JPH1135628A - Hardenable liquid resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject resin that can form membrane and give hardened membrane in no need of solvent by allowing an isocyanic ester bearing an unsaturated double bond to react with a specific (meth)acryl liquid resin. SOLUTION: The objective liquid resin is obtained by allowing (A) an unsaturated double bond-bearing isocyanic ester to react with (B) a (meth)acrylic liquid resin with a number-average molecular weight of 8,000-200,000 and a viscosity of 1-10,000 poise at 50 deg.C prepared by polymerization of (i) a (meth)acryl monomer of formula I (R<1> is H, CH3 ; R<2> is a 4-22C alkyl), (ii) a (meth)acryl monomer of formula II (R<3> is a 1-5C alkyl or phenyl; m is an integer of 2-25), (iii) a radically polymerizable monomer bearing an active hydrogen atom in its molecule and (iv) a polymerizable vinyl compound other than the components (i)-(iii) in a proportion (in wt.%) of (the component (i) + the component (ii))/the component (iii)/the component (iv)=(20-99.5)/(0.5-50)/(0-79.5).

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 cured film without using a solvent as a resin for a film-forming material such as paints and inks and for an adhesive. Further, the liquid resin obtained by the present invention can also be used as a compatibilizer, an interface modifier, and a pigment dispersant. Further, 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 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. One of the methods is to use powder and hot melt materials. However, it is very different from the conventional film forming and drying systems, so that it is necessary to introduce new equipment. In order to solve the above-mentioned problems, a solution-based resin has been made into a high solid, an aqueous resin has been improved, and the like, and it is considered that the use amount of the organic solvent will further decrease in the future due to such efforts. However, as a fundamental solution, there is a strong demand for the development of a solventless liquid resin which is free from problems of pollution, safety and health, ignition, explosion, etc., can be widely applied, and is easy to form and cure. Various radiation-curable resin compositions can be said to be quite promising as quick-drying, one-pack, non-solvent resins, but in conventional systems, the viscosity of the compositions was controlled by a large amount of low molecular weight components. Therefore, even after curing, it is environmentally unfavorable due to problems such as residual monomer odor. In addition, volume shrinkage during curing is large, and the cured coating film becomes brittle and adhesion to a substrate has been a problem. In order to improve the curing shrinkage rate, various measures were taken, such as using a monomer component having a relatively high molecular weight or adding a small amount of a high molecular weight component. In order to control the product within an appropriate viscosity range, the amount that can be added is limited, and these problems have narrowed the range of use of the radiation-curable resin composition.
The solventless resin composition is disclosed in JP-A-57-171. 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, 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 (Souichi Muroi, "Abstracts of the 1992 Adhesion and Coating Seminar", 4 pages, 1993). It is desired to increase the molecular weight of the polymer.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a curable resin having a high molecular weight and a liquid state, so that the compounding ratio of a low molecular weight compound having problems in safety and physical properties can be reduced or eliminated. This contributes to the improvement of the working environment. Another object of the present invention is to provide a curable liquid resin having improved volume shrinkage during curing and improved adhesion to metal and plastic films.

[0004]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted intensive studies on the correlation between the structure of various resin systems and the viscosity, and the like. The inventors have found a curable liquid resin which is within a viscosity range that can form a film by the method and 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), a radical polymerizable monomer having active hydrogen in the molecule (a-3) ) And a polymerizable vinyl compound (a-4) other than those described above with [(a-1) +
(A-2)]: (a-3): (a-4) = 20-99.
5: 0.5 to 50: 0 to 79.5 (% by weight), and has a number average molecular weight of 8,000 to 200,000.
0 and viscosity of 1 to 10,000 poise (50 ° C)
(Meth) acrylic liquid resin. CH ₂ ＣC (R ¹ ) COO—R ² (a-1) (wherein, R ¹ is a hydrogen atom or CH ₃ , and R ² is C 4
To 22 alkyl groups. ) CH ₂ ＣC (R ¹ ) COO (C _n H _2n O) _m R ³ (a-2) (wherein, R ¹ is a hydrogen atom or CH ₃ , and R ³ is carbon atom 1)
To 5 alkyl groups or phenyl groups, n represents an integer of 1 to 3, and m represents an integer of 2 to 25, respectively. )

Further, in the present invention, the compounding 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.
It relates to a curable liquid resin that is 1: 1.

