JPH0834826A - Curable liquid resin, production and use thereof - Google Patents

Abstract

PURPOSE:To provide a solventless liquid resin composition for a coating material not suffering from escape of solvent even when applied by a conventional coating method or dried by heating. CONSTITUTION:This curable liquid resin is one comprising 10-90wt.% monomer represented by formula (1): CH2=C(R<1>)COO-R<2> (wherein R<1> is hydrogen or CH3; and R<2> is a 4-22C alkyl) or formula (2): CH2=C(R<3>)COO(CnH2nO)mR<4> (wherein R<3> is hydrogen or CH3; R<4> is a 1-5C alkyl; n is an integer of 1-3; and m is an integer of 4-25), 5-90wt.% macromonomer prepared by reacting an ethylenically unsaturated epoxide with a fatty acid represented by the formula: R<5>COOH (wherein R<5> is a 3-30C unsaturated aliphatic hydrocarbon group having at least one double bond) and 0-40wt.% another polymerizable vinyl compound, and having a number-average molecular weight of 10000-200000 and a viscosity of 500-30000cps (at 50 deg.C).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid resin capable of forming a film and forming a cured film without using a solvent as a resin for a film forming material such as paint or ink, or an adhesive, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, resin systems containing organic solvents have been used for paints, adhesives, inks and the like. It is known that these resin systems scatter a large amount of organic solvent in coating, film forming processes such as printing processes, and curing and drying processes. With increasing interest in the global environment and the working environment, restrictions on the use of organic solvents have come to be imposed. For this reason, various countermeasures have been taken regarding the solvent-free use of the resin for the film-forming material.

The resin system used for solvent-free is roughly classified into a precursor system and a polymer system. Since the precursor system uses a low molecular weight monomer or prepolymer, it is a liquid having a low viscosity, and the conventional film forming method can be used as it is. However, in the precursor system containing a low molecular weight substance in the composition, further improvement in safety and hygiene such as scattering of low molecular weight substance is desired. In terms of physical properties, it is known that it is difficult to control the properties of cured products in the case of coatings composed of resins in the oligomer domain (Soichi Muroi, "1992 Adhesion and Painting Study Group Lectures") , P4, 1993), and an increase in molecular weight while maintaining low viscosity is desired. On the other hand, in the polymer system, it is necessary to liquefy the solid polymer by some method or change the film forming method. As a typical conventional method of liquefying without using an organic solvent, it has been pointed out that a plastisol system which is liquefied by a non-volatile plasticizer is difficult to obtain a hard cured product and the plasticizer migrates. Further, in latex systems such as emulsions and hydrosols, problems such as non-uniformity of cured products and slow drying speed have been pointed out. Even the water-soluble resin system, which is considered to be the most effective at the present time, has problems such as slow drying speed, water resistance, and wastewater treatment method. Most water-soluble resin systems contain 10% or more of an organic solvent in order to improve pigment dispersibility and film-forming property. Further, in the case of powder or hot melt resin system, since it is greatly different from the equipment by the conventional film forming method, it is necessary to introduce new equipment.

[0004]

DISCLOSURE OF THE INVENTION The present invention does not contaminate the working environment of the coating process with the organic solvent that scatters and does not discharge the organic solvent into the atmosphere, and thus does not require special exhaust gas treatment equipment. Further, a film forming method which has been conventionally used, for example, a film can be formed by a roll coater or a knife coater, and also provides a paint which does not dissipate the solvent even if it is subjected to conventional heat drying or air oxidation at room temperature. Is.

As a result of intensive studies on various resin systems for solving the above-mentioned problems, the present inventor has found that a film-forming method having a high molecular weight can be formed by a conventionally used film-forming method, for example, a roll coater or a knife coater. Furthermore, the inventors have found a composition for forming a solventless coating, which can be cured by conventional heat drying or air oxidation without using a curing agent, and arrived at the present invention.

