JPH09328635A - Ultraviolet-curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition capable of rapidly forming cured coating film when irradiated with ultraviolet rays, thus applicable to a wide range of base materials, comprising an alicyclic epoxy compound, other epoxy compound(s), cationic photoinitiator and pigment. SOLUTION: This ultraviolet-curable resin composition comprises (A) an alicyclic epoxy compound liquid at normal temperatures, (B) other epoxy compound(s), (C) such a cationic photoinitiator that the light absorption area corresponding to a wavelength of 350-450nm accounts for >=10% of the total light absorption area for the absorbance curve corresponding to a wavelength of 200-500nm and (D) a pigment. It is preferable that this composition comprises the components A, B and D and (E) a mixture of (i) a cationic initiator <10% in the aforementioned light absorption area fraction in the component C and (ii) a photosensitizer having hydrogen-pulling activity, in the component E, the aforementioned light absorption area fraction is >=10%, the component A accounts for >=50wt. of this composition, and the component B is glycidyl ether-type and/or novolak-type epoxy compound(s).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention allows a cured coating film to be rapidly formed by irradiation of ultraviolet rays, and the formed coating film is excellent in adhesion to a substrate, workability, surface hardness and the like. It is an ultraviolet-curable resin composition used as a coating material for paints, inks and the like that gives a cured coating film. Here, as the base material, tin-plated steel plate, zinc-plated steel plate, surface-treated steel plate such as electric field chrome-plated steel plate, aluminum plate, metal plate such as stainless steel, further vinyl chloride, polyethylene, polypropylene, polyester or other organic film coated steel plate, A wide range of plastic plates can be selected. Therefore, it can be used as a prepainted steel plate building material for household electric appliances such as refrigerators, steel plates for various containers such as cans, and paints and inks for electric circuit boards such as permanent resists.

[0002]

2. Description of the Related Art Conventionally, various UV-curable compositions useful for paints and inks have been proposed. However, for paints and inks containing the pigments that the present inventors desire, since the pigments contained have the property of blocking or reflecting ultraviolet rays,
In view of high-speed painting / printing, it must be said that the curing performance is still insufficient. Moreover, in the case of the conventional UV-curable resin composition, although it has advantages such as surface hardness, its processability and adhesion to the base material are poor, and it is used in applications such as pre-coated steel sheets that are processed after coating. There is also a problem that is difficult to apply.

That is, when a coating material or ink containing a pigment is irradiated with ultraviolet rays to cure the coating film, the ultraviolet rays applied to the surface of the coating film are not affected by reflection and absorption as much as possible and reach the deepest part of the coating film. It is desirable to reach. When this is hindered by the pigment, even if the coating film surface is sufficiently cured, the curing is insufficient at the interface between the coating film and the substrate, which is the deepest part of the coating film, causing problems such as a decrease in adhesion. Therefore, in paints and inks containing pigments, in order to fully cure the coating film to the deepest part, it is necessary to improve the transmission of ultraviolet rays or to use an initiator that is sensitive to the ultraviolet rays that pass through. Met.

For example, as disclosed in Japanese Patent Application Laid-Open No. 7-268222, a method in which the penetration of ultraviolet rays into a coating film is improved and the curing of the coating film is improved can be considered by controlling the particle diameter of the contained pigment. However, this method controls the dispersed secondary particles of the pigment which are originally unstable, and the control of the dispersion process is complicated. Moreover, the dispersed secondary particles of the pigment change with time after dispersion,
Practically, it is impossible to use this method stably.

As a method for improving the transmission of ultraviolet rays as a device on the side of the ultraviolet ray generating lamp, the wavelength range is set to 35 by changing the metal component enclosed in the ultraviolet ray generating lamp.
A lamp has been devised to generate long-wavelength ultraviolet light having a wavelength of 0 to 450 nm, thereby improving the transmission of the ultraviolet light into the coating film. However, in this case, development of the above-mentioned initiator sensitive to long-wavelength ultraviolet light and an ultraviolet curable resin composition suitable for the initiator is required.

Further, it is important to impart good processability and adhesiveness to the formed coating film even if it is sufficiently cured, and in the conventional ultraviolet curable paints and inks, this point is practical. I have to say there is a problem. In order to solve this problem, it has been proposed that a radical-based composition further contains an epoxy resin for a specific oligomer, as disclosed in, for example, Japanese Patent Publication No. 1-24168. The composition is processable,
There are many obstacles to adhesion, and there is a limit to improvement of this.

[0007]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a surface-treated steel plate, an aluminum plate, a plastic film-coated steel plate,
It can be applied to a wide range of base materials such as plastic plates,
It is an object of the present invention to provide an ultraviolet curable resin composition which, while containing a pigment, has excellent curability (surface curability, internal curability) and gives a coating film excellent in adhesion, processability, surface hardness and the like.

[0008]

The first aspect of the present invention is to provide an epoxy compound (A) that is liquid at room temperature, another epoxy compound (B), and 350 to 350 with respect to the total absorption area of the absorption curve in the range of 200 to 500 nm. An ultraviolet curable resin composition comprising a cationic photoinitiator (C1) having a light absorption area of 10% or more in a range of 450 nm and a pigment (E).

The second invention is an epoxy compound (A) which is liquid at room temperature, other epoxy compounds (B), 200 to 5
35 for the total absorbance area of the absorbance curve in the range of 00 nm
UV curable resin composition containing a mixture (D1) of a cationic initiator (C2) having a light absorption area of less than 10% in the range of 0 to 450 nm and a photosensitizer (C3) having a hydrogen abstraction action, and a pigment (E). And the mixture (D1) is 2
It is an ultraviolet curable resin composition characterized in that the absorption area in the range of 350 to 450 nm is 10% or more with respect to the total area of the absorption curve in the range of 00 to 500 nm.

