JPH09165436A - Ultraviolet-curable resin composition and coating agent containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ultraviolet-curable resin compsn. excellent in adhesive properties by compounding an epoxy compd., a copolymer among an α,β-unsatd. silicone compd., a specific α,β-unsatd. monomer, and another α,β-unsatd. monomer, and a cationic photopolymn. initiator together. SOLUTION: 1-70wt.% α,β-unsatd. silicone compd. (e.g. a silicone having a methacryloyl group), 1-80wt.% acrylic monomer having an alicyclic epoxy group, and another α,β-unsatd. monomer (e.g. styrene) are dropped into an org. solvent together with an org. peroxide at about 50-150 deg.C and are reacted to each other to give a polymer soln. with a solid content of about 50wt.%. An ultraviolet-curable resin compsn. is obtd. by mixing 100 pts.wt. epoxy compd. liq. at normal temp. and contg. at least 50wt.% alicyclic epoxy compd. such as one represented by the formula, 0.1-50 pts.wt. polymer soln. obtd. as above, and a cationic photopolymn. initiator (e.g. an aryldiazonium salt) in an amt. of 0.5-30wt.% of the sum of the epoxy compd. and the polymer soln.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition which is cured by irradiation with ultraviolet rays, and is particularly suitable for use as a coating agent for polyester film-coated squeezed cans, which has excellent adhesiveness,
The present invention relates to an ultraviolet curable resin composition having excellent coating film hardness, lubricity, retort resistance, and processability.

[0002]

2. Description of the Related Art A resin composition which is cross-linked and cured in a short time by irradiation with ultraviolet rays has hitherto been composed of a cationic polymerization composition using a cationic initiator and an epoxy resin, and a resin having a radical initiator and an unsaturated bond. The radical polymerization composition used was mainly. As a cationic polymerization type ultraviolet curable resin composition, in order to improve the physical properties of the cured coating film obtained, it has been studied to use an epoxy resin and another compound in combination, for example, an ultraviolet curable resin containing an epoxy resin and a polyester resin. Type resin composition is Japanese Patent Publication No. 2-30326
And JP-A-5-186755, and a photo-crosslinkable resin composition containing an acrylic resin having an alicyclic epoxy group and a photocationic polymerization initiator as essential components
Although disclosed in JP-A-289611, sufficient lubricity and retort resistance are not obtained.

Further, conventionally, in order to obtain a coating film having lubricity, a silicone compound has been used as a lubricity imparting component in a coating composition. However, these silicone compounds have the drawback that they are detached from the coating film due to abrasion of the surface after the coating film is formed, and the lubricity of the coating film deteriorates over time. In order to control the lubricity of the coating film due to desorption of the silicone compound after the coating film is formed, a silicone compound having a cationically polymerizable functional group is used, or in order to improve the compatibility with the coating resin, the compatibility is improved. Attempts have been made to use a silicone compound having a functional group or a modified silicone compound alone or in combination with another silicone compound, but under severe conditions such as retort treatment, these compounds are used. However, it was not possible to sufficiently control the deterioration of the lubricity of the coating film. Further, if the addition amount of the silicone compound is increased in order to improve the lubricity after the retort treatment, the compatibility of the silicone compound with other components such as an epoxy resin and a cationic photopolymerization initiator is decreased, and the cloudiness of the paint or the silicone compound is decreased. However, the adhesion, retort resistance and workability are not sufficiently obtained.

[0004]

An object of the present invention is to provide an ultraviolet-curable resin composition which gives a coating film having excellent adhesion, lubricity, retort resistance, coating hardness and workability to plastic films and metals. And the provision of coatings.

