JPH1053629A - Curable liquid resin composition - Google Patents

Abstract

(57) Abstract: A curable liquid resin composition that can be formed by a conventionally used coating method and printing method, and can be cured by a conventional curing method such as heat drying and irradiation. The purpose is to provide things. SOLUTION: The following (meth) acrylic liquid resin (A) 1
(Meth) acrylic monomer having an unsaturated double bond in the molecule and having a number average molecular weight of 1,000 or less (B)
1 to 1000 parts by weight of a curable liquid resin composition. (A) 10 to 100% by weight of an alkyl (meth) acrylate monomer represented by the following formula (1) and 0 to 90% by weight of other monomers, and the average molecular weight of all monomers is 100 to 100%. A liquid resin having a number average molecular weight of 10,000 to 200,000 and a viscosity of 1 to 10,000 poise (50 ° C.) obtained by polymerizing a monomer of 1500. 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. )

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 acrylic liquid resin obtained by the present invention,
A liquid resin composition comprising an ester resin and a (meth) acrylic monomer 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,
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. 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 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]

SUMMARY OF THE INVENTION The present invention reduces the content of a monomer used as a reactive diluent in a solvent-free curable resin composition containing no solvent, thereby reducing the working environment in the coating process. No special exhaust gas treatment equipment is required because the amount of low molecular weight compounds released into the atmosphere and the atmosphere is reduced.In addition, coating methods such as conventionally used roll coaters and knife coaters, offset printing, gravure printing,
Films can be formed by printing methods such as letterpress printing and screen printing.
After all conventional heating drying and electron beam, ultraviolet ray, visible light,
An object of the present invention is to provide a curable liquid resin composition that can be cured by irradiation with radiation such as 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. A curable liquid resin composition having a viscosity within a range in which a film can be formed by the method and which can be cured at a high speed by a conventional curing method has been found. Furthermore,
By using this, the amount of the monomer used as a reactive diluent can be drastically reduced, and the present invention has been achieved.

That is, the present invention relates to a (meth) acrylic liquid resin (A) 100 parts by weight 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 curable liquid resin composition comprising 1 to 1000 parts by weight; (A) 10 to 100% by weight of an alkyl (meth) acrylate monomer represented by the following formula (1), and 0 to 90% by weight of other monomers,
The number average molecular weight obtained by polymerizing monomers having an average molecular weight of 100 to 1500 is 10,000 to 200,
000 and a viscosity of 1 to 10,000 poise (50
C) liquid resin. 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. )

Further, the present invention relates to the above curable liquid resin composition, wherein the viscosity of the (meth) acrylic monomer (B) is 0.01 to 50 poise (50 ° C.). Furthermore, the present invention relates to a curable liquid resin composition, wherein R1 in the above formula (1) is a hydrogen atom. Further, the present invention relates to the above curable liquid resin composition, wherein the viscosity of the composition is 0.1 to 500 poise (50 ° C.). Furthermore, the present invention relates to the above-mentioned curable liquid resin composition which is of a radiation curing type. Further, the present invention relates to a curable printing ink comprising the above liquid resin composition. Further, the present invention relates to a paint using the above liquid resin composition.

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 (meth) acrylic resin liquid. As the alkyl group derivative represented by the general formula (1), for example, 2
-Ethylhexyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, heptyl (meth) acrylate, 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) acrylate, nonadecyl (meth) ) C4 to C2 of acrylate, icosyl (meth) acrylate, henycosyl (meth) acrylate, docosyl (meth) acrylate, etc.
There are 2 alkyl (meth) acrylates, among which acrylates having an alkyl group having 8 to 20 carbon atoms or corresponding methacrylates are preferred. 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. Incidentally, the film formation in the present invention, by a method such as printing and painting,
This refers to forming a resin film having a thickness of 0.1 to 500 μm on a substrate made of paper, metal, plastic, ceramics, or the like.