[0006]

The present invention provides (A) monomers 10 to 90 represented by the following formula (1) or formula (2).
^{_{Weight% CH 2 = C (R 1}} ) COO-R 2 (1) ( wherein, R ¹ represents a hydrogen atom or CH _3, R ² is 4 carbon
22 represents an alkyl group. ^{_{) CH 2 = C (R 3}} ) COO (C n H 2n O) m R 4 (2) ( wherein, R ³ is a hydrogen atom or CH _3, R ⁴ is 1 to carbon atoms
5, an alkyl group of 5, n is an integer of 1 to 3, and m is an integer of 4 to 25. (B) Epoxide (a) having an ethylenically unsaturated double bond and R ⁵ COOH (in the formula, R ⁵ is an unsaturated aliphatic hydrocarbon group having at least one double bond having 3 to 30 carbon atoms). 5 to 90% by weight of a macromonomer obtained by reacting with a fatty acid (b) represented by), and (C) other polymerizable vinyl compound 0 to 40% by weight, and having a number average molecular weight of 10,000 to 200, 000 and a viscosity of 500 cps to 30,000 cps (5
It is a curable liquid resin that is 0 ° C.). Also, the present invention
A method for producing a curable liquid resin, characterized by radically polymerizing the components (A) to (C) in a water-miscible solvent which may contain water. Furthermore, the present invention is a composition for film-forming material, which is obtained by adding a metal salt dryer to the curable liquid resin.

The monomer (A) represented by the formula (1) or the formula (2) is used as a constituent component for liquefying the copolymer. Examples of the monomer (A) represented by the formula (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)
Carbon number 4 such as acrylate, nonadecyl (meth) acrylate, icosyl (meth) acrylate, henicosyl (meth) acrylate, docosyl (meth) acrylate
~ 22 alkyl (meth) acrylates, and among them, acrylates having an alkyl group with 8 to 20 carbon atoms or the corresponding methacrylates are preferable. When the number of carbon atoms is 3 or less, it is difficult to obtain a liquid resin, and when the number of carbon atoms is 23 or more, it is difficult to increase the degree of polymerization, and at 50 ° C., it is a solid, so a dedicated melting system is required for film formation. Therefore, it is not preferable.

The monomer (A) represented by the formula (2) is, for example, tetraethylene 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, tetrapropylene glycol (meth) acrylate, methoxytetrapropylene glycol (meth) acrylate, ethoxytetrapropylene glycol (meth) acrylate , Propoxytetrapropylene glycol (meth) acrylate,
Examples include n-butoxytetrapropylene glycol (meth) acrylate, n-pentoxytetrapropylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, and ethoxy polyethylene glycol (meth) acrylate. The viscosity of the copolymer can be effectively reduced by using an acrylate having a polyoxyalkylene chain of 4 to 25, preferably 5 to 22 repeating units or a corresponding methacrylate. When the repeating unit is 3 or less, it is difficult to obtain a liquid resin, and when it is 26 or more, the degree of polymerization is hard to increase, and since it is solid at 50 ° C., a dedicated melting system is required at the time of film formation, which is preferable. Absent.

The amount of the monomer (A) used is 10 to 90% by weight, preferably 40 to 90% by weight, based on the liquid resin which is a copolymer.
80% by weight, and when the monomer (A) in the copolymer is less than 40% by weight, particularly less than 10% by weight, the copolymer cannot maintain the low viscosity required for film formation, and conversely 80% by weight. %,
Particularly, if it exceeds 90% by weight, a hard coating film cannot be obtained, which is not preferable. Two or more kinds of (A) may be used. In addition, it is preferable to use the monomer (A) represented by the formula (1) and the monomer (A) represented by the formula (2) in combination because a decrease in viscosity is observed. In this case, the ratio of the monomer (A) represented by the formula (1) and the monomer (A) represented by the formula (2) is preferably 1: 9 to 9: 1.
The film formation in the present invention means forming a resin film having a thickness of 0.1 to 100 μm on a substrate made of paper, metal, plastic, ceramics or the like by a method such as printing and painting. .

The macromonomer (B) of the present invention is obtained by reacting an epoxide (a) having an ethylenically unsaturated double bond with a fatty acid (b), and is mixed with the monomer (A). Having a polymerizable ethylenically unsaturated double bond, the unsaturated double bond derived from the fatty acid (b) incorporated in the side chain of the copolymer has a function of crosslinking by air oxidation to cure the film. It is applied to the polymer. Examples of the epoxide (a) having an ethylenically unsaturated double bond used for producing the macromer (B) include glycidyl (meth) acrylate, glycidyl cinnamate, allyl glycidyl ether, vinylcyclohexene monoepoxide, 1, Three
-Butadiene monoepoxide and the like include epoxides having a (meth) acrylic group, an allyl group, and a vinyl group.

