JPH1180273A - Curable liquid resin and radiation-curable resin composition - Google Patents

Abstract

(57) [Abstract] (Modified) [Problem] A curable liquid resin composition that can be formed by a conventional coating method and printing method, and can be cured by conventional heat drying, irradiation with electron beams, ultraviolet rays, or the like. I will provide a. (A) 20 to 95% by weight of a (meth) acrylic monomer of the formula (1) and / or (meth) acrylate monomer of the formula (2), Mn of 10,000 to 200,000 and viscosity of 1 to 2 composed of 60% by weight and 0 to 79% by weight of a polymerizable vinyl monomer other than the above.
A curable liquid resin having a viscosity of 0000 poise (50 ° C.). ^{_{CH 2 = C (R 1)}} COO-R 2
⁽¹⁾ (R 1 is H or CH _3, R ² is an alkyl group of _{C 4~22) CH 2 = C (} R 1) COO (CnH 2 nO) mR 3
(2) (R ¹ is H or CH ₃ , R ³ is H, C _1-5 alkyl group or phenyl group, n is 1-4, m is 3-25.) (A) 100 parts by weight and a molecule (Meth) acrylic monomer (B) having Mn 1000 or less having an unsaturated double bond therein
1 to 1000 parts by weight.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable liquid resin capable of forming a cured film without using a solvent as a resin for film forming materials such as paints and inks and an adhesive, and a radiation curable resin. It relates to a resin composition. Further, the radiation curable resin composition comprising the curable liquid resin and the (meth) acrylic monomer obtained by the present invention can be used 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] Further, 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,
Particularly, in the latter case, since the composition was solid, the amount that can be added was limited in order to keep the composition within an appropriate viscosity range. In addition, even after curing, the problem of containing a large amount of low molecular weight compounds such as odors due to residual monomers has 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 acrylic monomer is used, but further improvement is desired because the obtained resin is an oligomer. 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] From the conventional knowledge, a resin composition containing Si is expected to have water repellency, oil repellency and the like as characteristics of a cured coating film. In a conventional resin composition, Si is contained in either a monomer component or a high molecular weight resin component. However, when Si is contained in the monomer component, it can be said that there is a problem in durability of the coating film since the Si component is easily eluted from the coating film after film formation.
In addition, since the viscosity becomes too high only with the resin component containing Si, it is impossible to form a coating film by the conventional coating method. On the other hand, when the resin component in the composition contains Si, when the content of Si in the resin increases, the Si content increases.
Easily separates from other components that do not contain, and has poor compatibility. Further, in the present situation, characteristics of a coating film containing Si, such as water repellency or oil repellency, are not exhibited in a resin composition in which the content of Si is reduced in consideration of the compatibility of the resin composition.

[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 curability 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. The present invention provides a resin composition.

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 resin composition has been found which has a viscosity within a 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 a functional group having Si as a side chain component of a liquid resin having a high molecular weight and a low viscosity, a high molecular weight Si-containing resin having water / oil repellency could be obtained.

[0008]

That is, the present invention provides (A) an alkyl (meth) acrylic monomer represented by the following formula (1) and / or an alkylene glycol (meth) represented by the following formula (2): Acrylate monomer (a-1) 2
0 to 95% by weight, 1 to 60% by weight of a vinyl monomer (a-2) having a hydrolyzable silyl group, and 0 to 79% by weight of a polymerizable vinyl monomer (a-3) other than the above. Average molecular weight of 10,000 to 200,000
And a curable liquid resin having a viscosity of 1 to 20,000 poise (50 ° C.).

CH ₂ ＣC (R ¹ ) COO—R ² (1) (wherein, R ¹ is a hydrogen atom or CH ₃ , and R ² is C 4
To 22 alkyl groups. ^{_{) CH 2 = C (R 1}} ) COO (CnH 2 nO) mR 3 (2) ( wherein, R ¹ represents a hydrogen atom or CH _3, R ³ is a hydrogen atom, an alkyl group or a phenyl group having 1 to 5 carbon atoms , N represents an integer of 1 to 4, and m represents an integer of 3 to 25.)

Further, the present invention relates to the above curable liquid resin, wherein R1 in the above formulas (1) and (2) is a hydrogen atom. Further, the present invention relates to 100 parts by weight of the above-mentioned curable liquid resin (A) and (meth) having a number average molecular weight of 1,000 or less having an unsaturated double bond in the molecule.
The present invention relates to a radiation-curable resin composition comprising 1 to 1000 parts by weight of an acrylic monomer (B). Furthermore, the present invention relates to the above radiation-curable resin composition, wherein the viscosity of the (meth) acrylic monomer (B) is 0.01 to 60 poise (50 ° C.).

