JPH10287823A - Active energy beam-curable resin composition and coating formation of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain subject composition which is excellent in curability in the presence of oxygen, and the surface hardness and adhesiveness of the resultant coating film, by formulating an unsaturated compound having specific structure, an unsaturated compound having cyclic structure, a nitrogen-containing unsaturated compound, and unsaturated resin. SOLUTION: This composition is obtained by formulating (A) 1-70 wt.% of a tribromophenyl acrylate of formula I (R<1> is H or methyl; (n) is 0-8) (e.g. 2,4,6-tribromophenyl acrylate), (B) 20-80 wt.% of an unsaturated compound having cyclic structure other than the component A and weight-average molecular weight lower than 500 (preferably a compound of formula II or the like), (C) 1-50 wt.% of a nitrogen-containing unsaturated compound [preferably N- alkoxy(meth)acrylamide or the like], and (D) 10-70 parts, based on 100 parts of the sum of the components A-C, of an unsaturated resin having weight- average molecular weight of 500 or higher (e.g. urethane resin or acrylic resin). The coating film is formed by applying the composition onto the substrate so as to be 1-50 μm in the thickness of the resulting cured coating film, followed by curing with active energy beams.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel active energy ray-curable resin composition and a method for forming a film using the same.

[0002]

2. Description of the Related Art Conventionally, active energy ray-curable resin compositions which are cured by active energy rays such as ultraviolet rays and electron beams have been widely used for applications such as paints, inks and adhesives. In general, paint such as thermosetting paint and lacquer is not sufficiently cured immediately after finishing, and after a certain period of time (cooling, drying, etc.), winding, stacking, and transportation of products are performed. Therefore, there is a disadvantage that productivity is poor. In contrast, active energy ray-curable resin compositions can be cured in seconds and do not require heating, thus enabling high-speed curing and drying that could not be achieved with thermosetting paints and lacquer types. Widely used for suitable applications.

However, the conventional active energy ray-curable resin composition is inhibited from curing by oxygen, and is usually cured by an active energy ray in the presence of an inert gas such as nitrogen. For this reason, there are problems that the cost is increased due to the necessity of special equipment and that the inert gas is not good for the human body.

[0004] In addition, there have been problems that the cured film obtained conventionally has insufficient surface hardness and poor adhesion to a plastic film such as PET.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to develop an active energy ray-curable resin composition capable of forming a film excellent in curability in the presence of oxygen, surface hardness of the film, and adhesion. It was made.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, the conventional problems have been solved by blending a specific unsaturated compound. This led to the completion of the present invention.

That is, the present invention provides: (1) the following components (A):

[0008]

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(Wherein, R 1 represents a hydrogen atom or a methyl group, and n represents 0 or an integer of 1 to 8) Tribromophenyl acrylate monomer 1 to 70% by weight (B) Unsaturated compound having a cyclic structure other than A) and having a weight average molecular weight of less than 500 20 to 80% by weight (C) Nitrogen-containing unsaturated compound 1 to 50% by weight (D) Unsaturated resin having a weight average molecular weight of 500 or more An active energy ray-curable resin composition characterized in that 10 to 70 parts by weight is blended with respect to 100 parts by weight of the above (A) + (B) + (C) components. And a method for forming a coating film, which comprises applying the active energy ray-curable resin composition so that the applied amount is 1 to 50 microns in cured film thickness, and then irradiating with an active energy ray for curing.

The component (A) used in the resin composition of the present invention is a tribromophenyl acrylate monomer represented by the above general formula (1), and has an effect of particularly improving the hardness of a cured film. Specifically, 2, 4,
Examples thereof include 6-tribromophenyl acrylate and hydroxyethyl 2,4,6-tribromophenyl acrylate.

The component (B) used in the present invention is an unsaturated compound having a cyclic structure and a weight average molecular weight of less than 500 (this is abbreviated as "cyclic unsaturated compound (B)").
As the component, a conventional one can be used. In particular, the following unsaturated compounds have excellent compatibility with the components (A) and (C) and excellent adhesion to plastics such as PET. It is preferable to use this as it exerts its effects.

Cyclic unsaturated compound (B) -1

[0013]

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(Where A is

[0015]

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Wherein R1 has the same meaning as described above, R2 represents a hydrogen atom or a C1-C4 alkyl group, and R3 represents a C1-C4 alkylene group. Specific examples include the following.

