JPH03265669A - Active energy ray-curable resin composition and cured article prepared therefrom - Google Patents

Abstract

PURPOSE:To reduce viscosity to thereby enable coating and to improve curing rate, adhesion to paper, moldability such as foldability, and gloss by compounding two specific (meth)acrylic-esterified compds. and two (meth) acrylates. CONSTITUTION:A bisphenol epoxy resin is reacted with (meth)acrylic acid to give a (meth)acrylic-esterified bisphenol epoxy resin. The title compsn. is prepd. by compounding 5-30wt.% said resin, 10-45wt.% dicyclopentenyloxyethyl (meth)acrylate and/or dicyclopentanyl (meth)acrylate, 5-35wt.% tetrahydrofurfuryl (meth)acrylate, 10-45wt.% (meth)acrylic-estrifited phenyl glycidyl ether, and, if necessary, 10wt.% or lowe photopolymn. initiator, another monomer and/or prepolymer, an org. solvent, an additive, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an active energy ray-curable resin composition that is particularly useful for coating paper. It cures in an extremely short time by irradiation with ultraviolet rays or electron beams, has excellent adhesion to paper, and does not cause cracks when folded.
The present invention relates to an active energy ray-curable resin composition that is excellent in imparting gloss to paper, and a cured product thereof.

(Prior Art) In recent years, research on active energy ray-curable resin compositions for paper coating has been actively conducted, and efforts are being made to put them into practical use in the fields of printing inks, clear varnishes, and the like. These are composed of radically polymerizable monomers and prepolymers, and optionally a photopolymerization initiator, an organic solvent, a pigment, and the like.

(Problems to be Solved by the Invention) Since active energy ray-curable monomers and prepolymers are generally instantly cured by irradiation with active energy rays, internal stress is generated within the cured film. For this reason, products coated with these curable resin compositions and cured tend to crack when bent and have poor adhesion. Also, if high-speed curing requires high-speed coating, these monomers and prepolymers generally have high viscosities;
Low viscosity is required for high-speed coating applications such as spray application, gravure printing, and flexographic printing.

(Means for Solving the Problems) As a result of intensive research to improve these drawbacks, the present invention has been developed to provide a material that can be applied with low viscosity, has a fast curing speed, and has excellent workability such as adhesion to paper and bendability. We have now invented an active energy ray-curable resin composition that also has good gloss.

That is, the present invention provides: (1) (meth)acrylic acid ester of bisphenol type epoxy resin (A) and dicyclopentenyloxyethyl (meth)acrylate and/or dicyclopentanyl (meth)acrylate (B) and tetrahydrocarbon An active energy ray-curable resin comprising a (meth)acrylic acid ester of furfuryl (meth)acrylate (C) and phenyl glycidyl ether (D) and, if necessary, a photopolymerization initiator (E). The present invention relates to a composition, (2) the resin composition according to (1) above for coating paper, and (3) a cured product of the resin composition according to (1) or (2) above.

In the present invention, bisphenol type epoxy resin (meth)
An acrylic acid ester compound (A) is used. Specific examples of bisphenol type epoxy resins include bisphenol A type epoxy resins (manufactured by Mitsui Petrochemical Industries, Ltd., Epomic R-140, R-301, R-304, R
-307, manufactured by Shell Chemical ■, Epicoat 828, Epicoat 1001. Epikote 1004, etc.), bisphenol F type epoxy resin (made by Shell Chemical ■, Epikote 80)
7 etc.).

As mentioned above, by reacting epoxy resin and (meth)acrylic acid, (meth) of bisphenol type epoxy resin
Acrylic acid ester compound (A) can be obtained, and this is a known compound. This (A) component is (A) ~ (
It is preferably used in an amount of 5 to 30% by weight, particularly preferably 8 to 25% by weight, based on the total amount of component E). The result of this component is increased flexibility and better bendability. Moreover, the gloss becomes good.

In the present invention, dicyclopentenyloxyethyl (meth)
Acrylate and/or dicyclopentanyl (meth)acrylate (B) is used.