Further, the present invention provides a composition having a viscosity of 0.1-5.
The present invention relates to the radiation-curable resin composition described above, which has a temperature of 00 poise (50 ° C.). Furthermore, the present invention relates to a curable printing ink using the above radiation-curable resin composition. Further, the present invention provides a paint using the above radiation-curable resin composition.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION

In the present invention, the alkyl (meth) acrylate monomer represented by the general formula (1) is used to make the curable liquid resin liquid. Examples of the alkyl group derivative represented by the general formula (1) include 2-ethylhexyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate, and 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) acrylate, nonadecyl (meth) acrylate, icosyl (meth) acrylate, henycosyl (meth) acrylate, docosyl (meth) acrylate, etc. 4 to 22 carbon atoms
Acrylate having an alkyl group of preferably 8 to 20 carbon atoms, more preferably 10 to 18 carbon atoms, or a corresponding methacrylate gives a liquid resin having a preferable viscosity. 3 carbon atoms
Below, it is difficult to obtain a liquid resin, and the carbon number is 23.
Above this is not preferable because the degree of polymerization is difficult to increase, and the viscosity of the liquid resin obtained from the progress of crystallization is high, and a dedicated heating system is required for film formation.

The average molecular weight of the alkyl (meth) acrylate monomer used in the present invention is 15
0 or more, preferably in the range of 160 to 350. Outside this range, it is difficult to obtain a curable liquid resin having a preferable viscosity range.

In the present invention, the alkylene glycol (meth) acrylate-based monomer represented by the general formula (2) is used to convert the curable liquid resin into a liquid state or to change the polarity of the curable liquid resin so that other components can be used. Used to control compatibility with. Examples of the alkylene glycol (meth) acrylate represented by the general formula (2) include, for example, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, and ethoxytetraethylene glycol (meth).
Acrylate, propoxytetraethylene glycol (meth) acrylate, n-butoxytetraethylene glycol (meth) acrylate, n-pentaxytetraethylene glycol (meth) acrylate, tripropylene glycol (meth) acrylate, tetrapropylene glycol (meth) acrylate, Methoxytripropylene 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, polytetramethylene glycol (meth) acrylate, methoxypolytetramethylene glycol (meth) acrylate , Methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate or

Phenoxytriethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, phenoxytetrapropylene glycol (meth) acrylate, and the like. 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 proceeds in a curable manner. When the number of repeating units is 2 or less, it is difficult to obtain a liquid resin.
Since it is a solid at 50 ° C., a dedicated melting system is required for film formation, which is not preferable.

In the present invention, the average molecular weight of the polyalkylene glycol (meth) acrylate monomer is 220 or more, preferably in the range of 250 to 700. Outside this range, it is difficult to obtain a curable liquid resin having a preferable viscosity range.

The alkyl (meth) acrylic monomer or the polyalkylene glycol (meth) acrylate monomer (a-1) is used in an amount of 10 to 100% by weight, preferably 10 to 100% by weight, based on the monomer component constituting the curable liquid resin. 20 to 98% by weight, more preferably 40 to 95% by weight,
More preferably, the content is 40 to 90% by weight, and 40% by weight,
In particular, when the content is less than 20% by weight, and more preferably less than 10% by weight, it is not preferable because a desirable viscosity cannot be maintained. Also,
The (meth) acrylate-based monomer (a-1) may be used alone, but is preferably used in combination in view of decreasing the viscosity and improving the compatibility with other components. In this case, the ratio of the alkyl (meth) acrylic monomer and the polyalkylene glycol (meth) acrylate monomer is 1:99 to 95: 5, more preferably 5:95 to 9 by weight.
0: 5.

In the present invention, the vinyl monomer (a-2) having a hydrolyzable silyl group is used for promoting radiation crosslinking of the curable liquid resin and having water repellency, oil repellency and the like. Examples of such a siloxane-based vinyl monomer include (meth) acrylic such as γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, and γ- (meth) acryloxypropylmethyldimethoxysilane. Oxyalkylalkoxysilane, γ- (meth) acryloxypropyltriphenoxysilane, (meth) acryloxyalkylalkoxyalkylsilane, trimethoxyvinylsilane, dimethoxyethylsilane, triethoxyvinylsilane, triethoxyallylsilane, vinylmethyldimethoxysilane, vinylmethyl Diethoxysilane, vinyl tris (2-methoxyethoxy) silane and the like can be mentioned.