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

Examples of the alkyl group derivative represented by the general formula (a-1) include 2-ethylhexyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, heptyl (meth) acrylate, and hexyl (meth). Acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth)
Acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, There are alkyl (meth) acrylates having 4 to 22 carbon atoms such as nonadecyl (meth) acrylate, icosyl (meth) acrylate, henycosyl (meth) acrylate, docosyl (meth) acrylate, and among others, having an alkyl group having 8 to 20 carbon atoms. Acrylates or the 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. The film formation in the present invention is a method of printing and painting, on a substrate made of paper, metal, plastic, ceramics, etc., a resin having a thickness of 0.1 to 500 μm.
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-pentaxytetraethylene 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)
Acrylate, ethoxy polyethylene glycol (meth) acrylate or phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, phenoxytetrapropylene glycol (meth) acrylate, among others By using an acrylate having a polyoxyalkylene chain as a repeating unit of 2 to 25, preferably 3 to 22, or a corresponding methacrylate, the viscosity of the copolymer can be effectively reduced. In the case of the repeating unit 1, it is difficult to obtain a liquid resin, and when it is 26 or more, it is difficult to increase the degree of polymerization, and since it is a solid at 50 ° C., a dedicated melting system is required during film formation, which is not preferable. .

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

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 an isocyanate group of an isocyanate 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, as the radical polymerizable monomer having a carboxyl group in the molecule, for example, maleic acid,
Fumaric acid, itaconic acid, citraconic acid, or their alkyl or alkenyl monoesters, phthalic acid β- (meth) acryloxyethyl monoester, isophthalic acid β- (meth) acryloxyethyl monoester,
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 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-
Examples include amide group-containing vinyl monomers such as dialkylol (meth) acrylamide such as methoxymethyl-N- (pentoxymethyl) methacrylamide, and a plurality of these monomers can be used from these groups. The amount of the radical polymerizable monomer having a functional group used in the present invention is 0.5 to 50% by weight, preferably,
1 to 20% by weight. If the amount is less than this, the number of hardened sites to be introduced decreases, and sufficient hardenability cannot be obtained, which is not preferable.

In the present invention, other polymerizable vinyl monomers (a-4) can be used in order to improve the water resistance and hardness of the cured coating film as long as the liquid state and low viscosity of the resin can be maintained. Specific examples include alkoxy groups such as methoxydiethylene glycol (meth) acrylate and phenoxydiethylene glycol (meth) acrylate, (meth) acrylate monomers containing a phenoxy group, and aromatic monomers such as styrene and vinyltoluene. May be used plurally. The amount of the other polymerizable vinyl monomer (a-4) used is from 0 to 79.5% by weight, preferably from 1 to 79.5% by weight, based on the liquid resin as the copolymer.
If it is 40% by weight, especially more than 79.5% by weight, the viscosity of the liquid resin increases, which is not preferable.

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

The (meth) acrylic liquid resin of the present invention comprises:
The number average molecular weight is from 8,000 to 200,000, preferably from 10,000 to 100,000. When the number average molecular weight is smaller than the above value, it is difficult to isolate the resin component from the polymerization solution, and the mechanical properties such as flexibility are reduced, or the coating film properties such as solvent resistance and boiling water resistance are reduced. It is not preferable because it is lowered, and if it is larger than the above value, it is not preferable because the viscosity of the resin cannot be maintained.

In the present invention, the isocyanate (B) is an isocyanate compound having one isocyanate group and one or more unsaturated double bonds in the molecule, and the unsaturated diisocyanate is present on the side chain of the liquid resin. Used to introduce heavy bonds. Examples of the isocyanate compound (B) include methacryloyloxyethyl isocyanate, vinyl isocyanate, allyl isocyanate, and (meth) acryloyl isocyanate. Also, 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 2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate Also, a compound obtained by reacting a diisocyanate compound such as a methacrylate, m-tetramethylxylylene diisocyanate, p-tetramethyl xylylene diisocyanate, dimer acid diisocyanate, and the above hydroxyl group, carboxyl group, and amide group-containing vinyl monomer in an equimolar amount. 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 copolymer component of the liquid resin, to the isocyanate ester (B) is 1: 0.001 to 1: 1. 1: 1,
Preferably it is 1: 0.01-1.

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 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.

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.

The curable resin of the present invention may be prepared by adding the isocyanate compound (B) directly to the solvent after the synthesis of the above-mentioned acrylic liquid resin (A) without removing the solvent, or removing the solvent once. Then, it can be produced by reacting with an isocyanate compound (B) in a low molecular weight curable monomer.

In the present invention, generally used radical polymerization inhibitors such as hydroquinone, monomethoxyhydroquinone, and P-tert-butylphenol can be used to prevent gelation during the synthesis of the acrylic liquid resin. If the amount of the radical polymerization inhibitor is too large, the reactivity of the curable liquid resin at the time of curing reaction is undesirably deteriorated. Gelation can also be prevented by blowing air into the reaction vessel or increasing the oxygen concentration in the reaction atmosphere.

In order to promote the reaction of the isocyanate compound (B) with the acrylic liquid resin (A),
Known catalysts such as tin compounds, for example, tin 2-ethylhexanoate, dibutyltin dilaurate and the like can be used.
The amount of such a catalyst is from 0 to 1 mol%, preferably from 0.01 to 1 mol%, based on the isocyanate compound (B).
0.5 mol%. Although the reaction proceeds without using these catalysts, it is effective in shortening the reaction time.