[0005]

The present invention provides an epoxy compound (A) which is liquid at room temperature, an α, β-unsaturated silicone compound (a), and an α, β-unsaturated monocyclic unsaturated compound having an alicyclic epoxy functional group. A UV-curable resin containing a compound (B) obtained by polymerizing a monomer (b) and another α, β-unsaturated monomer (c), and a photocationic polymerization initiator (C). A composition is provided. The present invention also provides the above ultraviolet curable resin composition, wherein the epoxy compound (A) which is liquid at room temperature contains at least 50% by weight of an alicyclic epoxy compound. Further, the present invention provides the above ultraviolet curable resin composition, wherein the content ratio of the α, β-unsaturated silicone compound (a) in the total α, β-unsaturated monomers is 1 to 70% by weight. . Further, in the present invention, the content ratio of the α, β-unsaturated monomer (b) having an alicyclic epoxy functional group in the total α, β-unsaturated monomers is 1 to 80% by weight. An ultraviolet curable resin composition is provided. Further, the present invention provides the above ultraviolet curable resin composition, which comprises using an organic peroxide when the compound (B) is synthesized by polymerizing an α, β-unsaturated monomer. Furthermore, in the present invention, 0.1 to 50 parts by weight of the compound (B) and (A) and (B) of the cationic photopolymerization initiator (C) are added to 100 parts by weight of the epoxy compound (A) which is liquid at room temperature. The above ultraviolet curable resin composition is contained in an amount of 0.5 to 30% by weight based on the total weight of (1). Furthermore, the present invention provides a coating agent containing the above ultraviolet curable resin composition. Further, the present invention provides the above coating agent for coating use of a polyester film coated squeeze can.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The epoxy compound (A) which is liquid at room temperature in the present invention is a compound having at least one epoxy group, and is a conventionally known alicyclic epoxy compound, aliphatic epoxy compound, aromatic epoxy compound. They can be used alone or as a mixture depending on the required performance, but it is preferable to contain at least 50% by weight of an alicyclic epoxy compound from the viewpoint of the rapid curability of ultraviolet rays. As the alicyclic epoxy compound, a compound containing cyclohexene oxide or cyclopentene oxide in its molecular structure is preferably used.

[0007] Specific examples of the alicyclic epoxy compound are shown below.

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[0008]

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[0009]

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[0010]

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[0011]

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Examples of the aliphatic epoxy compound include polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether and trimethylolpropane triglycidyl ether. Examples of the aromatic epoxy compound include cresol novolac epoxy resin and bisphenol type epoxy resin.

An α, β-unsaturated silicone compound (a),
The compound (B) obtained by polymerizing the α, β-unsaturated monomer (b) having an alicyclic epoxy functional group and the other α, β-unsaturated monomer (c) is contained in the resin skeleton. Since it has a structure derived from a silicone compound, an alicyclic epoxy functional group, and other α, β-unsaturated monomer, the cured coating film containing this has lubricity, adhesion, coating hardness, and retort resistance. Excellent workability. Further, the compound (B) has good compatibility with the epoxy compound and the photocationic polymerization initiator. Specifically, since it has an alicyclic epoxy functional group that has a faster photocationic polymerization rate than an epoxy group such as a glycidyl group, the compound (B) is incorporated into the photocationic polymerization system, and the silicone compound The deterioration of the lubricity of the coating film over time due to desorption and the deterioration of the lubricity of the coating film due to the retort treatment are controlled. At the same time, the curability is good, and in addition, the adhesion, retort resistance, and workability are excellent. The materials and synthetic methods used when synthesizing the compound (B) are described below.

The α, β-unsaturated silicone compound (a) is not particularly limited as long as it is a silicone compound having a radical-polymerizable unsaturated double bond, and is dimethylsiloxane, methylhydrosiloxane, methylalkylsiloxane. , A compound having a (meth) acryloyl group or a vinyl group as a main chain skeleton of diphenylsiloxane, methylphenylsiloxane and the like, and a mixture thereof. Among them, a silicone compound having a (meth) acryloyl group at one end is preferably used from the viewpoint of polymerizability with other α, β-unsaturated monomer (c).
The content ratio of the α, β-unsaturated silicone compound (a) in all the α, β-unsaturated monomers is preferably 1 to 70% by weight. When the content ratio of the α, β-unsaturated silicone compound (a) in all the monomers is lower than 1% by weight, the improvement of lubricity by the silicone compound is difficult to be exhibited. On the other hand, if it is more than 70% by weight, the compound (B) obtained by the polymerization becomes cloudy and separated, and the compatibility with the epoxy resin and the cationic photopolymerization initiator is unavoidably deteriorated and further the processability is deteriorated.

