JPH1135846A - Active energy ray-curing resin composition and coating film formation using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition curable by active energy rays in the presence of air. SOLUTION: This resin composition is obtained by blending (A) 5-80 wt.% of an epoxy compound 160-2,000 in average molecular weight, (B) 20-95 wt.% of an acryloyl group-contg. Organic cyclic compound, and (C) 0.5-10 pts.wt., based on a total of 100 pts.wt. of the components A and B, of a photocationic polymerization initiator. The other objective method for coating film formation comprises as follows: the surface of a substrate is coated with the above resin composition in such amounts as to be 1-50 μm in cured film thickness followed by irradiating the coating film with active energy rays to effect curing the film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

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

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

[0004] As an active energy ray-curable resin composition, there is also known one in which a photocationic polymerization initiator is blended with an epoxy resin as a composition which is hardly hindered by curing by oxygen. In addition, when an acrylic monomer such as an alkyl (meth) acrylate is blended with the above compound, the curability in the presence of oxygen deteriorates.

[0005] In addition, there have been problems that the cured film obtained conventionally has insufficient surface hardness and poor adhesion to plastic films such as PET.

[0006]

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

[0007]

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, a specific amount of an epoxy compound, an organic cyclic unsaturated compound, and a cationic photopolymerization initiator are blended. As a result, they have found that the conventional problems can be solved, and have completed the present invention.

The present invention relates to: (1) 5 to 80% by weight of an epoxy compound having an average molecular weight of 160 to 2,000, (B) 20 to 95% by weight of an organic cyclic compound having a (meth) acryloyl group, and (C) light The cationic polymerization initiator is used in a total amount of 1 of the above components (A) and (B).
An active energy ray-curable resin composition characterized in that it is blended in an amount of 0.5 to 15 parts by weight per 00 parts by weight. The present invention relates to a method for forming a film, which comprises applying a cured film having a cured film thickness of 1 to 50 μm and then irradiating the film with an active energy ray to cure the film.

The epoxy compound (A) used in the present invention
Has an average molecular weight of from 160 to 2,000, especially from 2 to 3, having at least one, especially from 1 to 4 epoxy groups per molecule.
Epoxy compounds. If the number of epoxy groups is less than 1, the curability, surface hardness and the like will be poor. Average molecular weight of 16
Those having a value of less than 0 are difficult to obtain, while those having a value of more than 2,000 are not preferred because the coating workability and the like deteriorate.

The epoxy compound (A) includes a conventionally known alicyclic epoxy group (an epoxy group on an alicyclic hydrocarbon ring, an epoxy group directly bonded to a carbon atom forming an alicyclic hydrocarbon ring). (A-2)), an epoxy compound (A-2) containing an aliphatic epoxy group (an epoxy group other than the above and an epoxy group on a linear hydrocarbon), and an aliphatic compound And an epoxy compound (A-3) containing an alicyclic epoxy group. Epoxy compounds have an average molecular weight of about 160-2000, especially about 2
Those having a range of 00 to 1500 are preferred. Among the above, an epoxy resin having an alicyclic epoxy group has an advantage that the curability by irradiation with active energy rays is excellent.

The epoxy compound (A-1) includes, for example, a single radical polymer of an alicyclic epoxy group-containing radical polymerizable monomer (3,4-epoxycyclohexylmethyl (meth) acrylate), With a radical polymerizable monomer (e.g., an alkyl or cycloalkyl ester of (meth) acrylic acid having 1 to 24 carbon atoms, styrene, etc.), 3,4-epoxy-cyclohexylmethyl-3,4-epoxycyclohexanecarboxylate , Bis (2,3-epoxy-cyclopentyl) ether, dicyclopentagendioxide, bis (3,4-epoxy-cyclohexylmethyl) of ethylene glycol, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-cyclohexane Carboxyle G), bis (3,4-epoxy-cyclohexylmethyl) adipate, bis (3,4-epoxy-6-1-methyl-cyclohexyl methyl) adipate,
3,4-epoxy-cyclohexenecarboxylic acid ethylene glycol diester, bis (3,4-epoxy-cyclohexyl) acetal, 3,4-epoxy-cyclohexylmethyl-3,4-epoxy-cyclohexylmethyl-ε-caprolactone-modified-3,4-epoxy-cyclohexyl Carboxylate, 3,4-epoxy-cyclohexylvinyl, 3,4-epoxy-cyclohexylmethyl (meth) acrylate, 3,4-epoxy-cyclohexylmethyl-ε-caprolactone-modified (meth) acrylate, Epode GT300 (Daicel Chemical Industries, Ltd.) , Trade name, trifunctional alicyclic epoxy resin), Eporide GT400 (manufactured by Daicel Chemical Industries, Ltd., trade name, tetrafunctional alicyclic epoxy resin), EHPE (Daicel Chemical Industry Co., Ltd.) And epoxy compounds such as trade name, trifunctional alicyclic epoxy resin).