[0017]

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Cyclic unsaturated compound (B) -2

[0019]

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(Where B is

[0021]

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Where D is

[0023]

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Wherein R 1 and R 2 have the same meanings as described above, and m represents an integer of 1 to 8. Specific examples include the following.

[0025]

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Cyclic unsaturated compound (B) -3

[0027]

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(Where E is

[0029]

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Wherein R4 is a hydrogen atom, a methyl group or

[0031]

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Wherein R 1 and m have the same meaning as described above. Specific examples include the following.

[0033]

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Cyclic unsaturated compound (B) -4

[0035]

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(Wherein, R1 has the same meaning as described above, and G is

[0037]

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And E has the same meaning as described above. Specific examples include the following.

[0039]

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Cyclic unsaturated compound (B) -5

[0041]

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(In the formula, R1 has the same meaning as described above.) Specific examples include the following.

[0043]

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The component (C) used in the resin composition of the present invention is a nitrogen-containing unsaturated compound, and a conventional unsaturated compound can be used. In addition, since a film having a high surface hardness can be formed, it is preferable to use the following. The component (C) preferably has a weight average molecular weight of less than about 500.

Nitrogen-containing unsaturated compound (C) -1

[0046]

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(Wherein, R 1 and R 2 have the same meanings as described above.) Specific examples include the following.

[0048]

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Nitrogen-containing unsaturated compound (C) -2

[0050]

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(In the formula, R1 has the same meaning as described above.) Specifically, the following may be mentioned.

[0052]

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In addition to the above, N-vinylpyrrolidone, N-vinylformamide and N- (meth) acryloylmorpholine can be mentioned.

Of the above, N-alkoxy (meth) acrylamide and N- (meth) acryloylmorpholine of compound (C) -1 are preferred.

The mixing ratio of the above components (A) to (C) is the total ratio of the three components as follows.

(A): 1 to 70% by weight, preferably 5 to 70% by weight
50% by weight. If the amount is less than 1% by weight, the hardness of the coating decreases. On the other hand, if it exceeds 70% by weight, the workability of the coating film will be poor.

(B): 20 to 80% by weight, preferably 3
0 to 60% by weight. If the content is less than 20% by weight, the adhesion to the substrate is reduced. On the other hand, when the content exceeds 80% by weight, the workability of the coating film deteriorates.

(C): 1 to 50% by weight, preferably 5 to 50% by weight
30% by weight. If it is less than 1% by weight, the curability in the presence of oxygen will be poor. On the other hand, if it exceeds 50% by weight, the internal hardness of the coating will be poor.

The component (D) used in the resin composition of the present invention can be used to increase the viscosity of the resin composition to improve coating and printing workability, and to impart mechanical properties such as film workability. As the component (D), a conventionally known unsaturated resin having a weight average molecular weight of about 500 or more can be used.

Examples of the unsaturated resin (D) include a polymerizable unsaturated group in a resin such as a urethane resin, an acrylic resin, an alkyd resin, a polyester resin, a silicone resin, a fluororesin, a spirane resin, a polyether resin, and an epoxy resin. It is an introduced resin. As the polymerizable unsaturated group,
For example, a vinyl group, a (meth) acryloyl group, a styryl group, a group derived from maleic acid, and the like are included.

Representative examples of the unsaturated resin (D) include, for example, urethane resin acrylate, acrylic resin acrylate, acrylic resin malate, alkyd resin acrylate, polyester resin acrylate, polyester resin malate, silicone resin acrylate, fluororesin acrylate, and spirane resin. Acrylate, polyether resin acrylate, and the like.

The unsaturated resin (D) includes, for example, urethane resin, acrylic resin, alkyd resin, polyester resin,
Hydroxyl-containing resins such as silicone resin, fluororesin and polyether resin, and carboxyl-containing unsaturated compounds such as (meth) acrylic acid and (maleic anhydride) or isocyanate groups such as inisocyanatoethyl (meth) acrylate Reactant with unsaturated compound; Reactant of isocyanate group-containing resin such as urethane resin and acrylic resin with hydroxyl group-containing unsaturated monomer such as hydroxyethyl (meth) acrylate; acrylic resin (radical of glycidyl (meth) acrylate) ) Polymer)
Etc. can be used. These reactions can be performed by a conventionally known method.