The third invention is the ultraviolet-curable resin composition according to the first invention, which contains a photosensitizer (C3) having a hydrogen abstraction action.

A fourth invention is the ultraviolet-curable resin composition according to any one of claims 1 to 3, which contains 50% by weight or more of the alicyclic epoxy compound (A) which is liquid at room temperature. .

The fifth invention is characterized in that the other epoxy compound (B) is a glycidyl ether type epoxy compound which is solid at room temperature and / or a novolac type epoxy compound which is solid at room temperature. It is any one of the ultraviolet-curable resin compositions.

A sixth invention is the ultraviolet-curable resin composition according to any one of the first to fifth inventions, characterized by coating a metal or a metal coated with a plastic film.

A seventh invention is the ultraviolet-curable resin composition according to the sixth invention, wherein the metal is iron or aluminum.

An eighth invention is the ultraviolet-curable resin composition according to either the sixth invention or the seventh invention, characterized in that the metal or metal coated with a plastic film is plate-shaped or can-shaped. .

In a ninth aspect, the plastic film is
The ultraviolet-curable resin composition according to any one of the sixth to eighth inventions, which is a polyester film.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The alicyclic epoxy compound (A) which is liquid at room temperature in the present invention contains cyclohexene oxide or cyclopentene oxide in its molecular structure. Examples of the alicyclic epoxy compound (A) which is liquid at room temperature include those shown below,

[0018]

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[0019]

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[0020]

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[0021]

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Specifically, UVR-6110, UVR-6
199 (above UCC), Celoxide 2083, Celoxide 2085, Epolide GT-302, Epolide GT-303, Epolide GT-401, Epolide GT-402, ETHB, CHXO (above Daicel Chemical Company) and the like may be used. it can.

The alicyclic epoxy compound (A) which is liquid at room temperature can be used as a mixture with other epoxy compound (B) which will be described later. The content of the liquid alicyclic epoxy compound (A) is preferably 50% by weight or more, more preferably 70% by weight or more.

In the present invention, as the other epoxy compound (B) other than (A) used together with the alicyclic epoxy compound (A) which is liquid at room temperature, the epoxy compound which is liquid at room temperature is also solid at room temperature. Epoxy compounds can also be used. However, in order to improve the adhesion and processability of the cured coating film, a relatively large molecular weight solid epoxy compound at room temperature is preferable, and particularly a room temperature solid glycidyl ether type epoxy compound or a room temperature solid novolac type epoxy compound is preferable. It is preferably used.

Speaking of a glycidyl ether type epoxy compound which is solid at room temperature, it is effective in exerting adhesion.
Those having a molecular weight of 800 to 5000 and an epoxy equivalent of 400 to 4000 are preferable. If the molecular weight is higher than this, the curability may be impaired. If it is a bisphenol type epoxy compound,
Bisphenol F is preferable to bisphenol A because it tends to have a low viscosity. The novolac type epoxy compound that is solid at room temperature is more effective in exhibiting surface hardness than the glycidyl ether type epoxy compound. It does not matter whether it is a phenol type or a cresol type molecular skeleton, but the epoxy equivalent is preferably 150 or more for the phenol type and 170 or more for the novolac type, and if it is less than this, the adhesiveness may decrease. There is.

Alicyclic epoxy compound (A) which is liquid at room temperature
Among the epoxy compounds that are liquid at room temperature that can be used in combination with, glycidyl ether type epoxy compounds that are liquid at room temperature include aliphatic epoxy compounds and bisphenol type epoxy compounds. Examples of the aliphatic epoxy compound include polyethylene glycol diglycidyl ether (Denacol EX-800 series) and polypropylene glycol diglycidyl ether (Denacol EX-900).
Series), neopentyl glycol diglycidyl ether (Denacol EX-211), trimethylolpropane triglycidyl ether (Denacol EX-32)
1) (all manufactured by Nagase Kasei Kogyo Co., Ltd.) and the like, and examples of the bisphenol type epoxy compound include Epicoat 827, Epicoat 828, and Epicoat 834 (all manufactured by Yuka Shell Epoxy Co., Ltd.). UVR-6
Epoxidized hydrocarbons such as 200, UVR-6216 (manufactured by UCC) and the like can also be used.

Alicyclic epoxy compound (A) which is liquid at room temperature
As the other epoxy compound (B) used in combination with the glycidyl ether type epoxy compound which is solid at room temperature and is preferably used among the epoxy compounds solid at room temperature,
Bisphenol A type Epicoat 1001, Epicoat 1004, Epicoat 1007, Epicoat 1009
(Manufactured by Yuka Shell Epoxy Co., Ltd.) and Epicoat E-4004P and Epicoat E-40 using bisphenol F as a raw material
07P, Epicoat E-4009P (produced by Yuka Shell Epoxy Co., Ltd.) and the like. Further, as novolak type epoxy compounds which are solid at room temperature, EPPN-201, EPPN
-202 (manufactured by Nippon Kayaku Co., Ltd.), Epicoat 152, Epicoat 154 (manufactured by Yuka Shell Epoxy Co.), D.I. E. FIG. N
438, D.I. E. FIG. N 439, D.I. E. FIG. N444, QU
ATREX2010, QUATREX2410, QUA
TREX3310 QUATREX3410 (manufactured by Dow Chemical Co.) and the like can be used.