In the present invention, the amount of the vinyl monomer (a-2) having a hydrolyzable silyl group is from 1 to 60.
% By weight, preferably 5 to 50% by weight. If less than this, crosslinkability is insufficient, and the solvent resistance of the cured product is inferior because it is inferior, and if it is more than this, the viscosity becomes high or becomes a solid resin at room temperature, so as a solventless liquid resin It is not preferable because it is difficult to take out the composition and it is necessary to incorporate a large amount of a low molecular weight compound in order to make the composition low in viscosity suitable for film formation.

In the present invention, as a polymerizable vinyl monomer (a-3) for imparting radiation-induced crosslinkability to the curable liquid resin, a functional vinyl monomer having a radiation-active functional group inert to radical polymerization. Can be used. Examples of such a functional vinyl monomer include an epoxy vinyl monomer such as glycidyl (meth) acrylate having an epoxy group in the molecule. Among them, a curable liquid using a vinyl monomer containing an alicyclic epoxy group is preferred. Resins are preferable because of their high EB crosslinkability. Examples of such alicyclic epoxy group-containing vinyl monomer (a-3) include 3,4-epoxycyclohexylmethyl (meth) acrylate, 1-vinyl-3,4
-Epoxycyclohexane, (3,4-epoxycyclohexyl-5-hydroxyhexanoic carboxylate) (meth) acrylate, and the like.

In the present invention, a vinyl monomer having a radiation-inactive functional group can be used as the polymerizable vinyl monomer (a-3) for improving the hardness after curing as long as the liquid state of the resin can be maintained. . Examples of the vinyl monomer (a-3) include an alkyl (meth) acrylate having 3 or less carbon atoms, styrene, vinylbenzene, a vinyl monomer having a carboxyl group, a vinyl monomer having a hydroxyl group, a vinyl monomer having an amide group, and a vinyl monomer having a perfluoroalkyl group. Among them, a vinyl monomer containing a carboxyl group, a hydroxyl group, or an amide group is preferable because of its excellent effect of imparting adhesion to a substrate, and a vinyl monomer containing a perfluoroalkyl group is preferably a water repellent of a cured coating film. It is preferable from the viewpoint of improving chemical resistance.

Specifically, (meth) acrylate having an alkyl group having 3 or less carbon atoms, such as methyl methacrylate and ethyl methacrylate, methoxyethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate An alkylene glycol (meth) acrylate monomer containing an alkoxy group such as phenoxyethylene glycol (meth) acrylate, or a phenoxy group,

Aromatic vinyl monomers such as styrene and vinyltoluene maleic acid, fumaric acid, itaconic acid, citraconic acid, or their alkyl or alkenyl monoesters, phthalic acid β- (meth) acryloxyethyl monoester, isophthalic acid Acid β- (meth) acryloxyethyl monoester, terephthalic acid β- (meth) acryloxyethyl monoester, succinic acid β- (meth)
Carboxyl group-containing vinyl monomers such as acryloxyethyl monoester, acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid,

2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4
Hydroxyl-containing vinyl monomers such as -hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, dipropylene glycol monomethacrylate, (meth) acrylamide, N-methylol (meth) acrylamide, N- Methoxymethyl- (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-
Amide group-containing vinyl monomers such as dialkylol (meth) acrylamide such as methoxymethyl-N- (pentoxymethyl) methacrylamide;

Further, perfluoromethylmethyl (meth)
Acrylate, perfluoroethylmethyl (meth) acrylate, 2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorooctylethyl (meth)
Acrylate, 2-perfluoroisononylethyl (meth) acrylate, 2-perfluorononylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, perfluoropropylpropyl (meth) acrylate, perfluorooctylpropyl ( Perfluoroalkylalkyl (meth) acrylates having a perfluoroalkyl group having 1 to 20 carbon atoms, such as meth) acrylate, perfluorooctylamyl (meth) acrylate, and perfluorooctylundecyl (meth) acrylate; perfluorobutylethylene , Perfluoroalkyl such as perfluorohexylethylene, perfluorooctylethylene, and perfluorodecylethylene, and perfluoroalkyl group-containing vinyl monomers such as alkylenes. Can be exemplified, it is possible to use a plurality of these groups.

The vinyl monomer (a-3) in the present invention
Is used in an amount of 0 to the curable liquid resin as the copolymer.
It is preferably from 90 to 90% by weight, more preferably from 0 to 79% by weight, and still more preferably from 1 to 50% by weight.

When the curable resin composition obtained by the present invention is cured by electron beam irradiation, R1 represented by the general formula (1) is preferably hydrogen. The other vinyl monomer that can be used in this case is preferably an acrylic monomer, styrene, or the like that has no quaternary carbon in the main chain when copolymerized.

