JP2001329030A - Active energy ray-curable composition and film-formed body having cured coating film composed of the composition - Google Patents

Abstract

(57) [Problem] To provide an active energy ray-curable composition which is excellent in coating workability and can provide a cured coating film excellent in water resistance and moisture resistance. SOLUTION: At least one oligomer component (A) selected from the group consisting of polyester (meth) acrylate, urethane (meth) acrylate and epoxy (meth) acrylate, and at least three (meth) molecules per molecule.
Compound (B) other than the oligomer component having an acryloyl group, 2,4-diethyl-1,5-pentanediol di (meth) acrylate and / or 3-methyl-
An active energy ray-curable composition containing 1,5-pentanediol diacrylate (C) and a photopolymerization initiator (D).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an active energy ray-curable composition which is cured by irradiation with active energy rays such as ultraviolet rays, and a film-forming product having a cured coating film comprising the composition. The present invention relates to an active energy ray-curable composition useful for coating plastics and woods, in which a cured coating film obtained by curing has excellent water resistance and moisture resistance, and a film-formed body having a cured coating film comprising the composition.

[0002]

2. Description of the Related Art In recent years, due to problems such as environmental pollution, energy saving and working environment pollution, diluting solvents and the like are not substantially required, and the amount of energy required for curing a coating film is small. Active energy ray-curable compositions that cure by irradiation with radiation have attracted attention. Such an active energy ray-curable composition is used for coating plastic lenses, optical disks, sheets, films, optical fibers and the like; woodwork plywood, floorboards, furniture, musical instruments and other woodwork products; and inks and adhesives. It is increasingly used.

Such an active energy ray-curable composition mainly contains an oligomer such as an unsaturated polyester resin, a urethane acrylate resin, an epoxy acrylate resin, or a polyester acrylate resin, and therefore has a viscosity as it is. It was extremely expensive and difficult to handle as a paint. Generally, by mixing such oligomers and a low-viscosity reactive diluent having a radical polymerizable unsaturated bond, the coating operability of the active energy ray-curable composition is enhanced.

As reactive diluents, for example, acrylates containing a polyoxyalkylene chain such as tripropylene glycol diacrylate are disclosed in JP-A-4-149280, JP-A-7-330835, and JP-A-8-259.
No. 644. However, with these reactive diluents, the cured coating film obtained by using these reactive diluents tends to be inferior in water resistance and moisture resistance. Therefore, a diluent having good dilution performance and a cured coating film having excellent water resistance has been demanded.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a composition having a low viscosity and excellent workability during coating,
An object of the present invention is to provide an active energy ray-curable composition capable of obtaining a cured coating film excellent in water resistance and moisture resistance, and a film-formed body excellent in water resistance and moisture resistance.

[0006]

The active energy ray-curable composition of the present invention comprises at least one selected from the group consisting of polyester (meth) acrylate, urethane (meth) acrylate and epoxy (meth) acrylate.
Species oligomer component (A), compound (B) other than the above oligomer component having at least three (meth) acryloyl groups in the molecule, 2,4-diethyl-1,5-pentanediol di (meth) acrylate and / Or 3-
It is characterized by containing methyl 1,5-pentanediol di (meth) acrylate (C) and a photopolymerization initiator (D).

[0007] The film-formed body of the present invention is characterized by having a cured coating film comprising the active energy ray-curable composition of the present invention on the surface.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

In the present invention, “(meth) acrylic acid” is replaced with “acrylic acid and / or methacrylic acid”
“(Meth) acryloyl group” means “acryloyl group and / or methacryloyl group”, and “(meth) acrylate” means “acrylate and / or methacrylate”.
Respectively.

At least one oligomer component (A) selected from the group consisting of polyester (meth) acrylate, urethane (meth) acrylate and epoxy (meth) acrylate used in the present invention is an active energy ray-curable composition according to the present invention. Considering the required performance of the application of the product,
What is necessary is just to select suitably.