When a room temperature solid glycidyl ether type epoxy compound or a room temperature solid novolac type epoxy compound is used in combination with an alicyclic epoxy compound (A) which is liquid at room temperature, an ultraviolet curable resin composition is used as a coating material. It is also important to consider controlling viscosity in order to ensure coating / printing suitability when used as ink or the like. Therefore, in addition to the room temperature solid glycidyl ether type epoxy compound, the room temperature solid novolac type epoxy compound and the alicyclic epoxy compound (A) which is liquid at room temperature, other epoxy compounds which are liquid at room temperature and the reactivity described later. Diluents and solvents may be used.

Usual solvents may be used as the diluent, but a step of heating and removing the solvent as the diluent from the coating film before the irradiation of ultraviolet rays is required. Therefore, the UVR-6220 and UVR-62 shown above are preferred.
A dedicated diluent such as 16 (manufactured by UCC) or a compound having a structure capable of reacting with an epoxy group such as a vinyl ether group or a hydroxyl group is more preferable. Alternatively, an acrylate compound or a methacrylate compound which itself does not react with an epoxy group but has reactivity with ultraviolet rays may be used.

Next, the cationic photoinitiator used in the present invention will be described. The cationic photoinitiator used in the present invention has an absorption area in the range of 350 to 450 nm of 10 with respect to the total absorption area of the absorption curve in the range of 200 to 500 nm.
% Or more of the cationic photoinitiator (C1) The absorption area in the range of 350 to 450 nm is 10 with respect to the total absorption area of the absorption curve in the range of 200 to 500 nm.
% Of a cationic initiator (C2) and a photosensitizer (C3) having a hydrogen abstraction function (D1) Absorption area in the range of 350 to 450 nm relative to the total absorption area of the absorption curve in the range of 200 to 500 nm Is 10
% Or more of the cationic photoinitiator (C1) and the photosensitizer (C3) having a hydrogen abstraction function. In the case of, a cation initiator (C2) may be used together.

In the present invention, the above absorption range is important. That is, in the resin composition containing the pigment which is the object of the present invention, the pigment absorbs a certain wavelength range with respect to all wavelengths of incident light, and exhibits a specific hue by reflecting a certain wavelength range. It is a thing. For example,
A white pigment such as titanium oxide normally absorbs a wavelength range of 350 nm or less and reflects a wavelength range of 450 nm or more. Therefore, in the composition containing such a pigment, in order to cure not only the surface of the paint / ink coating film after coating but also the inside of the composition sufficiently and stably, it is necessary to set a wavelength of 350 to 450 nm located in the gap between the absorption region and the reflection region. The range is important, which is why a photoinitiator functional in this wavelength range is useful.

Here, the cationic photoinitiator (C1) (C2)
Is a compound that is excited by light in the ultraviolet region to generate a Bronsted acid or a Lewis acid that serves as a ring-opening catalyst for an epoxy group. Examples thereof include a diaryl iodonium salt having a low nucleophilic anion, a triaryl sulfonium salt and a related compound, or an aryl diazonium salt having a low nucleophilic anion, and an iron arene complex.

Among them, the cation initiator (C1) in the present invention may have any chemical structure so long as it satisfies the above-mentioned conditions, and a specific example thereof is CD-10 which is diaryliodonium hexafluoroantimonate.
12 (trade name: manufactured by SARTOMER), PCI-01
9, PCI-021 (trade name: manufactured by Nippon Kayaku Co., Ltd.) and the like. For example, CD-1012 has an absorption area in the range of 350 to 450 nm of 23% with respect to the total area of the absorption curve of 200 to 500 nm as illustrated in FIG.
And satisfies the conditions of the present invention. The light absorption area was determined according to the following conditions. Spectrophotometer: UV-160A manufactured by Shimadzu Corporation Measurement wavelength range: 200 to 500 nm Absorbance range: 0 to 2.0 Abs Measurement temperature: 23 ° C. Measurement concentration: 1.5 to 2.0 Abs at maximum peak
The sample concentration was adjusted so that Area ratio: The ratio in the 350 to 450 nm region relative to the total area of the absorbance curve of 200 to 500 nm was determined by the gravimetric method.

Next, a cationic initiator (C2) having an absorption area in the range of 350 to 450 nm of less than 10% with respect to the total absorption area of the absorption curve in the range of 200 to 500 nm and a photosensitizer having a hydrogen abstraction action ( Mixture of C3) (D1)
Is described. Such a mixture (D1) has a content of 200 to 5
350-450 for the total area of the absorbance curve at 00 nm
The area in the nm range may be adjusted to be 10% or more.

As the cation initiator (C2) used here, the same ones as the above-mentioned cation initiator (C1) can be exemplified, but only in that the light absorption area in the range of 350 to 450 nm is less than 10%. Is different. As such a cationic photoinitiator, any one can be used as long as it has an ability to initiate a curing reaction in the range of 200 to 500 nm.
For example, UVI-6990, UVI-6974 (trade name:
UCC), SP-150, SP-170 (trade name:
Asahi Denka Co., Ltd.), and further CI-2481, CI-262
4, CI-2638, CI-2734, CI-2855
(Product name: manufactured by Nippon Soda Co., Ltd.) is useful.

The photosensitizer (C3) having a hydrogen-abstracting action, which is used as a mixture, is a long wavelength region of ultraviolet rays, for example, 300 n.
Those having characteristic absorption in a long wavelength region of m or more are preferable.
As the photosensitizer (C3) having such a hydrogen abstraction action, benzophenone type and thioxanthone type are preferable.
For example, as thioxanthone type, ITX, QTX, CPTX, DETX-S from KAYACURE series
(Trade name: manufactured by Nippon Kayaku Co., Ltd.) and the like.

