JPH1087748A - Radiation curable liquid resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a radiation curable liquid resin composition capable of reducing the blending rate of a low molecular weight compound, contributing to an improvement of environment and being formed into a membrane by a conventional printing method by using a high molecular liquid polymer in a non-solvent curable resin composition. SOLUTION: This radiation curable liquid resin composition comprises (A) 10-95wt.% (meth)acrylic liquid resin and (B) 5-90wt.% (meth)acrylic compound having an unsaturated double bond in the molecule and <=1,000 number average molecular weight. The component A is formed out of 20-95wt.% alkylene glycol (meth)acrylate-based monomer of the formula CH2 =C(R<1> )COO(Cn H2n O)m R<2> [R<1> is H or CH3 ; R<2> is a 1-5C alkyl group or a phenyl group; (n) is 1-4; (m) is 3-25], 1-60wt.% vinyl monomer having alicyclic epoxy group in the molecule and 0-79wt.% polymerizable vinyl monomer and has 10,000-200,000 number average molecular weight and 1-10,000 poise viscosity (at 50 deg.C).

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 a paint or ink, or as an adhesive. Further, the acrylic liquid resin obtained by the present invention,
A liquid resin composition comprising a (meth) acrylic compound and a (meth) acrylic compound can be used as a radiation curable resin composition as a vehicle for printing inks, paints, adhesives, and the like.

[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:
The viscosity of the composition was controlled by a large amount of low molecular weight components. Therefore, it is not preferable in 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 cure shrinkage, use a monomer component with a relatively high molecular weight,
Although some efforts were made to add high molecular weight components,
In particular, in the latter case, since the composition was solid, the amount that could be added was limited in order to keep the composition 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. In this technique, a liquid resin using an acrylate monomer is used. However, since the obtained resin is an oligomer, further improvement is desired. 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, 4 pages, 1993
Years), it is desired to increase the molecular weight while maintaining low viscosity.

In the curing reaction of resins triggered by various radiations, radical crosslinking reactions and cationic crosslinking reactions are well known, but radical curing reactions are severely shrinkage, while alicyclic epoxy compounds Although the cationically curable composition using the composition improves curing shrinkage to some extent, especially when a low-molecular-weight alicyclic epoxy compound having a high diluting effect is used, there is also volume shrinkage during curing or variation. Many of them have high virginity, and in the case of a curing reaction by ultraviolet rays, it is necessary to add a large amount of initiator, and it can be said that there is still a problem in safety. Conventionally,
JVCrivello et al. Have pointed out that an initiator is also essential for the cationic reaction of alicyclic epoxy groups by electron beam irradiation, and the current situation deviates from the advantage of electron beam curing systems that no initiator is required. there were.

[0006]

DISCLOSURE OF THE INVENTION The present invention relates to a low-molecular-weight compound having problems in safety and physical properties by using a high-molecular-weight liquid polymer in a solvent-free curable resin composition containing no solvent. And contributes to the improvement of the working environment.The coating method used in the past, such as roll coater and knife coater, and printing methods such as offset printing, gravure printing, letterpress printing, and screen printing are used. Radiation-curing type that can be formed into a film and can be cured without using a catalyst or initiator in the case of conventional radiation such as ultraviolet rays, infrared rays, electron beams, and γ-rays, especially in the case of electron beams and γ-rays. A liquid resin composition is provided.

The inventor of the present invention has conducted intensive studies on the correlation between the structure and viscosity of various resin systems in order to solve the above-mentioned problems. A non-solvent radiation-curable liquid resin composition has been found which is within the viscosity range in which a film can be formed and which can be cured at a high speed by a conventional curing method using radiation as a trigger. Further, by introducing an alicyclic epoxy group as a side chain component of the high molecular weight liquid resin, a liquid high molecular weight alicyclic epoxy-containing resin containing no low molecular weight alicyclic epoxy compound or solvent can be obtained. Was. Further, it has become possible to obtain the above-mentioned radiation-curable resin composition of the interpenetration-curable type in which the amount of the (meth) acrylic compound used as a reactive diluent is reduced, thereby achieving the present invention.