As the epoxy compound (A-2), for example, a single radical polymer of a radical polymerizable monomer (for example, glycidyl (meth) acrylate) containing an aliphatic epoxy group, and the monomer and other radical polymerizable monomers ( For example, copolymers of (meth) acrylic acid with an alkyl or cycloalkyl ester having 1 to 24 carbon atoms, styrene, etc.), bisphenol-type epoxy resins, novolak-type epoxy resins, ε-caprolactam-modified bisphenol-type epoxy resins, (poly) Examples thereof include ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and trimethylolpropane triglycidyl ether.

As the epoxy compound (A-3), for example, a radical polymerizable monomer containing an aliphatic epoxy group, a radical copolymer with a radical polymerizable monomer containing an alicyclic epoxy group, and if necessary, And copolymers with the above-mentioned other radically polymerizable monomers, vinylcyclohexene diepoxide, and the like.

The component (B) used in the present invention has one or more (meth) acryloyl groups and a carbon cyclic structure in the molecule and has an average molecular weight of about 140 to 500. The component can use a conventional one,
In particular, the following organic cyclic compounds are preferred because they have excellent curability by irradiation with active energy rays in the presence of oxygen and exhibit an excellent effect of adhering to plastics such as PET.

As the organic cyclic compound, the following (B)
-1 to 4 are mentioned.

Organic cyclic compound (B) -1:

[0017]

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(Wherein R1 represents a hydrogen atom or a methyl group, and A is

[0019]

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

[0021]

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Organic cyclic compound (B) -2:

[0023]

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(Where B is

[0025]

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Where D is

[0027]

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

[0029]

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Organic cyclic compound (B) -3:

[0031]

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(Where E is

[0033]

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Wherein R4 is a hydrogen atom, a methyl group or

[0035]

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And R1 and m have the same meaning as described above. Specific examples include the following.

[0037]

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Organic cyclic compound (B) -4:

[0039]

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

[0041]

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Of the above-mentioned organic cyclic compounds, those having a benzene ring are preferably used.

The mixing ratio of the epoxy compound (A) and the organic cyclic compound (B) is 5 to 80% by weight, preferably 20 to 80% by weight, based on the total weight of the two.
50% by weight, 20 to 95% by weight of the organic cyclic compound (B),
Preferably, the range is 50 to 80% by weight. When the epoxy compound (A) is less than 5% by weight and the organic cyclic compound (B) is more than 95% by weight, the curability and hardness of the coating deteriorate, while the epoxy compound (A) exceeds 80% by weight, and When the amount of the organic cyclic compound (B) is less than 20% by weight, there is a disadvantage that the adhesion to a substrate and the processability are deteriorated.

As the cationic photopolymerization initiator (C) used in the present invention, conventionally known ones can be used. Preferred examples of the initiator (C) include aryldiazonium salts, aryliodonium salts, and arylsulfonium salts. Specifically, for example, Silacure UVI-6970, Silacure UVI
-6974, Cyracure UVI-6990, Cyracure UVI-6950 (all manufactured by Union Carbide, USA), Irgacure 261 (made by Ciba Geigy), SP-150, SP-170 (all manufactured by Asahi Denka Kogyo Co., Ltd.) ), CG-24-61 (manufactured by Ciba-Geigy), PI-2074 (manufactured by Rhone Poulin, pentafluorophenylborate toluylcumyl iodonium salt), FC-509 (manufactured by 3M), BBI102 (manufactured by Midori Kagaku), etc. Is mentioned.

The proportion of the cationic photopolymerization initiator (C) is 0.5 to 15 parts by weight, preferably 0.7 to 5 parts by weight, based on 100 parts by weight of the components (A) and (B). Department.

In the present invention, if necessary, an unsaturated resin other than those described above, a reactive diluent, a photopolymerization sensitizer, a photopolymerization accelerator, a filler, a colorant, a pigment, a fluidity regulator, a cissing prevention agent Agents and the like can be blended.

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

The composition of the present invention can be applied to substrates such as paper, plastic, metal, and combinations thereof.

In the method of forming a coating film of the present invention, the above active energy ray-curable resin composition is applied to the above-mentioned substrate surface so that the applied amount is 1 to 50 μm in the cured film thickness, and then the active energy ray is applied. Irradiation and curing.