The α, β-unsaturated monomer (b) having an alicyclic epoxy functional group is not particularly limited, and it is polymerized with another α, β-unsaturated monomer (c). From the viewpoint of properties, a compound having an alicyclic epoxy functional group and a (meth) acryloyl group is preferably used. Examples of the α, β-unsaturated monomer (b) having an alicyclic epoxy functional group include
Cyclomer M-100, Cyclomer M-101, Cyclomer A-200 (manufactured by Daicel Chemical Industries, Ltd.) can be mentioned. The content ratio of the α, β-unsaturated monomer (b) having an alicyclic epoxy functional group in all the α, β-unsaturated monomers is preferably 1 to 80% by weight. When the content ratio of the α, β-unsaturated monomer (b) having an alicyclic epoxy functional group in all the monomers is less than 1% by weight, deterioration of lubricity and coating film hardness due to aging and retort treatment may occur. It is unavoidable, and when it exceeds 80% by weight, the adhesion and workability are unavoidably deteriorated.

As the other α, β-unsaturated monomer (c), any monomer which can be radically polymerized by a usual method can be used without particular limitation. Specifically, vinyl monomers such as styrene, vinyltoluene, methylstyrene and vinyl acetate, methyl acrylate, ethyl acrylate, butyl acrylate, isopropyl acrylate, 2-ethylhexyl acrylate, 2-methoxyethyl acrylate, methyl methacrylate, Ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate,
(Meth) acrylic monomers such as 2-hydroxypropyl methacrylate, isooctyl acrylate and lauryl methacrylate, acrylamide, N-methylol acrylamide, N-methylol methacrylamide, N-methoxymethyl acrylamide, N-ethoxymethyl, acrylamide, N -Examples include acrylamide monomers such as butoxymethyl acrylamide. These monomers are used alone or as a mixture of two or more kinds.

Α, β-unsaturated silicone compound (a),
Polymerization of an α, β-unsaturated monomer (b) having an alicyclic epoxy functional group and another α, β-unsaturated monomer (c) is
Ordinary polymerization method, under an inert gas flow, 50-150 ° C
2 to 8 hours, and a solvent may be used at this time. As the polymerization initiator, an organic azo compound, an organic peroxide or the like is used in the range of 1 to 20% by weight with respect to the α, β-unsaturated monomer. In particular, it is preferable to use an organic peroxide. Examples of the organic peroxide include benzoyl peroxide, 1,1-bis-t-butylperoxy-
3,3,5-Tri-methylcyclohexane, dicumyl peroxide, t-butyl peroxybenzoate, di-t-butyl peroxide, di-t-butyl peroxydi-isopropylbenzene, 2,5-dimethyl-2 ，
5-di-t-butylperoxyhexane, 2,5-dimethyl-2,5-di-t-butylperoxyhexyne-3
Etc. are mentioned as an example. These organic peroxide type polymerization initiators are used alone or as a mixture of two or more kinds.

Α, β-unsaturated silicone compound (a),
The compound (B) obtained by polymerizing the α, β-unsaturated monomer (b) having an alicyclic epoxy functional group and the other α, β-unsaturated monomer (c) is a liquid at room temperature. It is preferably used in an amount of 0.1 to 50 parts by weight, more preferably 0.5 to 40 parts by weight, based on 100 parts by weight of the epoxy compound (A). When the amount of compound (B) is less than this range,
The lubricity of the coating film is unavoidably deteriorated, and if it exceeds this range, the coating hardness and workability are unavoidably deteriorated.

The cationic photopolymerization initiator is an initiator that releases a substance that initiates cationic polymerization upon irradiation with ultraviolet rays, and is an epoxy compound (A) and a compound (B) that are liquid at room temperature.
It is preferable to add 0.5 to 30% by weight, more preferably 2 to 20% by weight based on the total weight of the above. By blending within this range, it is possible to obtain a cured coating film with good adhesion to plastic films and metals, lubricity, retort resistance, coating film hardness, and processability. Examples of the cationic photopolymerization initiator include aryldiazonium salts (for example, P-33 (manufactured by Asahi Denka Co., Ltd.)), aryliodonium salts, arylsulfonium salts (for example, FC
-509 (manufactured by 3M), UVE1014 (manufactured by GE), UVI-6974, UVI-6970, UVI-.
6990, UVI-6950 (manufactured by Union Carbide Co.), SP-170, SP-150 (manufactured by Asahi Denka Kogyo Co., Ltd.), allene-ion complex (for example, CG-24-6).
1 (manufactured by Ciba Geigy).