In the present invention, the solvent used in the synthesis may be removed by a method such as precipitation purification or distillation after the synthesis to obtain a liquid resin, or after mixing with a low molecular weight curable monomer, only the solvent may be distilled off. And a 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 blended in order to enhance the curing characteristics of the coating of the curable liquid resin. 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. If necessary, a monomer, a small amount of a low-molecular compound, a compatibilizer, a surfactant or a lubricant may be added.

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

The composition for a film-forming material using the liquid resin of the present invention can be applied to a base material such as various steel plates, metal plates such as aluminum plates, plastic films, papers, plastic film laminated papers and the like by using a roll coater, a 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 to 1000 keV, more preferably 3
An electron beam irradiation device having an energy in the range of 0 to 300 keV is used. The irradiation dose (DOSE) is preferably 0.1 to 100 Mrad, more preferably 0.5 to 2 Mrad.
The range is 0 Mrad. If the amount is less than this, it is difficult to obtain a sufficiently cured product, and if it is more than this, damage to a coating film or a substrate is large, which is not preferable.

[0028]

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) The value of the shear rate 1 / sec according to the steady viscosity measurement method was adopted. ◎ The electron beam irradiation apparatus and irradiation conditions are shown below. 1) Area beam electron beam irradiation system Curetron EBC-200
-20-30 (Nisshin High Voltage) Electron beam acceleration: 200 keV DOSE was adjusted by the amount of current in the range of 0.5 to 8 Mrad. 2) MIN-EB (manufactured by AIT) Electron beam acceleration: 60 keV DOSE was adjusted at a belt conveyor speed in the range of 0.5 to 8 Mrad.

◎ Abbreviations of the following compounds used in Examples and Comparative Examples are described. 1) Compound used for the synthesis of acrylic liquid resin LA: lauryl acrylate EHA: 2-ethylhexyl acrylate AM-90G: methoxy poly (n = 9) ethylene glycol monoacrylate AM-20G: methoxy diethylene glycol monoacrylate AA: acrylic acid 4HBA: 4-hydroxybutyl acrylate HEA: 2-hydroxyethyl acrylate 2) Compound used for synthesis of curing site introduction MOI: methacryloyloxyethyl isocyanate TDI: tolylene diisocyanate

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

Table 1 Composition and Measurement of Physical Properties of Liquid Resin Having Hydroxyl Group in Side Chain ─── Mn viscosity Example composition (weight ratio) (): Mw / Mn (50 ゜ C) ───────────── 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 ──────────────────────────────────

Table 2 Composition of Curable Liquid Resin and Measurement Results of Physical Properties 粘度 Viscosity Example Composition (weight ratio) (50 ° C) [P (Voices)] ──── 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 resin (A) obtained in Examples 7 to 13 was applied on a PET film with a 0.5 mil applicator, and an electron beam was irradiated under various conditions. Irradiated. Table 3 shows the gel fraction (determined by the THF extraction rate of the cured product) of the coating film obtained by electron beam irradiation.

Table 3 Electron Beam Curing Properties of Curable Liquid Resin 硬化 Curability Resin irradiation dose 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 ───────────────────────── ─────────

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 (6)

[Claims] 1. 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), a radical polymerizable monomer having active hydrogen in the molecule (a-3) ) And a polymerizable vinyl compound (a-4) other than those described above with [(a-1) +
(A-2)]: (a-3): (a-4) = 20-99.
5: 0.5 to 50: 0 to 79.5 (% by weight), and has a number average molecular weight of 8,000 to 200,000.
0 and viscosity of 1 to 10,000 poise (50 ° C)
(Meth) acrylic liquid resin. CH ₂ ＣC (R ¹ ) COO—R ² (a-1) (wherein, R ¹ is a hydrogen atom or CH ₃ , and R ² is C 4
To 22 alkyl groups. ) CH ₂ ＣC (R ¹ ) COO (C _n H _2n O) _m R ³ (a-2) (wherein, R ¹ is a hydrogen atom or CH ₃ , and R ³ is carbon atom 1)
To 5 alkyl groups or phenyl groups, n represents an integer of 1 to 3, and m represents an integer of 2 to 25, respectively. ) 2. Curing wherein the molar ratio of the radical polymerizable monomer (a-3) having an active hydrogen in the molecule to the isocyanate compound (B) is 1: 0.001 to 1: 1. Liquid resin. 3. The compounding ratio of the (meth) acrylic monomer (a-1) to the (meth) acrylic monomer (a-2) is 0.1: 99.9 to 99.9 by weight. : The curable liquid resin according to claim 1, wherein the ratio is 0.1. 4. The curable liquid resin according to claim 3, which is of a radiation curing type. 5. The curable liquid resin according to claim 4, which is of an electron beam curing type. 6. A film-forming material comprising the curable resin according to claim 1.