The fatty acid (b) which is the other component of the macromonomer (B) of the present invention is, for example, hexenoic acid,
Heptenoic acid, caproreic acid, undecylenic acid, lauroleic acid, linderic acid, tohsuccinic acid, tzunic acid, myristoleic acid, palmitoleic acid, zomaleic acid, petroselinic acid, petrosecelaidic acid, oleic acid, elaidic acid, vaseric acid, gondoin. Acids, linear monoenoic acids such as erucic acid, brassic acid, and ceracoleic acid, 2-methyl-2-pentenoic acid, 2,5-dimethyl-2-tridecenoic acid, 2-methyl-9-octadecenoic acid, 2-ethyl-
Branched monoenoic acids such as 9-octadecenoic acid, 2,2-dimethyl-11-eicosenoic acid, 2-methyl-2-hexacosenoic acid, sorbic acid, linoleic acid, linoelaidic acid, α-eleostearic acid, β- Di-, tri-, such as eleostearic acid, linolenic acid, linolenic acid, pseudoeleostearic acid, α-parinaric acid, β-parinaric acid, arachidonic acid, and curpanodonic acid.
And tetraenoic acid, stearolic acid, behenolic acid,
There are acetylenic acids such as tarililic acid. Among these fatty acids, fatty acid (b) in which R ⁴ is an unsaturated aliphatic hydrocarbon group having one or more double bonds having 16 to 22 carbon atoms
Is preferred, and fatty acid (b) in which R ⁵ is an unsaturated aliphatic hydrocarbon group having two or more double bonds having 16 to 22 carbon atoms is more preferred. Among the above fatty acids, linoleic acid, linolenic acid and α-eleostearic acid are preferable.

In addition to the fatty acid (b), butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecyl acid, palmitic acid, heptadecyl acid. An appropriate amount of saturated fatty acid such as acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, heptacosanoic acid, montanic acid, and melissic acid may be added.

As the fatty acid (b) of the present invention, fatty acids constituting fats and oils can be used, and linseed oil, safflower oil, soybean oil, tung oil, rapeseed oil, cottonseed oil, olive oil, palm oil, coconut oil and other vegetable oils, Fatty acids forming animal oils such as beef tallow, lard, sheep fat, fish oil and whale oil are suitable as the fatty acid (b). Among these, linseed oil, safflower oil,
Fatty acids that make up soybean oil and tung oil are preferable for developing curability. However, the iodine value of these fatty acids is 1
It is at least 00, preferably at least 130.

The macromonomer (B) of the present invention can be obtained by reacting 1 mol of the fatty acid (b) with 1 mol of the epoxide (a) having an ethylenically unsaturated double bond. However, in the reaction for synthesizing the macromonomer (B), a reaction mixture obtained by reacting 1 mol of the epoxy group of the epoxide (a) with 0.5 to 2.0 mol of the carboxyl group of the (b) was used. May be.

The reaction for synthesizing the macromonomer (B) is
It is preferable to synthesize using a catalyst under heating. Although it can be synthesized without a catalyst, since the epoxide (a) has an ethylenically unsaturated double bond, in order to synthesize without a catalyst, they are reacted at a temperature at which radical polymerization does not occur, preferably at 130 ° C or lower. Let The catalyst is triethylamine, dimethylaminobenzylamine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl)
Tertiary amines such as phenol, tetramethylguanidine, dimethylaminomethylphenol, N, N-dimethylcyclohexylamine, N, N ′, N ″ -tris (dimethylaminopropyl) hexahydro-S-triazine, trimethylbenzylammonium chloride , Triethylbenzylammonium chloride, tetramethylammonium chloride, trioctylmethylammonium chloride, tributylbenzylammonium chloride, N
-Laurylpyridinium chloride, N-laurylpicolinium chloride, N-benzylpicolinium chloride,
Cetyltrimethylammonium chloride, phenyltrimethylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide,
Tetrabutylammonium bromide, triethylbenzylammonium bromide, trimethylphenylammonium bromide, tetrabutylammonium hydrogen sulfate, trimethylbenzylammonium oxalate, trimethylbenzylammonium oxalate, di (trimethylbenzylammonium) oxalate, trimethylbenzylammonium maleate,
Quaternary ammonium salts such as trimethylbenzyl ammonium tartrate and trimethylbenzyl ammonium glycolate are preferred.