The trade name of the unsaturated resin (D) is Actilan 210TP30 (trade name, manufactured by Nippon Sebel Hegner Co., Ltd., urethane acrylate, weight average molecular weight of about
00, unsaturation about 1), Viscoat # 700 (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name, polyether acrylate, weight average molecular weight about 510, unsaturation about 4), purple light U
V7510B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name,
Urethane acrylate, weight average molecular weight about 4,000,
Unsaturation degree 0.75), violet UV7550B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name, urethane acrylate, weight average molecular weight about 2,400, unsaturation degree 1.2), NK ester A-BPE-4 (Shin-Nakamura Chemical Co., Ltd., trade name, epoxy acrylate, weight average molecular weight 512,
Unsaturation degree 2).

The mixing ratio of the unsaturated resin (D) is from (A) to
10 to 70 parts by weight per 100 parts by weight of component (C),
Preferably it is in the range of 20 to 50 parts by weight. If the compounding ratio is less than 10 parts by weight, the viscosity of the resin composition becomes low, so that the coating film and the printing film cause sagging and the like, resulting in a poor finished appearance and a disadvantage that the film thickness cannot be increased. If the amount is more than the weight part, the viscosity becomes high and the finished appearance of the coating becomes poor.

In the resin composition of the present invention, for example, the following reactive diluent (E) can be used as necessary, in addition to the components (A) to (D).

As the reactive diluent (E), conventionally known diluents having a weight average molecular weight of less than 500 can be used. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) Acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) Alkyl or cycloalkyl ester monomers of (meth) acrylic acid such as acrylate, stearyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate; methoxybutyl (meth) acrylate, methoxyethyl (meth)
Acrylate, ethoxybutyl (meth) acrylate,
Alkoxyalkyl ester monomers of (meth) acrylic acid such as trimethylolpropane tripropoxy (meth) acrylate; aromatic vinyl monomers such as styrene, α-methylstyrene and vinyltoluene; α, such as (meth) acrylic acid and maleic acid; β-ethylenically unsaturated carboxylic acid monomer; acrylate phosphate monomers such as dimethyl phosphate ethyl acrylate and diethyl phosphate ethyl acrylate; epoxy groups such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and glycidyl ether -Containing unsaturated monomer; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, hydroxy Chill (meth) acrylate,
Hydroxyl-containing unsaturated monomers such as (poly) alkylene glycol monoacrylates and adducts of these monomers with lactones (such as ε-caprolactone);
Adducts of hydroxyalkyl esters of glycidyl (meth) acrylate or (meth) acrylic acid with monocarboxylic compounds such as capric acid, lauric acid, linoleic acid, and oleic acid;
Adducts with monoepoxy compounds such as 10 "(manufactured by Shell Chemical Co.); linear alkyl vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether and octyl vinyl ether; cyclopentyl vinyl ether, cyclohexyl vinyl ether, 1,4-cyclo Cycloalkyl vinyl ethers such as hexane dimethanol divinyl ether; allyl ethers such as allyl glycidyl ether and allyl ethyl ether; perfluorobutylethyl (meth) acrylate, perfluoroisononylethyl (meth) acrylate, and perfluorooctylethyl (meth) Fluorine-containing unsaturated monomers such as acrylates; (poly) ethylene glycol, (poly) propylene glycol, hexanedio Le, neopentyl glycol, trimethylol propane, obtained by a carboxyl group-containing monomers such as polyhydric alcohol compound and (meth) acrylic acid, such as glycerol reacted esterified 1
Monomers having two or more polymerizable unsaturated groups in the molecule can be exemplified.

The trade names of the reactive diluent (E) include, for example, Aronix M-305 (trade name, manufactured by Toagosei Co., Ltd., weight average molecular weight 298), and Biscoat # 215
(Trade name, manufactured by Osaka Organic Synthetic Chemical Industry Co., Ltd., weight average molecular weight 212, neopentyl glycol diacrylate), Kayamer PM2 (trade name, manufactured by Nippon Kayaku Co., Ltd.)
Acrylic phosphate ester monomer).

The amount of the reactive diluent (E) is usually about 0 to 60% by weight, preferably about 5 to 50% by weight, based on the total weight of the components (A) to (E). It is.

In the present invention, when an ultraviolet ray is used as an active energy ray, an active energy ray polymerization initiator (F) can be blended as required.

