A, and optionally (component D) ethylenically unsaturated other than components A to C. An active energy ray-curable metal anticorrosive coating composition comprising 0 to 30% by weight of a saturated compound is disclosed. And the coating film by this curable composition is said to show the effect that it is excellent in adhesion sufficiently with a metal substrate and excellent in acid resistance.

International Publication Number WO2013 / 151001 A1 JP 2014-98088 A

Although the known curable composition is presumed to have good paintability, the adhesion to a metal substrate and the rust-preventing power are not always sufficient (Patent Document 1). Even though it is excellent in adhesion to rust and rust preventive power, it is not always satisfactory, such as insufficient paintability (Patent Document 2). That is, when a conventional curable composition is applied to a metal substrate, the coating properties for the metal substrate, such as good paintability to the metal substrate, good adhesion to the metal substrate, and rust prevention, It has been difficult to satisfy various characteristics required for a well-balanced.

The object of the present invention is to solve the above-mentioned problems, that is, to have good paintability for a metal substrate such as a steel plate and aluminum, and the obtained coating film is good with the metal substrate. It is to provide an active energy ray-curable composition having adhesiveness and high rust prevention ability.

The inventors of the present invention have made extensive studies in order to achieve the above-mentioned problems, and the active energy ray-curable composition obtained by the means described below has good coating suitability for a metal substrate, Furthermore, the knowledge that the coating film obtained by hardening the said composition has favorable adhesiveness with respect to a metal base material and high rust prevention power was acquired. The present specification provides the following means based on such findings.

This invention which can solve said subject is a curable composition shown below.
An active energy ray-curable composition (A) a bisphenol-type epoxy (meth) acrylate compound,
(B) one or more monofunctional (meth) acrylate compounds selected from a monofunctional (meth) acrylate compound having both a carboxyl group and a cyclic skeleton, and a monofunctional (meth) acrylate compound having both a hydroxyl group and a cyclic skeleton,
(C) a monofunctional (meth) acrylate compound having a cyclic skeleton other than the compound (B),
(D) a (meth) acrylate compound having a phosphate group,
(E) a photopolymerization initiator, and (F) a modified siloxane compound,
An active energy ray-curable composition comprising:

The composition according to the present invention has good coating suitability for a metal substrate, and further, the coating film formed from the composition has good adhesion to the metal substrate, and also has a high protective property. It has the effect of demonstrating rust ability.

<Active energy ray-curable curable composition>
The present invention relates to (A) a bisphenol type epoxy (meth) acrylate compound, (B) a monofunctional (meth) acrylate compound having both a carboxyl group and a cyclic skeleton, and a monofunctional (meth) acrylate having both a hydroxyl group and a cyclic skeleton. One or more monofunctional (meth) acrylate compounds selected from the compounds, (C) monofunctional (meth) acrylate compounds having a cyclic skeleton other than the compound (B), (D) (meth) having a phosphate group The present invention relates to an active energy ray-curable composition containing an acrylate compound, (E) a photopolymerization initiator, and (F) a modified siloxane compound.

The active energy ray-curable composition disclosed herein (hereinafter also referred to as the present curable composition) has good coating suitability for metal substrates such as steel plates and aluminum, and the composition. The coating film obtained by curing the resin has good adhesion to the metal substrate, and further has a high rust prevention ability. That is, this curable composition is a composition which can form the coating film which satisfies various characteristics calculated | required as an object for metal base materials with sufficient balance.

Although the disclosure of the present invention is not limited, it is presumed that the present curable composition exhibits various performances by the following mechanism.
That is, high rust prevention power is expressed by the component (A), and good adhesion to various metal substrates is expressed by adding the component (D) together with the component (A). In addition to the fact that component (A) is less susceptible to shrinkage due to curing and has good compatibility with various metal substrates, the phosphate group of component (D) improves adhesion to metal substrates. It is estimated that Further, by adding the component (B), higher adhesion performance to various metal substrates is manifested together with the component (A) and the component (D). This is presumed to be the effect of the carboxyl group or hydroxyl group in component (B). Addition of component (C) reduces the viscosity of the composition, thereby improving coating suitability. Furthermore, the component (C) has a molecular structure in which curing shrinkage is unlikely to occur, and it is presumed that this also contributes to the adhesion described above. It is presumed that component (F) improves the wettability of the composition to the metal substrate by reducing the surface tension of the composition, thereby contributing to the improvement of coating suitability.

Hereinafter, each component of the present invention will be described in the order of components (A), (B), (C), (D), (E), and (F).
In the present specification, “to” represents the following from the above unless otherwise specified. Further, “(meth) acrylate” includes acrylate and methacrylate. The (meth) acryloyl group includes an acryloyl group and a methacryloyl group.

[Component (A): Bisphenol-type epoxy (meth) acrylate compound]
Component (A) is a bisphenol-type epoxy (meth) acrylate compound. The bisphenol type epoxy (meth) acrylate compound is obtained by adding an α, β-unsaturated monocarboxylic acid ester having an α, β-unsaturated monocarboxylic acid or a carboxyl group to an epoxy compound having two or more epoxy groups and a bisphenol skeleton. It is a (meth) acrylate compound obtained by addition. A hydroxyl group is generated by a reaction between an epoxy group and a carboxylic acid of an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group. In the present invention, any known epoxy (meth) acrylate compound having a bisphenol skeleton can be used without particular limitation.

Specific examples of the epoxy compound used as a raw material for the bisphenol type epoxy (meth) acrylate compound include a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound, a hydrogenated bisphenol A type epoxy compound, and a hydrogenated bisphenol F. Type epoxy compound, hydrogenated bisphenol S type epoxy compound, fluorinated bisphenol type epoxy compound, brominated bisphenol A type epoxy compound, brominated bisphenol F type epoxy compound, dicyclopentadiene phenol type epoxy compound, bisphenol A novolak type epoxy compound, etc. Can be mentioned.

Examples of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, (meta ) Monocarboxylic acid such as α-position haloalkyl, alkoxyl, halogen, nitro, cyano substituent of acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adipic acid, 2- ( (Meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- ( (Meth) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropyl tetrahydrophthalic acid, 2- (meth) a Acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyladipic acid, 2- (meth) acryloyl Loxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid, 2- (meth) acryloyloxybutylmaleic acid, (meth) acrylic acid with ε-caprolactone, β-propiolactone, γ-butyrolactone, Monomers added with lactones such as δ-valerolactone, or hydroxyalkyl (meth) acrylate, pentaerythritol tri (meth) acrylate with (anhydrous) succinic acid, (anhydrous) phthalic acid, (anhydrous) Monomers added with acid (anhydride) such as maleic acid, (meth) acrylic acid dimer, etc. And the like. Of these, (meth) acrylic acid is particularly preferable from the viewpoint of good reactivity with epoxy groups.

The amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group is 0.5 to 1.2 equivalents relative to 1 equivalent of the epoxy group of the bisphenol type epoxy compound. A range is preferable, and a range of 0.7 to 1.1 equivalents is more preferable.

The bisphenol type epoxy (meth) acrylate compound is synthesized by itself using the bisphenol type epoxy compound and the α, β-unsaturated monocarboxylic acid or the α, β-unsaturated monocarboxylic acid ester having a carboxyl group as described above. Alternatively, a commercially available product may be used as it is. When synthesizing by itself, the synthesis method is not particularly limited, and it may be synthesized by a known method. A bisphenol type epoxy compound and an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group can be mixed and reacted in the presence of a catalyst according to a conventional method.

For example, an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is added to a bisphenol-type epoxy compound itself or a solution containing the epoxy compound, and thermal polymerization is performed as necessary. A reactive solution is obtained by adding an inhibitor and a catalyst and mixing with stirring. By reacting this reactive solution at a reaction temperature of preferably 60 to 150 ° C., particularly preferably 80 to 120 ° C., a bisphenol type epoxy (meth) acrylate compound which is an addition reaction product can be obtained.

The bisphenol type epoxy compound, the α, β-unsaturated monocarboxylic acid or the α, β-unsaturated monocarboxylic acid ester having a carboxyl group, and the catalyst may be used alone or in combination of two or more. May be used in combination.

Examples of the thermal polymerization inhibitor include hydroquinone or hydroquinone monomethyl ether. Catalysts include tertiary amines such as benzyldimethylamine, benzyldiethylamine trimethylamine and triethylamine, and quaternary ammoniums such as tetramethylammonium chloride, tetraethylammonium chloride, dodecyltrimethylammonium chloride, trimethylbenzylammonium chloride and methyltriethylammonium chloride. Examples thereof include salts, triphenylphosphine, and triphenylstibine.

The bisphenol type epoxy (meth) acrylate compound may be synthesized by itself as described above, but a commercially available product may be used as it is. Specific examples of commercially available products include the following.

Unidic V-5500, V-5502 (manufactured by DIC Corporation), epoxy ester 3000A, epoxy ester 3000MK, epoxy ester 3002M (N), epoxy ester 3002A (N), epoxy ester EX-0205 (manufactured by Kyoeisha Chemical Co., Ltd.) Lipoxy SP-1506, SP-1509, VR-60, VR-77, VR-90, R802 (manufactured by Showa Polymer Co., Ltd.), Neopol 8026, 8101, 8125, 8197, 8250LMH, 8260, 8355, 8360BR, 8400 8411LH, 8327, 8351, 8475, 8476 (manufactured by Nippon Iupika Co., Ltd.), BAEA-100, BAEM-100, BAEM-50, BEEM-50, BFEA-50, CNEA-100, PNEM-50, RNEA 100 (manufactured by Keesuemu Co., Ltd.), GENOMER2263 (Rah made by AG Co., Ltd.), BISCOAT # 540 (manufactured by Osaka Organic Chemical Industry Co., Ltd.).

A bisphenol type epoxy (meth) acrylate compound may be used independently and may use 2 or more types together. As the bisphenol-type epoxy (meth) acrylate compound, di (meth) acrylate having two or more hydroxyl groups is preferable from the viewpoint that a coating film having excellent rust prevention ability can be obtained, and more specifically, bisphenol A-type epoxy. (Meth) acrylate compound, bisphenol F type epoxy (meth) acrylate compound, bisphenol A type EO modified epoxy di (meth) acrylate compound, bisphenol F type EO modified epoxy di (meth) acrylate compound, hydrogenated bisphenol A type epoxy (meth) acrylate Compounds are preferred, and bisphenol A type epoxy (meth) acrylate compounds are particularly preferred.

The weight average molecular weight of the bisphenol-type epoxy (meth) acrylate compound is preferably 200 to 3,000, particularly preferably 300 to 1,000. When the weight average molecular weight is 200 or more, the rust prevention power is excellent, while when the weight average molecular weight is 1,000 or less, the coating suitability tends to be excellent. In the present specification, the weight average molecular weight means a value measured under the following conditions.

Equipment used: HLC8220GPC (manufactured by Tosoh Corporation)
Columns used: TSKgel SuperHZM-M, TSKgel GMHXL-H, TSKgel G2500HXL, TSKgel G5000HXL (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Standard substance: TSKgel Standard polystyrene A1000, A2500, A5000, F1, F2, F4, F10 (manufactured by Tosoh Corporation)
Detector: RI
Eluent: Tetrahydrofuran flow rate: 1 ml / min

Content of the component (A) contained in this curable composition is not specifically limited, The quantity which can exhibit the performance calculated | required as a coating film should just be contained. For example, when the total amount of the present curable composition is 100% by mass, the component (A) is preferably 10 to 70% by mass, and more preferably 20 to 55% by mass. When the proportion of the component (A) is 70% by weight or less, a cured film having a uniform film thickness is easily obtained, and when it is 10% by mass or more, the adhesion to the metal substrate is good.

[Component (B): monofunctional (meth) acrylate compound having a carboxyl group and a cyclic skeleton, monofunctional (meth) acrylate compound having both a hydroxyl group and a cyclic skeleton]
Component (B) is at least one monofunctional selected from the group consisting of a monofunctional (meth) acrylate compound having both a carboxyl group and a cyclic skeleton, and a monofunctional (meth) acrylate compound having both a hydroxyl group and a cyclic skeleton. It is a (meth) acrylate compound. Hereinafter, a monofunctional (meth) acrylate compound having both a carboxyl group and a cyclic skeleton and a monofunctional (meth) acrylate compound having both a hydroxyl group and a cyclic skeleton will be described.