In the present invention, other vinyl compounds can be used 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 vinyl toluene, (meth) acrylates having an alkyl group having 3 or less carbon atoms, such as methyl methacrylate and ethyl methacrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxyethyl Propyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, dipropylene glycol monomethacrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) Acrylate,
Alkoxy groups such as phenoxydiethylene glycol (meth) acrylate and phenoxyethylene glycol (meth) acrylate, (meth) acrylate monomers containing a phenoxy group or a hydroxyl group, maleic acid, fumaric acid, itaconic acid, citraconic acid, or alkyl or alkenyl thereof Monoester, phthalic acid β-
(Meth) acryloxyethyl monoester, isophthalic acid β- (meth) acryloxyethyl monoester, terephthalic acid β- (meth) acryloxyethyl monoester, succinic acid β- (meth) acryloxyethyl monoester, acrylic acid And monomers containing a carboxylic acid such as methacrylic acid, crotonic acid, and cinnamic acid, and a plurality of monomers from these groups may be used. The amount of the other vinyl compound used is 0 to 90% by weight based on the liquid resin as the copolymer,
It is preferably from 10 to 60% by weight, and if it is more than 60% by weight, especially more than 90% by weight, the viscosity of the liquid resin is undesirably high. In the present invention, the average value of the molecular weight of the entire monomer used as a component of the (meth) acrylic liquid resin is 100 to 1500, preferably 130 to 11.
More preferably, it is in the range of 150 to 1,000.
Outside this range, a liquid resin having a preferable viscosity range cannot be obtained, which is not preferable.

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. Play a role for. Such a (meth) acrylic liquid resin (A) contains the alkyl (meth) acrylate monomer (1) in a monomer component in an amount of 10 to 100% by weight, preferably 40 to 100% by weight. If it is a polymer or a copolymer, and the amount of the alkyl (meth) acrylate-based monomer (1) in the polymer is less than 40% by weight, particularly less than 10% by weight, the desired viscosity cannot be maintained.

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. Other vinyl compounds that can be used in this case 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 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 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 resulting resin has a viscosity at 50 ° C. of 5
It is a liquid of 10,000 poise, preferably 8-1000 poise. 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 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 solventless liquid resin composition.
Examples of such (meth) acrylic monomer (B) include methyl (meth) acrylate, butyl (meth) acrylate, 2hydroxyethyl (meth) acrylate,
Monofunctional (meth) acrylic monomers such as phenoxyethyl (meth) acrylate, methylphenoxy (meth) acrylate and benzyl (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, 1,3 butylene glycol di (meth) acrylate, 1,6 hexanediol di (meth)
Acrylate, 1,9 nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2,2bis [4-{(meth) acryloxydiethoxy {phenyl] propane, 2,2bis [4-} ( Meth) acryloxyethoxydiphenyl] propane, 2,
2-bis [4-{(meth) acryloxy-polyethoxy}
Phenyl] propane, 2,2 bis [4-{(meth) acryloxydipropoxy} phenyl] propane, 2,2
Bifunctional (meth) acrylic monomers such as bis [4-{(meth) acryloxypropoxy} phenyl] propane and 2,2bis [4-{(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) acrylic monomers such as dipentaerythritol hexa (meth) acrylate. The viscosity of the (meth) acrylic monomer (B) is 0.01 to 50 poise (50 ° C).
Preferably, it is 0.1 to 20 poise (50 ° C.). Those lower than this are often low molecular weight ones, and those higher than this are not preferred because their contribution as viscosity modifiers is poor.

In the present invention, the mixing ratio of the (meth) acrylic liquid resin (A) and the (meth) acrylic monomer (B) is as follows.
The (meth) acrylic monomer (B) is used in an amount of 1 to 1000 parts by weight, preferably 2 to 500 parts by weight, based on 00 parts by weight. 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 500 poise (50 ° C.). To obtain a composition having a lower viscosity than this, it is necessary to mix more (meth) acrylic monomers. Not preferred. Further, a composition having a higher viscosity is not preferable because of poor processability.