The ultraviolet curable resin composition of the present invention may contain other conventional components, if necessary, such as organic or inorganic pigments, extender pigments, dyes, organic solvents, as long as the object is not impaired.
A coating agent can be obtained by blending a dispersion aid, a leveling agent, a crater inhibitor, a surfactant, an antifoaming agent, a slip agent, an ultraviolet sensitizer, and a coating additive such as a reactive or non-reactive diluent. To be

The ultraviolet curable resin composition of the present invention and the coating agent containing the same include polyethylene terephthalate (hereinafter abbreviated as "PET") film, polyethylene naphthalate film, nylon film, plastic film such as vinyl chloride film, iron, On the surface of metal such as aluminum, plated steel plate, tin-free steel, stainless steel, etc., a usual coating method, for example, roll coating,
It can be applied by gravure coating, gravure offset coating, curtain flow coating, reverse coating, screen printing, spraying and dipping. The thickness of the cured coating film is about 0.5 to 50 μm, preferably 1 to 20 μm
Is appropriate.

The ultraviolet-curable resin composition of the present invention and the coating material containing the same can be easily cured at room temperature in a short time by irradiating with ultraviolet rays. As the light source of this ultraviolet ray, a light source containing light with a wavelength in the range of 200 to 450 nm is usually used, for example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a xenon lamp, a carbon arc lamp or the like. The coating agent containing the ultraviolet-curable resin composition of the present invention can be suitably used for coating polyester film-coated squeeze cans.

[0023]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples without departing from the technical idea of the present invention. In addition,
In the examples, “parts” means “parts by weight”, and “%” means “% by weight”.
Represents

(Synthesis Example 1 of Compound) A separable four-necked flask was equipped with a temperature control regulator, a cooling pipe, and a stirrer, charged with 400 parts of propylene glycol monomethyl ether, heated to 120 ° C., and replaced with nitrogen in the reaction vessel. Then, from the dropping tube, methacryloyl group-containing silicone (“Cilaplane FM0721” manufactured by Chisso Corporation) 4
Part, acrylic monomer having alicyclic epoxy functional group ("Cyclomer A-200" manufactured by Daicel Chemical Industries, Ltd.)
80 parts, styrene 236 parts, ethyl acrylate 40
Parts, 40 parts of 2-ethylhexyl acrylate, and 20 parts of organic peroxide (“Perbutyl O” manufactured by NOF CORPORATION) were added dropwise over 3 hours. One hour after the completion of dropping, 2.0 parts of an organic peroxide (“Perbutyl O” manufactured by NOF CORPORATION) was added, and the reaction was continued for another hour to obtain a solution (1) of a compound having a solid content of 50%.

(Synthesis Example 2 of Compound) 400 parts of propylene glycol monomethyl ether were charged in the same reaction apparatus as in Synthesis Example 1 of compound, heated to 120 ° C., and the atmosphere in the reaction vessel was replaced with nitrogen, and then methacryloyl was added through a dropping pipe. Group-containing silicone ("Cilaplane FM072" manufactured by Chisso Corporation)
1]) 280 parts, an acrylic monomer having an alicyclic epoxy functional group ("Cyclomer A-" manufactured by Daicel Chemical Industries, Ltd.).
200 "), 40 parts of styrene, 80 parts of styrene, and 20 parts of organic peroxide (" Perbutyl O "manufactured by NOF CORPORATION) were added dropwise over 3 hours. One hour after the completion of dropping, 2.0 parts of an organic peroxide (“Perbutyl O” manufactured by NOF CORPORATION) was added, and the reaction was continued for another hour to obtain a solution (2) of a compound having a solid content of 50%.