As the mixture (D1) in the present invention, these cationic photoinitiators (C2) and the photosensitizer (C3) having a hydrogen abstraction action are appropriately mixed and used as described above. (D2) is a cationic initiator (C
As in the case of 1), it is not always clear in the resin composition containing a pigment that not only the surface of the paint / ink coating but also the inside can be sufficiently and stably cured.

As described in "UV / EB Curing Material", page 93 (published by CMC Co., Ltd., 1992), radicals can be expected to be involved in the step of generating Bronsted acid even in the cation curing mechanism. It is believed that a photosensitizer having a hydrogen-abstracting action may accelerate the generation of Bronsted acid and, in turn, a cation curing mechanism. Generation of Stead acid has not yet been confirmed.

With respect to the above mixture (D1), CI-2855 as a cation photoinitiator (C2) and KAYACURE as a photosensitizer (C3) having a hydrogen abstraction action.
DETX-S will be described as an example. The respective absorbance curves are as shown in FIGS. 2 and 3, and the measurement conditions are the same as above. 4 and 5 show the absorbance curves of the mixture. From FIG. 2, CI-2855 has a characteristic absorption of 331 nm, and DE
It can be seen that TX-S is 385.5 nm. The area ratios when these are mixed are shown in the table below.

[0040]

[Table 1]

In the present invention, the compositions of 2 and 3 in Table 1 are used as the mixture (D1). And D
Although it is possible to increase the amount of ETX-S, it is important that the thioxanthone photosensitizer easily causes yellowing of the coating film, and it is important to pay attention to the amount used, for example, CI-28.
55 parts by weight to 100 parts by weight of DETX-S are suitably 100 parts by weight or less.

In the present invention, as in the case of (D1), a cationic photoinitiator (C1) which can be used alone and a photosensitizer (C3) having a hydrogen abstraction action are used in combination, or It is also possible to use the cation photoinitiator (C1), the cation photoinitiator (C2) and the photosensitizer (C3) having a hydrogen abstraction action in combination.

The amount of the above cationic photoinitiator (C1), mixture (D1), mixture of the cationic photoinitiator (C1) and the photosensitizer (C3) having a hydrogen abstraction action, etc. is liquid at room temperature. It is preferably 0.1 parts by weight or more and 10 parts by weight or less, and more preferably 1 part by weight or more and 7 parts by weight or less with respect to 100 parts by weight of the epoxy compound (A). When the amount of the cation initiator (C1), the mixture (D1) and the like is small with respect to the epoxy compound (A) which is liquid at room temperature, the curing at the time of ultraviolet irradiation is likely to be insufficient. On the other hand, when the amount is too large, there is a concern that the generated Bronsted acid or the like may adversely affect the water resistance of the cured coating film.

Regarding the pigment (E), the pigment used in the present invention is not limited by its type such as an inorganic pigment and an organic pigment. Various pigments have characteristic absorption in a wavelength range corresponding to the pigment, but like the white pigment described above, various pigments other than white also have 350 to 450.
By using the cationic initiator (C1) or the mixture (D1) having an absorption area in the nm range of 10% or more, the reason is not clear, but a cured coating film excellent in adhesion, processability, etc. is obtained. be able to. As the inorganic pigment, chromate, ferrocyanide, oxides of various metals, sulfides, selenides, sulfates, silicates, carbonates, phosphates, etc. can be used. The use of such metal powders is also possible. Examples of oxides of various metals include titanium oxide and zinc oxide. As organic pigments,
Various pigments such as an insoluble azo pigment, a soluble azo pigment, a copper phthalocyanine pigment, a basic dyed lake pigment, an acidic dyed lake pigment, a quinacridone pigment, and a dioxazine pigment can be used.

In preparing the ultraviolet-curable resin composition of the present invention containing the pigment (E), it can be dispersed by a high-speed agitator, but more preferably, metal such as sand mill, ball mill, glass, ceramics, etc. A method using an impact force of bead media, a method using a mechanical high shearing force such as a three-roll, a two-roll can be used.

Further, it is possible to contain an acrylate compound or a methacrylate compound which does not itself react with an epoxy group but has radical reactivity to ultraviolet rays. In this case, the radical reactivity with respect to the cationic reaction has a high reaction speed and the reaction is completed in a short time, so that the tackiness after the irradiation of ultraviolet rays is quickly eliminated. Furthermore, it is effective in reducing the amount of ultraviolet irradiation (reducing the number of ultraviolet lamps). As the acrylate compound used, isoamyl acrylate, lauryl acrylate, stearyl acrylate, butoxy acrylate, ethoxydiethylene glycol acrylate, methoxytriethylene glycol acrylate, methoxydipropylene acrylate, phenoxyethyl acrylate, phenoxypreethylene glycol acrylate, tetrahydrofurfuryl acrylate, iso Bonyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl-2-hydroxyethyl phthalic acid, 2-acryloyloxyethyl-hexahydro Phthalic acid, 2-acryloyloxyethyl acid phosph , Ethylene glycol diacrylate, ethylene glycol multimer diacrylate, neopentyl glycol diacrylate, 1,6-hexanediodiacrylate, ethylene oxide-modified bisphenol A diacrylate, ethylene oxide multimer-modified bisphenol A diacrylate, acrylic acid adduct of bisphenol A diglycidyl ether, compounds in which these bisphenol A skeletons are changed to bisphenol F, trimethylolpropane triacrylate, ethylene oxide modified trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetra Acrylate, dipentaerythritol hexaacrylate, isocyanuric acid triacrylate, urea An acrylate having a skeleton, a acrylate having a reaction product of a dihydric alcohol and a dibasic acid as a skeleton, an acrylate having a reaction product of a polyhydric alcohol and a polybasic acid as a skeleton, and the like as a methacrylate compound. Examples thereof include a methacrylate compound which is a compound having a skeleton. At this time, more preferably, a radical photoinitiator which initiates a radical reaction upon irradiation with ultraviolet rays, or a photosensitizer suitable for the radical initiator used may be used. However, the amine-based photosensitizer may interfere with the cation reaction due to its basicity, which requires some consideration.