Specific examples of usable polyester (meth) acrylates include, for example, polybasic acids such as phthalic acid and adipic acid, ethylene glycol, neopentyl glycol, 1,6-hexanediol, polyethylene glycol, polytetramethylene Polyhydric alcohols such as glycol, and polyester (meth) acrylates obtained by reaction with (meth) acrylic acid or a derivative thereof, and the like.

Examples of usable urethane (meth) acrylates include, for example, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, norbornane Isocyanate compounds such as diisocyanate, polyethylene glycol, propylene glycol, polytetramethylene glycol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A,
Polyol compounds such as polyester polyol and polycarbonate diol, and 2-hydroxyethyl (meth)
Acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate,
Urethane di (meth) acrylates obtained by reacting hydroxyl group-containing (meth) acrylates such as polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate; hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate Polymers of isocyanate compounds such as isocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, norbornane diisocyanate, and the like are treated with 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
And urethane poly (meth) acrylates to which (meth) acrylates having a hydroxyl group such as hydroxybutyl (meth) acrylate and their caprolactone adducts are added.

Further, usable epoxy (meth) acrylates include, for example, glycidyl ether compounds such as phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A type epoxy resin and bisphenol F type epoxy resin. Epoxy poly (meth) acrylates obtained by reacting acrylic acid or a derivative thereof are exemplified.

In the present invention, at least 3
By using the compound (B) other than the oligomer component having two (meth) acryloyl groups, the curability of the active energy ray-curable composition can be improved,
In addition, the hardness of the cured coating film obtained therefrom can be improved.

Specific examples of component (B) include, for example, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, and propoxylated trimethylolpropane tri (meth) acrylate. Acrylate, glycerin tri (meth) acrylate, ethoxylated glycerin tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, ditrimethylolpropanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate ) Acrylates, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate (Meth) acrylic acid esters such as Le, and the like.

Further, in the present invention, 2,4-diethyl-1,5-pentanediol di (meth) acrylate and / or 3-methyl-1,5-pentanediol di (meth) acrylate (C) may be used as the oligomer component. By using as the reactive diluent (A), the coating workability of the active energy ray-curable composition can be improved.

Further, the water resistance and moisture resistance of the cured coating film obtained therefrom can be improved.

In the present invention, the component (A), the component (B) and the component (C) are mixed at a ratio of 5 to 9% of the total amount of 100% by mass.
The range is 0% by mass, particularly preferably 10 to 80% by mass.

When the composition ratio of the component (A) to the total amount of the components (A), (B) and (C) is less than 5% by mass, the curability of the active energy ray-curable composition becomes poor. It tends to decrease. Component (A) based on the total amount of component (A), component (B), and component (C)
When the composition ratio exceeds 90% by mass, the viscosity of the active energy ray-curable composition is too high, and the coating workability tends to decrease.

The constituent ratio of the component (B) is in the range of 5 to 50% by mass, particularly preferably 10 to 40% by mass.

When the constituent ratio of the component (B) to the total amount of the components (A), (B) and (C) is less than 5% by mass, the curability of the active energy ray-curable composition is It tends to decrease. Component (B) based on the total amount of component (A), component (B), and component (C)
When the composition ratio of the compound exceeds 50% by mass, the volume shrinkage of the active energy ray-curable composition during curing is too large,
It tends to have poor adhesion to the substrate.

The composition ratio of component (C) to the total amount of component (A), component (B) and component (C) is 5
-45 mass%, particularly preferably 10-40 mass%
Range.

When the constituent ratio of the component (C) to the total amount of the components (A), (B) and (C) is less than 5% by mass, the viscosity of the active energy ray-curable composition becomes high. Too much, and the coating workability tends to decrease.
When the constituent ratio of the component (C) to the total amount of the components (A), (B), and (C) exceeds 45% by mass, the curability of the active energy ray-curable composition tends to decrease. It is in.

The active energy ray-curable composition of the present invention is used by adding a photopolymerization initiator (D) to the blend of the components (A), (B) and (C).