As the initiator (F), conventionally known initiators can be used. Specifically, for example, 2, 4
-Trichloromethyl- (4'-methoxyphenyl) -6
-Triazine, 2,4-trichloromethyl- (4'-methoxynaphthyl) -6-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-triazine
Trichloromethyl- (4'-methoxystyryl) -6
Triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl)-
S-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -S-triazine, 2- [2- (4-dimethylamino-2-methylphenyl) ethenyl ] -4,6-bis (trichloromethyl) -S-triazine, 2- [2-dimethylaminoethyl) amino] -4,6-bis (trichloromethyl) -S
-Triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl)-
S-triazine, 2- (4-methoxyphenyl) -4,
6-bis (trichloromethyl) -S-triazine, 2-
Methyl-4,6-bis (trichloromethyl) -S-triazine, 2,4,6-tris (trichloromethyl) -S
-Triazine compounds such as triazine, tris (chloromethyl) triazine, 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, 4-tert-butyl-trichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl -1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane- 1-one, 4- (2-
(Hydroxyphenoxy) -phenyl (2-hydroxy-
Acetophenone-based compounds such as 2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1, thioxanthone, 2-chlorothioxanthone, 2-methyl Thioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone,
Examples thereof include thioxanthone compounds such as 2,4-dichlorothioxanthone, benzoin compounds such as benzoin and benzoin methyl ether, dimethylbenzyl ketal, and acylphosphine oxide.

The trade names include, for example, Irgacure 651 (trade name, acetophenone-based photopolymerization initiator, manufactured by Ciba-Geigy), Irgacure 184 (trade name, acetophenone-based photopolymerization initiator, manufactured by Ciba-Geigy), Irgacure 1850 (trade name) Ciba Geigy, trade name, acetophenone photopolymerization initiator), Irgacure 907 (Ciba Geigy, trade name, aminoalkylphenone photopolymerization initiator), Irgacure 369 (Ciba Geigy,
Trade name, aminoalkylphenone-based photopolymerization initiator), Lucirin TPO (manufactured by BASF, trade name, 2,4,6-trimethylbenzoyldiphenylphosphine oxide), Kayacure DETXS (manufactured by Nippon Kayaku Co., Ltd., trade name) ).

The mixing ratio of the above component (F) is
To (E) 0 to 15 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total components.

The resin composition of the present invention may further contain, if necessary, a photopolymerization sensitizer, a photopolymerization accelerator, a thermosetting accelerator, a filler, a colorant, a pigment, a fluidity regulator, a repelling inhibitor and the like. can do.

The resin composition of the present invention can be used for paints, inks, adhesives and the like.

The resin composition of the present invention can be used for paper, plastic,
It can be applied to substrates such as metals and combinations thereof.

In the film forming method of the present invention, the active energy ray-curable resin composition is applied to the substrate (including printing).
After that, a film can be formed by irradiating with active energy rays.

The coating can be performed by a conventionally known method, for example, a spray, a roll coater, a gravure coater, a screen or the like. The thickness of the coating is preferably in the range of about 1 to 50 microns, preferably about 3 to 20 microns in terms of cured film thickness.

Examples of the active energy rays include ultraviolet rays from a mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide, a gallium lamp, a β-ray, an electron beam, and the like.
The irradiation amount of the ultraviolet ray is not particularly limited, but is usually about 10
It is preferably within a range of 2,000 mj / cm 2. Also,
In the case of an electron beam, an electron beam of 50 to 300 Kev
Irradiation of up to 20 Mrad is preferred.

[0079]

EXAMPLES The resin composition of the present invention will be described in detail with reference to examples. In the examples and comparative examples, “parts” indicates “parts by weight”.

Example 1 30 parts of 2,4,6-tribromophenyl acrylate
Paracumylphenol ethylene oxide acrylate (Aronix M-110, manufactured by Toagosei Co., Ltd., trade name) 50 parts, N-methoxymethylacrylamide 20
Part, unsaturated polyester resin A (a mixture of isophthalic acid / terephthalic acid / neopentyl glycol / ethylene glycol / diethylene glycol was heated at 240 ° C. to carry out a dehydration condensation reaction to obtain a polyester having a hydroxyl value of 60 mg KOH / g. This was reacted with an adduct of isophorone diisocyanate and hydroxyethyl acrylate in an equimolar reaction, and the one having a molecular weight of about 1,800 and the number of polymerizable unsaturated groups per molecular weight of 0.5 per 1,000 was used. 30 parts), 5 parts of lucirin TPO (same as above) and 20 parts of neopentyl glycol diacrylate were added and mixed to obtain Example 1.