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 curable liquid 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, polystyrene and other general-purpose polymers, alkyd resins, rosin-modified alkyd resins, An unsaturated modified alkyd resin such as an oil-modified alkyd resin, a drying oil such as linseed oil, tung oil, soybean oil, and the like may be blended. However,
The amount of each of them is preferably 40 parts by weight, more preferably 20 parts 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 parts by weight, preferably 10 parts by weight.
Not more than parts by weight. Various amounts of the curable liquid resin obtained by the present invention can be obtained by adding dyes, carbon black, titanium white, phthalocyanine, azo dyes, coloring agents composed of pigments such as quinacridone, Si-based fine particles, and inorganic fillers such as mica in an appropriate amount. It can be used as a printing ink or a coloring paint. 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, plastic film laminated papers and the like by 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.

[0022]

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.

The methods for measuring the number average molecular weight and the viscosity in this example are described 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 and Comparative Examples are described. 1) Compound used for synthesis of acrylic liquid resin BA: butyl acrylate LA: lauryl acrylate EHA: 2-ethylhexyl acrylate AMP-20G: phenoxydiethylene glycol monoacrylate 2) Used as (meth) acrylic monomer (B) Compound POA: phenoxyethyl acrylate (Mn = 192, η = 0.1
0 P) BzA: benzyl acrylate (Mn = 162, η = 0.03 P) EGDA: ethylene glycol diacrylate (Mn = 170,
η = 0.06 P) NODA: 1,9 nonanediol diacrylate (Mn = 26
8, η = 0.073 P) BP4EA: 2,2-bis [4- {acryloxypolyethoxy} phenyl] propane (Mn = 512, η = 7.5 P) BP4PA: 2,2bis [4- {acryloxypolypropoxy} Phenyl] propane (Mn = 560, 17 P) TMPTA: trimethylolpropane triacrylate
(Mn = 296, η = 0.95 P)) DPHA: dipentaerythritol hexaacrylate
(Mn = 578, η = 50 P)

(Examples 1 to 9) 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 (Whey) ───────────────────────── ─────── 1 LA 1.27E4 (3.79) 35.3 2 LA: AMP20G = 80:20 1.68E4 (3.79) 100.0 3 LA: ST = 90:10 1.20E4 (3.17) 230.2 4 EHA 1.69E4 (4.17) 122.0 5 EHA: LA = 50:50 1.36E4 (3.24) 75.4 6 EHA: AMP20G = 80:20 1.58E4 (3.58) 348.6 7 EHA: ST = 95: 5 1.25E4 (3.17) 753.6 8 LA: EHA: ST: AMP20G = 30: 45: 5: 20 1.33E4 (3.98) 247.5 9 BA: EHA = 20:80 1.59E4 (2.97) 142.3 ───────────────────── ────────────

(Examples 10 to 38) The curable resin composition prepared using the acrylic liquid resin (A) obtained in Examples 1 to 9 and the acrylic monomer (B) was used in an amount of 0.5%. Apply on PET film with applicator of mill, 2Mr
The electron beam of the ad was irradiated. The composition of the curable resin composition used, and the curability of the coating film obtained by electron beam irradiation,
Table 2 shows the residual ratio obtained from the weight change before and after the MEK rubbing test 50 times.