[0008]

That is, the present invention provides the following (meth) acrylic liquid resin (A) in an amount of 10 to 95% by weight and a number average molecular weight of 100 having an unsaturated double bond in the molecule.
0 or less (meth) acrylate compound (B) 5 to 90
The present invention relates to a radiation-curable liquid resin composition comprising 0.1% by weight. (A) Alkylene glycol (meth) acrylate monomers (a-1) represented by the following formula (1): 20 to 95
% By weight, 1 to 60% by weight of a vinyl monomer (a-2) having an alicyclic epoxy group in the molecule, and 0 to 79% by weight of a polymerizable vinyl monomer (a-3) other than the above.
The number average molecular weight obtained by polymerizing monomers having an average molecular weight of 100 to 1500 is 10,000 to 20.
A liquid resin having a viscosity of 10,000 and a viscosity of 1 to 10,000 poise (50 ° C.). CH ₂ ＣC (R ¹ ) COO (C _n H _2n O) _m R ² (1) (where R ¹ is a hydrogen atom or CH ₃ , and R ² is a carbon atom 1)
To 5 alkyl groups or phenyl groups, n represents an integer of 1 to 4, and m represents an integer of 3 to 25, respectively. The present invention also relates to the above radiation-curable liquid resin composition, wherein the average molecular weight of the alkylene glycol (meth) acrylate-based monomer represented by the above formula (1) is 220 or more.

Further, the present invention relates to the above radiation-curable liquid resin composition wherein the viscosity of the (meth) acrylate compound (B) is 0.01 to 60 poise (50 ° C.). Further, the present invention relates to the above radiation-curable liquid resin composition, wherein R ¹ in the above formula (1) is a hydrogen atom. Furthermore,
The present invention relates to the above radiation-curable liquid resin composition, wherein the viscosity of the liquid resin composition is 0.1 to 500 poise (50 ° C.). Furthermore, the present invention relates to the above-mentioned radiation-curable liquid resin composition which is of an electron beam-curable type. Further, the present invention relates to a curable printing ink using the above radiation-curable liquid resin composition. Further, the present invention relates to a paint using the above radiation-curable liquid resin composition.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a (meth) acrylic liquid resin (A) contains 20 to 95% by weight of an alkylene glycol (meth) acrylate monomer (a-1), and an alicyclic epoxy group in the molecule. Vinyl monomer (a-
2) a composition for liquefying a radiation-curable resin composition, comprising 1 to 60% by weight and 0 to 79% by weight of a polymerizable vinyl monomer (a-3) other than the above, and It plays a role in imparting toughness and flexibility to the coating film.

In the present invention, the alkylene glycol (meth) acrylate monomer (a-1) represented by the general formula (1) is used to make the (meth) acrylic resin (A) liquid. As the alkylene glycol (meth) acrylate represented by the general formula (1), for example,
Methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, propoxytetraethylene glycol (meth) acrylate, n-butoxytetraethylene glycol (meth) acrylate, n-penta Xytetraethylene glycol (meth) acrylate, methoxytetrapropylene glycol (meth) acrylate, ethoxytetrapropylene glycol (meth) acrylate, propoxytetrapropylene glycol (meth) acrylate, n-butoxytetrapropylene glycol (meth) acrylate, n-penta Xytetrapropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) a Relate, ethoxy polyethylene glycol (meth) acrylate, methoxy triethylene butylene yellowtail call (meth) acrylate, methoxy tetrabutylene yellowtail call (meth) acrylate, methoxy polybutylene glycol (meth) acrylate, or

Phenoxytetraethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, and phenoxytetrapropylene glycol (meth) acrylate;
Among them, by using an acrylate having a polyoxyalkylene chain as a repeating unit of 3 to 25, preferably 4 to 22, or a corresponding methacrylate, the viscosity of the copolymer can be effectively reduced, and an electron beam or Curing by γ-ray irradiation is preferred because the crosslinking reaction of the polyoxyalkylene side chain effectively proceeds. When the number of repeating units is 2 or less, it is difficult to obtain a low-viscosity liquid resin, and when the number is 26 or more, the degree of polymerization is hard to increase, and since it is a solid at 50 ° C., a dedicated melting system is required at the time of film formation. Therefore, it is not preferable.

The alkylene glycol (meth) acrylate monomer (a-1) contains 20
９５95% by weight, preferably 40-90% by weight. When the amount of the alkylene glycol (meth) acrylate-based monomer (a-1) is less than 40% by weight, particularly less than 20% by weight, it is not preferable because a preferable viscosity cannot be maintained.