<< Monofunctional (meth) acrylate compound having both carboxyl group and cyclic skeleton >>
The monofunctional (meth) acrylate compound having both a carboxyl group and a cyclic skeleton is not particularly limited as long as it is a monofunctional (meth) acrylate compound having at least one carboxyl group and one cyclic skeleton in the molecule. Can be used. In the present specification, the cyclic skeleton means an alicyclic ring, an aromatic ring, or both skeletons.

Examples of such a compound include a compound having a carboxyl group and a cyclic skeleton directly bonded to a (meth) acryloyl group, and dehydration of (meth) acrylic acid and a monoalcohol having both a cyclic skeleton and a carboxyl group. An ester compound (a compound having a (meth) acryloyloxy group) or the like can be used.

Examples of the compound having a carboxyl group and having a cyclic skeleton directly bonded to a (meth) acryloyl group include vinyl benzoic acid, vinyl salicylic acid, and vinyl acetylsalicylic acid.

Examples of dehydrating ester compounds of (meth) acrylic acid and monoalcohols having both a cyclic skeleton and a carboxyl group include (meth) acryloyloxybenzoic acid and phthalic acid monofunctional (meth) acrylate compounds (monohydroxyethyl phthalate). (Meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid), 4- (meth) acryloxyethyl pyromellitic acid and the like.

These compounds may be used alone or in combination with a plurality of compounds. Moreover, you may use together with the monofunctional (meth) acrylate compound which has both the hydroxyl group and cyclic skeleton which are mentioned later.

In the present curable composition, the monofunctional (meth) acrylate compound having a carboxyl group and a cyclic skeleton is preferably a dehydrated ester compound of (meth) acrylic acid and a monoalcohol having both a cyclic skeleton and a carboxyl group. Of these, phthalic acid monofunctional (meth) acrylate compounds are particularly preferred.

<< Monofunctional (meth) acrylate compound having both hydroxyl group and cyclic skeleton >>
As the monofunctional (meth) acrylate compound having both a hydroxyl group and a cyclic skeleton, any known one may be used as long as it is a monofunctional (meth) acrylate compound having at least one hydroxyl group and one cyclic skeleton in the molecule. be able to.

Specific examples of such compounds include 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid, 2-hydroxy-3-phenoxypropyl acrylate, 2- (β-hydroxyphenethyl) ethyl acrylate, acrylic acid β -Hydroxyphenethyl, 4-hydroxyphenethyl acrylate, 1-phenyl-2-hydroxyethyl acrylate, 3-hydroxy-4-acetylphenyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 3-hydroxy-4 acrylate -Benzoylphenyl and the like can be mentioned, but are not limited thereto.

These compounds may be used alone or in combination with a plurality of compounds. Moreover, you may use together with the monofunctional (meth) acrylate compound which has both a hydroxyl group and cyclic skeleton mentioned above.

In the present curable composition, monofunctional (meth) acrylate compounds having both a hydroxyl group and a cyclic skeleton include 2- (meth) acryloyloxyethyl-2-hydroxyethyl-phthalic acid, 2-hydroxy-3-phenoxypropyl. One or more selected from the group consisting of (meth) acrylates are preferred, and 2- (meth) acryloyloxyethyl-2-hydroxyethyl-phthalic acid is particularly preferred among them.

The content of the component (B) contained in the present curable composition is not particularly limited as long as an amount capable of exhibiting the performance required as a coating film is included. For example, with respect to 100 parts by mass of the component (A), the component (B) can be contained in an amount of 10 to 200 parts by mass. Preferably they are 20 to 150 mass parts. If content of a component (B) is 10 mass parts or more, favorable adhesiveness with respect to a metal base material can be expressed, and if it is 200 mass parts or less, the fall of rust prevention power can be suppressed. .

[Component (C): Monofunctional (meth) acrylate compound having a cyclic skeleton other than the compound (B)]
Component (C) is a monofunctional (meth) acrylate compound having a cyclic skeleton other than the component (B) compound. In the present specification, a monofunctional (meth) acrylate compound having a cyclic skeleton other than the component (B) compound is a dehydrated ester of one (meth) acrylic acid and a monoalcohol having at least one cyclic skeleton. It is a compound obtained by converting.

Specific examples of the monofunctional (meth) acrylate compound having a cyclic skeleton include cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentenyloxyethyl (meth). Monofunctional (meth) acrylate compounds having an alicyclic ring such as acrylate, dimethylol dicyclopentane di (meth) acrylate, ethoxylated phenyl (meth) acrylate, isobornyl (meth) acrylate, nonylphenoxyethyl acrylate, phenoxyethyl (meth) And monofunctional (meth) acrylate compounds having an aromatic ring such as acrylate and phenoxydiethylene glycol (meth) acrylate. Among these, a monofunctional (meth) acrylate compound having both a cyclic skeleton and an ethylene oxide chain in its molecular structure is preferable, and a monofunctional (meth) acrylate compound having both an aromatic ring and an ethylene oxide chain is particularly preferable. Specific examples of the monofunctional (meth) acrylate compound having both an aromatic ring and an ethylene oxide chain include phenoxyethyl (meth) acrylate and phenoxydiethylene glycol (meth) acrylate.

Although it does not specifically limit as content of the component (C) contained in this curable composition, For example, a component (C) is 25 mass parts or more and 300 mass parts with respect to 100 mass parts of components (A). Part or less. More preferably, content of a component (C) is 40 to 250 mass parts. If content of a component (C) is 25 mass parts or more, the viscosity of a composition can be reduced, and if it is 300 mass parts or less, drying property will become favorable and the fall of rust prevention power can be suppressed. .

[Component (D): (Meth) acrylate compound having a phosphate group]
Component (D) is a (meth) acrylate compound having a phosphate group. The (meth) acrylate compound having a phosphate group has a function of improving adhesion to a metal substrate. The (meth) acrylate compound having a phosphate group is a (meth) acrylate compound containing at least one phosphate group in the molecule and having one or two (meth) acryloyl groups. It can be used without any particular limitation.

Examples of the (meth) acrylate compound having phosphoric acid include phosphoric acid (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, di- (2-methacryloyloxyethyl) -phosphate, 2- (meth) acrylic acid. Examples include leuoxypropyl acid phosphate, 2- (meth) acryloyloxybutyl butyl acid phosphate, acid phosphooxypolyoxypropylene glycol monomethacrylate, and acid phosphooxypolyoxyethylene glycol monomethacrylate. Examples also include butyrolactone-modified phosphoric acid (meth) acrylate, valerolactone-modified phosphoric acid (meth) acrylate, propiolactone-modified phosphoric acid (meth) acrylate, and caprolactone-modified phosphoric acid (meth) acrylate.