Various additives can be used in the ultraviolet curable resin composition of the present invention. That is, it is various additives such as pigment-based dispersant, color-separation-preventing agent, leveling agent, wettability improving agent, defoaming agent, lubricant, and other silicone-based, acrylic-based, and natural oil-based additives. Further, if necessary, reactive diluents and solvents for viscosity adjustment may be used in consideration of coating suitability, printing suitability and the like. Suitable as the reactive diluent here is a low-viscosity compound having reactivity with an epoxy group. A hydroxyl group and a vinyl ether group can be mentioned as the functional group having reactivity with the epoxy group, and a compound having a viscosity of 100 cps or less at 25 ° C. is most suitable. By using these reactive diluents and solvents, the leveling property at the time of coating can be improved.

Examples of the diluent having a vinyl ether group include triethylene glycol divinyl ether, cyclohexane dimethanol divinyl ether, hydroxybutyl vinyl ether, dodecyl vinyl ether, propenyl ether propylene carbonate, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, ethylene glycol. Monovinyl ether, diethylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol monovinyl ether, cyclohexyl vinyl ether, 2-
Chloroethyl vinyl ether, 2-hydroxyethyl vinyl ether, diethylene glycol divinyl ether, 2,2-bis (4-vinyloxyethoxyphenyl)
Propane, 1,4-bis (2-vinyloxyethoxy) benzene and the like are mentioned, and specifically, Lapicure DVE-
3, Lapicure CHVE, Lapicure HBVE, Lapicure PECP, Lapicure DDVE (above IS
P company), Vectomer 4010 (manufactured by Allied Signal), M-VE, E-VE, P-VE, iB-VE, E.
G-MVE, DGE-DVE, BD-DVE, HD-D
VE, CHDM-DVE, CH-VE (manufactured by BASF), CEVE, HEVE, DEG-DVE, TEG-.
DVE, PBA-DOVE, HQ-DOVE (manufactured by Nisso Maruzen Chemical Co., Ltd.) and the like can be appropriately used.

Diluents having a hydroxyl group include aliphatic,
Alternatively, aromatic alcohols, glycols, glycerin, ethylene glycol monoethers, propylene glycol monoethers, phenols and the like can be used.

The ultraviolet-curable resin composition of the present invention can be used for a substrate such as metal, wood, glass, plastic, etc., but is preferably applied (painted / cured) to metal, plastic film-coated metal. Therefore, it can be used as a paint / ink for pre-coated steel sheets for household electric appliances such as refrigerators, construction materials, various containers such as cans, and electric circuit boards such as permanent resists.

Metal, plastic film coated metal,
It is preferably a plate-shaped or can-shaped metal, or a plate-shaped or can-shaped plastic film-coated metal. In particular, it is preferably applied (painted / cured) to a drawn metal can coated with a plastic film. The plate shape may be a relatively short sheet shape, a relatively long roll shape, or a flat plate shape. In addition, the can shape refers to a shape having a cylindrical curved surface regardless of the presence or absence of a bottom and a lid, and irrespective of two pieces or three pieces.

Examples of the metal include tin-plated steel sheets, zinc-plated steel sheets, surface-treated steel sheets such as electric field chrome-plated steel sheets, metals such as aluminum and stainless steel, and various steels (steel sheets), aluminum and the like are preferably used. It

As the plastic film-coated metal,
The above various metals may be laminated with a plastic film such as polyethylene terephthalate, polyethylene, polypropylene, nylon, vinyl chloride, vinylidene chloride, or polycarbonate. The plastic film-coated drawn metal can is a plastic film-coated metal as described above, which is drawn into a cylindrical shape having a capacity of 200 ml to 500 ml. In the case of a plastic film-covered drawn metal can, a drawn metal can covered with a polyester film such as polyethylene terephthalate is preferred.

The ultraviolet-curable resin composition of the present invention is preferably used for metal cans and plastic film-coated squeezed metal cans as described above. It can also be used on the surfaces of polyethylene terephthalate, plastic films such as polyethylene, polypropylene, nylon, vinyl chloride, vinylidene chloride, and polycarbonate, and plastic molded products.

A roll coater, a spray coater, a dip coater, a gravure coater, or the like can be used as a method for applying these base materials, and as a printing method, offset, gravure, rubber letterpress, silk screen, etc. can be arbitrarily selected. It is possible.

Next, a lamp for irradiating ultraviolet rays can also be arbitrarily selected such as a high pressure mercury lamp, an ozoneless mercury lamp, and a metal halide lamp, but in order to further exert the effect of the present invention, it has an output wavelength of 300 nm or more. The use of lamps is preferred. Specifically, Fusion
The use of electrodeless lamps such as V bulbs and D bulbs, which are supplied by the company as trade names, gives good results.
Further, if necessary, heating may be performed after irradiation of ultraviolet rays to advance the curing reaction. In particular, this makes it possible to improve coating film physical properties such as surface hardness and water resistance.