In this reaction, as a polymerization inhibitor, hydroquinone, hydroquinone monomethyl ether, p-
Phenols such as t-butylcatechol, 2,5-di-t-butylhydroquinone, t-butylhydroquinone, 2,5-diamylhydroquinone and di-t-butylparacresol, p-benzoquinone, naphthoquinone, 2,5 It is also possible to use quinones such as -diphenyl-p-benzoquinone, oximes such as quinone dioxime and cyclohexanooxime, amidines such as acetamidine acetate, quaternary ammonium salts, hydrazine salts and amine hydrochlorides.

The amount of the macromonomer (B) used in the present invention is 5 to 90% by weight based on the liquid resin which is a copolymer.
It is preferably from 10 to 60% by weight, and when the component (B) in the copolymer is less than 10% by weight, particularly 5% by weight, it becomes difficult to obtain a hard coating film, and conversely 60% by weight, particularly 90% by weight. When the content is more than the weight%, the viscosity of the liquid resin becomes high and coating becomes difficult, which is not preferable.

The polymerizable vinyl compound (C) of the present invention is used for improving the water resistance and hardness of the coating film after curing, as long as the liquid state of the resin can be maintained. Specifically, aromatic monomers such as styrene and vinyltoluene, (meth) acrylate having an alkyl group having 3 or less carbon atoms such as methyl methacrylate and ethyl methacrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( Alkoxy such as (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, dipropylene glycol monomethacrylate, polyethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate Group or a monomer containing a hydroxyl group, maleic acid, fumaric acid, itaconic acid, citraconic acid, or their alkyl or alkenyl monoesters, phthalic acid β- ( Data) acryloxyethyl monoester, isophthalic acid beta-(meth) acryloxyethyl monoester, terephthalic acid β
-(Meth) acryloxyethyl monoester, succinic acid β- (meth) acryloxyethyl monoester, carboxylic acid-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, etc. You may use two or more. The amount of the polymerizable vinyl compound used is 0 to 40% by weight, preferably 0, based on the liquid resin which is a copolymer.
It is up to 30% by weight, and if it exceeds 30% by weight, especially 40% by weight, the viscosity of the liquid resin becomes high and coating becomes difficult.

The liquid resin of the present invention has a number average molecular weight of the copolymer of 10,000 to 200,000, preferably 1
It is 5,000 to 150,000. 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 lowers, and when it is larger than the above value, the resin cannot maintain a coatable viscosity, which is not preferable.

The liquid resin of the present invention is prepared by dissolving a mixture of the above monomers in a solution in the presence of a radical polymerization initiator,
It can be produced by radical polymerization by a method of dropping a mixture of monomers. Radical polymerization initiators include benzoyl peroxide, t-butyl peroxide, cumene hydroperoxide, lauroyl peroxide, and organic peroxides (Taiseisha, "Crosslinking Agent Handbook", p520-20.
535, second edition), known compounds such as peroxides, azo compounds such as azobisisobutyronitrile and azobiscyclohexanenitrile, and persulfate initiators such as potassium persulfate and ammonium persulfate. You can The amount of the radical polymerization initiator used is the amount of the component (A),
0.01 for 100 parts by weight of the total of (B) and (C)
-5 parts by weight is preferred.

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. Further, among the above solvents, if a water-miscible solvent such as dioxane, n-propanol, methanol, tetrahydrofuran, methyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol is used, water is used to isolate the resin component from the reaction solution. Is preferable because it may be added. The viscosity of the obtained resin is 500 to 30,000 cps at 50 ° C., preferably 80.
It is a liquid of 0 to 10,000 cps.

The composition for a film-forming material using the liquid resin of the present invention comprises the liquid resin itself which is a copolymer of the above-mentioned monomers, and can be used as a substantially solvent-free type. A small amount of water or an organic solvent may be added to improve the coatability, but the amount that can be added is up to 5% by weight based on the liquid resin. Metal salts such as cobalt naphthenate, cobalt octoate, manganese naphthenate, copper naphthenate, zirconium naphthenate, vanadyl octoate, calcium naphthenate, barium naphthenate, and zinc naphthenate to accelerate the oxidative polymerization reaction of paints. May use a dryer. Further, a curing agent resin such as an amino resin or a phenol resin may be added to this composition in order to enhance the curability of the coating material. Further, in order to improve the film performance, known acrylic resins, epoxy resins,
You may mix polyester, polystyrene, etc. However, the compounding amount of each of these is 20% by weight or less. Further, titanium white, colorants such as various pigments, lubricants and the like may be added.