Next, PE which has been subjected to corona treatment
A T (thickness: 100 μm) film was coated by a roll coater to a thickness of 10 μm. This coated material was exposed to 150 mj / c by a metal halide lamp in the presence of air.
m2 ultraviolet rays were applied.

As a result, the appearance and adhesion of the cured coating film were good, and the pencil hardness was good at 2H. The hardness was good 35 times.

Example 2 20 parts of 2,4,6-tribromophenyl acrylate
40 parts of 2-hydroxy-3-phenoxypropyl acrylate, 40 parts of acryloylmorpholine, 25 parts of unsaturated polyester resin A (same as above), 20 parts of 1,6-hexanediol diacrylate, Irgacure 3
69 parts (same as above) were mixed and dissolved to obtain Example 2.

This was applied to a primer-coated aluminum plate so as to have a thickness of 8 μm. The coating was irradiated with 100 mj / cm 2 of ultraviolet light from a high-pressure mercury lamp in the presence of air to cure the coating.

As a result, the appearance and adhesion of the cured coating film were good, and the pencil hardness was good at 3H. The hardness was good at 40 times.

Example 3 25 parts of hydroxyethyltribromophenol acrylate, 25 parts of 2-hydroxy-3-phenoxypropyl acrylate, 25 parts of N-methoxymethylacrylamide, paracumylphenol ethylene oxide acrylate (Aronix M-110, Toa Gosei Co., Ltd.
25 parts, NK ester A-BPE-4
(Same as above) 20 parts, Aronix M-305
Example 3 was obtained by mixing 10 parts (same as above), 4 parts of Irgacure 907 (same as above), and 1 part of Kayacure DETXS (same as above).

This was coated on a polybutylene terephthalate film so as to have a thickness of 5 μm, and was coated with a metal halide lamp in the presence of air at 200 mj / cm 2.
2 were irradiated.

As a result, the appearance and adhesion of the cured coating film were good, and the pencil hardness was good at 2H. The hardness was good 32 times.

Example 4 25 parts of 2,4,6-tribromophenyl acrylate
40 parts of paramylphenol ethylene oxide acrylate (Aronix M-110, manufactured by Toagosei Co., Ltd., trade name), 25 parts of acryloyloxyethyl hydrogen phthalate (Viscoat @ 2000, manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name) 25 parts, N-vinylformamide 1
0 parts, tripropylene glycol diacrylate 30
Parts, 15 parts of purple UV7550B (same as above),
5 parts of a photopolymerization initiator Irgacure 1850 (same as above) was added and mixed to obtain Example 4.

This was coated on a polyethylene terephthalate (50 μm) film so as to have a thickness of 5 μm, and was coated with a metal halide lamp in the presence of air.
The coating was cured by irradiating it with 50 mj / cm 2 of ultraviolet light.

As a result, the appearance and adhesion of the cured coating film were good, and the pencil hardness was good at H. Sword hardness is 2
Eight times were good.

Example 5 30 parts of 2,4,6-tribromophenyl acrylate
20 parts of Biscoat # 700 (same as above), paracumylphenol-hylene oxide acrylate 15
Part, 2-hydroxy-3-phenoxypropyl acrylate 40 parts, 1,3-butanediol diacrylate 1
0 parts, vinylcaprolactam 5 parts, N-vinylpyrrolidone 10 parts, photopolymerization initiator lucilin TPO (same as above) 5 parts, Irgacure 184 (same as above)
One part was mixed and dissolved to obtain Example 5.

This was coated on a coated paper so as to have a thickness of 10 μm, and irradiated with 150 mj / cm 2 ultraviolet rays by a metal halide lamp in the presence of air.

As a result, the appearance and adhesion of the cured coating film were good, and the pencil hardness was good at 2H. The hardness was good at 30 times.

Example 6 10 parts of 2,4,6-tribromophenyl acrylate
40 parts of menthyl acrylate, 10 parts of N-butoxymethylacrylamide, 10 parts of N-methoxymethylacrylamide, 30 parts of paracumylphenol ethylene oxide acrylate (Aronix M-110, manufactured by Toagosei Co., Ltd., trade name), unsaturated polyester Example A 6 was obtained by mixing 40 parts of A (same as above) and 5 parts of lucilin TPO (same as above).

This was applied on a corona-treated polypropylene film so as to have a thickness of 4 μm, and was coated with a metal halide lamp in the presence of air at 180 mj / cm.
2 were irradiated.

As a result, the appearance and adhesion of the cured coating film were good, and the pencil hardness was good at 2H. The hardness was good 31 times.