[0057]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples without departing from the technical idea of the present invention. In the examples, “part” means “part by weight” and “%” means “% by weight”. [Example 1] After the following components are dissolved and mixed, is added and sufficiently stirred, and further kneaded under high shear stress with a three-roll mill. After that, the mixture was added and sufficiently stirred again to obtain the ultraviolet curable resin composition of the present invention. UVR-6110 75 parts (Liquid room temperature alicyclic epoxy compound (A): bifunctional, manufactured by UCC) Epicoat 1004 20 parts (Epoxy compound (B) solid at room temperature: manufactured by Yuka Shell Epoxy Company) CD-10125 Parts (Cationic photoinitiator: (C1) component, manufactured by SARTOMER) R-580 100 parts (acid value titanium: pigment (E) component, manufactured by Ishihara Sangyo Co., Ltd.) This composition was treated with ethylene until it reached 500 cps at 25 ° C. A coating agent was prepared by diluting with glycol monoethyl ether. This coating is applied evenly on an aluminum plate with a roll coater to a thickness of 5 μm.
A sample plate for testing was prepared by curing under a V valve (240 w / cm) manufactured by the same company at a speed of 30 m / min.

Example 2 The same ultraviolet curable composition as in Example 1 was applied on a polyester-coated steel sheet in the same manner to prepare a test sample plate.

Example 3 The following ingredients were dissolved and mixed, then added and sufficiently stirred, and further kneaded under high shear stress with a three-roll mill. Then add and stir well again,
An ultraviolet curable resin composition of the present invention was obtained. UVR-6110 75 parts (Liquid room temperature alicyclic epoxy compound (A): bifunctional, manufactured by UCC) QUATREX2010 20 parts (Normal temperature solid epoxy compound (B): manufactured by Dow Chemical Co.) CD-1012 5 parts (cation Photoinitiator: (C1) component, manufactured by SARTOMER) R-580 100 parts (acid value titanium: pigment (E) component, manufactured by Ishihara Sangyo Co., Ltd.) This composition was treated with ethylene glycol monoethyl at 25 ° C. until it reached 500 cps. A coating agent was prepared by diluting with ether. This coating is applied evenly on an aluminum plate with a roll coater to a thickness of 5 μm.
A sample plate for testing was prepared by curing under a V valve (240 w / cm) manufactured by the same company at a speed of 30 m / min.

[Example 4] After the following was dissolved and mixed, was added and sufficiently stirred, and further kneaded with a three-roll under high shear stress. After that, the mixture was added and sufficiently stirred again to obtain the ultraviolet curable resin composition of the present invention. UVR-6110 50 parts (normal temperature liquid alicyclic epoxy compound (A): bifunctional, manufactured by UCC) EPOLIDE GT-401 25 parts (normal temperature liquid alicyclic epoxy compound (A): tetrafunctional, Daicel Chemical Company Epicoat 1004 20 parts (Epoxy compound (B) solid at room temperature: manufactured by Yuka Shell Epoxy Co., Ltd.) CD-1012 5 parts (Cationic photoinitiator: (C1) component, manufactured by SARTOMER) R-580 100 parts (acid Titanium: Pigment (E) component, manufactured by Ishihara Sangyo Kaisha, Ltd.) This composition was diluted with ethylene glycol monoethyl ether at 25 ° C. to 500 cps to obtain a coating agent. This coating is applied evenly on an aluminum plate with a roll coater to a thickness of 5 μm.
A sample plate for testing was prepared by curing under a V valve (240 w / cm) manufactured by the same company at a speed of 30 m / min.

[Embodiment 5] After the following are dissolved and mixed, is added and sufficiently stirred, and further kneaded under high shear stress with a three-roll mill. Then, was added and sufficiently stirred again to obtain the ultraviolet curable resin composition of the present invention. UVR-6110 50 parts (normal temperature liquid alicyclic epoxy compound (A): bifunctional, manufactured by UCC) EPOLIDE GT-401 25 parts (normal temperature liquid alicyclic epoxy compound (A): tetrafunctional, Daicel Chemical Company Epicoat 1004 20 parts (Epoxy compound (B) at room temperature solid: manufactured by Yuka Shell Epoxy Co., Ltd.) CI-2855 4.5 parts (Cationic photoinitiator: (C2) component, manufactured by Nippon Soda Co., Ltd.) KAYACURE DETX-S 0.5 parts (photosensitizer: (C3) component, manufactured by Nippon Kayaku Co., Ltd.) R-580 100 parts (acid value titanium: pigment (E) component, manufactured by Ishihara Sangyo Co., Ltd.) This composition was 500 cps at 25 ° C. It was diluted with ethylene glycol monoethyl ether until it became a coating material. This coating is applied evenly on an aluminum plate with a roll coater to a thickness of 5 μm.
A sample plate for testing was prepared by curing under a V valve (240 w / cm) manufactured by the same company at a speed of 30 m / min. At this time (C
Mixture of 2) component and (C3) component 200 of (D1) component
350 to the total area of the absorbance curve in the range of 500 nm
The absorption area in the range of ˜450 nm was 57%.

Example 6 A UV-curable composition similar to that of Example 5 was similarly applied onto a polyester-coated steel plate to prepare a test sample plate.