The composition for film-forming material using the liquid resin of the present invention is applied to various steel plates, metal plates such as aluminum plates, plastic films, and base materials such as paper in an amount of 1 to 30 μm.
It can be oxidatively polymerized and cured by oxygen in the air. Further, it can be cured by heating at 20 to 250 ° C. for 20 seconds to 5 days. Examples of the coating method include a roll coater and a knife coater. The liquid resin of the present invention can also be used as a compatibilizer, an interface modifier, a pigment dispersant, and the like.

[0024]

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. In the example,
% Means% by weight (Synthesis of Macromonomer 1) In a 500 ml four-neck round bottom flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a condenser, glycidyl methacrylate 71 g linolenic acid 139 g hydroquinone 0.7 g Was charged, the temperature in the flask was raised to 100 ° C., and the reaction was performed for 8 hours in a nitrogen atmosphere. Obtained macromonomer 1
Was an odorless viscous liquid, and the yield was 95% and the amount of polymer produced was 3% by GPC analysis.

(Synthesis of Macromonomer 2) 5 equipped with a stirrer, a nitrogen introducing tube, a temperature sensor, and a condenser
A 00 ml four-necked round bottom flask was charged with 71 g of glycidyl methacrylate, 139 g of linseed oil fatty acid and 0.7 g of hydroquinone, the temperature inside the flask was raised to 100 ° C., and the reaction was carried out under a nitrogen atmosphere for 8 hours. Macromonomer 2 obtained
Was an odorless viscous liquid, and the yield was 95% and the amount of polymer produced was 3% by GPC analysis.

EXAMPLE 1 Isopropyl alcohol (IPA) 200 ml Water 50 ml n-lauryl methacrylate 45 g Macromonomer 110 g in a 500 ml four-necked round bottom flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and condenser. AIBN 1 g is charged and the temperature in the flask is raised to 65 ° C. in a water bath. The reaction is continued for 4 hours as it is, and then 50 ml of water is added to the obtained polymer solution to precipitate the resin. When the sedimentation started, while swirling, the contents of the flask were transferred to a 500 ml beaker, the upper layer liquid was removed, and the mixture was transferred to a vacuum oven at 60 ° C as it was while maintaining 5 mmHg,
Vacuum drying was performed overnight. The yield was 95%. The obtained resin was an odorless viscous liquid, and had a number average molecular weight of 27,000 as measured by GPC (in terms of styrene). Rotational viscometer (Yamaichi Denki Co., Ltd. VM-10
0) was used to measure the viscosity at 50 ° C.
It showed 5,000 cps.

A coating composition was prepared by adding 0.03% of cobalt naphthenate to the obtained liquid resin. This coating composition was dropped on a hard aluminum plate on a hot plate kept at 80 ° C. and applied using a 1 mil applicator. During coating, there was no odor of low molecular weight organic compounds such as residual monomers. After coating, no cissing was observed on the coating film, and the coating film was allowed to stand at 20 ° C. for 24 hours to obtain a smooth cured coating film. An attempt was made to tack the finger on the surface of the coating film, but there was no tack. In the cross-cut peeling test, the coating film residual rate is 100%
Met. The coated aluminum pieces were kept in methyl ethyl ketone for 10 minutes and boiling water for 1 hour, but neither whitening nor peeling of the coating film occurred.

Next, the above coating composition was dripped onto a hard aluminum plate on a hot plate kept at 80 ° C., and 1 mil.
The coating was applied using the applicator of No. 1 and baked at 180 ° C. for 1 minute to obtain a smooth cured coating film. An attempt was made to tack the finger on the surface of the coating film, but there was no tack. In a cross-cut peeling test carried out as an adhesion test, the coating film residual rate was 100%. As a solvent resistance test and a boiling water resistance test, the coated aluminum pieces were kept in methyl ethyl ketone for 10 minutes and boiling water for 1 hour, but neither whitening nor peeling of the coating film occurred.