Preferable specific examples include 2- (meth) acryloyloxyethyl acid phosphate, di- (2- (meth) acryloyloxyethyl) phosphate, acid phosphooxypolyoxypropylene glycol monomethacrylate, acid phosphooxypolyoxyethylene glycol Monomethacrylate is mentioned.

The content of the component (D) contained in the present curable composition is not particularly limited as long as the amount capable of exhibiting the performance desired as a coating film is included. For example, with respect to 100 parts by mass of the component (A), the component (D) can be contained in an amount of 1 part by mass or more and 10 parts by mass or less, and more preferably 2 parts by mass or more and 8 parts by mass or less. If content of a component (D) is 1 mass part or more, the coating film obtained will express favorable adhesiveness with respect to a metal base material, and if it is 10 mass parts or less, it is contained in this curable composition. There is a tendency for compatibility with other components to be improved.

[Other (meth) acrylate compounds]
This curable composition contains (meth) acrylate compounds (hereinafter referred to as “other (meth) acrylate compounds”) other than the components (A), (B), (C), and (D) described above. be able to. Other (meth) acrylate compounds can be appropriately selected based on the type of metal substrate that is the object to be coated, the characteristics of the required coating film, and the like.

Other (meth) acrylate compounds are not particularly limited, and are appropriately selected from known (meth) acrylate compounds. For example, from the viewpoint of adhesion to the coated surface, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, Examples include methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, and acryloxymethyltriethoxysilane.

From the viewpoint of controlling the properties of the cured film, for example, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene di (meth) acrylate, Dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) a Relate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri Propylene oxide 3-mole addition triacrylate of methylolpropane, propylene oxide 6-mole addition triacrylate of trimethylolpropane, propylene oxide 3-mole addition triacrylate of trimethylolpropane, propylene oxide 6-mole addition triacrylate of trimethylolpropane Can do. Examples of other vinyl compounds include N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylacetamide, acryloylmorpholine, and the like.

[(E): Photopolymerization initiator]
Component (E) is a photopolymerization initiator. There is no particular limitation on the photopolymerization initiator that can be used in the present curable composition, and the photopolymerization initiator can be properly used depending on the application and purpose. Specifically, acetophenone compounds, benzyl compounds, anthraquinone compounds, benzyl methyl ketal compounds, α-hydroxyalkylphenone compounds, α-aminoalkylphenone compounds, acylphosphine oxide compounds, oxime ester compounds, biimidazoles Compounds, aryliodonium salt compounds, and the like.

Examples of acetophenone compounds include acetophenone, 2-hydroxy-2-phenylacetophenone, 2-ethoxy-2-phenylacetophenone, 2-methoxy-2-phenylacetophenone, 2-isopropoxy-2-phenylacetophenone, 2-isobutoxy. -2-phenylacetophenone and the like. Examples of the benzyl compound include benzyl and 4,4'-dimethoxybenzyl.

Examples of the anthraquinone compound include 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-phenoxyanthraquinone, 2- (phenylthio) anthraquinone, and 2- (hydroxyethylthio) anthraquinone. Examples of the benzylmethyl ketal compound include 2,2-dimethoxy-1,2-diphenylethane-1-one.

Examples of the α-hydroxyalkylphenone compound include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) -phenyl]. 2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methyl-1 -ON.

Examples of the α-aminoalkylphenone compounds include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzylmethyl 2-dimethylamino-1- (4-morpho Linophenyl) -1-butanone. Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.

Examples of the oxime ester compound include (2E) -2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] octane-1-one oxime ester, O-acetyl-1- [6- (2 -Methylbenzoyl) -9-ethyl-9H-carbazol-3-yl] ethanone oxime.

Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2 , 4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 , 5'-tetraphenyl-1,2'-biimidazole.

Examples of the aryliodonium salt-based compound include (4-methylphenyl) [4- (2-methylpropyl) phenyl] iodonium-hexafluorophosphate.
Examples of the arylsulfonium salt compounds include phenylthiophenyldiphenylsulfonium-hexafluorophosphate and phenylthiophenyldiphenylsulfonium-hexafluoroantimonate.

Component (E) is preferably an α-hydroxyalkylphenone compound having both a cyclic skeleton and a hydroxyl group from the viewpoint of compatibility with other components. Particularly preferred is 1-hydroxycyclohexyl phenyl ketone.

The quantity of the component (E) contained in this curable composition should just contain the quantity of the grade which can harden the said composition appropriately, and is not specifically limited. For example, the component (E) can be contained in an amount of 1 part by mass to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (A), (B), (C), and (D), and 2 parts by mass. More preferably, the content is 8 parts by mass or less. If the content of the component (E) is 1 part by mass or more, it becomes possible to give sufficient curability to the present curable composition, while the content of the photopolymerization initiator is 10 parts by mass or less. In this case, problems such as yellowing of the coating film and bleeding out of the photopolymerization initiator from the coating film are less likely to occur.

The present curable composition may contain various photosensitizers in addition to the photopolymerization initiator. Examples of the photosensitizer include trimethylamine, methyldimethanolamine, triethanolamine, p-dimethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N-dimethylbenzylamine and 4,4′-bis (diethylamino) benzophenone and the like can be used. Of course, it is preferable to select and use a photosensitizer that is excellent in solubility in the present curable compound and does not inhibit the function of the photopolymerization initiator.

[Component (F): Modified siloxane compound]
Component (F) is a modified siloxane compound. The modified siloxane compound has a function of improving wettability and leveling to the metal substrate. In the present specification, the modified siloxane compound refers to a compound having dimethylsiloxane as a basic skeleton and having a structure in which part or all of the side chain of dimethylsiloxane is replaced with another organic group from a methyl group.

Examples of the organic group include a polyether group, a polyalkyl group, an aralkyl group, a polyester group, and an acrylic group, and these may be used alone or in combination of two or more. Moreover, a polyether group refers to what is comprised with the homopolymer of ethylene oxide or a polypropylene oxide, or the copolymer of ethylene oxide or a polypropylene oxide.

The modified siloxane compound contained in the present curable composition is preferably at least one selected from polyether-modified polydimethylsiloxane, polyether-modified siloxane, and acrylic group-containing modified polydimethylsiloxane. Of these, polyether-modified polydimethylsiloxane is particularly preferred.

