JPH1046002A - Curable liquid resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition which can form film through a conventional technique and can be promptly cured by a conventional method, despite that it has a high molecular weight, by formulating a specific (meth) acrylic liquid resin and a specific polyester resin. SOLUTION: (A) A (meth)acrylic liquid resin is prepared by copolymerization of 20-98wt.% of a (meth)acrylic monomer of formula I (R<1> is H, methyl; R<2> is a 4-22C alkyl) and a (meth)acrylic monomer of formula II (R<3> is a 1-15C alkyl, phenyl; n is 1-3) in total, 1-50wt.% of a radically polymerizable monomer bearing a functional group selected from glycidyl, amide and the like and 0-79wt.% of other polymerizable vinyl compound, and (B) an ester resin is prepared by polymerizing a composition which is formed by formulating a hydroxy group-bearing compound to a mixture of an cyclic acid anhydride with a vinyl epoxy compound at a molar ratio of 10/8-10/12 in an amount of 1-20 moles per mole of the cyclic acid anhydride. Then, the component (A) and the component (B) are formulated at a weight ratio of 0.1/99.9-97/3 to give the objective curable liquid resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid resin composition capable of forming a cured film without using a solvent as a resin for a film-forming material such as paints and inks and for an adhesive. Further, the liquid resin composition obtained according to the present invention can also be used as a compatibilizer, an interface modifier, and a pigment dispersant. Further, the liquid resin composition comprising the acrylic liquid resin and the ester resin obtained by the present invention can be used as a radiation-curable resin composition.

[0002]

2. Description of the Related Art Conventionally, paints, adhesives, adhesives, inks,
Resin solutions containing organic solvents have been used for fillers and molding materials. These resin solutions scatter a large amount of organic solvent in the coating, filling and curing / drying steps. With increasing interest in the global and working environments, restrictions on the use of such resin solutions have been added. As one of the methods, use of an aqueous solution or powder of a resin, a hot melt material is mentioned, but the aqueous solution of the resin contains a small amount of an organic solvent in order to improve coatability, and that the odor in the working environment has been removed. Hard to say. In addition to the incineration of the released organic solvent, investment is required for wastewater treatment. Organic solvent emission into the atmosphere can be suppressed at painting and filling plants equipped with large-scale exhaust gas treatment facilities, but at small plants without such facilities, wastewater cannot be treated even if organic solvents can be treated. Having. Further, in the case of coating and filling of powder or hot melt, a new equipment has to be introduced because the method of coating and filling is greatly different from the conventional coating and filling equipment. In order to solve the above-mentioned problems, high solidification of the resin solution, improvement of the aqueous solution of the resin, etc. have been performed.
It is considered that the use amount of the resin solution will tend to decrease more in the future. But the fundamental solution is pollution,
There is a strong demand for the development of a solvent-free liquid resin which has no problems of safety and health, ignition, explosion, etc., can be widely applied, and can be easily applied and filled. In addition, these solvent-free liquid resins need to be formed into a film or molded product cured by a conventional drying apparatus.

[0003] Conventional radiation-curable resin compositions include:
Since it contains a large amount of low molecular weight components, it is not preferable in terms of working environment due to problems such as odor. Further, there has been a problem that the volume shrinkage during curing is large and the cured coating film becomes brittle.
In order to improve the curing shrinkage rate, a relatively high molecular weight monomer component was used, or a high molecular weight component was added.However, in the latter case, since the composition was solid, The amount that can be added was limited in order to keep the viscosity within an appropriate viscosity range. Further, even after curing, the problem of containing a large amount of low molecular weight compounds such as odor due to residual monomers has considerably narrowed the range of use of radiation-curable resin compositions.

[0004] Solvent-free resin compositions are disclosed in
No. 171 publication. This technique uses a liquid resin made of an acrylic monomer, but further improvement is desired because the obtained resin is an oligomer and contains a residual monomer in the composition. In terms of physical properties, it is known that it is difficult to control the physical properties of the coating after curing in the case of a coating composed of a resin in the oligomer region (Souichi Muroi, “Lecture on Adhesion and Painting in 1992” Abstracts of the lecture, p. 4, 1993), it is desired to increase the molecular weight while maintaining low viscosity.

[0005]

DISCLOSURE OF THE INVENTION The present invention has a special effect because it does not contaminate the working environment in the coating process with flying low molecular weight compounds and does not release low molecular weight compounds such as organic solvents and monomers into the atmosphere. No exhaust gas treatment equipment is required, and the film can be formed by coating methods such as roll coater and knife coater which are conventionally used, offset printing, gravure printing, letterpress printing, etc. An object of the present invention is to provide a curable liquid resin composition that can be cured by irradiation with radiation such as rays, ultraviolet rays, visible rays, and infrared rays.

[0006]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted intensive studies on the correlation between the structure of various resin systems and the viscosity, and the like. The present invention has found a curable liquid resin composition which is within a viscosity range in which a film can be formed by a method and which can be cured at a high speed by a conventional curing method. That is, the present invention provides the following (meth) acrylic liquid resin (A) and the following ester resin (B) as (A):
(B) = A curable liquid resin composition formulated in a ratio of 0.1: 99.9 to 97: 3 (% by weight). (A) a functional group selected from a carboxyl group, a glycidyl group, an amide group and a hydroxyl group in the following (meth) acrylic monomer (a-1) and the following (meth) acrylic monomer (a-2) And a polymerizable vinyl compound (a-4) other than the above,
{(A-1) + (a-2)}: (a-3): (a-4)
= 20 to 98: 1 to 50: 0 to 79 (% by weight), and has a number average molecular weight of 10,000 to 20.
(Meth) acrylic liquid resin having a viscosity of 5 to 10,000 poise (50 ° C.).

CH ₂ ＣC (R ¹ ) COO—R ² (a-1) (wherein R ¹ is a hydrogen atom or CH ₃ , and R ² is C 4
To 22 alkyl groups. ) CH ₂ ＣC (R ¹ ) COO (C _n H _2n O) _m R ³ (a-2) (wherein, R ¹ is a hydrogen atom or CH ₃ , and R ³ is carbon atom 1)
To 5 alkyl groups or phenyl groups, n represents an integer of 1 to 3, and m represents an integer of 4 to 25, respectively. (B) a cyclic acid anhydride (b-1), an epoxy compound (b-2-1) containing one epoxy group in the molecule, and one epoxy group and an unsaturated double bond in the molecule. The vinyl epoxy compound (b-2-2) having (b-1):
{(B-2-1) + (b-2-2)} = 10: 8-1
0:12 (molar ratio), and the hydroxyl group-containing compound (b-3) was added in an amount of 1 to 20 with respect to 1 mol of (b-1).
An ester resin obtained by reacting a composition mixed at a ratio of 0 mol.

The present invention further relates to an epoxy compound (b-2)
-1) and the vinyl-based epoxy compound (b-2-2) are (b-2-1) :( b-2-2) = 0: 100 to 9
The curable liquid resin composition according to claim 1, wherein the ratio is 5: 5 (mol%). Further, the present invention provides an ester-based resin (B)
Is a number average molecular weight of 300 to 50,000 and a viscosity of 1 to 10,000 poise (50 ° C.). Further, the present invention relates to a monomer (a-
1) and the ratio of the monomer (a-2) is (a-1) :( a-
2) = 0.1: 99.9-99.9: 0.1 (% by weight)
And the curable liquid resin composition.

