JP3456374B2 - Curable liquid resin - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid resin capable of forming a film and forming a cured film without using a solvent as a resin for a film forming material such as a paint or ink, or an adhesive. The liquid resin obtained by the present invention can also be used as a compatibilizer, an interface modifier, and a pigment dispersant. Furthermore, the curable liquid resin obtained by the present invention can be used as a radiation curable resin.

[0002]

2. Description of the Related Art Conventionally, paints, adhesives, adhesives, inks,
Resin solutions containing organic solvents have been used as fillers and molding materials. These resin solutions scatter a large amount of organic solvents in the painting, filling and curing / drying steps. With increasing interest in the global environment and working environment, restrictions on the use of such resin solutions are being imposed. One of the methods is the use of powders and hot melt materials, but it is necessary to introduce new equipment because it is very different from the conventional film forming and drying systems. In order to solve the above-mentioned problems, solution type resins have been made high solid and water-based resins have been improved. It is considered that with such efforts, the amount of organic solvent used will further decrease in the future. However, as a fundamental solution, there is a strong demand for the development of a solventless liquid resin which is free from problems such as pollution, safety and hygiene, ignition and explosion, can be applied in a wide range, and can be easily formed into a film and cured. Although various radiation-curable resin compositions can be said to be quite promising as quick-drying, one-pack type solventless resins, in the conventional system, the viscosity of the composition was controlled by a large amount of low molecular weight components. Therefore, even after curing, it is unfavorable from the environmental point of view due to problems such as residual monomer odor. In addition, volume shrinkage during curing was large, and the cured coating film became brittle and adhesion to the substrate was a problem. In order to improve the curing shrinkage, various measures such as using a monomer component having a relatively high molecular weight or adding a small amount of a high molecular weight component have been made, but in the latter case, in particular, the composition is solid. The amount that can be added is limited in order to control the material within an appropriate viscosity range, and these problems make the range of use of the radiation curable resin composition considerably narrow.
The solventless resin composition is disclosed in JP-A-57-171. This technique uses a liquid resin made of an acrylic monomer, but further improvement is desired because the obtained resin is an oligomer. In terms of physical properties, in the case of a paint composed of a resin in the oligomer region,
It is known that it is difficult to control the physical properties of the coating film after curing (Soichi Muroi, “1992 Adhesive and Painting Study Group Lecture Abstracts”, page 4, 1993), while maintaining low viscosity. It is desired to increase the molecular weight.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a curable resin having a high molecular weight and a liquid state, thereby reducing the compounding ratio of a low molecular weight compound having a problem in terms of safety and physical properties, and making it unnecessary. This contributes to the improvement of the working environment. Further, the present invention provides a curable liquid resin having improved volume shrinkage upon curing and improved adhesiveness to a metal or plastic film.

[0004]

Means for Solving the Problems In order to solve the above problems, the present inventor has conducted diligent research on the correlation between the structure of various resin systems and the viscosity, and as a result, has found that the conventional film-forming method has a high molecular weight. The present invention has been accomplished by finding a curable liquid resin that is within a viscosity range capable of forming a film by a method and that can be cured at a high speed by a conventional curing method.

That is, the present invention relates to a curable liquid resin obtained by reacting a (meth) acrylic liquid resin (A) having the following active hydrogen with an isocyanate compound (B) having an unsaturated double bond. (A) The following (meth) acrylic monomer (a-1), the following (meth) acrylic monomer (a-2), and a radical polymerizable monomer (a-3) having active hydrogen in the molecule. ) And a polymerizable vinyl compound (a-4) other than the above, [(a-1) +
(A-2)]: (a-3): (a-4) = 20 to 99.
Polymerized at a ratio of 5: 0.5 to 5: 0 to 79.5 (% by weight) and a number average molecular weight of 8,000 to 200,000.
0 and viscosity of 1 to 10,000 poise (50 ° C)
Is a (meth) acrylic liquid resin. ^{_{CH 2 = C (R 1)}} COO-R 2 (a-1) ( wherein, R ¹ represents a hydrogen atom or CH _3, R ² is 4 carbon atoms
And each represents an alkyl group of 22. ^{_{) CH 2 = C (R 1}} ) COO (C n H 2n O) m R 3 (a-2) ( wherein, R ¹ represents a hydrogen atom or CH _3, R ³ is C 1 -C
~ 5 alkyl group or phenyl group, n is an integer of 1 to 3, m is an integer of 2 to 25, respectively. )

Further, in the present invention, the mixing ratio of the radically polymerizable monomer (a-3) having active hydrogen in the molecule and the isocyanate compound (B) is 1: 0.001 to a molar ratio.
1: 1 curable liquid resin.