The curable liquid resin of the present invention has a number average molecular weight of 10,000 to 200,000, preferably 11,100.
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, or the mechanical properties such as flexibility are reduced due to the high content of low molecular weight components, or the solvent resistance, It is not preferable because the physical properties of the coating film, such as boiling water, are deteriorated, or the odor of the monomer becomes intense. Not preferred.

The curable liquid resin 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 radical polymerization, which is a method of dropping a mixture of monomers. be able to. Examples of the radical polymerization initiator include benzoyl peroxide, t-butyl peroxide, cumene hydroperoxide, lauroyl peroxide, and organic peroxides (Taiseisha, “Crosslinking Agent Handbook”, p.
520-535, 2nd printing), using known compounds such as peroxides, azo compounds such as azobisisobutyronitrile and azobiscyclohexanenitrile, and persulfate initiators such as potassium persulfate and ammonium persulfate. However, it is preferable to use an initiator having a low hydrogen abstracting property, since the polymerization can easily proceed stably. In particular, when an alicyclic epoxy group-containing vinyl monomer is used as the functional vinyl monomer (a-3), it is preferable to use an initiator having a low hydrogen abstraction property, such as an azo initiator.

As the solvent used, 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, a curable liquid resin is obtained by removing the solvent used during the synthesis by a method of precipitation purification and distillation after the synthesis. The viscosity of the obtained curable liquid resin and its modified product at 50 ° C. is 1 to 10,000 poise, preferably 5 to 10,000 poise, more preferably 8 to 1000 poise. It is not preferable that the viscosity of the curable liquid resin is low because it causes bleeding at the time of film coating and causes soaking at the time of coating or printing on paper. If the viscosity is higher than this range, a large amount of the acrylic monomer (B) is added to lower the viscosity, which is not preferable.

In the present invention, (meth) having a number average molecular weight of 1000 or less having one or more unsaturated double bonds in the molecule.
The acrylic monomer (B) is used for adjusting the viscosity and curability of the radiation-curable resin composition.

Examples of the (meth) acrylic monomer (B) include, for example, methyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate,
Monofunctional (meth) acrylic monomers such as phenoxymethyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentynyl (meth) acrylate, and (dicyclopentenyl) oxy (meth) acrylate ,

Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate Acrylate, polypropylene glycol di (meth) acrylate, 1,3 butylene glycol di (meth) acrylate, 1,6 hexanediol di (meth) acrylate, 2-methyl-1,8-octanediol diacrylate, 1,9 nonanediol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2,2bis [4-{(meth) acryloxydiethoxy} phenyl] propane, 2,2bis [4-} (meth) Methacryloxy ethoxy} phenyl] propane, 2,2-bis [4 - {(meth) acryloxy polyethoxy} phenyl] propane, 2,2-bis [4-
{(Meth) acryloxy dipropoxy} phenyl] propane, 2,2bis [4-{(meth) acryloxypropoxy} phenyl] propane, 2,2bis [4-{(meth) acryloxypolypropoxy} phenyl] propane Bifunctional (meth) acrylic monomers such as tricyclo [5.2.1.02,6] decanyldi (meth) acrylate,

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) acrylic monomers such as dipentaerythritol hexa (meth) acrylate. The viscosity of the (meth) acrylic monomer (B) is 0.01 to 60 poise (50 ° C).
Preferably 0.1 to 50 poise (50 ° C.) or 0.0
It is 1 to 100 poise (30 ° C.), and those lower than this are often low molecular weight, and those higher than this are not preferred because the contribution as a viscosity modifier becomes poor.

In the present invention, the mixing ratio of the curable liquid resin and the (meth) acrylic monomer (B) is as follows:
(Meth) acrylic monomer (B) is used in an amount of 1 to 1000 parts by weight, preferably 2 to 5 parts by weight, per 100 parts by weight of the curable liquid resin.
00 parts by weight. If the compounding ratio of the (meth) acrylic monomer (B) is higher than this, the properties of the curable liquid resin are not utilized, so that the volume shrinkage during curing increases, the adhesion to the substrate is poor, It is not preferable because the cured product becomes brittle. Conversely, if the content is less than this, the curability is poor and the solvent resistance and the like are unfavorably deteriorated. The viscosity of the composition obtained in the present invention is from 0.01 to 1000 poise, preferably from 0.1 to 500 poise (50 ° C.).
An acrylic monomer must be added, which is not preferable.
Further, a composition having a higher viscosity is not preferable because of poor processability.

In the present invention, the radiation-curable resin composition is generally obtained by mixing a curable liquid resin and an acrylic monomer (B). By adding the composition to a curable liquid resin polymerization solution, the composition can be simultaneously formed with the solvent.