Further, the present invention relates to the above curable liquid resin composition, wherein R1 in the monomer (a-1) and the monomer (a-2) is a hydrogen atom. Further, the present invention provides that the composition has a viscosity of 1 to 10,000 poise (50
C)). Furthermore, the present invention relates to the above curable liquid composition which is a radiation-curable type. Further, the present invention relates to a printing ink using the curable liquid resin composition. Further, the present invention relates to a coating composition using the curable liquid resin composition.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION

In the present invention, the (meth) acrylic liquid resin (A) is a composition for liquefying a curable resin composition, and imparts toughness and flexibility to a cured coating film. Such a (meth) acrylic liquid resin (A) comprises a (meth) acrylic monomer (a-1) or (a-2) and a carboxyl group, a glycidyl group, an amide group, or a hydroxyl group in the molecule. Obtained by copolymerizing a monomer composition comprising a radical polymerizable monomer having at least one functional group selected from the group consisting of:

In the present invention, a (meth) acrylic monomer having an alkyl group represented by the general formula (a-1) or a poly (alkylene) oxy group represented by the general formula (a-2) is bonded. The (meth) acrylic monomer is used to make the (meth) acrylic resin liquid. Examples of the alkyl group derivative represented by the general formula (a-1) include 2-ethylhexyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, heptyl (meth) acrylate, and hexyl (meth).
Acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate,
Undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth)
C4 such as acrylate, nonadecyl (meth) acrylate, icosyl (meth) acrylate, henycosyl (meth) acrylate, docosyl (meth) acrylate
There are alkyl (meth) acrylates having from 22 to 22, and among them, acrylates having an alkyl group having 8 to 20 carbon atoms or corresponding methacrylates are preferable. If the number of carbon atoms is 3 or less, it is difficult to obtain a liquid resin, and if the number of carbon atoms is 23 or more, the degree of polymerization is difficult to increase, and since the crystallization proceeds, the viscosity of the liquid resin obtained is high, and it is dedicated to film formation. It is not preferable because a heating system is required.

The film formation in the present invention means that a resin having a thickness of 0.1 to 5 is coated on a substrate made of paper, metal, plastic, ceramics or the like by a method such as printing and painting.
This means that a 00 μm film is formed.

As the poly (alkylene) oxy group derivative represented by the general formula (a-2), for example, methoxytetraethylene glycol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, propoxytetraethylene glycol (meth) acrylate ,
n-butoxytetraethylene glycol (meth) acrylate, n-pentaxytetraethylene glycol (meth) acrylate, methoxytetrapropylene glycol (meth) acrylate, ethoxytetrapropylene glycol (meth) acrylate, propoxytetrapropylene glycol (meth) acrylate, n-butoxytetrapropylene glycol (meth) acrylate, n
-Pentaxytetrapropylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, or phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) ) Acrylate, phenoxy polyethylene glycol (meth) acrylate, phenoxy tetrapropylene glycol (meth) acrylate,
Above all, by using an acrylate having a polyoxyalkylene chain as a repeating unit of 4 to 25, preferably 5 to 22 or a corresponding methacrylate, the viscosity of the copolymer can be effectively reduced. When the number of repeating units is 3 or less, it is difficult to obtain a liquid resin.
Above this is not preferred because the degree of polymerization is hard to increase and since it is a solid at 50 ° C., a dedicated melting system is required for film formation.

In the present invention, the (meth) acrylic monomer (a-1) or (a-2) is added in an amount of 10 to 98% by weight, preferably 40 to 95% by weight in the monomer composition.
% By weight. 40% by weight of (meth) acrylic monomer (a-1) or (a-2) in the monomer composition, especially 20%
If the amount is less than 10% by weight, the obtained (meth) acrylic liquid resin cannot maintain a preferable viscosity. Further, the (meth) acrylic monomers (a-1) and (a-2) may be used alone, but are preferably used in combination in terms of decreasing the viscosity and improving the compatibility with other compositions. . In this case, the ratio of the (meth) acrylic monomer (a-1) to (a-2) is preferably from 0.1: 99.9 to 99.9: 0.1 in molar ratio.

In the present invention, the radical polymerizable monomer (a-3) having at least one functional group selected from a carboxyl group, a glycidyl group, an amide group, and a hydroxyl group in the molecule is (meth) acrylic. It is used for the purpose of enhancing the compatibility between the system liquid resin and another composition, and enhancing the adhesiveness (adhesion) with the substrate during curing. In the present invention, as the radical polymerizable monomer having a carboxyl group in the molecule, for example, maleic anhydride, maleic acid,
Fumaric acid, itaconic acid, citraconic acid, or their alkyl or alkenyl monoesters, phthalic acid β- (meth) acryloxyethyl monoester, isophthalic acid β- (meth) acryloxyethyl monoester,
Examples include terephthalic acid β- (meth) acryloxyethyl monoester, succinic acid β- (meth) acryloxyethyl monoester, acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid.

Examples of the radical polymerizable monomer having an epoxy group in the molecule include glycidyl (meth) acrylate, glycidyl cinnamate, allyl glycidyl ether, vinylcyclohexene monoepoxide, 1,3
-Butadiene monoepoxide. The radical polymerizable monomer having an amide group in the molecule is a monomer represented by the following general formula. CH ₂ ＣC (R ¹ ) CONR ⁴ R ⁵ wherein R ¹ represents a hydrogen atom or CH _3. R ⁴ and R ⁵ are selected from a hydrogen atom or a functional group represented by CH ₂ OR ⁶ R ⁶ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.) The radical polymerizability having such an amide group is, for example, (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxy. Methyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, N
Monoalkylol (meth) acrylamide such as -propoxymethyl- (meth) acrylamide, N-butoxymethyl- (meth) acrylamide, N-pentoxymethyl- (meth) acrylamide, N, N-di (methylol) acrylamide, N -Methylol-N-methoxymethyl (meth) acrylamide, N, N-di (methoxymethyl) acrylamide, N-ethoxymethyl-N-methoxymethylmethacrylamide, N, N-di (ethoxymethyl) acrylamide, N-ethoxymethyl -N-propoxymethyl methacrylamide, N, N-di (propoxymethyl) acrylamide, N-butoxymethyl-
N- (propoxymethyl) methacrylamide, N, N
-Di (butoxymethyl) acrylamide, N-butoxymethyl-N- (methoxymethyl) methacrylamide,
N, N-di (pentoxymethyl) acrylamide, N-
There is dialkylol (meth) acrylamide such as methoxymethyl-N- (pentoxymethyl) methacrylamide.