(B) Ingredients can be easily obtained from the market.
. For example, manufactured by Hitachi Chemical ■, FA-512A, FA
-512M, FA-513A, FA-513M, etc. Component (B) is 1 out of the total amount of components (A) to (E).
It is preferable to use it in the range of 0 to 45% by weight, especially 1
It is preferably used in a range of 5 to 40% by weight. This component provides excellent adhesion to paper.

In the present invention, tetrahydrofurfuryl (meth)acrylate (C) is used. Component (C) can be easily obtained from the market. For example, Viscoat 150 manufactured by Osaka Organic Industry ■ is used. (C) Ingredients are (A) to (E
) It is preferably used in a range of 5 to 35% by weight, particularly preferably in a range of 10 to 25% by weight, based on the total amount of components. This component provides excellent adhesion to paper. In the present invention, a (meth)acrylic acid ester of phenyl glycidyl ether (D) is used. Component (D) can be easily obtained from the market. For example, KAYARADR-12 manufactured by Nippon Kakami Co., Ltd.
8. KAYARAD R-12El! There is something like that. (D)
The component is preferably used in an amount of 10 to 45% by weight, particularly preferably 15 to 38% by weight, based on the total amount of components (A) to (E). This component provides excellent adhesion to paper. The present invention
This relates to a resin composition that is cured by irradiation with active energy rays, and when curing by irradiation with ultraviolet rays, a photopolymerization initiator (E) must be added. Component (E) is 1 in the total amount of components (A) to (E).
It is preferably used in an amount of 0% by weight or less, particularly preferably in a range of 4 to 9% by weight. When curing by electron beam irradiation, it is not necessary to add (E) Jff1. The photopolymerization initiator (E) may be any known photopolymerization initiator. For example, penyne alkyl ethers such as benzoin ethyl ether and benzoin isobutyl ether, acetophenones such as 2,2-jethoxyacetophenone and 4'-phenoxy-2,2-dichloroacetophenone, and 2-hydroxy-2-methylpropylene Propiophenones such as piophenone, anthraquinones such as benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone and 2-ethylanthraquinone, 2-chloroanthraquinone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, etc. Examples include thioxanthone photopolymerization initiators.

The composition of the present invention may contain other monomers and/or prepolymers as required. Examples of monomers include monofunctional monomers such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, methyl acrylate, ethyl acrylate, butyl acrylate, and ethylene glycol, propylene glycol, 1,4-butanediol, α, β with dialcohols such as diethylene glycol, triethylene glycol, polyethylene glycol, neopentyl glycol, or their modified products with ethylene oxide, propylene oxide, or lactone.
- Polyfunctional monomers such as diesters with unsaturated carboxylic acids are exemplified. Examples of the prepolymer include acrylate modified products and methacrylate modified products based on polyurethane, polyester, silicone resin, alkyd resin, phenolic resin, and the like.

The composition of the present invention may or may not contain an organic solvent, and depending on the application, it may be preferable to use an organic solvent to adjust the viscosity. If an organic solvent is added, it is desirable to remove it using a hot air dryer after coating. For this purpose, it is better to add as little amount as possible. Considering that it will be removed by hot air drying after coating, it is preferable to use a solvent with a boiling point of 70-150"C, which is as harmless and safe as possible. For example, esters such as ethyl acetate and butyl acetate, aromatic substances such as toluene and xylene. Group hydrocarbons, ketones such as methyl ethyl ketone, methyl butyl ketone, etc. can be used.Also, it can be used as a mixed solvent with other solvents.

The composition of the present invention may contain additives such as pigments, dyes, antifoaming agents, leveling agents, slip agents, and matting agents, as required.

The composition of the present invention can be obtained by uniformly mixing each component.

The composition of the present invention can be cured by active energy rays. As active energy rays, electron beams, ultraviolet rays, etc. can be used, and the composition of the present invention is cured by irradiation with these in a conventional manner.

The composition of the present invention is useful for coating paper, particularly for coating paper with oats, but it can also be used as a coating agent for plastic substrates such as polycarbonate, glass, and the like.

When the composition of the present invention is used for coating paper, for example, the composition of the present invention is applied to paper printed or coated with printing ink or coating liquid to a thickness of preferably 2 to 6 μm using a flexo printing machine or the like. Paper coated with a cured film can be obtained by coating the paper with a hardened film and removing the solvent if it contains a hardened film.