In the present invention, a curing agent resin such as an amino resin or a phenol resin may be blended in order to enhance the film-forming properties and curing properties of the radiation-curable resin composition.
In addition, in order to improve the coating performance, known polyamide resins, cellulose derivatives, vinyl resins, polyolefins, natural rubber derivatives, acrylic resins, epoxy resins, polyesters, polystyrenes and other general-purpose polymers, urethane acrylic resins, epoxy acrylic resins, alkyds A reactive resin having an unsaturated group such as a resin, a rosin-modified alkyd resin, and a linseed oil-modified alkyd resin, and a drying oil such as linseed oil, tung oil, and soybean oil may be blended. However,
The amount of each of them is preferably 40% by weight, more preferably 20% by weight or less. Further, a solvent, a compatibilizer, a surfactant, a lubricant, or the like may be added as necessary. The amount of these components is 20% by weight, preferably 1%.
0% by weight or less.

The radiation-curable resin composition obtained according to the present invention may contain a coloring agent comprising a dye, a pigment such as carbon black, titanium white, phthalocyanine, an azo dye or quinacridone, or an inorganic filler such as Si-based fine particles, mica or calcium carbonate. Can be used as various printing inks and colored paints by adding an appropriate amount of 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 curable liquid resin of the present invention is prepared by coating a base material such as various steel plates, aluminum plates and other metal plates, plastic films, paper, plastic film laminated paper, etc. with a roll coater or knife coater. By a conventional method such as a coating method such as offset printing, gravure printing, letterpress printing, silk screen printing, or the like, a film having a thickness of 0.1 to 500 μm can be formed, and heating or electron beam, ultraviolet light, It can be cured by irradiating radiation such as visible light and infrared light. When curing by electron beam irradiation, preferably 10 to 1000 keV, more preferably 30 to 3 keV.
An electron beam irradiation device having an energy in the range of 00 keV is used. The irradiation dose (DOSE) is preferably between 0.
1 to 100 Mrad, more preferably 0.5 to 20 Mr
range of ad. 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 a coating film or a substrate is large, which is not preferable.

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 composition for a film-forming material using the curable liquid resin of the present invention can be applied to a base material such as various steel plates, metal plates such as aluminum plates, plastic films, paper, plastic film laminated paper and the like by a roll coater or a knife coater. With a conventional method such as a coating method such as offset printing, gravure printing, letterpress printing, silk screen printing, etc., a film can be formed to a thickness of 0.1 to 500 μm, and heated or electron beam, ultraviolet light, It can be cured by irradiating radiation such as visible light and infrared light. When curing by electron beam irradiation, preferably 10 to 1000 keV, more preferably 30 to 3 keV.
An electron beam irradiation device having an energy in the range of 00 keV is used. The irradiation dose (DOSE) is preferably between 0.
1 to 100 Mrad, more preferably 0.5 to 20 Mr
range of ad. 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 a coating film or a substrate is large, which is not preferable.

[0044]

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) 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 0.5 Adjusted at belt conveyor speed in the range of 〜8 Mrad.

◎ Abbreviations of the following compounds used in Examples and Comparative Examples are described. 1) Compound used for synthesis of curable liquid resin (a-1-1) LA: lauryl acrylate EHA: 2-ethylhexyl acrylate (a-1-2) MTGA: methoxytriethylene glycol monoacrylate AM90G: methoxypolyethylene glycol ( Degree of polymerization 9) Monoacrylate AMP-60G: Phenoxyhexaethylene glycol monoacrylate (a-2) Si-1: γ- (meth) acryloxypropyltrimethoxysilane Si-2: γ- (meth) acryloxypropyltriethoxy Silane Si-3: γ- (meth) acryloxypropyl triphenoxysilane (a-3) AA: acrylic acid GMA: glycidyl methacrylate 4HBA: 4-hydroxybutyl acrylate AAm: acrylamide ST: polystyrene 2) (meth) Compound POA was used as the acrylic monomer (B): polyphenylene carboxyethyl acrylate (Mn = 192, η = 0.1
0 P) BzA: benzyl acrylate (Mn = 162, η = 0.03 P) PEG9DA: polyethylene glycol diacrylate
(Mn = 170, η = 0.362 P) NODA: 1,9 nonanediol diacrylate (Mn = 26
8, η = 0.073 P) BP4EA: 2,2-bis [4- {acryloxy-polyethoxy} phenyl] propane (Mn = 512, η = 7.5 P) BP4PA: 2,2-bis [4- {acryloxy-polypropoxy} phenyl ] Propane (Mn = 560, 17P) TMPTA: Trimethylolpropane triacrylate
(Mn = 296, η = 0.95 P)) DPHA: dipentaerythritol hexaacrylate
(Mn = 578, η = 50 P)