Further, in the present invention, the mixing ratio of the (meth) acrylic monomer (a-1) and the (meth) acrylic monomer (a-2) is 0.1: 99.9 by weight. 99.9: 0.1
Which is a curable liquid resin. Further, the present invention relates to a curable liquid resin which is a radiation curable type. Further, the present invention is
The present invention relates to a curable liquid resin that is an electron beam curable type. Further, the present invention relates to a film forming material made of a curable liquid resin.

In the present invention, a (meth) acrylic monomer having an alkyl group represented by the general formula (a-1) or a poly (alkylene) oxy group represented by the general formula (a-2) is bonded. The (meth) acrylic monomer is used to make the (meth) acrylic resin into a liquid state.

Examples of the alkyl group derivative represented by the general formula (a-1) include 2-ethylhexyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, heptyl (meth) acrylate and hexyl (meth). Acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth)
Acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, There are alkyl (meth) acrylates having 4 to 22 carbon atoms such as nonadecyl (meth) acrylate, icosyl (meth) acrylate, henicosyl (meth) acrylate, and docosyl (meth) acrylate, and among others, having an alkyl group having 8 to 20 carbon atoms. Acrylate or the corresponding methacrylate is preferred.
When the carbon number is 3 or less, it is difficult to obtain a liquid resin, and when the carbon number is 23 or more, it is difficult to increase the degree of polymerization, and the viscosity of the liquid resin obtained due to the progress of crystallization is high. It is not preferable because the heating system is required. The film formation in the present invention means that a resin having a thickness of 0.1 to 500 μm is formed on a substrate made of paper, metal, plastic, ceramics or the like by a method such as printing and painting.
It means to form a film.

As the poly (alkylene) oxy group derivative represented by the general formula (a-2), for example, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol ( (Meth) acrylate, methoxytetraethylene glycol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, propoxytetraethylene glycol (meth) acrylate, n-butoxytetraethylene glycol (meth) acrylate, n-pentoxytetraethylene glycol ( (Meth) acrylate, methoxytetrapropylene glycol (meth) acrylate, ethoxytetrapropylene glycol (meth ) Acrylate, propoxy tetrapropylene glycol (meth) acrylate, n- butoxy tetrapropylene glycol (meth) acrylate, n- penta alkoxy tetrapropylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth)
There are acrylate, ethoxy polyethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, phenoxytetrapropylene glycol (meth) acrylate, among others. The viscosity of the copolymer can be effectively reduced by using an acrylate having a polyoxyalkylene chain having 2 to 25, preferably 3 to 22 repeating units or a corresponding methacrylate. In the case of repeating unit 1, it is difficult to obtain a liquid resin, and it is difficult to increase the degree of polymerization at 26 or more, and since it is solid at 50 ° C., a dedicated melting system is required at the time of film formation, which is not preferable. .

In the present invention, the compounding amount of the (meth) acrylic monomer (a-1) or (a-2) is 10 to 98% by weight, preferably 40 to 95% by weight in the monomer composition.
% By weight. The (meth) acrylic monomer (a-1) or (a-2) in the monomer composition is 40% by weight, particularly 10
When the amount is less than the weight%, the obtained (meth) acrylic liquid resin cannot maintain a preferable viscosity. Further, the combined use of (meth) acrylic monomers (a-1) and (a-2) is preferable from the viewpoint of decreasing the viscosity and improving the compatibility with other compositions. In this case, the weight ratio of the (meth) acrylic monomers (a-1) to (a-2) is 0.1: 99.9-9.
It is preferably 9.9: 0.1.