In the present invention, the average molecular weight of the alkylene glycol (meth) acrylate monomer represented by the above formula (1) used as a component of the (meth) acrylic liquid resin (A) is at least 220, preferably at least 220. , 250-700. Outside this range, a liquid resin having a preferable viscosity range cannot be obtained, which is not preferable.

When the curable resin composition obtained by the present invention is cured by electron beam irradiation, or when it is desired to obtain a liquid resin having a lower viscosity, R ¹ represented by the general formula (1) is hydrogen. It is preferred that

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.

The alkylene glycol (meth) acrylate-based monomer (a-1) contains 20
To 95% by weight, preferably 60 to 90% by weight. When the amount of the alkylene glycol (meth) acrylate-based monomer (a-1) is less than 60% by weight, particularly less than 20% by weight, it is not preferable because a preferable viscosity cannot be maintained.

In the present invention, the vinyl monomer (a-2) having an alicyclic epoxy group in the molecule is used to promote the radiation crosslinkability of the (meth) acrylic liquid resin. Such an alicyclic epoxy group-containing vinyl monomer (a-
The compound (2) is not particularly limited as long as it has a vinyl group having radical polymerizability in a molecule and a compound having an alicyclic epoxy group. Among them, when a compound represented by the following general formula is used, alkylene glycol ( It is preferable because troubles such as gelation hardly occur during a copolymerization reaction with a (meth) acrylate-based monomer or during solvent removal.

[0019]

Embedded image

(In each formula, R ¹ represents a hydrogen atom or a methyl group. Y is a divalent group represented by-{R ² COO} _n R ^3- , and R ² has 1 to 10 carbon atoms. , R ³ is a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, n is 0 or 1 to 5
Indicates an integer. Examples of such alicyclic epoxy group-containing vinyl monomer (a-2) include 3,4-epoxycyclohexylmethyl (meth) acrylate, 1-vinyl-3,4-epoxycyclohexane, (3,4- Epoxycyclohexyl-
5-hydroxyhexanoic carboxylate) (meth) acrylate and the like.

The amount of the vinyl monomer (a-2) having an alicyclic epoxy group used in the present invention is 1 to 60% by weight, preferably 5 to 40% by weight.
If the amount is less than this, the crosslinking property is insufficient and the solvent resistance is poor, which is not preferable.If the amount is more than this, it is difficult to take out as a solventless liquid resin because the viscosity becomes high, and the composition is suitable for film formation. In addition, a large amount of a low molecular weight compound needs to be blended to obtain low viscosity, which is not preferable.

In the present invention, other polymerizable vinyl monomers (a-3) can be used to improve the water resistance and hardness of the cured coating film as long as the liquid state and low viscosity of the resin can be maintained. Specifically, aromatic monomers such as styrene and vinyltoluene, alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, and methoxydiethylene glycol (meth) acrylate An alkoxy group such as phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate,
There are (meth) acrylate monomers containing a phenoxy group, and a plurality of these may be used from these groups.

Other polymerizable vinyl monomers (a-3)
Is used in an amount of 0 to 79 with respect to the liquid resin as a copolymer.
%, Preferably 5 to 40% by weight, and more than 40% by weight, especially 79% by weight is not preferred because the viscosity of the liquid resin increases. Also, hydroxyl group, carboxyl group,
A vinyl monomer having a functional group that easily reacts with an alicyclic epoxy group during the synthesis of the (meth) acrylic liquid resin (A) such as an amino group is not preferable because it easily causes gelation or the like.

In the present invention, the average molecular weight of the monomer used as a component of the (meth) acrylic liquid resin (A) is from 100 to 1500, preferably from 150 to 1500.
1100. Outside this range, a liquid resin having a preferable viscosity range cannot be obtained, which is not preferable.

The (meth) acrylic liquid resin (A) of the present invention has a number average molecular weight of 10,000 to 200,000.
0, preferably 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 a large amount of a low molecular weight compound needs to be added to obtain a viscosity at which the resin can form a film.