The modified siloxane compound may be synthesized by itself, or a commercially available product may be used as it is. Examples of commercially available products include SF8428, FZ-2162, 8032ADDITIVE, SH3749, FZ-77, L-7001, L-7002, FZ-2110, FZ-2110, FZ-2123, SH8400 manufactured by Toray Dow Corning Co., Ltd. , SH3773M, BYK-307, BYK-333, BYK-345, BYK-346, BYK-347, BYK-348 manufactured by Big Chemie Japan Co., Ltd., TEGO Wet250, TEGO Wet260, TEGO Wet270, TEGO Wet280 manufactured by Evonik Degussa KF-351A, KF-352A, KF-353L, KF-354L, KF-355A, KF-615A, KF-640, KF-642, KF-643, and the like manufactured by Shin-Etsu Chemical Co., Ltd. are exemplified. Among these modified siloxane compounds, a solventless type is preferable. These may be used alone or in combination of two or more.

Content of the component (F) contained in this curable composition should just contain the quantity of the grade which improves the coating property with respect to the metal base material of this curable composition, and is not specifically limited. . For example, 0.05-5 mass parts can be included with respect to 100 mass parts of the total amount of component (A), (B), (C), and (D), Preferably it is 0.2-3 mass parts. . If the content of the component (F) is 0.05 parts by mass or more, sufficient coating suitability for the metal substrate can be exhibited, and if it is 5 parts by mass or less, the component (F) is a coating film. This makes it difficult to cause troubles such as bleeding out.

The present curable composition may further contain components other than the components (A) to (F) (hereinafter referred to as “other components”) as long as the effects of the present invention are not impaired. Specific examples of other components include pigments, dyes, metal oxide fine particles, thermal polymerization inhibitors, antioxidants such as hindered phenols and phosphites, light stabilizers (HALS) such as hindered amines, and ultraviolet absorbers. (UVA), surfactant, heat ray reflection / absorption imparting agent, flexibility imparting agent, antistatic agent, antifouling property imparting agent, water repellency imparting agent, antifoaming agent, leveling agent, plasticizer, foaming agent, Examples include flame retardants, antistatic agents, anti-aging agents, and antibacterial / antifungal agents.

Although the present curable composition exhibits a low viscosity excellent in coating suitability even without a solvent, an organic solvent may be added as necessary. For example, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, cyclic ethers such as tetrahydrofuran and dioxolane, esters such as methyl acetate, ethyl acetate and butyl acetate, aromatics such as toluene and xylene, carbitol, cellosolve, Examples include alcohols such as methanol, toluene, isopropanol, butanol, and propylene glycol monomethyl ether. These may be used alone or in combination of two or more.

[Production method]
This curable composition can be manufactured by mixing and stirring each component demonstrated above. For stirring, a general stirring device used for coating production may be appropriately selected and used.

The viscosity (mPa · s) of the present curable composition is not particularly limited, and may be adjusted as appropriate by adjusting the composition of the composition according to the coating method, but may be 100 mPa · s to 800 mPa · s. The range of s is preferable, and the range of 200 mPa · s to 450 mPa · s is particularly preferable. Within such a viscosity range, the present curable composition can be applied to the substrate with a uniform thickness even under high-speed coating conditions such as spray coating. In addition, the viscosity (mPa · s) of the curable composition in the present specification means a value measured with a B-type viscometer at 23 ° C. and a rotational speed of 60 rpm.

The curable composition preferably has a surface tension of 35 mN / m or less, particularly preferably 20 to 32 mN / m. If the surface tension is within such a range, it is possible to apply the coating without any problem even if the metal base material that is the object to be coated is not subjected to a treatment such as degreasing. In addition, the surface tension (mN / m) of the curable composition in this specification is a value by the surface tension measured at 23 degreeC.

The surface tension can be determined by using a ring method (Dunoi method) or a platinum plate method (Wilhelmy method) as described in reference books for general surface chemistry and colloid chemistry. In this specification, the surface tension value (mN / m) measured by a platinum plate method is indicated. The surface tension measured by the platinum plate method can be measured using, for example, a surface tension meter CBVP-Z manufactured by Kyowa Interface Science Co., Ltd.

<Coating film>
The coating film of this invention consists of hardened | cured material of said main curable composition. As a method for forming a coating film, for example, the present curable composition is coated on a metal substrate by a known method, dried if necessary, and then irradiated with active energy rays. Cured and a coating film is formed.

It does not specifically limit as a metal base material which coats this curable composition, A well-known metal base material can be used. Examples of the metal substrate include stainless steel, steel, aluminum, titanium, copper and cast iron. Examples of cast iron include gray cast iron, spheroidal graphite cast iron, black core malleable cast iron, pearlite malleable cast iron, ductile iron cast product, and malleable iron cast product.

Examples of the method for applying the curable composition to a metal substrate include gravure coating, roll coating, comma coating, air knife coating, kiss coating, spray coating, transfer coating, dip coating, spinner coating, wheeler coating, and brush coating. Examples thereof include solid coating using a silk screen, wire bar coating, and flow coating. Among these, spray coating, gravure coating, roll coating, comma coating, air knife coating, kiss coating, wire bar coating, and flow coating are preferable because a coating film having a constant thickness is easily obtained. A particularly preferred coating method is spray coating.

As the active energy ray, at least one selected from the group consisting of ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays, laser rays, alpha rays, beta rays, electron rays, radiation, and microwaves can be used. As the irradiation source of active energy rays, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps or metal halide lamps, and UV-LED irradiation devices can be used. It is possible to adjust the arrangement of the light sources as appropriate. Although it does not specifically limit as an irradiation amount of the active energy ray for hardening this curable composition, For example, the range of 100-3,000 mJ / cm < ² > is preferable, More preferably, it is 200-2. 000 mJ / cm ² , particularly preferably in the range of 400 to 1,500 mJ / cm ² . Irradiation of active energy rays may be performed in a nitrogen atmosphere to suppress curing failure, or may be controlled in the air. The preferable range of the oxygen concentration in the atmosphere when irradiating the active energy rays is 100 ppm to 50% by volume, more preferably 0.1% to 21% by volume.

Although the atmospheric temperature at the time of hardening this curable composition by irradiation of an active energy ray is not specifically limited, It is preferable that it is under atmospheric temperature below the heat-resistant temperature of the base material which is to-be-coated object. The atmospheric temperature is preferably 0 to 150 ° C, more preferably 10 to 80 ° C, and still more preferably 20 to 60 ° C.