Examples 1 to 17 Synthesis of Curable Liquid Resin 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 of Curable Liquid Resin and Measurement Results of Physical Properties ────────────────────────────────── Mn Viscosity Example Composition (weight ratio) (): Mw / Mn (50 ° C) [P (poise)] ───────────────────────── １ 1 LA: Si-1 = 60: 40 1.75E4 (3.6) 53 2 LA: Si-1 = 90: 10 1.60E4 (3.1) 84 3 LA: MTG: Si-1 = 60:30:10 1.82E4 (2.8) 110 4 LA: AM90G: Si-1 = 60: 20: 20 1.73E4 (2.5) 925 LA: AM90G: Si-1: AA = 60: 20: 10: 10 1.91 E4 (3.4) 506 LA: AM90G: Si-1: 4HBA = 60: 20: 10: 10 1.53E4 (2.2) 94 7 EHA: Si-1 = 95: 5 1.48E4 (2.6) 170 8 EHA: Si- 1 = 80: 20 2.26E4 (4.1) 220 9 EHA: MTG: Si-1 = 60: 30: 10 1.82E4 (2.8) 110 10 EHA: AM90G: Si-1 = 60: 20: 20 3.60E4 (4.8 ) 127 1 1 EHA: AM90G: Si-1: AA = 60: 20: 10: 10 2.54E4 (3.1) 150 12 EHA: AM90G: Si-1: 4HBA = 60: 20: 10: 10 3.03E4 (3.3 ) 164 13 EHA: AM90G: Si-1: GMA = 60: 20: 10: 10 2.72E4 (2.7) 194 14 EHA: AM90G: Si-1: AAm = 60: 20: 10: 10 2.01E4 (3.4 ) 217 1 5 EHA: AM90G: Si-1: AMP20G = 60: 20: 10: 10 2.44E4 (2.2) 174 16 EHA: AMP-60G: Si-1: AAm = 60: 20: 10: 10 2.31E4 (2.8) 254 17 EHA: AMP-60G: Si-1: 4HBA = 60: 20: 10: 10 2.57E4 (2.5) 271 18 EHA: AM90G: Si-2 = 60: 20: 20 1.97E4 (2.6) 140 19 EHA: Si-2 = 60: 40 2.26E4 (3.8) 113 20 EHA: AM90G: Si-3 = 60: 20: 20 2.31E4 (3.0) 186 21 EHA: Si-3 = 60: 40 1.96E4 (2.9) 134 ──────────────────────────────────

(Examples 18 to 43) The radiation curable resin compositions prepared using the curable liquid resin (A) obtained in Examples 1 to 17 and the acrylic monomer (B) were used in 0.1%.
Apply on PET film with 5 mil applicator and apply 2
An Mrad electron beam was applied. Table 2 shows the composition of the radiation-curable resin composition used, the curability 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 radiation-curable resin composition Actual radiation-curable resin composition (Example No.) Viscosity Curable MEK rubbing applied (10 / s) ○: Cured (after 50 times) Example (A): (B) [P] △: With tack Residual rate No (Weight ratio) ×: uncured [%] ────────────────────────────────── 18 Example 1: NODA = 2: 8 0.27 ○ 95 19 Example 2: NODA = 2: 8 0.30 ○ 100 20 Example 3: NODA = 2: 8 0.32 ○ 100 21 Example 4: NODA = 2: 8 0.30 ○ 100 22 Example 5: NODA = 2: 8 0.27 ○ 95 23 Example 6: NODA = 2: 8 0.31 ○ 100 24 Example 7: NODA = 2: 8 0.34 ○ 95 25 Example 7: BP4PA = 2: 8 26.94 ○ 100 26 Example 7: BP4PA = 4: 6 42.70 ○ 90 27 Example 7: (BP4PA: TMPTA) = 4: (3: 3) 17.97 ○ 95 28 Example 7: TMPTA = 4: 6 7.57 ○ 100 29 Example 8 : NODA = 2: 8 0.36 ○ 100 30 Example 9: NODA = 2: 8 0.32 ○ 100 31 Actual Example 10: NODA = 2: 8 0.32 ○ 95 32 Example 11: BP4PA = 4: 6 40.62 ○ 90 33 Example 11: (BP4PA: TMPTA) = 4: (3: 3) 17.10 ○ 95 34 Example 11: TMPTA = 4: 6 7.20 ○ 95 35 Example 12: NODA = 2: 8 0.34 ○ 100 36 Example 13: NODA = 2: 8 0.35 ○ 100 37 Example 14: (BP4PA: BzA) = 2: (7: 1) 15.01 ○ 95 38 Example 15: BP4EA = 2: 8 14.07 ○ 95 39 Example 15: (BP4EA: DPHA) = 4: (3: 3) 46.60 ○ 100 40 Example 15: (BP4EA: DPHA) = 4: (4: 2) 38.55 ○ 100 41 Example 15: (PEG9DA: DPHA) = 4: (2: 4) 30.73 ○ 95 42 Example 16: (BP4PA: POA) = 2: (7: 1) 17.47 ○ 95 43 Example 17: (NODA: DPHA) = 2: (4: 4) 1.05 ○ 100 44 Example 18: (NODA: DPHA) = 2: (4: 4) 4.43 ○ 100 45 Example 19: ( NODA: TMPTA) = 2: (2: 6) 9.13 ○ 95 46 Example 20: (NODA: DAPHA) = 2: (4: 4) 4.70 ○ 100 47 Example 21: (NODA: TMPTA) = 2 :( 2: 6) 9.50 ○ 95 ──────────────────────────────────