The radical polymerizable monomer having a hydroxyl group in the molecule in the present invention includes, for example, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, Tetraethylene glycol (meta)
Acrylate, tetrapropylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, ethylene glycol acrylate, 4-hydroxybutyl acrylate, 3-hydroxypropyl acrylate, tetraethylene glycol acrylate, tetrapropylene glycol acrylate, polyethylene glycol acrylate, N- ( There are (meth) acrylates having a hydroxyl group such as (hydroxymethyl) acrylamide, N- (hydroxyethyl) acrylamide, and diacetone acrylamide. Further, for example, allyl alcohol, 4-hydroxy-1-butene, 4-hydroxymethylstyrene, 4-hydroxyethylstyrene,
A vinyl monomer containing a primary hydroxyl group such as 1,4-dihydroxy-2-butene can also be used.

The amount of the radical polymerizable monomer (a-3) used in the present invention is 1 to 50% by weight, preferably 5 to 20% by weight. If less than this,
The compatibility between the (meth) acrylic liquid resin (A) and other components is poor, and when cured, the adhesion to the substrate is weak, which is not preferable.

In the present invention, a vinyl compound (a-4) other than those described above can be used in order to improve the water resistance and hardness of the cured coating film as long as the liquid state of the resin can be maintained. Specifically, aromatic monomers such as styrene and vinyltoluene; (meth) acrylates having an alkyl group having 3 or less carbon atoms, such as methyl methacrylate and ethyl methacrylate; 2-hydroxyethyl (meth) acrylate;
Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, dipropylene glycol monomethacrylate, methoxydiethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth)
Acrylate, phenoxyethylene glycol (meth)
(Meth) acrylate monomers containing an alkoxy group such as acrylate, phenoxy group or hydroxyl group, maleic acid, fumaric acid, itaconic acid, citraconic acid, or alkyl or alkenyl monoesters thereof, β- (meth) acryloxyethyl phthalate Monoester, β- (meth) acryloxyethyl monoester isophthalate, β- (meth) acryloxyethyl monoester terephthalate, β- (meth) acryloxyethyl monosuccinate, acrylic acid, methacrylic acid, crotonic acid ,
There are monomers containing a carboxylic acid such as cinnamic acid, and a plurality of these monomers may be used. The amount of the polymerizable vinyl compound (a-4) to be used is 0 to 40% by weight, preferably 1 to 20% by weight, based on the liquid resin as the copolymer,
If it is more than 20% by weight, especially more than 40% by weight, the viscosity of the liquid resin becomes high, and it becomes difficult to form a film.

When the curable resin composition obtained by the present invention is cured by electron beam irradiation, R1 represented by the general formulas (a-1) and (a-2) is preferably hydrogen. The other vinyl compounds are preferably those having no quaternary carbon in the main chain when copolymerized, such as acrylic monomers and styrene.

The (meth) acrylic liquid resin of the present invention comprises:
The number average molecular weight is from 10,000 to 200,000, preferably from 11,000 to 100,000. When the number average molecular weight is smaller than the above value, it is difficult to isolate the resin component from the polymerization solution, and the mechanical properties such as flexibility are reduced, or the coating film properties such as solvent resistance and boiling water resistance are reduced. It is not preferable because it is lowered, and if it is larger than the above value, it is not preferable because the viscosity of the resin cannot be maintained.

The acrylic liquid resin (A) of the present invention is prepared by dissolving a mixture of the above monomers in a solvent in the presence of a radical polymerization initiator, or by dropping a mixture of the monomers by radical polymerization. Can be manufactured. Examples of the radical polymerization initiator include those described in benzoyl peroxide, t-butyl peroxide, cumene hydroperoxide, lauroyl peroxide, and organic peroxides (Taisei Co., Ltd., "Crosslinking Agent Handbook", pp. 520-535, second print). Peroxide,
Known compounds such as azo compounds such as azobisisobutyronitrile and azobiscyclohexanenitrile, and persulfate initiators such as potassium persulfate and ammonium persulfate can be used.

The solvents used include ethyl acetate, toluene, methyl ethyl ketone, benzene, dioxane, n
-Propanol, methanol, isopropanol, tetrahydrofuran, n-butanol, sec-butanol, tert-butanol, isobutanol, methyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol, methyl cellosolve acetate, ethyl cellosolve acetate, diacetone alcohol, etc. I can give it. In the present invention, the solvent used during the synthesis is removed after the synthesis by a method such as precipitation purification or distillation to obtain a liquid resin. The obtained resin has a viscosity at 50 ° C. of 5 to 10,000 poise, preferably 8 to 100 poise.
It is a liquid of 0 poise.

In the present invention, the ester resin (B) is
A cyclic acid anhydride (b-1), an epoxy compound (b-2-1) containing one epoxy group in the molecule, and one epoxy group and one or more unsaturated double bonds in the molecule. A composition comprising a vinyl-based epoxy compound (b-2-2) and a hydroxyl group-containing compound (b-3) is reacted to play a role as a cross-linking agent or a viscosity regulator. In the present invention, the cyclic acid anhydride (b-1) is a constituent component of the ester resin, such as succinic anhydride, itaconic anhydride, maleic anhydride, glutaric anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, and the like. Aliphatic cyclic anhydride or phthalic anhydride, isatoic anhydride, aromatic cyclic acid anhydride such as diphenic anhydride, or a saturated or unsaturated aliphatic hydrocarbon group, an aryl group,
A derivative having a halogen group, a heterocyclic group, or the like bonded thereto can be used.

Further, by using cyclic acid anhydrides represented by the following general formulas a to e, an ester resin having a number average of 1,000 or more can be liquefied, which is effective for lowering the viscosity of a curable liquid resin composition. is there.

[0027]

Embedded image

In the formula, R7 is a saturated or unsaturated aliphatic hydrocarbon group having 4 to 25, preferably 5 to 22 carbon atoms. When the number of carbon atoms is more than 22, especially 25, the degree of polymerization is hardly increased. Since the melting point is high, a dedicated heating system is required during film formation, which is not preferable. Conversely, if the number of carbon atoms is less than 4 or there is no substituent, the desired liquid polyester can be obtained. It is not preferable because the viscosity is high or the viscosity becomes high. Further, as the aliphatic hydrocarbon group, both a linear type and a branched type can be used, but the linear type is preferable in terms of viscosity reduction.