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

Examples of the active energy ray include a mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide, a gallium lamp, an excimer, and ultraviolet rays, β rays and electron rays. The irradiation amount of the ultraviolet ray is not particularly limited,
Usually, it is preferably in the range of about 10 to 2,000 mj / cm2. In the case of an electron beam, it is preferable to irradiate an electron beam of 50 to 300 Kev usually for 1 to 20 Mrad.

[0052]

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

Example 1 50 g of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 50 g of paracumylphenol ethylene oxide acrylate,
A composition obtained by mixing 4 g of Thyracure UVI-6990 (a triarylsulfonium hexafluorophosphate mixture, 50% by weight solution manufactured by Union Carbide Co., Ltd.).

The above composition was applied to a surface of a polyethylene terephthalate film (thickness: 100 μm) so as to have a thickness of 10 μm by a bar coater, and then irradiated with 150 mj / cm 2 ultraviolet light in the air using a metal halide lamp to form a cured coating. I got

Appearance (Note 1), good adhesion (Note 2)
Good, Pencil hardness (Note 3) H, Sword hardness was good at 25 times.

Example 2 45 g of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 40 g of phenoxydiethylene glycol acrylate, 15 g of dicyclopentenyloxyethyl acrylate, PI-2
No. 074 (pentafluorophenyl borate tolylcumyl iodonium salt, manufactured by Rhone Poulin Co.).

The above composition was applied to the surface of a polybutylene terephthalate film (thickness: 100 μm) with a bar coater so as to have a thickness of 15 μm, and then cured by irradiating with ultraviolet rays of 200 mj / cm 2 in air using a high pressure mercury lamp. A coating was obtained.

Appearance (Note 1), good adhesion (Note 2)
Good, pencil hardness (Note 3) H, Sword hardness was good at 23 times.

Example 3 Bis (3,4-epoxycyclohexyl) adipate 4
0 g, 2-hydroxy-3-phenoxypropyl acrylate 50 g, phenoxyethyl acrylate 10 g,
A composition containing 1.5 g of BBI-102 (manufactured by Midori Kagaku).

An aluminum plate (thickness: 5)
(Μm) to a thickness of 8 μm with a bar coater, and then 250 m in air using a metal halide.
The cured film was obtained by irradiating j / cm2 with ultraviolet rays.

Appearance (Note 1), good adhesion (Note 2)
Good, pencil hardness (Note 3) H, Sword hardness was good at 22 times.

Example 4 40 g of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 40 g of paracumylphenol ethyl oxide acrylate, 10 g of cyclohexyl acrylate, 10 g of isobonyl acrylate and 60 g of titanium dioxide were mixed and dispersed with a shaker. A white enamel was produced, and then 100 g of the white enamel was mixed with 1 g of PI-2074 (same as above) and 0.3 g of diethylthioxanthone to obtain a composition.

The above composition was applied to a surface of a polybutylene terephthalate film (thickness: 100 μm) so as to have a thickness of 15 μm by a bar coater.
Irradiated with Mrad to form a cured film.

Appearance (Note 1), good adhesion (Note 2)
Good, pencil hardness (Note 3) 2H, Sword hardness was good at 30 times.

Comparative Example 1 A compound was prepared in the same manner as in Example 1 except that 50 g of paracumylphenol ethylene oxide acrylate was replaced with 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate. Was formed.

Appearance (Note 1), good adhesion (Note 2)
Was peeled off by 50%, the pencil hardness (Note 3) was 3H, and the hardness was 27 times.

Comparative Example 2 Comparative Example 1 was obtained by blending in the same manner as in Example 1 except that paracumylphenol ethylene oxide acrylate was replaced with butyl acrylate. Next, a film was formed on the substrate in the same manner as in Example 1.

The appearance of the coating (Note 1) was good, but the coating did not cure and the surface was sticky, so that the test could not be performed.

Tests and evaluations in Examples and Comparative Examples were performed as follows.

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

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

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

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

[0074]

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

Claims (2)

[Claims] (1) 5 to 80% by weight of an epoxy compound having an average molecular weight of 160 to 2,000, (B) 20 to 95% by weight of an organic cyclic compound having a (meth) acryloyl group, and (C) a cationic photopolymerization initiator. An active energy ray-curable resin composition comprising 0.5 to 15 parts by weight per 100 parts by weight of the total of the components (A) and (B). 2. The method according to claim 1, wherein the active energy ray-curable resin composition is applied to the surface of a substrate so that the applied amount is 1 to 50 μm in a cured film thickness, and then cured by irradiating with an active energy ray. Characteristic film forming method.