(Examples 48 to 52) Examples 25, 28 and 3
30 parts by weight of titanium white was added to 70 parts by weight of the radiation-curable resin composition obtained in 6, 40 and 42, mixed and dispersed by a sand mill to obtain a white ink. This ink was applied on coated paper with a 1.0 mil applicator and
Upon irradiation with rad, a cured coating film having excellent gloss was obtained. Results of MEK rubbing test and bending test of the obtained cured coating film (measurement of angle and number of times until the coating film is broken using a 1 mm metal test rod: ：: 180 degrees, 5 times or more,
○: 180 degrees, 1 to 4 times, Δ: 90 to 180 degrees, ×: <
90 °) are shown in Table 3 together with the viscosity of the ink at 30, 50 ° C.

Table 3 Viscosity and curing characteristics of electron beam curable ink Viscosity used [P] MEK Rubbing Bending test Application Radiation curability (10 / s) (50 times) Example Resin composition 30 ゜ C 50 ゜ C Residual rate [%] Example No. ─────── ─────────────────────────── 48 Example 25: 273.5 110.7 95 ○ 49 Example 28: 125.5 67.6 100 ◎ 50 Example 36: 86.3 36.4 100 ◎ 51 Example 40: 453.2 231.0 100 ○ 52 Example 42: 500.7 90.6 100 ◎ ──────────────────────────── ──────

[0053]

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.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] September 16, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0047

[Correction method] Change

[Correction contents]

(Examples 1 to 21) Synthesis and Measurement of Physical Properties of Curable Liquid Resin A 500 ml four-necked round bottom flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a condenser was prepared.
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.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0049

[Correction method] Change

[Correction contents]

(Examples 22 to 51) The radiation curable resin composition prepared using the curable liquid resin (A) obtained in Examples 1 to 22 and the acrylic monomer (B) was used in 0.1%.
Apply on PET film with 5 mil applicator and apply 2
An Mrad electron beam was applied. Table 2 shows the composition of the radiation-curable resin composition used, the curability 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.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0050

[Correction method] Change

[Correction contents]

Table 2 Composition and curing characteristics of radiation-curable resin composition Actual radiation-curable resin composition (Example No.) Viscosity Curable MEK rubbing applied (10 / s) ○: Cured (after 50 times) Example (A): (B) [P] △: With tack Residual rate No (Weight ratio) ×: uncured [%] ────────────────────────────────── 22 Example 1: NODA = 2: 8 0.27 ○ 95 23 Example 2: NODA = 2: 8 0.30 ○ 100 24 Example 3: NODA = 2: 8 0.32 ○ 100 25 Example 4: NODA = 2: 8 0.30 ○ 100 26 Example 5: NODA = 2: 8 0.27 ○ 95 27 Example 6: NODA = 2: 8 0.31 ○ 100 28 Example 7: NODA = 2: 8 0.34 ○ 95 29 Example 7: BP4PA = 2: 8 26.94 ○ 100 30 Example 7: BP4PA = 4: 6 42.70 ○ 90 31 Example 7: (BP4PA: TMPTA) = 4: (3: 3) 17.97 ○ 95 32 Example 7: TMPTA = 4: 6 7.57 ○ 100 33 Example 8 : NODA = 2: 8 0.36 ○ 100 34 Example 9: NODA = 2: 8 0.32 ○ 100 35 Actual Example 10: NODA = 2: 8 0.32 ○ 95 36 Example 11: BP4PA = 4: 6 40.62 ○ 90 37 Example 11: (BP4PA: TMPTA) = 4: (3: 3) 17.10 ○ 95 38 Example 11: TMPTA = 4: 6 7.20 95 95 39 Example 12: NODA = 2: 8 0.34 100 100 40 Example 13: NODA = 2: 8 0.35 100 41 Example 14: (BP4PA: BzA) = 2: (7: 1) 15.01 ○ 95 42 Example 15: BP4EA = 2: 8 14.07 ○ 95 43 Example 15: (BP4EA: DPHA) = 4: (3: 3) 46.60 ○ 100 44 Example 15: (BP4EA: DPHA) = 4: (4: 2) 38.55 ○ 100 45 Example 15: (PEG9DA: DPHA) = 4: (2: 4) 30.73 ○ 95 46 Example 16: (BP4PA: POA) = 2: (7: 1) 17.47 ○ 95 47 Example 17: (NODA: DPHA) = 2: (4: 4) 1.05 ○ 100 48 Example 18: (NODA: DPHA) = 2: (4: 4) 4.43 ○ 100 49 Example 19: ( NODA: TMPTA) = 2: (2: 6) 9.13 ○ 95 50 Example 20: (NODA: DAPHA) = 2: (4: 4) 4.70 ○ 100 51 Example 21: (NODA: TMPTA) = 2 :( 2: 6) 9.50 ○ 95 ──────────────────────────────────