In the present invention, the radical-polymerizable monomer (a-3) having an active hydrogen such as a carboxyl group, a hydroxyl group or an amide group in the molecule is the isocyanate group of an isocyanic acid ester having an unsaturated double bond. It is used to introduce an unsaturated double bond into the side chain by reacting. In the present invention, the radically polymerizable monomer having a carboxyl group in the molecule, for example, maleic acid,
Fumaric acid, itaconic acid, citraconic acid, or alkyl or alkenyl monoesters thereof, phthalic acid β- (meth) acryloxyethyl monoester, isophthalic acid β- (meth) acryloxyethyl monoester,
Carboxyl group-containing vinyl monomers such as terephthalic acid β- (meth) acryloxyethyl monoester, succinic acid β- (meth) acryloxyethyl monoester, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid,

2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4
Hydroxy group-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) acrylamides 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-propoxymethylmethacrylamide, 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-
Examples thereof include amide group-containing vinyl monomers such as dialkylol (meth) acrylamide such as methoxymethyl-N- (pentoxymethyl) methacrylamide, and a plurality of them can be used from these groups. The amount of the radically polymerizable monomer having a functional group used in the present invention is 0.5 to 50% by weight, preferably,
It is 1 to 20% by weight. If the amount is less than this, the amount of the curing site to be introduced is reduced, and sufficient curability cannot be obtained, which is not preferable.

In the present invention, other polymerizable vinyl monomer (a-4) can be used for improving the water resistance and hardness of the coating film after curing as long as the liquid state and low viscosity of the resin can be maintained. Specifically, there are alkoxy groups such as methoxydiethylene glycol (meth) acrylate and phenoxydiethylene glycol (meth) acrylate, (meth) acrylate-based monomers containing a phenoxy group, and aromatic monomers such as styrene and vinyltoluene. You may use two or more from the group. The amount of the other polymerizable vinyl monomer (a-4) used is 0 to 79.5% by weight, preferably 1 to 7% by weight based on the liquid resin which is a copolymer.
It is 40% by weight, and if it exceeds 40% by weight, particularly 79.5% by weight, the viscosity of the liquid resin becomes high, which is not preferable.

When the curable resin composition obtained by the present invention is cured by electron beam irradiation, R ¹ represented by the general formulas (a-1) and (a-2) is preferably hydrogen. Further, other vinyl compounds are preferably those which do not have quaternary carbon in the main chain when they are copolymerized such as acrylic monomers and styrene.

The (meth) acrylic liquid resin of the present invention is
The number average molecular weight is 8,000 to 200,000, preferably 10,000 to 100,000. If the number average molecular weight is smaller than the above value, it is difficult to isolate the resin component from the polymerization solution, mechanical properties such as flexibility are deteriorated, and solvent resistance, boiling water resistance, and other coating film physical properties are It is not preferable because it decreases, and when the value is larger than the above value, the resin cannot maintain a viscosity capable of forming a film, which is not preferable.

In the present invention, the isocyanate ester (B) is an isocyanate ester compound having one isocyanate group and one or more unsaturated double bonds in the molecule, and has an unsaturated diester in the side chain of the liquid resin. Used to introduce heavy bonds. Examples of such an isocyanate compound (B) include methacryloyloxyethyl isocyanate, vinyl isocyanate, allyl isocyanate, (meth) acryloyl isocyanate and the like. Further, 1,6-diisocyanatohexane, isophorone diisocyanate, 4,4′-diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, xylylene diisocyanate, tolylene 2,4-diisocyanate, toluene diisocyanate, 2,4-diisocyanate Toluene, hexamethylene diisocyanate, 4-methyl-m-phenylene diisocyanate, naphthylene diisocyanate, paraphenylene diisocyanate, tetramethyl xylylene diisocyanate, cyclohexyl methane diisocyanate, hydrogenated xylylene diisocyanate, cyclohexyl diisocyanate, tolidine diisocyanate, 2,2 , 4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate Compounds such as diisocyanate ester compounds such as nate, m-tetramethylxylylene diisocyanate, p-tetramethylxylylene diisocyanate, and dimer acid diisocyanate, and the above hydroxyl group, carboxyl group, and amide group-containing vinyl monomer in equimolar amounts. Isocyanate compound (C)
Can be used as The amount of the isocyanate ester (B) used is such that the molar ratio of the radical polymerizable monomer (a-3) having active hydrogen, which is a copolymerization component of the liquid resin, and the isocyanate ester (B) is 1: 0.001 to 1: 1. 1: 1,
It is preferably 1: 0.01 to 1.