The (meth) acrylic liquid resin (A) of the present invention is produced 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 do. Examples of the radical polymerization initiator include benzoyl peroxide, t-butyl peroxide, cumene hydroperoxide, lauroyl peroxide, and organic peroxides (Taiseisha,
"Handbook of Crosslinking Agents", p520-535, 2nd printing)
And azo compounds such as azobisisobutyronitrile and azobiscyclohexanenitrile, and persulfate initiators such as potassium persulfate and ammonium persulfate.

Examples of the solvent to be used include ethyl acetate, toluene, methyl ethyl ketone, benzene, dioxane, tetrahydrofuran, and a mixed solvent thereof.

In the present invention, the solvent used in the synthesis is removed by a method such as precipitation purification or distillation after the synthesis to obtain a solventless liquid resin. The resulting resin has a viscosity at 50 ° C. of 1 to 10,000 poise, preferably 5 to 7000 poise.
Poise is a liquid. If the viscosity is low, it is liable to cause bleeding at the time of film coating, and it is not preferable because it soaks in printing on paper. If the viscosity is higher than this range, a large amount of the acrylate compound (B) will be added to lower the viscosity to a level suitable for film formation, which is not preferable.

In the present invention, (meth) having a number average molecular weight of 1,000 or less having one or more unsaturated double bonds in the molecule.
The acrylate compound (B) is used to adjust the viscosity and curability of the radiation-curable liquid resin composition. Examples of such a (meth) acrylate compound (B) include methyl (meth) acrylate, butyl (meth) acrylate, 2hydroxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate,
Monofunctional (meth) acrylate compounds such as methylphenoxy (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acryloylmorpholine, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol Di (meth) acrylate,
Polyethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3 butylene glycol di (meth) acrylate, 1,6 hexanediol di (meth) acrylate, 1,9 nonanediol di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, 2,2bis [4-{(meth) acryloxy diethoxy} phenyl] propane,
2,2bis [4-{(meth) acryloxyethoxy} phenyl] propane, 2,2bis [4-{(meth) acryloxypolyethoxy} phenyl] propane, 2,2bis [4-} (meth) acryloxy -Dipropoxydiphenyl] propane, 2,2bis [4-{(meth) acryloxypropoxydiphenyl] propane, 2,2bis [4
Bifunctional (meth) acrylate compounds such as-{(meth) acryloxy-polypropoxy} phenyl] propane;

Trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, Examples thereof include trifunctional or higher functional (meth) acrylate compounds such as dipentaerythritol hexa (meth) acrylate. Among the above compounds,
It is preferable to use an acrylate compound having an oxyalkylene moiety because a crosslinking reaction is caused by EB or γ-ray irradiation.

Further, when the curable resin composition obtained in the present invention is cured by electron beam irradiation, it is preferably an acrylic compound. The viscosity of the (meth) acrylate compound (B) is 0.01 to 100 poise (30
° C) preferably 0.1 to 20 poise (30 ° C),
Those having a lower molecular weight are often of low molecular weight, while those having a higher molecular weight are not preferred because their contribution as a viscosity modifier is poor. The average molecular weight Mn of the (meth) acrylate compound (B) used in the present invention is 1000.
Hereinafter, it is preferably in the range of 150 to 700, and if it is larger than this, it is not preferable because the viscosity becomes high and it becomes difficult to function as a viscosity modifier, and if it is smaller than this, volatility and skin irritation become high. Therefore, it is not preferable for safety and health.

In the present invention, the (meth) acrylic liquid resin (A) and the (meth) acrylate compound (B)
(A) :( B) = 10 to 95: 5
９０90 (weight ratio). If it is less than this, the change in viscosity is poor, and if it is more than this, it is not preferable because the amount of residual monomer after curing increases, volume shrinkage during curing is observed, and the cured product becomes brittle. The viscosity of the composition obtained in the present invention is 0.1 to 5
In order to obtain a composition having a viscosity of 00 poise (50 ° C.) lower than this, it is necessary to mix more (meth) acrylate-based compounds, which is not preferable. Further, a composition having a higher viscosity is not preferable because of poor film-forming properties.