(Synthesis Example 3 of Compound) 400 parts of propylene glycol monomethyl ether were charged in the same reaction apparatus as in Synthesis Example 1 of compound, heated to 120 ° C., and the inside of the reaction vessel was replaced with nitrogen, and then methacryloyl was added through a dropping pipe. Group-containing silicone ("Cilaplane FM072" manufactured by Chisso Corporation)
1]) 120 parts, an acrylic monomer having an alicyclic epoxy functional group ("Cyclomer A-" manufactured by Daicel Chemical Industries, Ltd.).
200 "), 4 parts of styrene, 236 parts of styrene, 40 parts of ethyl acrylate, and 20 parts of organic peroxide (" Perbutyl O "manufactured by NOF CORPORATION) were added dropwise over 3 hours. One hour after completion of dropping, organic peroxide (“Perbutyl O” manufactured by NOF CORPORATION)
2.0 parts was added and the reaction was continued for another 1 hour to obtain a compound solution (3) having a solid content of 50%.

(Synthesis Example 4 of Compound) 400 parts of propylene glycol monomethyl ether were charged in the same reaction apparatus as in Synthesis Example 1 of compound, the temperature was raised to 120 ° C. and the inside of the reaction vessel was replaced with nitrogen, and then methacryloyl was added from a dropping pipe. Group-containing silicone ("Cilaplane FM072" manufactured by Chisso Corporation)
1]) 40 parts, an acrylic monomer having an alicyclic epoxy functional group ("Cyclomer A-2" manufactured by Daicel Chemical Industries, Ltd.
00 "), 40 parts of styrene, and 20 parts of organic peroxide (" Perbutyl O "manufactured by NOF CORPORATION) were added dropwise over 3 hours. One hour after the completion of dropping, 2.0 parts of organic peroxide (“Perbutyl O” manufactured by NOF CORPORATION) was added, and the reaction was continued for another hour to obtain a solution (4) of a compound having a solid content of 50%.

(Synthesis Example 5 of Compound) 400 parts of propylene glycol monomethyl ether was charged in the same reaction apparatus as in Synthesis Example 1 of compound, the temperature was raised to 120 ° C. and the inside of the reaction vessel was replaced with nitrogen, and then methacryloyl was introduced from a dropping pipe. Group-containing silicone ("Cilaplane FM072" manufactured by Chisso Corporation)
1]) 120 parts, an acrylic monomer having an alicyclic epoxy functional group ("Cyclomer A-" manufactured by Daicel Chemical Industries, Ltd.).
200 "), 80 parts of styrene, 200 parts of styrene, and 20 parts of organic peroxide (" Perbutyl O "manufactured by NOF CORPORATION) were added dropwise over 3 hours. One hour after the completion of dropping, 2.0 parts of organic peroxide (“Perbutyl O” manufactured by NOF CORPORATION) was added, and further 1 part was added.
The reaction is continued for a time, and a solution of a compound having a solid content of 50% (5)
I got

(Synthesis Example 6 of Compound) 400 parts of propylene glycol monomethyl ether was charged in the same reaction apparatus as in Synthesis Example 1 of compound, heated to 120 ° C., and the inside of the reaction vessel was replaced with nitrogen, and then methacryloyl was added through a dropping pipe. Group-containing silicone ("Cilaplane FM072" manufactured by Chisso Corporation)
1]) 120 parts, an acrylic monomer having an alicyclic epoxy functional group ("Cyclomer M-" manufactured by Daicel Chemical Industries, Ltd.).
101 "), 200 parts of styrene, and 20 parts of organic peroxide (" Perbutyl O "manufactured by NOF CORPORATION) were added dropwise over 3 hours. One hour after the completion of dropping, 2.0 parts of organic peroxide (“Perbutyl O” manufactured by NOF CORPORATION) was added, and further 1 part was added.
The reaction is continued for a time, and a solution of a compound having a solid content of 50% (6)
I got

(Synthesis Example 7 of Compound) 400 parts of propylene glycol monomethyl ether were charged in the same reaction apparatus as in Synthesis Example 1 of compound, the temperature was raised to 120 ° C. and the inside of the reaction vessel was replaced with nitrogen, and then methacryloyl was introduced from a dropping pipe. Group-containing silicone ("Cilaplane FM072" manufactured by Chisso Corporation)
1]) 120 parts, 200 parts of styrene, 40 parts of ethyl acrylate, 40 parts of 2-ethylhexyl acrylate, and 20 parts of organic peroxide (“Perbutyl O” manufactured by NOF CORPORATION) were added dropwise over 3 hours. One hour after the completion of dropping, 2.0 parts of an organic peroxide (“Perbutyl O” manufactured by NOF CORPORATION) was added, and the reaction was continued for another hour to obtain a solution (7) of a compound having a solid content of 50%.