The acrylic liquid resin (A) of the present invention is prepared by radical polymerization by dissolving a mixture of the above monomers in a solvent in the presence of a radical polymerization initiator, or by dropping the mixture of the monomers. It can be manufactured. Examples of the radical polymerization initiator include benzoyl peroxide, t-butyl peroxide, cumene hydroperoxide, lauroyl peroxide, and organic peroxides (Taiseisha, "Crosslinking Agent Handbook", p520 to 535, second edition). 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 solvent used is 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 you.

For the curable resin of the present invention, after synthesis of the acrylic liquid resin (A), without removing solvent, the isocyanate compound (B) is added to the solvent as it is, or the solvent is removed once. It can be produced by reacting with an isocyanate compound (B) in a low molecular weight curable monomer.

In the present invention, in order to prevent gelation during the synthesis of the acrylic liquid resin, generally used radical polymerization inhibitors such as hydroquinone, monomethoxyhydroquinone and P-tert-butylphenol can be used. If the amount of the radical polymerization inhibitor added is too large, the reactivity at the time of curing reaction of the curable liquid resin is deteriorated, which is not preferable. Gelation can also be prevented by blowing air into the reaction vessel or increasing the oxygen concentration in the reaction atmosphere.

For the purpose of promoting the reaction of the acrylic acid liquid resin (A) with the isocyanate compound (B),
A known catalyst such as a tin compound, for example, tin 2-ethylhexanoate, dibutyltin dilaurate, or the like can be used.
The amount of such a catalyst to be compounded is 0 to 1 mol%, preferably 0.01 to 10% by mol based on the isocyanate compound (B).
It is 0.5 mol%. The reaction proceeds even if these catalysts are not used, but it is effective in shortening the reaction time.

In the present invention, the solvent used in the synthesis is removed by a method such as precipitation purification and distillation after the synthesis to obtain a liquid resin, or after mixing with a low molecular weight curable monomer, only the solvent is distilled off. Resin composition. The obtained resin is a liquid having a viscosity at 50 ° C. of 1 to 10,000 poise, preferably 5 to 5000 poise.

In the present invention, a curing agent resin such as an amino resin or a phenol resin may be added in order to enhance the curing characteristics of the coating film of the curable liquid resin. Further, in order to improve the coating performance, general-purpose polymers such as known polyamide resins, cellulose derivatives, vinyl resins, polyolefins, natural rubber derivatives, acrylic resins, epoxy resins, polyesters and polystyrenes, alkyd resins, rosin-modified alkyd resins, flaxseed. Unsaturated modified alkyd resins such as oil-modified alkyd resins, drying oils 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. If necessary, a monomer, a small amount of a low molecular weight compound, a compatibilizer, a surfactant or a lubricant may be added.

To the curable liquid resin obtained by the present invention, a dye, carbon black, titanium white, phthalocyanine, azo dye, a colorant composed of a pigment such as quinacridone, Si type fine particles, an inorganic filler such as mica, etc. are added in an appropriate amount. As a result, it can be used as various printing inks, colored paints and the like. Further, in the case of curing by irradiation with radiation, known photopolymerization sensitizers and initiators can be added.

The composition for a film-forming material using the liquid resin of the present invention is a base material such as various steel plates, metal plates such as aluminum plates, plastic films, papers, plastic film laminated papers, roll coaters, knife coaters, etc. By a conventional method such as a coating method or a printing method such as offset printing, gravure printing, letterpress printing, silk screen printing, a film having a film thickness of 0.1 to 500 μm can be formed,
It can be cured by heating or irradiation with radiation such as electron beam, ultraviolet ray, visible ray, and infrared ray.

In the case of 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
It is in the range of 0 Mrad. If it is less than this range, it is difficult to obtain a sufficiently cured product, and if it is more than this range, the coating film or the base material is greatly damaged, which is not preferable.

[0028]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention thereto. W in the example
The term "t%" means "% by weight".

◎ Methods for measuring the number average molecular weight and the viscosity in this example are shown below. 1) Number average molecular weight: The styrene conversion value in gel permeation chromatography (Tosoh SC-8020) was adopted. Further, as the molecular weight distribution (Mw / Mn), the value obtained by the same measuring device was adopted. 2) Viscosity: Rheometer (RDS-made by Rheometrics Inc.)
II, RFS-II) The value of shear rate 1 / sec by the steady-state viscosity measurement method was adopted. ◎ The electron beam irradiation equipment and irradiation conditions are shown below. 1) Area beam type electron beam irradiation equipment Curetron EBC-200
-20-30 (NISSIN 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.