Examples of the cyclic anhydride having an aliphatic hydrocarbon group include butyl succinic anhydride, hexyl succinic anhydride, octyl succinic anhydride, dodecyl succinic anhydride, tetradecyl succinic anhydride, and hexadecyl succinic anhydride. Decyl succinic anhydride, octadecyl succinic anhydride, nonenyl succinic anhydride, icosyl succinic anhydride, henicosyl succinic anhydride, docosyl succinic anhydride, decenyl succinic anhydride, tetradecenyl succinic anhydride, hexa General formula a such as decenyl succinic anhydride, heptadecenyl succinic anhydride, octadecenyl succinic anhydride, icosenyl succinic anhydride, henicosenyl succinic anhydride, docosenyl succinic anhydride, etc. Alkyl succinic anhydride, butyl maleic anhydride, pentyl maleic anhydride represented by , Hexylmaleic anhydride, octylmaleic anhydride, decylmaleic anhydride, dodecylmaleic anhydride, tetradecylmaleic anhydride, hexadecylmaleic anhydride, octadecylmaleic anhydride, icosylmaleic anhydride Product, henicosyl maleic anhydride, docosyl maleic anhydride, decenyl maleic anhydride, tetradecenyl maleic anhydride, hexadecenyl maleic anhydride, octadecenyl maleic anhydride, ico Alkyl maleic anhydride, butyl glutaric anhydride, hexyl glutaric anhydride represented by the above general formula b, such as senyl maleic anhydride, henicocenyl maleic anhydride, docosenyl maleic anhydride, Heptyl glutaric anhydride, octyl glutaric anhydride, decyl glutaric anhydride, Deshirugurutaru anhydride, tetradecyl glutaric acid anhydride, hexadecyl glutaric acid anhydride, octadecyl glutaric acid anhydride,
Icosyl glutaric anhydride, docosyl glutaric anhydride, decenyl glutaric anhydride, tetradecenyl glutaric anhydride, hexadecenyl glutaric anhydride, octadecenyl glutaric anhydride, nonadecenyl glutaric acid Alkyl glutaric anhydride represented by the above general formula c, such as anhydride, icosenyl glutaric anhydride, henicocenyl glutaric anhydride, docosenyl glutaric anhydride, 4-
n-butylcyclohexanedicarboxylic anhydride, 4-n
-Dodecylcyclohexanedicarboxylic anhydride, 4-n
-Tetradecylcyclohexanedicarboxylic anhydride, hexadecylcyclohexanedicarboxylic anhydride, octadecylhexahydrophthalic anhydride, docosylcyclohexanedicarboxylic anhydride, dodecylcyclohexanedicarboxylic anhydride, tetradecylcyclohexanedicarboxylic anhydride, hexadecylcyclohexane Carboxylic anhydride, octadecylcyclohexanedicarboxylic anhydride, icosylcyclohexanedicarboxylic anhydride, docosylcyclohexanedicarboxylic anhydride, decenylcyclohexanedicarboxylic anhydride, hexadecenylcyclohexanedicarboxylic anhydride, octadece Nylcyclohexanedicarboxylic anhydride, docosenylcyclohexanedicarboxylic anhydride, triicosenylcyclohexanedicarboxylic anhydride, etc. Alkyl cyclohexane dicarboxylic acid anhydride represented by the general formula d, and, 4-n
-Butyl phthalic anhydride, hexyl phthalic anhydride, octyl phthalic anhydride, decyl phthalic anhydride, dodecyl phthalic anhydride, tetradecyl phthalic anhydride, pentadecyl phthalic anhydride, hexadecyl phthalic anhydride, octadecyl phthalic anhydride, nonadecyl phthalic anhydride And alkyl phthalic anhydride represented by the above general formula e, such as icosyl phthalic anhydride, henycosyl phthalic anhydride, docosyl phthalic anhydride, decenyl phthalic anhydride, hexadecenyl phthalic anhydride and heptadecenyl phthalic anhydride.

When an ester resin having a number average molecular weight of 1,000 or more is liquefied, the cyclic acid anhydride having a substituent such as a saturated or unsaturated aliphatic hydrocarbon group is used as the compound (b-1) as a whole. 5 mol% or more, preferably 20 mol% or more is blended.

In the present invention, the epoxy compound (b-2)
-1) is a constituent component of the polyester, and is not particularly limited as long as it is a compound having one epoxy group in the molecule, and an epoxy compound having a saturated or unsaturated aliphatic hydrocarbon group is a compound of the curable resin composition. It is effective for lowering viscosity and improving compatibility. As such a compound (b-2-1), for example, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether,
Octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether,
Pentadecyl glycidyl ether, hexadecyl glycidyl ether, heptadecyl glycidyl ether, octadecyl glycidyl ether, nonadecyl glycidyl ether, icosyl glycidyl ether, henycosyl glycidyl ether, docosyl glycidyl ether, triicosyl glycidyl ether, tetricosyl glycidyl Ether, pentycosyl glycidyl ether, decenyl glycidyl ether, undecenyl glycidyl ether, tetradecenyl glycidyl ether, hexadecenyl glycidyl ether, heptadecenyl glycidyl ether, octadecenyl glycidyl ether, nonade Cenyl glycidyl ether, icosenyl glycidyl ether, henicocenyl glycidyl ether, docosenyl glycidyl ether Torii co Seni glycidyl ether, tetra equalizer Seni glycidyl ether, and the like pen Tyco Seni glycidyl ether.

Among them, the use of a compound having a saturated or unsaturated aliphatic hydrocarbon group having 1 to 25, preferably 4 to 22 carbon atoms can effectively lower the viscosity of the copolymer. it can. Further, both linear and branched aliphatic hydrocarbon groups can be used,
The straight-chain type is preferred in terms of viscosity reduction. In the present invention, the epoxy compound (b-2-1) may be, for example, phenyl glycidyl ether, butyl phenyl glycidyl ether, phenyl nitro glycidyl ether or the like in order to adjust solvent resistance, mechanical properties, and compatibility. And aromatic ones.

Further, in the present invention, the vinyl epoxy compound (b-2-2) having one epoxy group and one or more unsaturated double bonds in the molecule imparts a radical crosslinking property to the ester resin. Used to Examples of the vinyl epoxy compound (b-2-2) include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, glycidyl cinnamate, and the like. In the present invention, the epoxy compound (b-
The compounding ratio of (2-1) and the vinyl epoxy compound (b-2-2) is (b-2-1) :( b-2-2) = 0: 100 to
95: 5 (mol%), preferably 5:95 to 60:40
(Mol%). Vinyl epoxy compound (b-2-
2) is 40 mol%, especially 5 mol% of the whole epoxy compound
If the amount is smaller, the effect as a crosslinking agent is poor, and a hard film is hardly obtained.

As the cyclic acid anhydride (b-1), the epoxy compound (b-2-1) and the vinyl epoxy compound (b-2-2) in the present invention, one kind each usually selected from the above is used. However, two or more kinds can be used in combination. The compounding ratio of the cyclic acid anhydride (b-1) to the epoxy compound (b-2-1) and the vinyl-based epoxy compound (b-2-2) is determined as follows:
(B-1): ｛(b-2-
1) + (b-2-2)｝ = 10: 8 to 10:12 (molar ratio), but basically equimolar.

In the present invention, the hydroxyl-containing compound (b-
3) is a cyclic acid anhydride (b-1) and an epoxy compound (b
-2-1) and a vinyl epoxy compound (b-2-)
It is used as an initiator when 2) reacts or for adjusting the molecular weight and viscosity of the liquid polyester. Such hydroxyl-containing compounds include, for example, methyl alcohol,
Ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, Heptadecyl alcohol, octadecyl alcohol, nonadecyl alcohol, icosyl alcohol, henycosyl alcohol, docosyl alcohol, triicosyl alcohol, tetricosyl alcohol, pentaicosyl alcohol, decenyl alcohol, methoxyethylene glycol, methoxydiethylene glycol , Methoxytriethylene glycol, methoxytetraethylene glycol, etc. Family alcohols or ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, polypropylene - polyethylene glycol, 1,4
-Butylene glycol, 1,3-butylene glycol,
Aliphatic diols such as polybutylene glycol, hexanediol and cyclohexanediol; aromatic diols such as bisphenol, bis (hydroxyphenyl) methane and 2,2′-bis (hydroxyphenyl) propane; polyether diols and polyester diols. Can be used.