Specific examples of the photopolymerization initiator (D) include, for example, benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, methylorthobenzoylbenzoate, 4-phenylbenzophenone, t -Butyl anthraquinone, 2
Thioxanthones such as -ethylanthraquinone, 2,4-diethylthioxanthone, isopropylthioxanthone and 2,4-dichlorothioxanthone; diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal ,
1-hydroxycyclohexyl-phenyl ketone, 2-
Acetophenones such as methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone; benzoin methyl ether, benzoin ethyl ether, Benzoin ethers such as benzoin isopropyl ether and benzoin isobutyl ether; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2 4,6-trimethylbenzoyl)-
Examples include acylphosphine oxides such as phenylphosphine oxide, methylbenzoyl formate, 1,7-bisacridinylheptane, 9-phenylacridine and the like.

These photopolymerization initiators (D) can be used alone or in combination of two or more.

In the present invention, the photopolymerization initiator (D) is
It is preferably 0.01 to 15 parts by mass based on 100 parts by mass of the blend comprising the components (A), (B) and (C).
It is added in the range of parts by mass, particularly preferably in the range of 0.1 to 10 parts by mass.

When the amount of the photopolymerization initiator is less than 0.01 parts by mass, the photocurability is extremely reduced, and is not suitable for industrial production. If the amount exceeds 15 parts by mass, odor tends to remain in the cured coating film when the irradiation light amount is small.

The active energy ray-curable composition of the present invention may further contain, if necessary, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, methyl 4-dimethylaminobenzoate,
Known photosensitizers such as ethyl 4-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, and 4-dimethylaminoacetophenone may be added.

The active energy ray-curable composition of the present invention may optionally contain a compound having a radically polymerizable ethylenically unsaturated bond other than those described above.

Specific examples thereof include N-vinylformamide, N-vinylacetamide, N-vinyl-
Vinyl ester monomers such as 2-pyrrolidone, N-vinylcaprolactam and divinyl adipate; vinyl ethers such as ethyl vinyl ether and phenyl vinyl ether; acrylamide, N-methylolacrylamide, N-methoxymethylacrylamide, N-butoxymethylacrylamide, N- acrylamides such as t-butylacrylamide, acryloylmorpholine, and methylenebisacrylamide; (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate,
Propyl (meth) acrylate, n- (meth) acrylate
Butyl, i-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (Meta)
Tetrahydrofurfuryl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycidyl (meth) acrylate, dimethylamino (meth) acrylate Ethyl, diethylaminoethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, allyl (meth) acrylate, (meth) ) Acrylic acid 2
Ethoxyethyl, isobornyl (meth) acrylate,
Phenyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate,
Polyethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, di ( 1,9-nonanediol meth) acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol hydroxypivalate di (meth) acrylate, propylene glycol di (meth) acrylate, di (meth) acrylic acid Dipropylene glycol, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, di (meth) acrylic acid Polyethoxylated bisph Nord A, di (meth) acrylate poly ethoxylated bisphenol F, etc. (meth)
Acrylic esters are mentioned.

These can be used alone or in combination of two or more.

Of these, acryloylmorpholine, 2-ethylhexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, ) 2-hydroxypropyl acrylate, 4-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate,
Phenoxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, di (meth) acrylic acid It is preferable to use 1,9-nonanediol, neopentyl glycol di (meth) acrylate, neopentyl glycol hydroxypivalate di (meth) acrylate, and the like.

The active energy ray-curable composition of the present invention further comprises a releasing agent, a lubricant, a plasticizer, an antioxidant, an antistatic agent, a light stabilizer, an ultraviolet absorber, a flame retardant, and a flame retardant auxiliary. ,
Known additives such as a polymerization inhibitor, a filler, a pigment, a dye, and a silane coupling agent can be appropriately added according to the application.

Examples of the object to be coated include an optical disk, a lens, an optical fiber, a sheet, a film, paper, glass, metal, wood, and a composite material, but are not particularly limited.