Comparative Example 1 IPA 200 ml Water 50 ml Macromonomer 1 45 g AIBN 1 g was charged into a 500 ml four-necked round bottom flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a condenser, and placed in a hot water bath. The temperature inside the flask is raised to 65 ° C. The reaction is continued for 4 hours as it is, and then 50 ml of water is added to the obtained polymer solution to precipitate the resin. When the sedimentation started, while swirling, the contents of the flask were transferred to a 500 ml beaker, the upper layer liquid was removed, and the mixture was transferred to a vacuum oven at 60 ° C as it was while maintaining 5 mmHg,
Vacuum drying was performed overnight. The yield was 95%. The obtained resin was an odorless viscous liquid, and had a number average molecular weight of 30,000 as measured by GPC (in terms of styrene), but was solid at room temperature (25 ° C) and heated to 90 ° C. However, the viscosity could not be measured.

Comparative Example 2 A 500 ml four-necked round bottom flask equipped with a stirrer, a nitrogen introducing tube, a temperature sensor, and a condenser was charged with IPA 200 ml water 50 ml n-lauryl methacrylate 45 g macromonomer 12 g AIBN 1 g. After charging, the temperature inside the flask is raised to 65 ° C. in a hot water bath. The reaction is continued for 4 hours as it is, and then 50 ml of water is added to the obtained polymer solution to precipitate the resin. When the sedimentation started, while swirling, the contents of the flask were transferred to a 500 ml beaker, the upper layer liquid was removed, and the mixture was transferred to a vacuum oven at 60 ° C as it was while maintaining 5 mmHg,
Vacuum drying was performed overnight. The yield was 95%. The obtained resin was an odorless viscous liquid, and had a number average molecular weight of 28,000 as measured by GPC (in terms of styrene), and viscosity was measured at 50 ° C.
s. The obtained resin was added with cobalt naphthenate 0.
03% was added, and it was dripped on a hard aluminum plate on a hot plate at 80 ° C., and coated using a 1 mil applicator. After coating, no cissing was seen on the coating film,
It was left standing at ℃ for 24 hours, and a smooth coating film was obtained. However, when tacking the finger touch of the coating film surface, it was not cured at all and there was tack. When the coated aluminum pieces were kept in methyl ethyl ketone for 10 minutes and boiling water for 1 hour, the coating film dissolved or whitened in both cases.

Example 2 With the formulation of Example 1, the same reaction was carried out with the amount of water charged to 25 ml and the amount of IPA charged to 225 ml. The yield of the obtained resin was 97%, and the number average molecular weight was 32,000.
And the viscosity was 18,000 cps at 50 ° C. A coating composition prepared by adding 0.03% of cobalt naphthenate to this resin was applied in the same manner as in Example 1, and the results of the performance test of the coating film cured at 20 ° C. for 24 hours are shown in Table 1. .

Example 3 A 500 ml four-necked round bottom flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a condenser was charged with IPA 200 ml water 50 ml n-lauryl methacrylate 45 g macromonomer 2 10 g AIBN 1 g. After charging, the temperature inside the flask is raised to 65 ° C. in a hot water bath. The reaction is continued for 4 hours as it is, and 50 ml of water is added to the obtained polymer solution to precipitate the resin. When settling started, while swirling, the contents of the flask were transferred to a 500 ml beaker, the upper layer liquid was removed, 300 ml of dioxane was added here to redissolve the resin, and 100 ml of methanol was added to reprecipitate the supernatant. Except,
Vacuum drying was performed at 50 ° C. overnight. The resin yield was 95%. The obtained resin was an odorless viscous liquid and had a number average molecular weight of 24,000. When the viscosity was measured at 50 ° C., it showed 16,000 cps. A coating composition obtained by adding 0.03% of cobalt naphthenate to this resin was applied in the same manner as in Example 1, and the results of the performance test of the coating film cured at 20 ° C. for 24 hours are shown in Table 1. .

Example 4 IPA 220 ml water 60 ml n-pentadecyl methacrylate 55 g macromonomer 1 10 g AIBN 1 in a 500 ml four-necked round bottom flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and condenser. g, and the temperature inside the flask was raised to 65 ° C. in a water bath,
The reaction was continued for 4 hours as it was. The resin yield was 96%. The obtained resin was an odorless viscous liquid and had a number average molecular weight of 20,000. When the viscosity was measured at 50 ° C., it showed 16,500 cps. A coating composition obtained by adding 0.03% of cobalt naphthenate to this resin is
The results of the performance test of the coating film coated in the same manner as in Example 1 and cured at 20 ° C. for 24 hours are shown in Table 1.