Example 7 The following were dissolved and mixed, then, was added and sufficiently stirred, and then was added and sufficiently stirred again to obtain an ultraviolet curable resin composition of the present invention. UVR-6110 50 parts (normal temperature liquid alicyclic epoxy compound (A): bifunctional, manufactured by UCC) EPOLIDE GT-401 25 parts (normal temperature liquid alicyclic epoxy compound (A): tetrafunctional, Daicel Chemical Company Epicoat 1004 20 parts (Epoxy compound (B) at room temperature solid: manufactured by Yuka Shell Epoxy Co., Ltd.) CI-2855 4.5 parts (Cationic photoinitiator: (C2) component, manufactured by Nippon Soda Co., Ltd.) KAYACURE DETX-S 0.5 part (photosensitizer: (C3) component, manufactured by Nippon Kayaku Co., Ltd.) CR-50FM 20 parts (aluminum paste: pigment (E) component, manufactured by Asahi Kasei Co., Ltd.) This composition becomes 500 cps at 25 ° C. Until then, it was diluted with ethylene glycol monoethyl ether to obtain a coating agent. This coating is applied evenly on an aluminum plate with a roll coater to a thickness of 5 μm.
A sample plate for testing was prepared by curing under a V valve (240 w / cm) manufactured by the same company at a speed of 30 m / min.

Example 8 The same ultraviolet curable composition as in Example 7 was applied on a polyester-coated steel sheet in the same manner to prepare a test sample plate.

[Embodiment 9] The following ingredients are dissolved and mixed, then added and sufficiently stirred, and further kneaded under high shear stress with a three-roll mill. Then, was added and sufficiently stirred again to obtain the ultraviolet curable resin composition of the present invention. UVR-6110 75 parts (Liquid room temperature alicyclic epoxy compound (A): bifunctional, manufactured by UCC) Neopentylglycol diglycidyl ether 25 parts (Room temperature liquid epoxy compound (B): Bifunctional, Nagase Chemical Industries Co., Ltd. CI-2855 4.5 parts (cationic photoinitiator: (C2) component, manufactured by Nippon Soda Co., Ltd.) KAYACURE DETX-S 0.5 part (photosensitizer: (C3) component, manufactured by Nippon Kayaku Co., Ltd.) R-580 100 parts (acid value titanium: pigment (E) component, manufactured by Ishihara Sangyo Co., Ltd.) This composition was diluted with ethylene glycol monoethyl ether at 25 ° C. to 500 cps to obtain a coating agent. This coating is applied evenly on an aluminum plate with a roll coater to a thickness of 5 μm.
A sample plate for testing was prepared by curing under a V valve (240 w / cm) manufactured by the same company at a speed of 30 m / min.

[Embodiment 10] The following ingredients are dissolved and mixed, then added and sufficiently stirred, and further kneaded under high shear stress with a three-roll mill. Then, was added and sufficiently stirred again to obtain the ultraviolet curable resin composition of the present invention. UVR-6110 75 parts (Liquid room temperature alicyclic epoxy compound (A): bifunctional, manufactured by UCC) Neopentylglycol diglycidyl ether 25 parts (Room temperature liquid epoxy compound (B): Bifunctional, Nagase Chemical Industries Co., Ltd. CD-1012 4.5 parts (cationic photoinitiator: (C1) component, manufactured by SARTOMER) KAYACURE DETX-S 0.5 part (photosensitizer: (C3) component, manufactured by Nippon Kayaku Co., Ltd.) R -580 100 parts (acid value titanium: pigment (E) component, manufactured by Ishihara Sangyo Co., Ltd.) This composition was diluted with ethylene glycol monoethyl ether to 25 cps at 500 cps to obtain a coating agent. This coating is applied evenly on an aluminum plate with a roll coater to a thickness of 5 μm.
A sample plate for testing was prepared by curing under a V valve (240 w / cm) manufactured by the same company at a speed of 30 m / min. At this time, the absorption area in the range of 350 to 450 nm, which is the total area of the absorbance curve in the range of 200 to 500 nm, of the mixture of the C1 component and the C3 component was 63%.

[Embodiment 11] The following ingredients are dissolved and mixed, then added and sufficiently stirred, and further kneaded under high shear stress with a three-roll mill. After that, the mixture was added and sufficiently stirred again to obtain the ultraviolet curable resin composition of the present invention. UVR-6110 45 parts (Liquid room temperature alicyclic epoxy compound (A): bifunctional, manufactured by UCC) QUATREX2010 50 parts (Room temperature solid epoxy compound (B): manufactured by Dow Chemical Co.) CD-1012 5 parts (cation Photoinitiator: (C1) component, manufactured by SARTOMER) R-580 100 parts (acid value titanium: pigment (E) component, manufactured by Ishihara Sangyo Co., Ltd.) This composition was treated with ethylene glycol monoethyl at 25 ° C. until it reached 500 cps. A coating agent was prepared by diluting with ether. This coating is applied evenly on an aluminum plate with a roll coater to a thickness of 5 μm.
A sample plate for testing was prepared by curing under a V valve (240 w / cm) manufactured by the same company at a speed of 30 m / min.

[Comparative Example 1] The following ingredients were dissolved and mixed, then added and sufficiently stirred, and further kneaded under high shear stress with a three-roll mill. Then add and stir well again,
An ultraviolet curable resin composition of the present invention was obtained. UVR-6110 75 parts (Liquid room temperature alicyclic epoxy compound (A): bifunctional, manufactured by UCC) Epicoat 1004 20 parts (Epoxy compound (B) solid at room temperature: manufactured by Yuka Shell Epoxy Co.) CI-2855 5 Parts (cationic photoinitiator: (C2) component, manufactured by Nippon Soda Co., Ltd.) R-580 100 parts (acid value titanium: pigment (E) component, manufactured by Ishihara Sangyo Co., Ltd.) A coating agent was prepared by diluting with ethylene glycol monoethyl ether. This coating is applied evenly on an aluminum plate with a roll coater to a thickness of 5 μm.
A sample plate for testing was prepared by curing under a V valve (240 w / cm) manufactured by the same company at a speed of 30 m / min.