Comparative Example 1 Comparative Example 1 was obtained in the same manner as in Example 1, except that n-butyl acrylate was used instead of N-methoxymethylacrylamide. next,
This was used to form a coating in the same manner as in Example 1.

As a result, the appearance and adhesion of the cured coating film were good, and the pencil hardness was poor at B. The steel hardness was bad at eight times.

Comparative Example 2 Comparative Example 2 was obtained in the same manner as in Example 1 except that n-butyl acrylate was used instead of 2,4,6-tribromophenyl acrylate. . Next, a film was formed on the substrate in the same manner as in Example 1.

As a result, the appearance and adhesion of the cured coating film were good, and the pencil hardness was poor at 2B. The hardness was poor four times.

Comparative Example 3 Example 2 was repeated except that 2-ethylhexyl acrylate was used instead of acryloylmorpholine.
The compound of Comparative Example 3 was obtained in the same manner as described above. Next, a film was formed on the film in the same manner as in Example 2.

As a result, the appearance and adhesion of the cured coating film were good, and the pencil hardness was poor at 2B. The hardness was poor at six times.

Comparative Example 4 A compound of Comparative Example 4 was obtained in the same manner as in Example 3, except that 2-ethylhexyl acrylate was used instead of N-methoxymethylacrylamide. Next, a film was formed on this film in the same manner as in Example 3.

As a result, the appearance and adhesion of the cured coating film were good, and the pencil hardness was poor at B. The hardness of the steel was bad 9 times.

Comparative Example 5 Example 4 was repeated, except that 2-ethylhexyl acrylate was used in place of N-vinylformamide.
The compound of Comparative Example 5 was obtained in the same manner as described above. Next, a film was formed on this film in the same manner as in Example 4.

As a result, the appearance and adhesion of the cured coating film were good, and the pencil hardness was poor at 2B. Sword hardness is 11
It was bad at times.

Comparative Example 6 A compound of Comparative Example 6 was obtained in the same manner as in Example 5 except that n-butyl acrylate was used instead of N-vinylpyrrolidone and vinylcaprolactam. Next, a film was formed on the resultant in the same manner as in Example 5.

As a result, the appearance and adhesion of the cured coating film were good, and the pencil hardness was poor in B. The hardness of the steel was poor at 12 times.

Comparative Example 7 A compound of Comparative Example 7 was obtained in the same manner as in Example 6, except that n-butyl acrylate was used instead of N-methoxymethylacrylamide. next,
This was used to form a coating in the same manner as in Example 6.

As a result, the appearance and adhesion of the cured coating film were good, and the pencil hardness was poor in B. The steel hardness was bad at 11 times.

In the examples and comparative examples, tests and evaluations were performed as follows.

Appearance of cured coating: An abnormality in the coating, such as cracking, cracking or reduction in gloss, of the coating was visually observed.

Adhesion: 100 cross-cuts of 1 × 1 mm were made on the coating with a sharp cutter to reach the material, and an adhesive cellophane tape was adhered to the surface of the cross-cuts, and the cross-cuts after abruptly peeling it off The degree of adhesion was visually evaluated.

Pencil hardness: This was measured according to JIS K-5400. The evaluation was performed by abrasion.

Sword hardness: ASTM section 6
Coatings, and aromatics Vol 06.01 Pa
int tests for chemical, physical, and optical proper
The test was performed based on the description in ties; appearance.

[0117]

According to the present invention, since it has the above-mentioned structure, it can be cured by an active energy ray even in the presence of air to obtain a film having high hardness.

Claims (2)

[Claims] 1. The following component (A): The following general formula (1) (Wherein, R1 represents a hydrogen atom or a methyl group, and n represents 0 or an integer of 1 to 8.) 1 to 70% by weight of a tribromophenyl acrylate monomer represented by the following formula (B): Component (A) 20 to 80% by weight of unsaturated compound having a weight-average molecular weight of less than 500 having a cyclic structure other than (C) 1 to 50% by weight of a nitrogen-containing unsaturated compound. ) + (B) + (C) An active energy ray-curable resin composition characterized by comprising 10 to 70 parts by weight per 100 parts by weight of the component. 2. The method according to claim 1, wherein the active energy ray-curable resin composition is applied to the surface of a substrate so that the applied amount is 1 to 50 μm in a cured film thickness, and then cured by irradiating with an active energy ray. Characteristic film forming method.