(Example) Hereinafter, the present invention will be specifically explained with reference to Examples.

Note that parts in the examples are parts by weight.

[Synthesis Example 1] In a 2L separable flask equipped with a stirrer, temperature control device, thermometer, condenser, and dry air blowing device, Evomic R-304 (bisphenol A type epoxy resin: manufactured by Mitsui Petrochemical Industries, Ltd., epoxy Equivalent weight: 916.8)
800 parts, acrylic acid 59.2 parts, hydroquinone monoethyl ether 0.86 parts, dicyclopentenyloxyethyl acrylate (manufactured by Hitachi Chemical Co., Ltd., FA-512)
878 parts of A) and 8.6 parts of triphenylstibine were charged and reacted for 30 hours at 90°C under dry air blowing to produce acrylic acid esterification of bisphenol-type epoxy resin (A).
) was obtained.

[Synthesis Example 2] In a 2L separable flask equipped with a stirrer, a temperature control device, a thermometer, a condenser, and a dry air blowing device, Epomic, R-304 (bisphenol A type epoxy resin manufactured by Nimitsui Petrochemical Industry Co., Ltd.), Epoxy equivalent: 916,8)
800 parts of acrylic acid, 59.2 parts of hydroquinone monoethyl ether, 878 parts of dicyclopentanyl acrylate (manufactured by Hitachi Chemical Co., Ltd., FA-513A), and 8.6 parts of triphenylstibine, and dried air. The mixture was reacted for 31 hours at 90°C under blowing to obtain a mixture containing an acrylic ester of bisphenol type epoxy resin (A).

[Synthesis Example 3] In a 2L separable flask equipped with a stirrer, a temperature control device, a thermometer, a condenser, and a dry air blowing device, Evomic, R-140 (bisphenol A type epoxy resin manufactured by Nimitsui Petrochemical Industry Co., Ltd.), Epoxy equivalent: 189) 121
5 parts of acrylic acid, 458.6 parts of acrylic acid, 0.84 parts of hydroquinone monoethyl ether, and 0.6 parts of 2.4.6 tris(dimethylaminomethyl)phenol, and reacted at 90°C for 12 hours under dry air blowing. , an acrylic acid ester of bisphenol type epoxy resin (A) was obtained.

[Synthesis Example 4] In a 2L separable flask equipped with a stirrer, a temperature control device, a thermometer, a condenser, and a dry air blowing device, Epicoat 807 (Hisphenol F type epoxy resin manufactured by Nigel Chemical Co., Ltd., epoxy equivalent: 170) 1215 509.8 parts of acrylic acid, 0.86 parts of hydroquinone monoethyl ether, and 0.6 parts of 2.4.6 tris(dimethylaminemethyl)phenol, and reacted at 90°C for 12 hours under dry air blowing. An acrylic acid ester of bisphenol type epoxy resin (A) was obtained.

[Example of resin composition]

Example 1 18.2 parts of a mixture containing an acrylic acid ester of the bishenol type epoxy resin obtained in Synthesis Example 1, 23.2 parts of dicyclopentenyloxyethyl acrylate (manufactured by Hitachi Chemical Co., Ltd., FA-512A), Tetrahydrofurfuryl acrylate (manufactured by Osaka Organic Industry, Viscoat 150)
) 13.5 parts, acrylic acid ester of phenylglycidyl ether (Nipponka seasoning type, KAYARAD R
-128) 31.5 parts, polyethylene glycol diacrylate (Nipponka seasoning type, KAYARADPEG-40
0DA) 8.1 parts, 1-hydroxycyclohexylphenyl ketone (manufactured by Ciba Geigy, Irgacure 18
4) Resin composition A was prepared by mixing 5.5 parts. The properties of the cured product are shown in Table 1.