Of these, aliphatic alcohols and aliphatic diols are preferable for reducing the viscosity of the liquid polyester. In addition, compounds having three or more hydroxyl groups such as hexamethylolmelamine, cyclodextrin, glycerin, trimethylolpropane, and 1,2,6-hexanetriol can also be used. Further, when it is desired to impart a radical crosslinkability to the terminal,
Hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, diethylene glycol mono (meth)
Acrylate, tetraethylene glycol mono (meth)
One such as acrylate, polyethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, glycerol di (meth) acrylate, tetramethylolmethane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol triacrylate The hydroxyl group-containing compound having the above unsaturated double bond can be used. When the liquid resin composition obtained by the present invention is cured by an electron beam, it is preferable to use the above-mentioned hydroxyl group-containing compound having an acrylic unsaturated double bond.

The above-mentioned hydroxyl group-containing compound (b-3) is preferably used in combination of two or more types in consideration of compatibility between compatibility and curability. In the present invention, the amount of the hydroxyl group-containing compound (b-3) varies depending on the required molecular weight of the ester resin, but the preferred amount of the (b-3) is 1 mol of the compound (b-1). On the other hand, (b-3) is used in an amount of 1 to 200 mol, more preferably 2 to 50 mol.

In the present invention, in order to prevent gelling during the synthesis of the ester resin, a generally used radical polymerization inhibitor such as hydroquinone, monomethoxyhydroquinone, P-tert-butylphenol, etc. is added to the compound B in an amount of 0.1 to 1%. 1-4% by weight, preferably 0.1-1.
It is preferable to add 0% by weight. If the amount of the radical polymerization inhibitor is less than 0.1% by weight, the ethylenically unsaturated group reacts during the synthesis of the liquid polyester, and a sufficient amount of the ethylenically unsaturated group cannot be obtained. And it becomes difficult to continue a stable reaction. Conversely, if the added amount of the radical polymerization inhibitor is more than 1% by weight, especially more than 4% by weight, the reactivity at the time of curing reaction of such a liquid polyester is not preferable. Gelation can also be prevented by blowing air into the reaction vessel or increasing the oxygen concentration in the reaction atmosphere.

For the purpose of accelerating the ester-based resin synthesis reaction, known catalysts such as Lewis bases or tertiary amines, for example, sodium hydroxide, potassium hydroxide, lithium chloride, diethylzinc, tetra (n-butoxy)
Titanium, N, N-dimethylbenzylamine and the like can be used. As the compounding amount of such a catalyst, the cyclic acid anhydride (b-
0 to 1 mol% with respect to 1), preferably 0.01 to
0.5 mol%. Although the reaction proceeds without using these catalysts, it is effective in shortening the reaction time. However, such catalysts may be used in 0.5, in particular 1
If more than 1% is blended, the liquid polyester will turn yellow,
It is not preferable because it is difficult to obtain a high molecular weight liquid polyester.

The ester resin (B) of the present invention has a number average molecular weight (polystyrene) measured by a GPC method (gel permeation chromatography) by adjusting the amount of the hydroxyl group-containing compound (b-3) or the catalyst. Conversion) of 300 to 50,000, preferably 500 to 10,000.
000. If the number average molecular weight is smaller than the above value, the volume shrinkage at the time of curing increases, which may lead to a decrease in mechanical properties such as distortion and detachment from the substrate, and various physical properties such as solvent resistance and boiling water resistance. If the number average molecular weight is larger than the above value, it is not preferable because a low viscosity at which a film can be formed cannot be maintained. The viscosity of the ester resin (B) in the present invention is from 1 to 10,000 poise (50 ° C.), preferably 5
~ 1000 poise (50 ° C). If the viscosity is too low, it is not preferable because it causes repelling on a plastic film or seepage into paper. On the other hand, if the viscosity is too high, many acrylic monomers (C) are added, which is not preferable.

The ester resin (B) of the present invention can be produced by heating in a temperature range of 60 to 120 ° C. by a known ring-opening copolymerization method without a solvent. In the present invention, a solvent may be used in order to lower the viscosity of the reaction solution or to allow the copolymerization reaction to proceed stably. As the solvent used for this purpose, a solvent having a boiling point of 70 to 85 ° C. is preferable in order to facilitate the temperature control during the reaction depending on the boiling point. For example, ethyl acetate, benzene,
Methyl ethyl ketone and the like are common. As the compounding amount, if the amount of the solvent increases, the reactivity of the polymerization decreases and the production takes too much time, which is not practical. Therefore, 0 to 60% by weight, preferably 5 to 30% by weight of the total amount of the composition. %. It is necessary to remove the solvent after the completion of the reaction, and it is preferable not to use the solvent.

In the present invention, the curable liquid resin composition comprises:
The (meth) acrylic liquid resin (A) and the ester resin (B) are mixed at a ratio of 0.1: 99.9 to 97: 3, preferably 1:99 to 90:10 (% by weight). It can be obtained by: If the amount of the (meth) acrylic liquid resin composition (A) is too small, the cured product tends to become brittle. Under the curing conditions described above, it is not preferable because a sufficient curing reaction hardly proceeds. The viscosity of the obtained curable resin composition at 50 ° C. is 1 to 10,000 poise, preferably 5 to 10 poise.
00 poise. If the viscosity is too low, it tends to cause bleeding when coating the film, and it is not preferable because it too much soaks in printing on paper. If the viscosity is higher than this range, it is not preferable because film formation is difficult.

In the present invention, a small amount of a low molecular weight compound, a solvent, a monomer and the like may be blended in order to improve the film forming property and curability of the curable liquid resin composition. The amount that can be blended is up to 10 parts by weight based on 100 parts by weight of the curable liquid resin. The composition may contain a curing agent resin such as an amino resin or a phenol resin in order to enhance the curing properties of the coating. Further, in order to improve the coating performance, known polyamide resins, cellulose derivatives, vinyl resins, polyolefins, natural rubber derivatives,
Formulated with general-purpose polymers such as acrylic resin, epoxy resin, polyester, and polystyrene, unsaturated modified alkyd resins such as alkyd resin, rosin-modified alkyd resin, linseed oil-modified alkyd resin, and drying oils such as linseed oil, tung oil, and soybean oil. You may. However, the amount of each of them is preferably 40 parts by weight, more preferably 20 parts by weight or less. Further, if necessary, a compatibilizer, a surfactant, a lubricant, or the like may be added.

To the curable liquid resin obtained by the present invention, an appropriate amount of a dye, a coloring agent composed of a pigment such as carbon black, titanium white, phthalocyanine, an azo dye or quinacridone, or an inorganic filler such as Si-based fine particles or mica is added. Thereby, it can be used as various printing inks and coloring paints. In the case of curing by irradiation with a radiation, a known photopolymerization sensitizer or initiator can be added.