(Synthesis Example 8 of Compound) 400 parts of propylene glycol monomethyl ether were charged in the same reaction apparatus as in Synthesis Example 1 of compound, heated to 120 ° C., and the inside of the reaction vessel was replaced with nitrogen, and then the oil was added from the dropping pipe. Acrylic monomer having cyclic epoxy functional group ("Cyclomer A-200" manufactured by Daicel Chemical Industries, Ltd.) 80 parts, styrene 240 parts, ethyl acrylate 40 parts, 2-ethylhexyl acrylate 40 parts, organic peroxide (NOF Corporation) (Manufactured by "Perbutyl O") was added dropwise over 3 hours. One hour after completion of dropping, organic peroxide (“Perbutyl O” manufactured by NOF CORPORATION)
2.0 parts was added and the reaction was further continued for 1 hour to obtain a compound solution (8) having a solid content of 50%.

[Example 1] 3,4-epoxycyclohexylmethyl-3,4-epoxy cyclohexylcarboxylate 100 parts ("UVR-6110" manufactured by Union Carbide Co.) Compound solution (1) 10 parts Photocationic polymerization initiation 6 parts of agent ("UVI-6990" manufactured by Union Carbide Co., Ltd.) 1 part of a surfactant ("L-7604" manufactured by Nippon Unicar Co., Ltd.) was mixed and stirred to prepare coating material 1. This is thickness 30
100 μm PET on 0 μm tin-free steel plate
Material laminated with film (hereinafter referred to as "PET / TF
Abbreviated as S]. ) On PET film, and thickness 300
It was coated on an aluminum plate of μm to a film thickness of 7 μm, and 10 m under one high pressure mercury lamp of 80 W / cm each.
It was passed at a speed of / min to cure the coating film.

Example 2 A coating material 2 was prepared and applied in the same manner as in Example 1 except that the compound solution (2) was used in place of the compound solution (1), and the coating film was cured. Let Example 3 A coating material 2 was prepared and applied in the same manner as in Example 1 except that the compound solution (3) was used in place of the compound solution (1), and the coating film was cured. Example 4 A coating material 2 was prepared and applied in the same manner as in Example 1 except that the compound solution (4) was used in place of the compound solution (1), and the coating film was cured.

Example 5 A coating material 2 was prepared and applied in the same manner as in Example 1 except that the compound solution (5) was used in place of the compound solution (1), and the coating film was cured. Let Example 6 A coating material 2 was prepared and applied in the same manner as in Example 1 except that the compound solution (6) was used in place of the compound solution (1), and the coating film was cured.

[Example 7] 3,4-epoxycyclohexylmethyl-3,4-epoxy cyclohexylcarboxylate 100 parts ("UVR-6110" manufactured by Union Carbide Co.) Compound solution (5) 0.1 part Photocation Polymerization initiator 6 parts ("UVI-6990" manufactured by Union Carbide Co., Ltd.) 1 part of a surfactant ("L-7604" manufactured by Nippon Unicar Co., Ltd.) were mixed and stirred to prepare paint 7. Example 1
The coating method was applied in the same manner as in, and the coating film was cured.

Example 8 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate 100 parts ("UVR-6110" manufactured by Union Carbide Co.) Compound solution (5) 50 parts Photocationic polymerization initiation Agent 6 parts ("UVI-6990" manufactured by Union Carbide) 1 part of a surfactant ("L-7604" manufactured by Nippon Unicar Co., Ltd.) were mixed and stirred to prepare a coating material 8. Example 1
The coating method was applied in the same manner as in, and the coating film was cured.