The abbreviations of the following compounds used in Examples and Comparative Examples are shown below. 1) Compound used in the synthesis of acrylic liquid resin LA: lauryl acrylate EHA: 2-ethylhexyl acrylate AM-90G: methoxypoly (n = 9) ethylene glycol monoacrylate AM-20G: methoxydiethylene glycol monoacrylate AA: acrylic acid 4HBA: 4 hydroxybutyl acrylate HEA: 2 hydroxyethyl acrylate 2) Compound used for the synthesis of introducing a cure site MOI: methacryloyloxyethyl isocyanate TDI: tolylene diisocyanate

Synthesis of (meth) acrylic liquid resin (A) and measurement of physical properties (Examples 1 to 5 and 7 to 12) 500 ml four-necked circle equipped with a stirrer, nitrogen introducing tube, temperature sensor, and condenser. A bottom flask was blended with the compound having the composition shown in Table 1, and azobisisobutyronitrile (AIBN) was used as an initiator (1% by weight based on the total charged amount of the monomer) in an ethyl acetate solvent (at the time of charging the monomer). (Concentration: 33% by weight), the mixture was refluxed for 6 hours in a water bath set at 85 ° C, the temperature was lowered to 70 ° C, and hydroquinone (MOI ratio 0.1% by weight) was added. Table 1 shows the measurement results of the number average molecular weight (Mn), the molecular weight distribution (Mw / Mn), and the viscosity (50 ° C.) of the obtained resin. The MOI and the catalyst were added thereto, and the mixture was stirred for 3 hours. After completion of the reaction, the solvent was completely distilled off by depressurizing to obtain a viscous liquid resin. Table 2 shows the measurement results of the viscosity (50 ° C.) of the obtained resin. (Examples 6 and 13) A compound of the composition shown in Table 1 was added to a 500 ml four-necked round bottom flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a condenser, and azobisisobutyronitrile was added. Using (AIBN) as an initiator (1% by weight based on the total amount of charged monomers) in an ethyl acetate solvent (concentration at the time of charged monomers: 33% by weight),
After refluxing for 6 hours in a water bath set at 85 ° C., the temperature was lowered to 70 ° C. and hydroquinone (isocyanate compound ratio 0.1% by weight) was added. Table 1 shows the measurement results of the number average molecular weight (Mn), the molecular weight distribution (Mw / Mn), and the viscosity (50 ° C.) of the obtained resin. Next, in a 500 ml four-necked round bottom flask equipped with a stirrer, a nitrogen introducing tube, a temperature sensor, and a condenser, diisocyanate and ethyl acetate as a solvent were put and stirred,
A hydroxyl group-containing (meth) acrylate in an equimolar amount with diisocyanate and a catalyst were added, and the mixture was stirred at 70 ° C. for 3 hours. This solution was added to the above liquid resin solution at the ratio shown in Table 2, a catalyst was added, and the mixture was stirred at 70 ° C. for 3 hours. After the reaction,
The solvent was completely distilled off by reducing the pressure to obtain a viscous liquid resin. Table 2 shows the measurement results of the viscosity (50 ° C.) of the obtained resin.

[0032] Table 1 Composition and physical property measurement results of liquid resin having hydroxyl group in side chain   ───────────────────────────────────                                       Mn viscosity   Example composition (weight ratio) (): Mw / Mn (50 ° C)                                                     [P]   ───────────────────────────────────       1 EHA: 4HBA = 60: 40 1.48E4 (3.5) 589       2 LA: 4HBA = 80: 20 1.54E4 (2.2) 78       3 EHA: AM90G: 4HBA = 57: 38: 5 1.43E4 (2.8) 30       4 EHA: AM90G: 4HBA = 50: 25: 25 1.61E4 (3.4) 85       5 LA: AM20G: HEA = 60: 35: 5 1.53E4 (3.2) 162       6 EHA: 4HBA = 80: 20 1.51E4 (2.8) 270   ───────────────────────────────────