As a method for applying the active energy ray-curable composition of the present invention to an object to be coated, known methods such as a bar coater method, a curtain flow coater method, a roll coater method, a spin coater method, a dipping method and the like are used. Applicable. Incidentally, the active energy ray-curable composition of the present invention,
It is not limited to a paint, and can be used, for example, as a cast polymerization composition or a potting composition.

The types of light used for curing the active energy ray-curable composition of the present invention include electron beams, ultraviolet rays,
Active energy rays such as visible light can be used. Above all, it is preferable to use ultraviolet rays from the viewpoint of apparatus cost and productivity.

As a light source, an ultra-high pressure mercury lamp,
High-pressure mercury lamps, medium-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, high-frequency induction mercury lamps and the like are suitable.

The atmosphere during the curing of the active energy ray-curable composition of the present invention may be air, nitrogen, or an inert gas such as argon.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

Example 1 20 parts by mass of a bisphenol A type epoxy diacrylate as the component (A), 40 parts by mass of trimethylolpropane triacrylate as the component (B), and 2,4-diethyl-diethyl as the component (C)
40 parts by mass of 1,5-pentanediol diacrylate,
And as a component (D), 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone was mixed to obtain a composition 1. When the viscosity of the composition 1 at 25 ° C. was measured,
It was 80 mPa · s.

Next, Panlite AD9 manufactured by Teijin Chemicals Ltd.
Optical disk obtained by injection molding of 000TG (diameter 12 cm, thickness 1.2 with compact disk test signal)
mm), a sputtering device (manufactured by Balzers Co., Ltd.)
By CDI-900), aluminum was deposited to a thickness of 50 nm.
To obtain an optical disk having an aluminum reflective film on the signal recording surface.

Composition 1 was coated on this reflective film using a spin coater so as to have an average film thickness of 6 μm, and a high-pressure mercury lamp (80 W / cm) having a lamp height of 10 cm was used to obtain an integrated light amount of 300 mJ / cm ² . By curing with an energy amount, an optical disk having a protective coating layer was obtained.

The appearance of the protective coating surface of the obtained optical disk was good, and the average C1 error value of all tracks was measured using an optical disk error counter (DX610A manufactured by Shibasoku Co., Ltd.).
Met.

In order to evaluate the moisture resistance of the optical disk, the obtained optical disk was left in a constant temperature and humidity chamber of 85 ° C. and 95% RH for 500 hours. After taking out, C
When one error average value was measured, 6 frames / s
ec, and almost no signal deterioration was observed, indicating good moisture resistance.

Comparative Example 1 A composition 2 was obtained in the same manner as in Example 1 except that 40 parts by mass of tripropylene glycol diacrylate was used instead of the component (C).
When the viscosity of the composition 2 at 25 ° C. was measured, 80
mPa · s.

In the same manner as in Example 1, the composition 2 was applied to the surface of the optical disk substrate having the reflective film and cured to obtain an optical disk having a protective coating layer. The appearance of the protective coating surface of the obtained optical disk was good, and the C1 error average value of all tracks was measured in the same manner as in Example 1, and it was 5 frames / sec.

Regarding the durability of this optical disk,
After the same moisture resistance test as in Example 1 was performed, the C1 error average value was measured again, and the result was 100 frames / s.
ec, and deterioration of signal characteristics was observed.

That is, since the cured coating film has poor moisture resistance,
It was found that moisture penetrated through the cured coating film and corroded the aluminum reflective film.

(Example 2) As the component (A), urethane acrylate UK-6091 manufactured by Mitsubishi Rayon Co., Ltd.
0 parts by mass, 20 parts by mass of dipentaerythritol hexaacrylate as the component (B), and 2 parts by mass as the component (C).
30 parts by mass of 4-diethyl-1,5-pentanediol diacrylate and 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone as component (D) were mixed,
Composition 3 was obtained. It was 400 mPa * s when the viscosity at 25 degreeC of the composition 3 was measured.