The composition for a film-forming material using the liquid resin of the present invention can be applied to a base material such as various steel plates, aluminum plates and other metal plates, plastic films, papers and plastic film laminated papers by using a roll coater, knife coater or the like. A coating method, or a conventional method such as offset printing, gravure printing, letterpress printing, silk screen printing, etc., can be formed into a film with a thickness of 0.1 to 500 μm,
Curing can be performed by heating or irradiating with radiation such as electron beam, ultraviolet ray, visible light ray, and infrared ray. When curing by electron beam irradiation, preferably 10
Up to 1000 keV, more preferably 30 to 300 keV
An electron beam irradiation device having an energy in the range of V is used. The irradiation dose (DOSE) is preferably 0.1 to 10
0 Mrad, more preferably in the range of 0.5 to 20 Mrad. If the amount is less than this, it is difficult to obtain a sufficiently cured product, and if it is more than this, damage to the coating film and the substrate is large, such being undesirable.

[0046]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. W in the example
The term "t%" indicates% by weight.

A method for measuring the number average molecular weight and the viscosity in this example is shown below. 1) Number average molecular weight: The value in terms of styrene in gel permeation chromatography (TOSOH SC-8020) was adopted. As the molecular weight distribution (Mw / Mn), a value obtained by using the same measuring instrument was adopted. 2) Viscosity: Rheometer (manufactured by Rheometrics: RDS-)
II, RFS-II) The value of the shear rate 1 / sec according to the steady viscosity measurement method was adopted. ◎ The electron beam irradiation apparatus and irradiation conditions are shown below. 1) Area beam electron beam irradiation system Curetron EBC-200
-20-30 (Nisshin High Voltage) Electron beam acceleration: 200 keV DOSE was adjusted by the amount of current in the range of 0.5 to 8 Mrad. 2) MIN-EB (manufactured by AIT) Electron beam acceleration: 60 keV DOSE was adjusted at a belt conveyor speed in the range of 0.5 to 8 Mrad.

◎ Abbreviations of the following compounds used in Examples and Comparative Examples are described. 1) Compound used for synthesis of acrylic liquid resin LA: lauryl acrylate EHA: 2-ethylhexyl acrylate PEG4A: methoxytetraethylene glycol monoacrylate AMP-20G: phenoxydiethylene glycol monoacrylate AA: acrylic acid GMA: glycidyl methacrylate 4HBA: 4 Hydroxybutyl acrylate HEA: 2-hydroxyethyl acrylate AAm: acrylamide ST: styrene 2) Compound used in the synthesis of ester resin SAH: succinic anhydride DdAH: dodecyl succinic anhydride PAH: phthalic anhydride HHPA: hexahydrophthalic anhydride MHPA: 4-methylcyclohexanedicarboxylic anhydride GMA: glycidyl methacrylate PGE: phenylglycidyl NDdOH: n-dodecyl alcohol DEG: diethylene glycol HEA: 2-hydroxyethyl acrylate TMAT: tetramethylol methane triacrylate 3) Compound used for preparing curable liquid resin composition and EB curable ink FH2269: epoxy ester resin DAP: Diallyl phthalate-based prepolymer (Duptote DT = 150; manufactured by Toto Kasei, Mn = 65
30, Mw / Mn = 2.14)

(Examples 1 to 15) Synthesis of (meth) acrylic liquid resin (A) and measurement of physical properties In a 500 ml four-necked round bottom flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a condenser,
Compounds were blended according to the composition shown in Table 1, azobisisobutyronitrile (AIBN) was used as an initiator (1% by weight based on the total monomer charge), and in an ethyl acetate solvent (concentration at the time of monomer charge: 33% by weight). %), Refluxed for 6 hours in a hot water bath set at 85 ° C., and further added AIBN by 0.1% by weight.
The mixture was added, and heating and stirring were continued for another 2 hours. After the completion of the reaction, a diversion tube was set between the reactor and the condenser, the temperature of the hot water bath was raised to 95 ° C., and the solvent was distilled off while stirring at normal pressure, and the pressure was further reduced to 40 mmHg or less under the same temperature conditions. The solvent was completely distilled off to obtain a viscous liquid resin. Table 1 shows the measurement results of the number average molecular weight (Mn), molecular weight distribution (Mw / Mn), and viscosity (50 ° C.) of the obtained resin.

Table 1 Composition and physical property measurement results of (meth) acrylic liquid resin ─ Mn viscosity Example composition (weight ratio) (): Mw / Mn (50 ゜ C) [P (voice)] ─────────────────────── ────────── 1 LA: AA = 95: 5 1.52E4 (3.6) 40 2 LA: AA = 90: 10 1.55E4 (3.2) 54 3 LA: AA = 60: 40 1.62E4 (2.8 ) 500 4 LA: GMA = 90: 10 1.43E4 (2.5) 42 5 LA: AAm = 90: 10 1.91E4 (3.4) 50 6 LA: HEA = 80: 20 1.53E4 (2.2) 94 7 LA: 4HBA = 80 : 20 1.54E4 (2.2) 78 8 LA: AMP20G: AA = 80: 15: 5 1.36E4 (2.3) 80 9 LA: PEG4A: AA = 80: 15: 5 1.45E4 (2.8) 76 10 LA: BA: AA = 80: 15: 5 1.67E4 (3.1) 70 11 EHA: AA = 95: 5 1.48E4 (2.6) 170 12 EHA: GMA = 90: 10 1.38E4 (2.3) 168 13 EHA: AAm = 90: 10 1.74E4 (3.5) 200 14 EHA: 4HBA = 90: 10 1.48E4 (2.5) 188 15 EHA: 4HBA: ST = 80: 15: 5 1.29E4 (2.1) 400 16 EHA: AMP20G: AA = 80: 15: 5 1.68E4 (3.4) 600 17 EHA: PEG4A: AA = 80: 15: 5 1.55E4 (2.5) 530 ────────── ───────────────────────

(Examples 18 to 47) Synthesis of ester resin (B) and measurement of physical properties In a 500 ml four-necked round bottom flask equipped with a stirrer, an air inlet tube, a temperature sensor, and a condenser,
Compounds having the composition shown in Table 2 were added, and dimethylbenzylamine (DBA) was added in an amount of 0.2 mol per mol of the hydroxyl group-containing compound, and hydroquinone was added in an amount of 1 w% based on the charged amount of the vinyl epoxy compound. Air was introduced into the flask at a flow rate of 50 ml / min in a hot water bath set at ° C., and the mixture was heated and stirred for 12 hours. Table 2 shows the measurement results of the number average molecular weight (Mn), molecular weight distribution (Mw / Mn), and viscosity (50 ° C.) of the obtained resin.