Example 2 18.2 parts of a mixture containing an acrylic acid ester of the bisphenol-type epoxy resin obtained in Synthesis Example 2, dicyclopentanyl acrylate (manufactured by Hitachi Chemical Co., Ltd., FA-51)
3A) 23.2 parts, 13.5 parts of tetrahydrofurfuryl acrylate (manufactured by Osaka Organic Industry ■, Viscoat 150), acrylic acid ester of phenyl glycidyl ether (KAYARAD R-128, manufactured by Nippon Kakami) 31
．． 5 parts, polyethylene glycol diacrylate (KAYARAD PEG-400DA manufactured by Nippon Kajimi Co., Ltd.) 8
．． 1 part, l-hydroxycyclohexylphenyl ketone (manufactured by Ciba Geigy, Irgacure 184) 5.5
A resin composition B was prepared by mixing the following parts.

The properties of the cured product are shown in Table 1.

Example 3 18 parts of acrylic acid ester of bisphenol type epoxy resin obtained in Synthesis Example 3, dicyclopentenyloxyethyl acrylate (manufactured by Hitachi Chemical Industries, Ltd., FA-512A)
) 23.2 parts, tetrahydrofurfuryl acrylate (
Osaka Organic Industry Co., Ltd., Viscoat 150) 13.5 parts, phenyl glycidyl ether acrylic ester (
31.7 parts of polyethylene glycol diacrylate (KAYARAD PEG-400DA, manufactured by Nippon Kayami Co., Ltd., 8.1 parts of 1-hydroxycyclohexylphenyl ketone (manufactured by Ciba, Geigy, Iruga) 5.5 parts of Cure 184) were mixed to prepare resin composition C.

The properties of the cured product are shown in Table 1.

Example 4 18 parts of acrylic ester of bisphenol type epoxy resin obtained in Synthesis Example 4, dicyclopentenyloxyethyl acrylate (manufactured by Hitachi Chemical Co., Ltd., FA-512A)
) 23.2 parts, tetrahydrofurfuryl acrylate (
Osaka Organic Industry ■, Viscoat 150) 13.5 parts, phenyl glycidyl ether acrylic ester (
KAYARAD R-128) 31.7, made by Nippon Kakami
Part, polyethylene glycol diacrylate (KAYARAD PEG-400DA, manufactured by Nippon Kajimi Co., Ltd.) 8.1
and 5.5 parts of 1-hydroxycyclohexylphenyl ketone (manufactured by Ciba Geigy, Irgacure 184) were mixed to prepare a resin composition. The properties of the cured product are shown in Table 1.

Comparative Example 1 18 parts of the acrylic acid ester of the bisphenol type epoxy resin obtained in Synthesis Example 3, 13 parts of tetrahydrofurfuryl acrylate (manufactured by Osaka Organic Industry ■, Viscoat 150)
．． 5 parts, acrylic acid ester of phenyl glycidyl ether (Nipponka seasoning type, KAYARAD R-12
8) 31.7 parts, polyethylene glycol diacrylate (Nipponka seasoning type, KAYARAD PEG-40O
DA) 31.3 parts, 1-hydroxycyclohexylphenyl ketone (manufactured by Ciba Geigy, Irgacure 18
4) 5.5 parts were mixed to prepare resin composition E. The properties of the cured product are shown in Table 1.

Comparative Example 2 18 parts of the acrylic acid ester of the bisphenol-type epoxy resin obtained in Synthesis Example 3, dicyclopentenyloxyethyl acrylate (manufactured by Hitachi Chemical Co., Ltd., FA-512A)
) 23.2 parts, acrylic acid ester of phenylglycidyl ether (KAYARAD R- manufactured by Nipponka Yakumi Co., Ltd.)
128) 31.7 parts, polyethylene glycol diacrylate (KAYARAD PEG-40, manufactured by Nippon Kagami Co., Ltd.)
0DA) 21.6 parts, 1-hydroxycyclohexylphenyl ketone (manufactured by Ciba Geigy ■, Irgacure 1
84) 5.5 parts were mixed to prepare resin composition F. The properties of the cured product are shown in Table 1.