The irradiation amount of the active energy ray and the ambient temperature can be set independently, but it is more preferable to set the preferable conditions in combination. Specifically, it is particularly preferable to carry out under conditions of an atmospheric temperature of 20 to 60 ° C. and an irradiation amount of 400 to 1,5000 mJ / cm ² .

As described above, the present curable composition is irradiated with active energy rays under appropriate setting conditions as described above, so that at least the components (A), (B), (C), and A coating film can be obtained by polymerizing (D). If it is the coating film obtained in this way, while having sufficient adhesiveness to a metal base material, the coating film which is excellent also in rust prevention power can be provided.

The thickness of the coating film formed by curing the present curable composition is not particularly limited and may be appropriately selected depending on the intended use, but it is preferably 1 to 100 μm and exhibits sufficient rust prevention ability. Therefore, 5-80 micrometers is preferable. Especially preferably, it is 20 micrometers-50 micrometers.

<Coated article>
The coated article of the present invention comprises the above-mentioned coating film. Examples of the coated article include articles in various fields such as vehicles such as automobiles, airplanes and ships whose appearance is important, building materials, electronic / electrical / OA equipment, and miscellaneous goods.

EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to these Examples.

<Synthesis of epoxy (meth) acrylate compound>
(Synthesis Example 1)
A flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel was charged with 100 parts by mass of hydrogenated bisphenol A diglycidyl ether (Epolite 4000, epoxy equivalents 215 to 245 manufactured by Kyoeisha Chemical Co., Ltd.) and heated to 80 ° C. .
Next, a mixture of 30 parts by mass of acrylic acid, 0.05 parts by mass of p-methoxyphenol as a polymerization inhibitor and 0.5 parts by mass of triphenylphosphine was dropped into the flask over 2 hours from the dropping funnel.
After completion of dropping, the temperature was raised to 105 ° C. and stirred for 5 hours. The reaction was terminated when the acid value (obtained by a measurement method according to JIS K0070) reached 2 mgKOH / g or less, and an acrylic acid adduct of hydrogenated bisphenol A diglycidyl ether (hereinafter referred to as “a-1”). Obtained).

(Synthesis Example 2)
A flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel was charged with 100 parts by mass of neopentyl glycol diglycidyl ether (Epolite 1500NP, epoxy equivalent 140-160, manufactured by Kyoeisha Chemical Co., Ltd.), and the temperature was raised to 80 ° C.
Subsequently, a mixture of 48 parts by mass of acrylic acid, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor and 1 part by mass of triphenylphosphine was dropped into the flask from the dropping funnel over 2 hours.
After completion of dropping, the temperature was raised to 105 ° C. and stirred for 5 hours. The reaction was terminated when the acid value (obtained by a measurement method according to JIS K0070) reached 2 mgKOH / g or less, and acrylic acid adduct of neopentyl glycol diglycidyl ether (hereinafter referred to as “a-2”). Got.

As epoxy (meth) acrylate compounds other than a-1 and a-2, the following commercially available products were used as they were.
-Bisphenol A type epoxy acrylate: DIC Corporation, Unidic V-5500
・ Bisphenol F type epoxy acrylate: KSEA Co., Ltd., BFEA-50

<Preparation of active energy ray-curable composition>
Example 1
100 parts by mass of bisphenol A type epoxy acrylate (DIC Corporation, V-5500), 100 parts by mass of monohydroxyethyl acrylate phthalate (manufactured by Kyoeisha Chemical Co., Ltd., HOA-MPL (N)), phenoxyethyl acrylate (Kyoeisha Chemical Co., Ltd.) 200 parts by mass, light acrylate PO-A), 6 parts by mass of 2-methacryloylethyl acid phosphate (manufactured by Kyoeisha Chemical Co., Ltd., light ester P-1M), 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184) ) 12 parts by mass and 4 parts by mass of polyether-modified polydimethylsiloxane (FZ-2215 manufactured by Toray Dow Corning Co., Ltd.) were mixed and stirred for 1 hour to obtain an active energy ray-curable composition.

(Examples 2-15, Comparative Examples 1-9)
According to the composition shown in Table 1, active energy ray-curable compositions of Examples 2 to 15 and Comparative Examples 1 to 9 were obtained.

<Evaluation>
The following evaluation was performed about the obtained various active energy ray hardening composition. About the result, it described in Table 1-Table 3 with the mixing | blending of various active energy ray curable compositions.

[Characteristics of active energy ray-curable composition]
(viscosity)
Using a B-type viscometer “LVDV-E” manufactured by BROOKFIELD, the viscosity of each curable composition was measured under the conditions of 23 ° C. and a rotation speed of 60 rpm.

(surface tension)
About each curable composition, the surface tension was measured using Kyowa Interface Science Co., Ltd. surface tension meter CBVP-Z on 23 degreeC conditions.

(Paintability)
Each curable composition is sprayed onto a non-degreased cold rolled steel sheet (manufactured by TP Giken Co., Ltd., test piece according to JIS G 3141: size 50 mm × 25 mm × 2 mm, hereinafter referred to as “SPCC-SD plate”). Coating was performed with a gun (“W-100” manufactured by Anest Iwata Co., Ltd., discharge pressure: 0.3 MPa) so that the coating film thickness was 50 μm. The appearance of the coating film immediately after coating was visually observed and evaluated according to the following evaluation criteria.
○ ··············································································································································· 2 X .... Repelled remarkably and the paint surface is not smooth.