EXAMPLE 5 IPA 200 ml Water 25 ml Stearyl acrylate 40 g Macromonomer 1 10 g Styrene 3 g AIBN In a 500 ml four-necked round bottom flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, dropping funnel and condenser. 0.6 g was charged, and the temperature inside the flask was raised to 65 ° C. in a water bath. The reaction was continued for 4 hours as it was. Resin yield is 93%
Met. The obtained resin was an odorless viscous liquid and had a number average molecular weight of 13,000. When the viscosity was measured at 50 ° C., it was 23,000 cps. A coating composition prepared by adding 0.03% of cobalt naphthenate to this resin was applied in the same manner as in Example 1, and the results of the performance test of the coating film cured at 20 ° C. for 24 hours are shown in Table 1. .

Example 6 In a 500 ml four-necked round bottom flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a condenser, IPA 150 ml water 100 ml CH ₂ = C (CH ₃ ) COO (CH ₂ CH ₂ O) ₉ H 45 g Macromonomer 1 10 g Potassium persulfate 0.5 g was charged, and the temperature inside the flask was raised to 65 ° C. in a water bath. The reaction is continued for 4 hours as it is, and then 50 ml of water is added to the obtained polymer solution to precipitate the resin. When settling started, while swirling, the contents of the flask were transferred to a 500 ml beaker, the upper layer liquid was removed, and the mixture was transferred to a vacuum oven at 60 ° C. as it was while maintaining 5 mmHg,
Vacuum drying was performed overnight. The yield was 95%. The obtained resin was an odorless viscous liquid, and had a number average molecular weight of 25,000 as measured by GPC (in terms of styrene). A viscosity measurement showed 9,000 cps. A coating composition prepared by adding 0.03% of cobalt naphthenate to this resin was applied in the same manner as in Example 1 to obtain 20
Table 1 shows the results of the performance test of the coating film cured by baking at 24 ° C. for 24 hours and at 180 ° C. for 1 minute.

Example 7 With the formulation of Example 6, the same reaction was carried out with 50 ml of water charged and 200 ml of IPA charged. The yield of the obtained resin was 97%, and the number average molecular weight was 32,000.
And the viscosity was 12,000 cps at 50 ° C. A coating composition prepared by adding 0.03% of cobalt naphthenate to this resin was applied in the same manner as in Example 1, and the results of the performance test of the coating film cured at 20 ° C. for 24 hours are shown in Table 1. .

Example 8 In a 500 ml four-necked round bottom flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a condenser, IPA 150 ml water 100 ml CH ₂ ═C (CH ₃ ) COO (CH ₂ CH ₂ O) ₉ H 45 g Macromonomer 210 g AIBN 1 g are charged, and the temperature inside the flask is raised to 65 ° C. in a water bath. The reaction is continued for 4 hours as it is, and 50 ml of water is added to the obtained polymer solution to precipitate the resin. When settling started, while swirling, the contents of the flask were transferred to a 500 ml beaker, the upper layer liquid was removed, 300 ml of dioxane was added here to redissolve the resin, and 100 ml of methanol was added to reprecipitate the supernatant. Except,
Vacuum drying was performed at 50 ° C. overnight. The resin yield was 95%. The obtained resin was an odorless viscous liquid and had a number average molecular weight of 22,000. When the viscosity was measured at 50 ° C., it showed 10,000 cps. A coating composition prepared by adding 0.03% of cobalt naphthenate to this resin was applied in the same manner as in Example 1, and the results of the performance test of the coating film cured at 20 ° C. for 24 hours are shown in Table 1. .

Example 9 In a 500 ml four-neck round bottom flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and condenser, IPA 150 ml water 100 ml CH ₂ = C (CH ₃ ) COO (CH ₂ CH ₂ O) ₄ H 45 g Macromonomer 1 10 g Potassium persulfate 0.5 g was charged, and the temperature inside the flask was raised to 65 ° C. in a water bath,
The reaction was continued for 4 hours as it was. The resin yield was 96%. The obtained resin was an odorless viscous liquid and had a number average molecular weight of 22,000. When the viscosity was measured at 50 ° C., it showed 15,000 cps. A coating composition obtained by adding 0.03% of cobalt naphthenate to this resin is
The results of the performance test of the coating film coated in the same manner as in Example 1 and cured at 20 ° C. for 24 hours are shown in Table 1.