[Comparative Example 2] The following ingredients were added and sufficiently stirred, and further kneaded with a three-roll mill under high shear stress. Then, was added and sufficiently stirred again to obtain the ultraviolet curable resin composition of the present invention. UVR-6110 95 parts (Liquid room temperature alicyclic epoxy compound (A): bifunctional, manufactured by UCC) CI-2855 4.5 parts (cation photoinitiator: (C2) component, manufactured by Nippon Soda Co., Ltd.) KAYACURE DETX -S 0.5 part (photosensitizer: (C3) component, manufactured by Nippon Kayaku Co., Ltd.) R-580 100 parts (acid value titanium: pigment (E) component, manufactured by Ishihara Sangyo Co., Ltd.) Was diluted with ethylene glycol monoethyl ether to 500 cps to obtain a coating agent. This coating is applied evenly on an aluminum plate with a roll coater to a thickness of 5 μm.
A sample plate for testing was prepared by curing under a V valve (240 w / cm) manufactured by the same company at a speed of 30 m / min.

[Comparative Example 3] The following ingredients were added and sufficiently stirred, and kneading was further carried out under high shear stress with a three-roll mill. Then, was added and sufficiently stirred again to obtain the ultraviolet curable resin composition of the present invention. Neopentyl glycol diglycidyl ether 95 parts (normal temperature liquid epoxy compound (B): bifunctional, manufactured by Nagase Kasei Co., Ltd.) CI-2855 4.5 parts (cationic photoinitiator: (C2) component, manufactured by Nippon Soda Co., Ltd.) KAYACURE DETX-S 0.5 part (photosensitizer: (C3) component, manufactured by Nippon Kayaku Co., Ltd.) R-580 100 parts (acid value titanium: pigment (E) component, manufactured by Ishihara Sangyo Co., Ltd.) It was diluted with ethylene glycol monoethyl ether until it reached 500 cps at 25 ° C. to obtain a coating agent. This coating is applied evenly on an aluminum plate with a roll coater to a thickness of 5 μm.
A sample plate for testing was prepared by curing under a V valve (240 w / cm) manufactured by the same company at a speed of 30 m / min.

The following tests were conducted on the above Examples and Comparative Examples for evaluation. 1. Adhesion According to JIS K5400, it is indicated by the area where the coating film remains by a cellophane tape peeling test after cutting the edges. 2. Pencil hardness According to JIS K5400, Mitsubishi pencil "Uni" at room temperature
The maximum hardness that the coating film peels off and does not reach the base material is displayed. 3. Workability Using a 1/2 inch rod with 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 ○: Some cracks were generated Δ: Some cracks were generated ×: Cracks were generated on the entire surface The evaluation results are shown in the following table.

[0072]

[Table 2]

[0073]

According to the present invention, a cationic UV curable resin composition containing a pigment and having good curability can be obtained. This composition shows good adhesion to metals and plastics, and also shows excellent results which are not found in the processability of the coating film formed after ultraviolet irradiation.

[Brief description of drawings]

FIG. 1: Absorption curve of CD-1012 alone

FIG. 2 Absorption curve of CI-2855 alone

FIG. 3 Absorption curve of DETX-S alone

FIG. 4 CI-2855 / DETX-S = 100/1
Absorption curve of the mixture

FIG. 5: CI-2855 / DETX-S = 100/5
Absorption curve of the mixture

Claims (9)

[Claims] 1. An alicyclic epoxy compound (A) which is liquid at room temperature, other epoxy compounds (B), 200 to 50.
350 for the total absorption area of the absorbance curve in the range of 0 nm
A UV-curable resin composition comprising a cationic photoinitiator (C1) having a light absorption area of 10% or more in the range of to 450 nm and a pigment (E). 2. An alicyclic epoxy compound (A) which is liquid at room temperature, other epoxy compounds (B), 200 to 50.
350 for the total absorption area of the absorbance curve in the range of 0 nm
UV-curable resin composition containing a mixture (D1) of a cationic initiator (C2) having a light absorption area of less than 10% in the range of ˜450 nm and a photosensitizer (C3) having a hydrogen abstraction action, and a pigment (E). And the mixture (D1) is 2
An ultraviolet curable resin composition, wherein the absorption area in the range of 350 to 450 nm is 10% or more with respect to the total area of the absorption curve in the range of 00 to 500 nm. 3. A photosensitizer having a hydrogen-abstracting action (C
The ultraviolet-curable resin composition according to claim 1, further comprising 3). 4. The ultraviolet curable resin composition according to claim 1, containing 50% by weight or more of an alicyclic epoxy compound (A) which is liquid at room temperature. 5. The other epoxy compound (B) is a glycidyl ether type epoxy compound which is solid at room temperature and / or a novolac type epoxy compound which is solid at room temperature. UV curable resin composition. 6. The ultraviolet curable resin composition according to claim 1, which is coated with a metal or a metal coated with a plastic film. 7. The ultraviolet curable resin composition according to claim 6, wherein the metal is iron or aluminum. 8. The ultraviolet curable resin composition according to claim 6, wherein the metal or the metal coated with a plastic film is plate-shaped or can-shaped. 9. The ultraviolet curable resin composition according to claim 6, wherein the plastic film is a polyester film.