(Curable)
Using the bar coater, the produced active energy ray-curable composition was coated on the SPCC-SD plate so as to have a thickness of 50 μm. Using the high-pressure mercury lamp (made by Eye Graphic Co., Ltd.), the obtained coating was cured by irradiating with ultraviolet rays under the condition of an integrated light quantity of 500 mJ / cm ² or 1000 mJ / cm ² . The cured state of the coating film after irradiation with each accumulated amount of ultraviolet rays was evaluated according to the following evaluation criteria.
5 ... It is fully cured and there is no tackiness 4 ... There is a tackiness, but even if it touches with a finger, a fingerprint does not remain
3 ... There is a feeling of tack, and fingerprints remain when touched with a finger
2 ... When the finger touches the paint film, the paint component is attached to the finger, but it is thickened (cured) 1 ... Not cured at all

[Physical properties of coating film]
(Adhesion)
In the “curability” evaluation, an SPCC-SD plate provided with a coating obtained by curing under the condition of an integrated light quantity of 1000 mJ / cm ² was used as a test plate. Furthermore, the following two types of metal substrates were also coated in the same manner as described above and cured at an integrated light quantity of 1000 mJ / cm ² to prepare test plates each having a coating film.
-SS-400 ... TP Giken Co., Ltd., general structural rolled steel test piece according to JIS G3101, size 50 mm x 25 mm x 2 mm
・ Aluminum 6063 ... TP Giken Co., Ltd., corrosion-resistant aluminum alloy test piece, size 50 mm x 25 mm x 2 mm
Each of the three types of test plates was tested based on JIS K5600-5-6 (1999) “Mechanical properties of the coating film—adhesiveness (cross-cut method)” to determine the adhesion of the coating film to various substrates. Evaluation was made based on the following evaluation criteria.
5 ... The edges of the cut are completely smooth and there is no peeling in any of the lattice eyes. 4 ... There is a small peeling of the coating film at the intersection of the cut, and the area of the peeled portion is less than 5%. The area of the peeled portion is 5% or more and less than 15% 2 ... The area of the peeled portion is 15% or more and less than 35% 1 ... The area of the peeled portion is 35% or more

Regarding the physical properties evaluation (pencil hardness, impact resistance, flex resistance, cupping resistance, neutral salt spray resistance, chemical resistance) of the following coating films, 1000 mJ / cm ² in the above (curability) evaluation. The test board provided with the coating film (the base material is an SPCC-SP board) obtained when cured by the above method was used.

(Pencil hardness)
Using a surface property measuring instrument (manufactured by Shinto Kagaku Co., Ltd., Tribogear 14FW) and a pencil hardness measuring pencil (Mitsubishi Uni by Mitsubishi Pencil Co., Ltd.), JIS K5600-5-4 (1999) “Mechanical properties of coating film” A test based on “scratch hardness (pencil method)” was conducted. The measurement load was 750 g, the measurement speed was 30 mm / min, and the measurement distance was 5 mm. The measurement was performed 5 times, and the hardness of the pencil having a pass number exceeding 4/5 was used as the evaluation result.

(Impact resistance)
Using a DuPont impact resistance tester under conditions of a temperature of 23 ° C. and a relative humidity of 50%, the weight of the test plate is 500 g, the shot-type tip diameter is 1/2 inch, and the drop altitude is 10 to 50 cm. An impact test was performed under the conditions, and the maximum height (cm) at which the coating film was not broken was measured.

(Flexibility)
A test plate was deformed by performing a flex test in accordance with JIS K5600-5-1 (1999) “Mechanical properties of coating film—flex resistance (cylindrical mandrel method)”. The coating state after the test was visually observed and evaluated according to the following criteria. The test was performed using a type 1 test apparatus using a cylindrical mandrel with a diameter of 3 mm.
○ ... There is no crack in the coating film.

(Copping resistance)
Using a cupping tester described in JIS K5600-5-2 (1999) "Mechanical properties of coating film-resistance to cupping" under the condition of a temperature of 23 ° C and a relative humidity of 50%, the speed is 0.2 mm / s. The test plate was deformed by pressing 6 mm from the back surface (the surface not provided with the coating film) of the test plate. The state of the coating film after the test plate was deformed was observed and evaluated according to the following criteria.
○ ... There is no crack in the coating film.

(Neutral salt spray resistance)
For each test plate, a cut with a width of 1 mm was applied so as to cross diagonally inward about 10 mm from the end of the test plate so as to reach the base of the test plate. Using the cut test plate, a salt spray test was conducted for 240 hours by a method in accordance with JIS K5600-7-1 (1999) “long-term durability of coating film—neutral salt spray resistance”. After spraying with salt water, the test plate was dried by leaving it at room temperature for 3 hours. 24mm wide adhesive tape (industrial cellophane tape manufactured by Nichiban Co., Ltd.) is pressure-bonded uniformly to the dried test plate with your fingertips so that no air bubbles remain (along the cut line and the cut line becomes the center) Thus, after crimping the adhesive tape, the tape was peeled off from the coating film by holding the end of the tape and pulling it at an angle of 60 degrees with respect to the coating film surface. After peeling off the tape, the maximum peel width on one side of the coating film with the cut line as the center was measured and evaluated based on the following evaluation criteria. It shows that the smaller the peel width, the better the rust prevention power.
5 ... Peeling width less than 1mm 4 ... Peeling width 1mm or more and less than 3mm 3 ... Peeling width 3mm or more and 6mm or less 2 ... Peeling width 5mm or more and less than 7mm 1 ... Peeling width 7mm or more

(chemical resistance)
Absorbent cotton sufficiently soaked with methyl ethyl ketone was placed on the coating film of each test plate, and 20 reciprocating rubbing was performed in a state where a load of 100 g was applied to the absorbent cotton. Thereafter, the absorbent cotton was removed, the state of the coating film was visually observed, and evaluated based on the following evaluation criteria.
○: No abnormality is observed in the coating film Δ: The gloss of the coating film is reduced ×: The coating film is dissolved