Comparative Example 1 A coating material 9 was prepared and applied in the same manner as in Example 1 except that the compound solution (1) was removed, and the coating film was cured. [Comparative Example 2] A coating material 10 was prepared and applied in the same manner as in Example 1 except that the compound solution (7) was used in place of the compound solution (1), and the coating film was cured. Comparative Example 3 A coating material 11 was prepared and applied in the same manner as in Example 1 except that the compound solution (8) was used in place of the compound solution (1), and the coating film was cured.

The coating films obtained in Examples 1 to 8 and Comparative Examples 1 to 3 were evaluated for adhesion, lubricity, retort resistance, pencil hardness and workability. Table 1 shows the evaluation results. The evaluation was performed as follows. (1) Adhesion Based on JIS K5400, 100 goggles and the number of goggles in which the coating film was not peeled by a cellophane tape peeling test were displayed. (2) Lubricity Surface property measuring instrument ("HEIDON-14" manufactured by Shinto Scientific Co., Ltd.)
The dynamic friction coefficient was measured at 25 ° C. and 50% RH under the conditions of a load of 200 g, a ball indenter φ of 10 mm, and a moving speed of 100 mm / min. The same measurement was performed on the cured coating film after the treatment with boiling water for 30 minutes. ○ -Dynamic friction coefficient of less than 0.1 △ -Dynamic friction coefficient of 0.1 or more and less than 0.2 × -Dynamic friction coefficient of 0.2 or more (3) Retort resistance The coated plate is treated in high temperature and high pressure steam (125 ° C) for 30 minutes. The subsequent whitening of the coating film and the adhesion were evaluated. (4) Pencil hardness Based on JIS K5400, Mitsubishi pencil "Uni" at room temperature
The highest altitude at which the coating film peeled off and did not reach the base was evaluated. (5) Workability (evaluated by the coating film applied to the aluminum plate) Using a 1/2 inch rod in a DuPont impact tester,
A weight of 500 g was dropped from a height of 50 cm from the back side of the coating film surface, and cracks generated in the coating film were visually evaluated. ○ -No abnormality △ -Slight cracks were generated × -Cracks were generated on the entire surface

[0039]

[Table 1]

[0040]

According to the present invention, an ultraviolet curable resin composition suitable for vehicles such as varnishes, paints and inks was obtained. The ultraviolet curable resin composition of the present invention and the coating agent containing the same have excellent adhesion to plastic films and metals, retort resistance, lubricity, coating film hardness, and processability.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location C09D 163/00 PJK C09D 163/00 PJK PJL PJL

Claims (8)

[Claims] 1. An epoxy compound (A), α, which is liquid at room temperature.
β-unsaturated silicone compound (a), α, β-unsaturated monomer having an alicyclic epoxy functional group (b) and other α,
a compound (B) obtained by polymerizing the β-unsaturated monomer (c),
An ultraviolet curable resin composition comprising a photocationic polymerization initiator (C). 2. The ultraviolet curable resin composition according to claim 1, wherein the epoxy compound (A) which is liquid at room temperature contains at least 50% by weight of an alicyclic epoxy compound. 3. α, β in all α, β-unsaturated monomers
-The content ratio of the unsaturated silicone compound (a) is 1 to 70
The ultraviolet curable resin composition according to claim 1 or 2, wherein the ultraviolet curable resin composition is in a weight percentage. 4. The content of the α, β-unsaturated monomer (b) having an alicyclic epoxy functional group in the total α, β-unsaturated monomers is 1 to 80% by weight. The ultraviolet curable resin composition according to any one of claims 1 to 3, which is characterized in that. 5. The ultraviolet-curable type according to any one of claims 1 to 4, wherein an organic peroxide is used when the compound (B) is synthesized by polymerizing an α, β-unsaturated monomer. Resin composition. 6. An epoxy compound (A) 100 which is liquid at room temperature.
0.1 to 50 parts by weight of the compound (B) with respect to parts by weight,
6. The ultraviolet curable resin composition according to claim 1, wherein the cationic photopolymerization initiator (C) is contained in an amount of 0.5 to 30% by weight based on the total weight of (A) and (B). Stuff. 7. A coating agent containing the ultraviolet curable resin composition according to claim 1. 8. The coating agent according to claim 7, which is used for coating a polyester film-coated squeeze can.