In the present invention, known polyamide resins, cellulose derivatives, vinyl resins, polyolefins, natural rubber derivatives, acrylic resins, epoxy resins, etc. are used to improve the film forming properties, curing properties, and film properties of the curable liquid resin composition. Resin, polyester, polystyrene, general-purpose polymer such as polyurethane, alkyd resin, rosin-modified alkyd resin, unsaturated modified alkyd resin such as linseed oil-modified alkyd resin, linseed oil, tung oil, drying oil such as soybean oil Good. However, the blending amount thereof is 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the total amount of the (meth) acrylic liquid resin (A) and the (meth) acrylate compound (B). is there. Further, a solvent, a compatibilizer, a surfactant, a lubricant, or the like may be added as necessary. The amount of these components is 20 parts by weight, preferably 10 parts by weight or less, based on 100 parts by weight of the total amount of the (meth) acrylic liquid resin (A) and the (meth) acrylate compound (B).

To the curable liquid resin obtained according to the present invention, an appropriate amount of a dye, a coloring agent composed of a pigment such as carbon black, titanium white, phthalocyanine, azo dye, 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 electron beam, γ-ray or the like, addition of an initiator, a catalyst, etc. is not particularly necessary. However, in the case where a curing reaction is required or a cationic reaction-based crosslinking reaction is required. Can be added with a known photopolymerization sensitizer or initiator. Examples of the initiator used for this purpose include complexes such as aromatic onium salts such as aromatic iodonium salts, aromatic sulfonium salts, aromatic phosphonium salts, and pyridinium salts of heteropolyacids. The preferable addition amount of the initiator is 0.0005 to 0.1 mol per 1 mol of the alicyclic epoxy group contained in the (meth) acrylic liquid resin (A).
1, more preferably 0.001 to 0.05 mol. If the amount is more than this, it is not preferable because it becomes an extract from the coating film.

The composition for a film-forming material using the liquid resin of the present invention can be applied to base materials such as various steel plates, aluminum plates and other metal plates, plastic films, papers, plastic film laminated papers and the like, such as roll coaters and knife coaters. 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 to 1000 keV, more preferably 3
An electron beam irradiation device having an energy in the range of 0 to 300 keV is used. The irradiation dose (DOSE) is preferably 0.1 to 100 Mrad, more preferably 0.5 to 2 Mrad.
The range is 0 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.

[0038]

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. 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) A shear rate of 1 to 10 / sec by a 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 are described. 1) Compound used for synthesis of acrylic liquid resin AM40G: methoxytetraethylene glycol acrylate AM90G: methoxypolyethylene glycol (degree of polymerization 9) acrylate EHA: 2-ethylhexyl acrylate M-100: 3,4-epoxycyclohexylmethyl methacrylate AMP60G : Phenoxyhexaethylene glycol acrylate 2) Compound used as (meth) acrylate compound (B) PEG9DA: Polyethylene glycol diacrylate
(Mn = 508, η = 0.362 P) NODA: 1,9 nonanediol diacrylate (Mn = 26
8, η = 0.073 P) TPGDA: Tripropylene glycol diacrylate
(Mn = 184, η = 0.12 P) BP4PA: 2,2-bis [4- {acryloxydipropoxy} phenyl] propane (Mn = 560, 10.5 P) TMPTA: EO-modified trimethylolpropane triacrylate Shin-Nakamura Chemical Co., Ltd. ) NK Ester A-TMPT-3EO
(Mn = 428, η = 0.50 P))

Examples 1 to 6 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 solvent was distilled off while the water bath temperature was kept at 85 ° C. and stirring at normal pressure, and the solvent was further reduced to 60 mmHg or less at 60 ° C. to remove the solvent. It was completely distilled off to obtain a viscous liquid resin. Number average molecular weight (Mn), molecular weight distribution (Mw /
Table 1 shows the measurement results of Mn) and viscosity (50 ° C.).

Table 1 Composition and physical property measurement results of (meth) acrylic liquid resin ─ Mn viscosity Example composition (weight ratio) (): Mw / Mn (50 ゜ C) [P (Whey)] ─────────────────────── ────────── 1 AM40G: M-100 = 80: 20 2.26E4 (4.1) 956 2 AM40G: M-100 = 70: 30 3.60E4 (4.8) 1676 3 AM90G: M-100 = 80 : 20 1.75E4 (3.6) 583 4 AMP60G: M-100 = 80: 20 2.64E4 (4.5) 745 5 AM90G: EHA: M-100 = 30: 30: 40 3.67E4 (2.9) 1580 6 AM90G: EHA: M -100 = 40: 40: 20 1.91E4 (3.4) 1080 ─────────────────────────────────

(Examples 7 to 18) The radiation-curable liquid resin composition prepared using the acrylic liquid resin (A) obtained in Examples 1 to 6 and the acrylate compound (B) was used in an amount of 0.5%. It was applied on a PET film with a mill applicator and irradiated with an electron beam under various conditions. Table 2 shows the composition of the curable resin composition used, the curability and flexibility of the coating film obtained by electron beam irradiation, and the residual ratio determined from the weight change before and after 50 MEK rubbing tests.