(Description of raw materials used in Table 1, Table 2 and Table 3)
(A) Component / Bisphenol A type epoxy acrylate: DIC Corporation, Unidic V-5500
・ Bisphenol F type epoxy acrylate: KSEA Co., Ltd., BFEA-50
Hydrogenated bisphenol A diglycidyl ether: Epolite 4000 manufactured by Kyoeisha Chemical Co., Ltd.
Component (A '): Neopentyl glycol diglycidyl ether: Epolite 1500NP manufactured by Kyoeisha Chemical Co., Ltd.
(B) Component-Phthalic acid monohydroxyethyl acrylate: manufactured by Kyoeisha Chemical Co., Ltd., HOA-MPL (N)
2-hydroxy-3-phenoxypropyl acrylate: manufactured by Kyoeisha Chemical Co., Ltd., epoxy ester M-600A
Component (B ') 2-acryloyloxyethyl succinic acid: manufactured by Kyoeisha Chemical Co., Ltd., HOA-MS (N)
・ 2-hydroxybutyl acrylate: Kyoeisha Chemical Co., Ltd., light acrylate HOB-A
Component (C): Phenoxyethyl acrylate: Kyoeisha Chemical Co., Ltd., light acrylate PO-A
Phenoxydiethylene glycol acrylate: Kyoeisha Chemical Co., Ltd., light acrylate P2H-A
・ Benzyl acrylate: manufactured by Hitachi Chemical Co., Ltd., FANCLIL FA-BZA
Isobornyl acrylate: Kyoeisha Chemical Co., Ltd., light acrylate IB-XA
・ Dicyclopentenyloxyethyl acrylate: manufactured by Hitachi Chemical Co., Ltd., Fancryl FA-512S
・ Dicyclopentanyl acrylate: manufactured by Hitachi Chemical Co., Ltd., Fancryl FA-513AS
Component (C ′): Methoxyethyl acrylate: Osaka Organic Chemical Industry Co., Ltd. (D) Component: 2-Methacryloylethyl acid phosphate: Kyoeisha Chemical Co., Ltd., Light Ester P-1M
(E) Component 1-hydroxycyclohexyl phenyl ketone: Irgacure 184, manufactured by BASF
Component (F): Polyether-modified polydimethylsiloxane: FZ-2215 manufactured by Toray Dow Corning Co., Ltd.
-Polyether-modified siloxane: BYK-345, manufactured by BYK Japan
Acrylic group-containing modified polydimethylsiloxane: BYK-UV 3570, manufactured by BYK Japan

(Examples 1-14)
As shown in Tables 1 and 2, in the curable compositions of Examples 1 to 14 according to the present invention, good results were obtained in all evaluation items.

(Comparative Examples 1-5)
As shown in Table 3, Comparative Example 1 containing no component (A) resulted in extremely poor curability. In Comparative Example 1, since the curing did not proceed properly, evaluation after adhesion was not performed. In Comparative Example 2 that does not contain the component (C), the viscosity is high, and coating (by spraying) is not successfully performed. In the comparative example 3 which does not contain a component (B), it became a result with poor neutral resistance salt-water spray property. In the comparative example 4 which does not contain a component (D), the adhesiveness with respect to various metal base materials is remarkably bad. In the comparative example not containing the component (F), although there was no problem with the coating viscosity, the wettability to the metal base material was extremely poor and the material surface was repelled. For this reason, evaluations other than paint suitability could not be performed.

From the above results, it is understood that sufficient performance is exhibited only by including all of the components (A) to (F) as in the present invention.

(Comparative Example 6)
In the component (A), in the curable composition of Comparative Example 6 using an epoxy (meth) acrylate using neopentyl glycol diglycidyl ether as a raw material instead of a bisphenol type epoxy (meth) acrylate, the adhesiveness was lowered. In addition, the results showed poor resistance to neutral salt spray. That is, it can be seen that in component (A), the bisphenol skeleton contributes to the improvement of the neutral salt spray property.

(Comparative Examples 7 and 8)
In the component (B), in Comparative Example 7 having a carboxyl group and not having a cyclic skeleton, the adhesiveness was lowered and the salt sprayability was poor. The same result was obtained in Comparative Example 8 having a hydroxyl group and not having a cyclic skeleton. From these results, it is understood that the component (B) having either a carboxyl group or a hydroxyl group and having a cyclic skeleton contributes to improvement in adhesion and salt sprayability.

In addition, the component (B) does not have any particular example of using a compound having neither a carboxyl group nor a hydroxyl group and having a cyclic skeleton. This is because the compound corresponds to the phenoxyethyl acrylate of the component (C), does not contain the component (B), and only the result of Comparative Example 3 containing only the phenoxyethyl acrylate needs to be confirmed. Not shown separately from 3.

(Comparative Example 9)
In Comparative Example 9 using a monofunctional (meth) acrylate having no cyclic skeleton in the component (C), the adhesion and pencil hardness were poor and the salt sprayability was poor. That is, as the component (C), it can be seen that the monofunctional (meth) acrylate having a cyclic skeleton contributes to performance such as adhesion, pencil hardness, and salt sprayability.

Claims (10)

An active energy ray-curable composition (A) a bisphenol-type epoxy (meth) acrylate compound,
(B) One or more monofunctional (meth) selected from the group consisting of a monofunctional (meth) acrylate compound having both a carboxyl group and a cyclic skeleton, and a monofunctional (meth) acrylate compound having both a hydroxyl group and a cyclic skeleton Acrylate compounds,
(C) a monofunctional (meth) acrylate compound having a cyclic skeleton other than the compound (B),
(D) a (meth) acrylate compound having a phosphate group,
(E) a photopolymerization initiator, and (F) a modified siloxane compound,
An active energy ray-curable composition comprising: A monofunctional (meth) acrylate compound having both a carboxyl group and a cyclic skeleton,
A phthalic acid-based monofunctional (meth) acrylate compound,
The active energy ray-curable composition according to claim 1. The phthalic acid monofunctional (meth) acrylate compound is
It is at least one compound selected from the group consisting of monohydroxyethyl (meth) acrylate phthalate and 2- (meth) acryloyloxyethyl hexahydrophthalic acid,
The active energy ray-curable composition according to claim 2. A monofunctional (meth) acrylate compound having both the hydroxyl group and the cyclic skeleton,
2- (meth) acryloyloxyethyl-2-hydroxyethyl-phthalic acid and one or more compounds selected from the group consisting of 2-hydroxy-3-phenoxypropyl (meth) acrylate,
The active energy ray-curable composition according to any one of claims 1 to 3. The compound (C) is
A monofunctional (meth) acrylate compound having both a cyclic skeleton and an ethylene oxide chain.
The active energy ray-curable composition according to any one of claims 1 to 4. A monofunctional (meth) acrylate compound having both the cyclic skeleton and the ethylene oxide chain,
A monofunctional (meth) acrylate compound having both an aromatic ring and an ethylene oxide chain.
The active energy ray-curable composition according to claim 5. A monofunctional (meth) acrylate compound having both the aromatic ring and the ethylene oxide chain,
It is one or more compounds selected from the group consisting of phenoxyethyl (meth) acrylate and phenoxydiethylene glycol (meth) acrylate,
The active energy ray-curable composition according to claim 6. The compound (F) is
A polyether-modified siloxane compound,
The active energy ray-curable composition according to any one of claims 1 to 7. The coating film which consists of hardened | cured material of the active energy ray curable composition of any one of Claims 1 thru | or 8. A coated article comprising the coating film according to claim 9.