Comparative Example 3 18 parts of the acrylic acid ester of the bisferrule type epoxy resin obtained in Synthesis Example 3, dicyclopentenyloxyethyl acrylate (manufactured by Hitachi Chemical Co., Ltd., FA-512A)
) 23.2 parts, tetrahydrofurfuryl acrylate (
Osaka Organic Industrial Refinery, Viscoat 150) 13.5 parts,
39.8 parts of polyester glycol diacrylate (KAYARAD PEG-400DA) and 5.5 parts of 1-hydroxycyclohexylphenyl ketone (manufactured by Ciba Geigi ■, Irgacure 184) were mixed to form a resin composition. G was prepared. The characteristics of the cured product are as follows.
Shown in the table.

Comparative Example 4 23.2 parts of dicyclopentenyloxyethyl acrylate (manufactured by Hitachi Chemical Co., Ltd., FA-512A), 13.5 parts of tetrahydrofurfuryl acrylate (manufactured by Osaka Organic Industry Co., Ltd., Viscoat 150), acrylic acid of phenyl glycidyl ether Esterified product (Japanese condiment type, KAYAR
AD R-128) 31.7 parts, polyethylene glycol diacrylate (KAYARADPE manufactured by Nippon Kajimi Co., Ltd.)
Resin composition H was prepared by mixing 26.1 parts of G-40ODA) and 5.5 parts of 1-hydroxycyclohexylphenyl ketone (Irgacure 184, manufactured by Ciba Geigy). The properties of the cured product are shown in Table 1.

Example 5 18 parts of the acrylic acid ester of the bisphenol-type epoxy resin obtained in Synthesis Example 3, dicyclopentenyloxyethyl acrylate (manufactured by Hitachi Chemical Co., Ltd., FA-512A)
) 28.7 parts, tetrahydrofurfuryl acrylate (
Osaka Organic Industry Phase Type, Viscoat 150) 13.5 parts, acrylic ester of phenyl glycidyl ether (
Manufactured by Nippon Kayaku (lid), KAYARADR-128) 3
1.7 parts, polyethylene glycol diacrylate (Nippon Kaji), KAYARAD PEG-400DA
) were mixed to prepare Resin Composition 1. The properties of the cured product are shown in Table 1.

Table 1: Evaluation method (1) The viscosity was determined to be O when the viscosity of the resin composition itself obtained in each example and comparative example was 500 cps or less.

(2) Apply the resin composition to the paper coated with water-based ink to a thickness of 5μ using a flexo printing machine, and apply this using an ultraviolet irradiator using a high-pressure mercury 80W bulb at a distance of 8 cI! ], speed 5m/
Hardened in minutes.

In addition, only Composition I in Table 1 was cured with an electron beam of 3 Mrad.

The curing speed was determined by the presence or absence of tack on the surface after curing.

○: No tack △: Slight tack ×: Considerable tack The gloss was determined by looking at the gloss after curing.

○: Excellent gloss ×: Insufficient gloss Hardness was determined by bending the paper after curing and checking for cracks in the resin part.

○: No cracks ×: Quite a few cracks To check the adhesion, apply cellophane tape to the surface after curing and peel it off.If the cured resin film and water-based ink part are peeled off from the underlying paper, or only the cellophane tape is peeled off. ○: When only the cured film of the coated resin peeled off, it is marked as ×, and △ is in between.

The evaluation results are as shown in Table 1.

Examples 6 to 10 Resin compositions were prepared in the same manner as in Examples 1 to 5 except that polyethylene glycol diacrylate was not added, and evaluation tests were conducted in the same manner. The results were obtained.

(Effects of the invention) By using the active energy ray-curable resin composition of the present invention, the viscosity can be reduced and coating can be performed at high speed, and when irradiated with ultraviolet rays or electron beams, it can be cured at high speed and workability is greatly improved. improved. The coating obtained by further curing had good adhesion and flexibility, and a product with excellent gloss was obtained.

Claims (1)

[Claims] 1. (meth)acrylic acid ester of bisphenol type epoxy resin (A), dicyclopentenyloxyethyl (meth)acrylate and/or dicyclopentanyl (meth)acrylate (B), and tetrahydrofuryl An active energy ray-curable resin composition comprising a (meth)acrylic acid ester of furyl (meth)acrylate (C) and phenyl glycidyl ether (D) and, if necessary, a photopolymerization initiator (E). . 2. The resin composition according to claim 1 for coating paper. 3. A cured product of the resin composition according to claim 1 or 2.