Table 2 Composition of ester resin (B) and measurement results of physical properties Actual composition (molar ratio) Number average viscosity Application molecular weight (50 ° C) Example (b-1) :( b-2-1) :( b-2-2) :( b-3) Mn (): Mw / Mn P (voice) ───────────────────────────────── 18 SAH: ---: GMA: nDdOH = 3 :-: 3: 1 890 (1.5) 7.3 19 SAH: ---: GMA: DEG = 3:-: 3: 1 770 (1.2) 8.2 20 SAH: ---: GMA: HEA = 2:- -: 2: 1 600 (1.2) 10.2 21 SAH: ---: GMA: HEA = 3:-: 3: 1 830 (1.1) 32.2 22 SAH: ---: GMA: HEA = 5:-: 5: 1 1300 (1.3) 74.5 23 SAH: PGE: GMA: HEA = 3: 1: 2: 1 840 (1.2) 40.5 24 SAH: ---: GMA: TMAT = 3:-: 3: 1 1100 ( 1.4) 82.7 25 SAH: ---: GMA: (TMAT: nDdOH) = 3:-: 3: (0.5: 0.5) 950 (1.3) 52.8 26 SAH: PGE: GMA: nDdOH = 3: 1: 2: 1 910 (1.3) 15.6 27 PAH: ---: GMA: nDdOH = 3:-: 3: 1 1030 (1.3) 33.5 28 PAH: ---: GMA: HEA = 3:-: 3: 1 970 (1.3) 59.3 29 PAH: ---: GMA: TMAT = 3:-: 3: 1 1160 (1.3) 12 3.5 30 PAH: ---: GMA: (TMAT: nDdOH) = 3:-: 3: (0.5: 0.5) 1080 (1.3) 90.9 31 HHPA: ---: GMA: nDdOH = 3:-: 3 : 1 1050 (1.3) 20.6 32 HHPA: ---: GMA: HEA = 3:-: 3: 1 990 (1.2) 47.5 33 HHPA: PGE: GMA: HEA = 3: 1: 2: 1 1000 (1.3 ) 55.8 34 HHPA: ---: GMA: TMAT = 3:-:: 3 1 1170 (1.3) 98.2 35 HHPA: ---: GMA: (TMAT: nDdOH) = 3:-: 3: (0.5 : 0.5) 1120 (1.3) 70.4 36 MHPA: ---: GMA: nDdOH = 3:-: 3: 1 1100 (1.2) 17.9 37 MHPA: ---: GMA: HEA = 3:-: 3: 1 1020 (1.2) 39.4 38 MHPA: ---: GMA: HEA = 5:-: 5: 1 1720 (1.4) 68.4 39 MHPA: PGE: GMA: HEA = 3: 1: 2: 1 1040 (1.2) 47.3 40 MHPA: ---: GMA: TMAT = 3:-: 3: 1 1220 (1.4) 78.2 41 MHPA: ---: GMA: (TMAT: nDdOH) = 3:-: 3: (0.5: 0.5) 1160 (1.5) 61.2 42 MHPA: PGE: GMA: (TMAT: nDdOH) = 3: 1: 2: (0.5: 0.5) 1160 (1.3) 67.9 43 (DdAH: PAH): ---: GMA: nDdOH = (1: 2):-: 3: 1 1160 (1.4) 20.6 44 (DdAH: PAH): ---: GMA: HEA = (1: 2):-: 3: 1 1090 (1.2) 35.3 45 (DdAH: HHPA): ---: GMA: nDdOH = (1: 2):-: 3: 1 1160 (1.4) 25.3 46 (DdAH: HHPA): ---: GMA: HEA = (1: 2):-: 3: 1 1080 (1.3) 20.2 47 DdAH: ---: GMA: HEA = 3:-: 3: 1 1290 (1.5) 14.8 ── ───────────────────────────────

Embodiments 48 to 54 Embodiments 2, 8, and 1
Acrylic liquid resin obtained in 3, 16 and Example 2
A peroxide-based initiator was added to the curable liquid resin composition prepared by using the ester-based resin obtained in Examples 2, 24, 28, 37, 38, and 40 in an amount of 0.1 to 100 parts by weight of the ester-based resin. One part by weight was mixed and applied on a PET film with a 0.5 mil applicator. A peeled PET film was placed on the coating film, and the adhered PET film was heated in an oven at 150 ° C. for a certain time. The composition of the curable liquid resin composition used, and the curability of the coating film obtained by the heat treatment
Table 3 shows the THF extraction ratio determined by evaporating the soluble matter after immersion in THF at room temperature for 1 hour to dryness.

Table 3 Composition and thermosetting properties of curable liquid resin composition ─ Curable resin composition (Example No.) Viscosity Heat curable THF extraction rate Example ────────────── (10 / s) Time ○: Cured (1h) (acrylic (Liquid resin): (ester resin) [P] (min) △: With tack [%] (weight ratio) ×: Uncured ──────────────────── ───────────── 48 Example 2: Example 22 = 2: 8 69.8 2 ○ 90 49 Example 2: Example 24 = 2: 8 75.9 2 ○ 95 50 Example 8: Example 28 = 2: 8 63.0 2 ○ 90 51 Example 8: Example 29 = 2: 8 113.2 2 ○ 100 52 Example 13: Example 38 = 2: 8 84.8 2 ○ 95 53 Example 13: Example 40 = 2: 8 94.4 2 ○ 100 54 Example 16: Example 37 = 2: 8 64.6 2 ○ 95 ───────────────────────── ─────── ─

(Examples 55 to 99) The acrylic liquid resin (A) obtained in Examples 1 to 17 and Examples 18 to 4
The curable resin composition prepared using the ester-based resin (B) obtained in Step 7 was coated on a coated paper and a PET film with a 0.5-mil applicator, and irradiated with electron beams under various conditions. . The composition of the curable liquid resin composition used,
Table 4 shows the curability of the coating film obtained by electron beam irradiation and the extraction ratio of THF obtained by evaporating and drying the soluble matter after immersing the film in THF at room temperature for 1 hour.

Table 4 Composition of curable liquid resin composition and electron beam curing properties ─ Curable resin composition (Example No.) Viscosity Irradiation amount Curable THF extraction rate Example ─────────────── (10 / s) (Dose) ○: Cure (1h ) (Acrylic liquid resin) :( Ester resin) [P] [Mrad] △: Tacked [%] (weight ratio) ×: Uncured ──────────────── ───────────────── 55 Example 1: Example 21 = 2: 8 24.0 2 ○ 96 56 Example 2: Example 21 = 2: 8 25.4 2 ○ 98 57 Example 3: Example 21 = 2: 8 40.0 2 ○ 100 58 Example 11: Example 21 = 2: 8 31.9 2 ○ 100 59 Example 4: Example 37 = 2: 8 37.9 2 ○ 94 60 Example 12: Example 37 = 2: 8 50.0 2 ○ 100 61 Example 5: Example 37 = 2: 8 39.3 2 ○ 98 62 Example 13: Example 37 = 2: 8 51.9 2 ○ 100 63 Example 6: Example 37 = 2: 8 44.6 2 ○ 100 64 Example 7: Example 37 = 2: 8 43.0 2 ○ 95 65 Example 14: Example 37 = 2: 8 51.2 2 ○ 98 66 Example 15: Example 37 = 2: 8 59.6 2 ○ 100 67 Example 8: Example 37 = 2: 8 43.2 2 ○ 96 68 Example 16: Example 37 = 2: 8 64.6 2 ○ 100 69 Example 17: Example 37 = 2: 8 63.0 2 ○ 98 70 Example 2: Example 18 = 2: 8 10.9 2 ○ 90 71 Example 2: Example 19 = 2: 8 11.9 2 ○ 94 72 Example 2: Example 20 = 2: 8 14.2 2 ○ 96 73 Example 2 : Example 22 = 2: 8 69.8 2 ○ 100 74 Example 2: Example 24 = 2: 8 75.9 2 ○ 100 75 Example 2: Example 25 = 2: 8 53.0 2 ○ 100 76 Example 8: Execution Example 23 = 2: 8 46.4 2 ○ 96 77 Example 8: Example 26 = 2: 8 21.6 2 ○ 98 78 Example 8: Example 27 = 2: 8 39.9 2 ○ 96 79 Example 8: Example 28 = 2: 8 63.0 2 ○ 94 80 Example 8: Example 29 = 2: 8 113.2 2 ○ 100 81 Example 8: Example 30 = 2: 8 88.6 2 ○ 100 82 Example 8: Example 33 = 2 : 8 60.0 2 ○ 99 83 Example 8: Example 39 = 2: 8 52.5 2 ○ 100 84 Example 8: Execution 42 = 2: 8 70.2 2 ○ 100 85 Example 13: Example 31 = 2: 8 32.4 2 ○ 96 86 Example 13: Example 32 = 2: 8 63.3 2 ○ 98 87 Example 13: Example 33 = 2: 8 72.0 2 ○ 100 88 Example 13: Example 34 = 2: 8 113.2 2 ○ 100 89 Example 13: Example 35 = 2: 8 86.8 2 ○ 98 90 Example 13: Example 36 = 2: 8 29.0 2 ○ 96 91 Example 13: Example 37 = 2: 8 54.5 2 ○ 100 92 Example 13: Example 38 = 2: 8 84.8 2 ○ 100 93 Example 13: Example 40 = 1: 9 85.9 1 ○ 95 94 Example 13: Example 40 = 1: 9 85.9 2 ○ 100 95 Example 13: Example 40 = 2: 8 94.4 2 ○ 100 96 Example 13: Example 40 = 3: 7 118.2 2 ○ 90 97 Example 13: Example 40 = 4: 6 103.6 2 ○ 80 98 Example 13: Example 40 = 4: 6 103.6 4 ○ 95 99 Example 13: Example 41 = 2: 8 84.3 2 ○ 98 ─ ─────────────────────────────────