The obtained composition 3 was coated on a polyester film A-4100 manufactured by Toyobo Co., Ltd. using a bar coater # 3, and a high-pressure mercury lamp (120 w / c) having a lamp height of 20 cm was used.
m), curing was performed with an energy amount of an integrated light amount of 300 mJ / cm ² to obtain a hard-coated film.

The appearance of the obtained film was good.
When the pencil hardness was measured by the method described in IS K-5400, it was HB.

When the obtained film was immersed in warm water of 60 ° C. for 10 days and taken out, there was no change in the appearance. The pencil hardness was measured in the same manner as above.
B was good without any change from the initial stage.

Comparative Example 2 A composition 4 was obtained in the same manner as in Example 2, except that 30 parts by mass of tripropylene glycol diacrylate was used instead of the component (C). When the viscosity of the composition 4 at 25 ° C. was measured, it was 500
mPa · s.

The obtained composition 4 was coated and cured on a polyester film in the same manner as in Example 2 to obtain a hard coat-treated film.

The appearance of the obtained film was good.
When the pencil hardness was measured by the method described in IS K-5400, it was HB.

Further, the obtained film was immersed in warm water of 60 ° C. for 10 days and then taken out. As a result, the appearance was cloudy. When the pencil hardness was measured in the same manner as in Example 2, it was B and the hardness was reduced. From these, it was found that the coating film obtained by curing the composition 4 was inferior in water resistance.

Example 3 As a component (A), polyester acrylate UK-4003 manufactured by Mitsubishi Rayon Co., Ltd.
40 parts by mass, as component (B), 30 parts by mass of ditrimethylolpropane tetraacrylate, 30 parts by mass of 2,4-diethyl-1,5-pentanediol diacrylate, which is component (C), and component (D) As 1-
Composition 5 was obtained by mixing 5 parts by mass of hydroxycyclohexyl phenyl ketone. When the viscosity of the composition 5 at 25 ° C. was measured, it was 500 mPa · s.

The obtained composition 5 was coated on a straight grain oak wood veneer plywood with a bar coater # 60, and was coated at 80 w / cm.
High-pressure mercury lamp, lamp height 15 cm, integrated light amount 15
When cured with an energy amount of 0 mJ / cm ^{2 and} the appearance of the painted surface was observed, it was good. The unpainted surface of the resulting hardened plywood was sealed with epoxy resin,
After immersion in warm water of 10 ° C. for 10 days, the appearance of the painted surface was good without any change from the initial stage.

Comparative Example 3 A composition 6 was obtained in the same manner as in Example 3, except that 30 parts by mass of tripropylene glycol diacrylate was used as the component (A) instead of the component (C). When the viscosity of the composition 6 at 25 ° C. was measured, it was 500 mPa · s.

The obtained composition 6 was coated on a straight grain oak wood veneer plywood with a bar coater # 60, and was coated at 80 w / cm.
High-pressure mercury lamp, lamp height 15 cm, integrated light amount 15
When cured with an energy amount of 0 mJ / cm ^{2 and} the appearance of the painted surface was observed, it was good. The unpainted surface of the resulting hardened plywood was sealed with epoxy resin,
After immersion in warm water of 10 ° C. for 10 days, the appearance of the painted surface was observed, and it was found to be white and poor in appearance. This proved that the coating film obtained by curing the composition 6 had poor water resistance.

Example 4 20 parts by mass of bisphenol A type epoxy diacrylate as component (A), 40 parts by mass of trimethylolpropane triacrylate as component (B), and 3-methyl-1 as component (C) , 5-
Composition 7 was obtained by mixing 40 parts by mass of pentanediol diacrylate and 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone as component (D). When the viscosity of the composition 7 at 25 ° C. was measured, it was found to be 60 mPa
-It was s.

Next, Panlite AD9 manufactured by Teijin Chemicals Ltd.
Optical disk obtained by injection molding of 000TG (diameter 12 cm, thickness 1.2 with compact disk test signal)
mm), a sputtering device (manufactured by Balzers Co., Ltd.)
By CDI-900), aluminum was deposited to a thickness of 50 nm.
To obtain an optical disk having an aluminum reflective film on the signal recording surface.