Table 2 Composition and Curing Characteristics of Curable Liquid Resin Composition Actual curable resin composition Viscosity Curable MEK plastic (10 / s) ○: Cured (after 50 times) Example (A (Example No.)): (B) [P] △: tackiness Residual rate No (weight ratio) ×: uncured [%] ────────────────────────── ──────── 7 Example 1: TPGDA = 4: 6 4.36 ○ 100 ○ 8 Example 2: TPGDA = 4: 6 5.46 ○ 100 ○ 9 Example 3: PEG9DA = 4: 6 6.94 ○ 100 ◎ 10 Example 4: PEG9DA = 4: 6 7.66 100 100 ◎ 11 Example 5: NODA = 4: 6 3.96 100 100 ○ 12 Example 5: NODA = 6: 4 29.14 ○ 100 ◎ 13 Example 6: NODA = 4 : 6 3.40 ○ 95 ○ 14 Example 6: (NODA: TMPTA) = 6: (2: 2) 25.62 ○ 100 ○ 15 Example 1: BP4PA = 2: 8 25.88 ○ 100 ◎ 16 Example 3: BP4PA = 2 : 8 23.45 ○ 100 ◎ 17 Example 5: (BP4PA: TPGDA) = 4: (2: 4) 13.04 ○ Example 6: (BP4PA: TPGDA) = 4: (2: 4) 11.20 ○ 100 ◎ ──────── Flexibility test: Using a 1 mm metal test rod, measure the angle and number of times until the coating film breaks ◎: 180 degrees, 5 times or more ○: 180 degrees, 1 to 4 times △: 90 to 180 degrees ×: <90 degrees

[0045]

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 FI C09D 163/00 C09D 163/00 C09J 4/02 C09J 4/02

Claims (8)

[Claims] 1. The following (meth) acrylic liquid resin (A)
A radiation-curable liquid resin composition comprising 10 to 95% by weight and 5 to 90% by weight of a (meth) acrylate compound (B) having an unsaturated double bond in the molecule and having a number average molecular weight of 1,000 or less. (A) Alkylene glycol (meth) acrylate monomers (a-1) represented by the following formula (1): 20 to 95
% By weight, a vinyl monomer having an alicyclic epoxy group in the molecule (a-2) 1 to 60% by weight, and a polymerizable vinyl monomer (a-3) other than the above 0 to 79% by weight has a number average molecular weight of 10,000-200,000,
A (meth) acrylic liquid resin having a viscosity of 1 to 10,000 poise (50 ° C.). CH ₂ ＣC (R ¹ ) COO (C _n H _2n O) _m R ² (1) (where R ¹ is a hydrogen atom or CH ₃ , and R ² is a carbon atom 1)
To 5 alkyl groups or phenyl groups, n represents an integer of 1 to 4, and m represents an integer of 3 to 25, respectively. ) 2. The radiation-curable liquid resin composition according to claim 1, wherein the average molecular weight of the alkylene glycol (meth) acrylate-based monomer represented by the formula (1) is 220 or more. 3. The radiation-curable liquid resin composition according to claim 1, wherein the viscosity of the (meth) acrylic compound (B) is 0.01 to 60 poise (50 ° C.). 4. The radiation-curable liquid resin composition according to claim ¹ , wherein R ¹ in the formula (1) is a hydrogen atom. 5. A liquid resin composition having a viscosity of 0.1 to 500.
The radiation-curable liquid resin composition according to any one of claims 1 to 4, wherein the composition has a poise (50 ° C). 6. The radiation-curable liquid resin composition according to claim 1, which is of an electron beam-curable type. 7. A curable printing ink comprising the radiation-curable liquid resin composition according to any one of claims 1 to 6. 8. A paint comprising the radiation-curable liquid resin composition according to any one of claims 1 to 6.