Embodiments 100 to 108 Embodiments 56 and 6
To the curable resin composition obtained in 8, 74, 92 and 94, 20 parts by weight of carbon black and other components were added and mixed, and the mixture was sufficiently kneaded with three rolls.
A black ink of ~ 600 poise was obtained. This ink was no.
When coated on a carton paper with a bar coater No. 2 and irradiated with 2 Mrad, a coating film excellent in gloss was obtained. Table 5 shows the results of the MEK rubbing test and cellophane peel test of the coating film obtained by electron beam irradiation together with the ink composition.

Table 5 Composition and Curing Characteristics of Curable Liquid Resin Composition Curable resin composition (Example No.) Irradiation amount Curable MEK Laminate Cellotaph Example Example (Dose) ○: Curing Residual rate Peeling [Mrad] △: Tack Existence (after 50 times) Residual rate ×: Uncured [%] [%] ──────────────────────────────── ── 100 Example 56 2 ○ 100 100 101 Example 56: FH2269 = 90:10 2 ○ 100 90 102 Example 68 2 ○ 100 100 103 Example 68: FH2269 = 90:10 2 ○ 100 95 104 Example 74 2 ○ 100 100 105 Example 74: DAP = 90: 10 2 ○ 98 95 106 Example 74: DAP: FH2269 = 85: 5: 10 2 ○ 100 90 107 Example 92 2 ○ 100 95 108 Example 94 2 ○ 100 95 ──────────────────────────────────

[0059]

As described above, according to the present invention, a special exhaust gas treatment facility can be provided to prevent contamination of the working environment in the coating process with low molecular weight compounds scattered and to release low molecular weight compounds such as organic solvents and monomers into the atmosphere. It is not necessary, and it is possible to form a film by a coating method such as a roll coater and a knife coater which have been conventionally used, offset printing, gravure printing, letterpress printing, and the like. A curable liquid resin composition that can be cured by irradiation with radiation such as visible light and infrared light can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C09D 163/00 PKE C09D 163/00 PKE 167/02 PLA 167/02 PLA // C08L 33/06 LJE C08L 33/06 LJE 33/14 33/14 C09D 133/06 PGG C09D 133/06 PGG 133/14 133/14 155/00 PGZ 155/00 PGZ

Claims (9)

[Claims] 1. The following (meth) acrylic liquid resin (A)
And the following ester resin (B) as (A) :( B) =
A curable liquid resin composition formulated in a ratio of 0.1: 99.9 to 97: 3 (% by weight). (A) a functional group selected from a carboxyl group, a glycidyl group, an amide group and a hydroxyl group in the following (meth) acrylic monomer (a-1) and the following (meth) acrylic monomer (a-2) And a polymerizable vinyl compound (a-4) other than the above,
{(A-1) + (a-2)}: (a-3): (a-4)
= 20 to 98: 1 to 50: 0 to 79 (% by weight), and has a number average molecular weight of 10,000 to 20.
(Meth) acrylic liquid resin having a viscosity of 5 to 10,000 poise (50 ° C.). CH ₂ ＣC (R ¹ ) COO—R ² (a-1) (wherein, R ¹ is a hydrogen atom or CH ₃ , and R ² is C 4
To 22 alkyl groups. ) CH ₂ ＣC (R ¹ ) COO (C _n H _2n O) _m R ³ (a-2) (wherein, R ¹ is a hydrogen atom or CH ₃ , and R ³ is carbon atom 1)
To 5 alkyl groups or phenyl groups, n represents an integer of 1 to 3, and m represents an integer of 4 to 25, respectively. (B) a cyclic acid anhydride (b-1), an epoxy compound (b-2-1) containing one epoxy group in the molecule, and one epoxy group and an unsaturated double bond in the molecule. The vinyl epoxy compound (b-2-2) having (b-1):
{(B-2-1) + (b-2-2)} = 10: 8-1
0:12 (molar ratio), and the hydroxyl group-containing compound (b-3) was added in an amount of 1 to 20 with respect to 1 mol of (b-1).
An ester resin obtained by reacting a composition mixed at a ratio of 0 mol. 2. The compounding ratio of the epoxy compound (b-2-1) and the vinyl epoxy compound (b-2-2) is (b-2-
1): The curable liquid resin composition according to claim 1, wherein (b-2-2) = 0: 100 to 95: 5 (mol%). 3. An ester resin (B) having a number average molecular weight of 3
00 to 50,000 and a viscosity of 1 to 10,000
The curable liquid resin composition according to claim 1, which is poise (50 ° C.). 4. The ratio of monomer (a-1) to monomer (a-2) is (a-1) :( a-2) = 0.1: 99.9-9.
4. The curable liquid resin composition according to claim 1, wherein the ratio is 9.9: 0.1 (% by weight). 5. The monomer (a-1) and the monomer (a-
5. The curable liquid resin composition according to claim 1, wherein R1 is a hydrogen atom in 2). 6. The curable liquid resin composition according to claim 1, wherein the viscosity of the composition is from 1 to 10,000 poise (50 ° C.). 7. The curable liquid composition according to claim 5, which is a radiation-curable type. 8. A printing ink comprising the curable liquid resin composition according to claim 7. 9. A paint comprising the curable liquid resin composition according to claim 7.