Composition 1 was coated on this reflective film using a spin coater so as to have an average film thickness of 6 μm, and a high-pressure mercury lamp (80 W / cm) having a lamp height of 10 cm was used to obtain an integrated light amount of 300 mJ / cm ² . By curing with an energy amount, an optical disk having a protective coating layer was obtained.

The appearance of the protective coating surface of the obtained optical disk was good, and the average C1 error value of all tracks was measured using an optical disk error counter (DX610A manufactured by Shibasoku Co., Ltd.).
Met.

In order to evaluate the moisture resistance of the optical disk, the obtained optical disk was left in a constant temperature and humidity chamber of 85 ° C. and 95% RH for 500 hours. After taking out, C
When one error average value was measured, 6 frames / s
ec, and almost no signal deterioration was observed, indicating good moisture resistance.

Comparative Example 4 20 parts by mass of bisphenol A type epoxy diacrylate as component (A), 40 parts by mass of trimethylolpropane triacrylate as component (B), and tripropylene glycol diacrylate as component (C) 40 parts by mass of acrylate, 1-hydroxycyclohexyl phenyl ketone 5 as component (D)
The composition 8 was obtained by mixing parts by mass. 25 ° C. of composition 8
Was 80 mPa · s.

In the same manner as in Example 4, the composition 8 was applied and cured on the surface of the optical disk substrate having the reflective film to obtain an optical disk having a protective coating layer. The appearance of the protective coating surface of the obtained optical disk was good, and the C1 error average value of all tracks was measured in the same manner as in Example 1, and it was 5 frames / sec.

Regarding the durability of this optical disk,
After the same moisture resistance test as in Example 4 was performed, the C1 error average value was measured again, and the result was 100 frames / sec.
c, and deterioration of the signal characteristics was observed. That is, it was found that the cured coating film was inferior in moisture resistance, so that moisture penetrated through the cured coating film and corroded the aluminum reflective film.

(Example 5) As the component (A), urethane acrylate UK-6091 manufactured by Mitsubishi Rayon Co., Ltd. was used.
0 parts by mass, 20 parts by mass of dipentaerythritol hexaacrylate as the component (B), and 3- (the component (C))
Methyl-1,5-pentanediol diacrylate 30
The composition 9 was obtained by mixing 5 parts by weight of 1 part by weight of 1-hydroxycyclohexyl phenyl ketone as the component (D). It was 400 mPa * s when the viscosity at 25 degreeC of the composition 9 was measured.

The obtained composition 9 was coated on a polyester film A-4100 manufactured by Toyobo Co., Ltd. using a bar coater # 3, and a high-pressure mercury lamp (120 w / c) having a lamp height of 20 cm was used.
m), curing was performed with an energy amount of an integrated light amount of 300 mJ / cm ² to obtain a hard-coated film.

The appearance of the obtained film was good.
When the pencil hardness was measured by the method described in IS K-5400, it was HB.

When the obtained film was immersed in warm water at 60 ° C. for 10 days and taken out, the appearance did not change. The pencil hardness was measured in the same manner as above.
B was good without any change from the initial stage.

Comparative Example 5 A composition 10 was obtained in the same manner as in Example 5 except that the component (A) was replaced by 30 parts by mass of tripropylene glycol diacrylate instead of the component (C). When the viscosity of the composition 10 at 25 ° C. was measured, it was 500 mPa · s.

The obtained composition 10 was applied and cured on a polyester film in the same manner as in Example 5 to obtain a hard coat-treated film.

The appearance of the obtained film was good.
When the pencil hardness was measured by the method described in IS K-5400, it was HB.

Further, the obtained film was immersed in warm water of 60 ° C. for 10 days and then taken out. As a result, turbidity appeared in the appearance. When the pencil hardness was measured in the same manner as described above, it was B, indicating that the hardness had decreased. From these, it was found that the coating film obtained by curing the composition 10 was inferior in water resistance.