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0051

[Correction method] Change

[Correction contents]

(Examples 52 to 56) Examples 29, 32, and 4
30 parts by weight of titanium white was added to 70 parts by weight of the radiation-curable resin compositions obtained in Nos. 0, 44 and 46, mixed and dispersed by a sand mill to obtain a white ink. This ink was applied on coated paper with a 1.0 mil applicator and
Upon irradiation with rad, a cured coating film having excellent gloss was obtained. Results of MEK rubbing test and bending test of the obtained cured coating film (measurement of angle and number of times until the coating film is broken using a 1 mm metal test rod: ：: 180 degrees, 5 times or more,
○: 180 degrees, 1 to 4 times, Δ: 90 to 180 degrees, ×: <
90 °) are shown in Table 3 together with the viscosity of the ink at 30, 50 ° C.

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0052

[Correction method] Change

[Correction contents]

Table 3 Viscosity and curing characteristics of electron beam curable ink Viscosity used [P] MEK Rubbing Bending test Application Radiation curability (10 / s) (50 times) Example Resin composition 30 ゜ C 50 ゜ C Residual rate [%] Example No. ─────── ─────────────────────────── 52 Example 25: 273.5 110.7 95 ○ 53 Example 28: 125.5 67.6 100 ◎ 54 Example 36: 86.3 36.4 100 ◎ 55 Example 40: 453.2 231.0 100 ○ 56 Example 42: 500.7 90.6 100 ◎ ──────────────────────────── ──────

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 43/04 C08L 43/04 C09D 4/02 C09D 4/02

Claims (7)

[Claims] (A) an alkyl (meth) acrylic monomer represented by the following formula (1) and / or the following formula (2):
20 to 95% by weight of an alkylene glycol (meth) acrylate-based monomer (a-1), 1 to 60% by weight of a vinyl monomer (a-2) having a hydrolyzable silyl group, and a polymerizable vinyl monomer other than the above (A-3)
Having a number average molecular weight of 10,
000 to 200,000 and a viscosity of 1 to 20,000
A curable liquid resin having a poise (50 ° C.). CH ₂ = C (R ¹ ) COO-R ² (1) (wherein, R ¹ is a hydrogen atom or CH ₃ , and R ² is carbon number 4
To 22 alkyl groups. ^{_{) CH 2 = C (R 1}} ) COO (CnH 2 nO) mR 3 (2) ( wherein, R ¹ represents a hydrogen atom or CH _3, R ³ is a hydrogen atom, an alkyl group or a phenyl group having 1 to 5 carbon atoms , N represents an integer of 1 to 4, and m represents an integer of 3 to 25.) 2. The curable liquid resin according to claim ¹ , wherein R ¹ in the formulas (1) and (2) is a hydrogen atom. 3. A curable liquid resin (A) according to claim 1 or 2, and a (meth) acrylic monomer (B) having an unsaturated double bond in the molecule and having a number average molecular weight of 1,000 or less. A) a radiation-curable resin composition comprising 1 to 1000 parts by weight; 4. The radiation-curable resin composition according to claim 3, wherein the viscosity of the (meth) acrylic monomer (B) is 0.01 to 60 poise (50 ° C.). 5. The radiation-curable resin composition according to claim 1, wherein the viscosity of the composition is 0.1 to 500 poise (50 ° C.). 6. A curable printing ink comprising the radiation-curable resin composition according to claim 5. 7. A paint comprising the radiation-curable resin composition according to claim 5.