Table 2 Composition and Curing Characteristics of Curable Liquid Resin Composition Curable resin composition (Example No.) Viscosity Curable MEK resin (10 / s) ○: Cured (after 50 times) Example (A): ( B) [P] △: With tack Residual rate No (weight ratio) ×: Uncured [%] ─────────────────────────── ────── 10 Example 1: NODA = 2: 8 0.15 ○ 95 11 Example 4: NODA = 2: 8 0.32 ○ 100 12 Example 4: (NODA: TMPTA) = 2: (7: 1) 0.41 ○ 100 13 Example 5: NODA = 2: 8 0.29 ○ 100 14 Example 9: NODA = 2: 8 0.33 ○ 95 15 Example 2: NODA = 2: 8 0.31 ○ 100 16 Example 2: BP4EA = 2 : 8 12.59 ○ 95 17 Example 2: BP4PA = 2: 8 24.23 ○ 100 18 Example 2: BP4PA = 4: 6 34.54 ○ 90 19 Example 2: (NODA: TMPTA) = 3: (6: 1) 0.82 ○ 95 20 Example 6: NODA = 2: 8 0.40 ○ 100 21 Example 6: BP4EA = 2: 8 16.16 ○ 95 22 Example 6: BP 4PA = 2: 8 31.09 ○ 100 23 Example 6: BP4PA = 3: 7 42.05 ○ 95 24 Example 6: EGDA = 2: 8 0.34 ○ 100 25 Example 6: TMPTA = 2: 8 3.09 ○ 100 26 Example 6: DPHA = 3: 7 89.53 ○ 100 27 Example 6: (BP4PA: POA) = 2: (7: 1) 15.09 ○ 95 28 Example 3: (BP4PA: POA) = 2: (7: 1) 5.77 ○ 95 29 Example 3: (BP4EA: BzA) = 2: (7: 1) 8.56 ○ 95 30 Example 3: BP4PA = 2: 8 18.62 ○ 100 31 Example 7: (BP4PA: POA) = 2 :( 7: 1) 21.71 ○ 95 32 Example 7: (BP4EA: BzA) = 2: (7: 1) 10.86 ○ 95 33 Example 7: BP4EA = 2: 8 18.86 ○ 100 34 Example 9: NODA = 3: 8 0.33 ○ 95 35 Example 8: BP4EA = 2: 8 15.09 ○ 100 36 Example 8: BP4PA = 2: 8 29.03 ○ 100 37 Example 8: (BP4EA: DPHA) = 2: (7: 1) 18.23 ○ 100 38 Example 8: (BP4PA: TMPTA) = 2: (6: 2) 16.39 ○ 100 ─────

(Examples 39 to 43)
Curable resin composition 7 obtained in 22, 27 and 38
30 parts by weight of titanium white was added to 0 parts by weight, mixed and dispersed by a sand mill to obtain a white ink. 0.5 of this ink
Apply on coated paper with mill applicator, 2Mrad
Upon irradiation, 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, ○: 18)
0 degree, 1-4 times, Δ: 90-180 degrees, ×: <90 degrees)
Are shown in Table 4 together with the viscosity of the ink at 30, 50 ° C.

Table 4 Viscosity and Curing Characteristics of Electron Curable Ink ─────────────────────────────── Actually Used Viscosity [P] MEK Lapink bending test Application Curable resin composition (10 / s) (50 times) Example Example No. 30 ゜ C 50 ゜ C Residual rate [%] ─────────── ──────────────────── 39 Example 12: 17.2 12.2 100 ○ 40 Example 17: 152 126.8 100 ○ 41 Example 22: 354 223.9 100 ◎ 42 Example 27: 110 78.3 90 ◎ 43 Example 38: 124 90.6 100 ◎ ────────────────────────────────

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.

Claims (7)

[Claims] 1. The following (meth) acrylic liquid resin (A)
A curable liquid resin composition comprising 100 parts by weight and 1 to 1000 parts by weight of 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) 10 to 100% by weight of an alkyl (meth) acrylate monomer represented by the following formula (1) and 0 to 90% by weight of other monomers, and the average molecular weight of all monomers is 100 to 100%. A liquid resin having a number average molecular weight of 10,000 to 200,000 and a viscosity of 1 to 10,000 poise (50 ° C.) obtained by polymerizing a monomer of 1500. 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. ) 2. The curable liquid resin composition according to claim 1, wherein the viscosity of the (meth) acrylic monomer (B) is 0.01 to 50 poise (50 ° C.). 3. The curable liquid resin composition according to claim ¹ , wherein R ¹ in the formula (1) is a hydrogen atom. 4. The curable liquid resin composition according to claim 1, wherein the viscosity of the composition is 0.1 to 500 poise (50 ° C.). 5. The curable liquid resin composition according to claim 3, which is a radiation-curable type. 6. A curable printing ink comprising the liquid resin composition according to claim 5. 7. A paint comprising the liquid resin composition according to claim 5.