(Example 6) Polyester acrylate UK-4003 manufactured by Mitsubishi Rayon Co., Ltd. was used as the component (A).
40 parts by mass, as component (B), 30 parts by mass of ditrimethylolpropane tetraacrylate, 30 parts by mass of 3-methyl-1,5-pentanediol diacrylate, which is component (C), and as component (D), Composition 1 was obtained by mixing 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone. When the viscosity of the composition 11 at 25 ° C. was measured, it was 400 mPa · s.

The obtained composition 11 was coated on a straight grain oak wood veneer plywood with a bar coater # 60, and was coated at 80 w / c.
m high-pressure mercury lamp, lamp height 15 cm, integrated light quantity 1
When cured with an energy amount of 50 mJ / cm ^{2 and} the appearance of the painted surface was observed, it was good. The unpainted surface of the resulting hardened plywood was sealed with epoxy resin,
After immersion in hot water of 0 ° C. for 10 days, the appearance of the painted surface was good without any change from the initial stage.

(Comparative Example 6) A composition 12 was obtained in the same manner as in Example 6 except that 30 parts by mass of tripropylene glycol diacrylate was used instead of the component (C). When the viscosity of the composition 12 at 25 ° C. was measured, 50
It was 0 mPa · s.

The obtained composition 12 was coated on a straight grain oak wood veneer plywood with a bar coater # 60, and was coated at 80 w / c.
m high-pressure mercury lamp, lamp height 15 cm, integrated light quantity 1
When cured with an energy amount of 50 mJ / cm ^{2 and} the appearance of the painted surface was observed, it was good. The unpainted surface of the resulting hardened plywood was sealed with epoxy resin,
After immersion in hot water at 0 ° C. for 10 days, the appearance of the painted surface was observed. This proved that the coating film obtained by curing the composition 12 had poor water resistance.

[0082]

As described above, the active energy ray-curable composition of the present invention comprises at least one kind selected from the group consisting of polyester (meth) acrylate, urethane (meth) acrylate and epoxy (meth) acrylate. Oligomer component (A), at least 3 in the molecule
(B) other than the oligomer component having two (meth) acryloyl groups, 2,4-diethyl-1,5-pentanediol di (meth) acrylate and / or 3-methyl-1,5-pentanediol Since it contains an acrylate (C) and a photopolymerization initiator (D),
Low viscosity of the composition, excellent coating workability, good appearance,
A cured coating film having excellent water resistance and moisture resistance can be obtained.
Such an active energy ray-curable composition is industrially very useful as a coating composition for plastics and woodwork paints.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4D075 CA38 CA47 DB21 DB31 EA21 EB22 EC37 4J011 AC04 QA03 QA07 QA12 QA13 QA22 QA23 QA24 QA33 QA38 QB14 QB19 QB20 QB24 SA01 SA02 SA05 SA12 SA21 SA22 SA24 SA31 SA51 SA63 UA03 UA06 VA01 WA02 4J027 AB15 AB17 AB18 AB23 AB24 AE02 AE03 AE04 AG03 AG04 AG09 AG13 AG14 AG23 AG24 AG27 BA19 BA25 BA26 BA27 BA28 CB10 CC04 CC05 CC06 CD08 4J038 FA122 FA152 FA172 FA251 FA261 FA281 KA03 PC02 P15 PC08 PC10

Claims (2)

[Claims] 1. At least one oligomer component (A) selected from the group consisting of polyester (meth) acrylate, urethane (meth) acrylate and epoxy (meth) acrylate, and at least three (meth) acryloyl groups in the molecule A compound (B) other than the oligomer component having 2,4-diethyl-1,5-pentanediol di (meth) acrylate and / or 3-methyl-1,5-pentanediol di (meth) acrylate (C), And an active energy ray-curable composition comprising a photopolymerization initiator (D). 2. A film-formed body having a cured coating film comprising the active energy ray-curable composition according to claim 1 on the surface.