[0033] Table 2 Composition and physical property measurement results of curable liquid resin   ───────────────────────────────────                                                 viscosity     Example composition (weight ratio) (50 ° C)                                                [P (House)]   ───────────────────────────────────       7 Example 1: MOI = 100: 20 1315       8 Example 1: MOI = 100: 40 2532       9 Example 2: MOI = 100: 20 326      10 Example 3: MOI = 100: 5 104      11 Example 4: MOI = 100: 25 372      12 Example 5: MOI = 100: 5 477      13 Example 6: (TDI: 4HBA = 1: 1) = 100: 20 4573   ───────────────────────────────────

(Examples 14 to 22) The curable liquid resins (A) obtained in Examples 7 to 13 were coated on a PET film with an applicator of 0.5 mil, and electron beams were applied under various conditions. Irradiated. Table 3 shows the gel fraction of the coating film obtained by electron beam irradiation (determined by the THF extraction rate of the cured product).

[0035]   Table 3 Electron beam curing characteristics of curable liquid resin   ───────────────────────────────────                 Curable resin Irradiation gel fraction Example ────────────── (Dose)                 (Example No.) [Mrad] [%]   ───────────────────────────────────   14 Example 7 2 91   15 Example 7 4 93   16 Example 7 8 96   17 Example 8 2 96   18 Example 9 2 90   19 Example 10 2 75   20 Example 11 2 86   21 Example 12 2 81   22 Example 13 2 93   ───────────────────────────────────

EFFECTS OF THE INVENTION According to the present invention, a special exhaust gas treatment facility is provided because it does not contaminate the working environment of the coating process with low molecular weight compounds that scatter and does not release low molecular weight compounds such as organic solvents and monomers into the atmosphere. No need, and coating methods such as roll coaters and knife coaters that have been used conventionally, offset printing, gravure printing, can be formed into a film by a printing method such as letterpress printing, still conventional heating and drying, electron beam, ultraviolet rays, A curable liquid resin composition that can be cured by irradiation with radiation such as visible light and infrared rays can be provided.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A 61-64772 (JP, A) JP-A 8-198918 (JP, A) JP-A 9-194548 (JP, A) JP-A 63- 37114 (JP, A) JP-B Sho-49-26061 (JP, B1) JP-A-11-511201 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 8/00-8 / 50

Claims (6)

(57) [Claims] 1. A curable liquid resin obtained by reacting the following (meth) acrylic liquid resin (A) having active hydrogen with an isocyanate compound (B) having an unsaturated double bond. (A) The following (meth) acrylic monomer (a-1), the following (meth) acrylic monomer (a-2), and a radical polymerizable monomer (a-3) having active hydrogen in the molecule. ) And a polymerizable vinyl compound (a-4) other than the above, [(a-1) +
(A-2)]: (a-3): (a-4) = 20 to 99.
Polymerized at a ratio of 5: 0.5 to 5: 0 to 79.5 (% by weight) and a number average molecular weight of 8,000 to 200,000.
0 and viscosity of 1 to 10,000 poise (50 ° C)
Is a (meth) acrylic liquid resin. ^{_{CH 2 = C (R 1)}} COO-R 2 (a-1) ( wherein, R ¹ represents a hydrogen atom or CH _3, R ² is 4 carbon atoms
And each represents an alkyl group of 22. ^{_{) CH 2 = C (R 1}} ) COO (C n H 2n O) m R 3 (a-2) ( wherein, R ¹ represents a hydrogen atom or CH _3, R ³ is C 1 -C
~ 5 alkyl group or phenyl group, n is an integer of 1 to 3, m is an integer of 2 to 25, respectively. ) 2. Curing in which the molar ratio of the radical polymerizable monomer (a-3) having active hydrogen in the molecule and the isocyanate compound (B) is 1: 0.001 to 1: 1. Liquid resin. 3. A weight ratio of the (meth) acrylic monomer (a-1) to the (meth) acrylic monomer (a-2) is 0.1: 99.9 to 99.9. The curable liquid resin according to claim 1, wherein the curable liquid resin is 0.1. 4. The curable liquid resin according to claim 3, which is a radiation curable resin. 5. The curable liquid resin according to claim 4, which is an electron beam curable type. 6. A film-forming material comprising the curable resin according to claim 1.