Example 10 IPA 150 ml water 100 ml CH ₂ ═C (CH ₃ ) COO (CH ₂ CH ₂ ) in a 500 ml four-necked round bottom flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, dropping funnel and condenser. O) ₄ H 40 g Macromonomer 1 10 g Styrene 3 g Potassium persulfate 0.5 g are charged, and the temperature inside the flask is raised to 65 ° C. in a water bath. The reaction was continued for 4 hours as it was. Resin yield is 93%
Met. The obtained resin was an odorless viscous liquid and had a number average molecular weight of 20,000. When the viscosity was measured at 50 ° C., it showed 20,000 cps. A coating composition prepared by adding 0.03% of cobalt naphthenate to this resin was applied in the same manner as in Example 1, and the results of the performance test of the coating film cured at 20 ° C. for 24 hours are shown in Table 1. .

Comparative Example 3 In a 500 ml four-necked round bottom flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a condenser, IPA 150 ml water 100 ml CH ₂ = C (CH ₃ ) COO (CH ₂ CH ₂ O) ₉ H 45 g Macromonomer 12 g Potassium persulfate 0.5 g is charged, and the temperature inside the flask is raised to 65 ° C. in a water bath. The reaction is continued for 4 hours as it is, and then 50 ml of water is added to the obtained polymer solution to precipitate the resin. When the sedimentation started, while swirling, the contents of the flask were transferred to a 500 ml beaker, the upper layer liquid was removed, and the mixture was transferred to a vacuum oven at 60 ° C as it was while maintaining 5 mmHg,
Vacuum drying was performed overnight. The yield was 95%. The obtained resin was an odorless viscous liquid, and had a number average molecular weight of 28,000 as measured by GPC (in terms of styrene), and viscosity was measured at 50 ° C.
s. Cobalt naphthenate 0.03% in this resin
Table 1 shows the results of the performance test of the coating composition obtained by applying the coating composition to which was added in the same manner as in Example 1 and curing at 20 ° C. for 24 hours.

Example 11 In a 500 ml four-neck round bottom flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, dropping funnel and condenser, IPA 150 ml water 100 ml lauryl methacrylate 10.2 g CH ₂ ═C (CH ₃ ) COO (CH ₂ CH ₂ O) ₉ H 29.8 g Macromonomer 1 10 g Styrene 3 g Potassium persulfate 0.5 g are charged, and the temperature inside the flask is raised to 65 ° C. in a water bath. The reaction was continued for 4 hours as it was. Resin yield is 92%
Met. The obtained resin was an odorless viscous liquid and had a number average molecular weight of 12,000. When the viscosity was measured at 50 ° C., it showed 8,000 cps. A coating composition prepared by adding 0.03% of cobalt naphthenate to this resin was applied in the same manner as in Example 1, and the results of the performance test of the coating film cured at 20 ° C. for 24 hours are shown in Table 1. .

Table 1 ─────────────────────────────────── Liquid resin Curing conditions Tack Solvent resistance Boiling water resistance Adhesion (%) ─────────────────────────────────── Example 1 20 ° C. 24 hours ○ Note 1 ) ◯ 100 Note 2) Example 1 180 ° C. for 1 minute ○ ○ ○ 100 Example 2 20 ° C. for 24 hours ○ ○ ○ 100 Example 3 20 ° C. for 24 hours ○ ○ ○ 100 Example 4 20 ° C. for 24 hours ○ ○ △ 90 Example 5 20 ° C 24 hours ○ △ △ 80 Comparative Example 2 20 ° C 24 hours ○ × △ 70 Example 6 20 ° C 24 hours ○ ○ ○ 100 Example 6 180 ° C 1 minute ○ ○ ○ 100 100 Example 7 20 ° C 24 hours ○ ○ ○ 100 Example 8 20 ° C 24 hours ○ ○ ○ 100 Example 9 20 ° C 24 hours ○ ○ △ 90 Example 10 20 ° C 24 hours ○ △ △ 80 Comparative Example 3 20 ° C 24 hours ○ × △ 70 Example 11 20 ° C 24 hours ○ ○ ○ 100 ────────────── ──────────────────── Note 1) ○: No tack (tack), no whitening (solvent resistance, boiling water resistance) △: Some tack (tack) ), Slightly cloudy (solvent resistance, boiling water resistance) X: with tack (tack), whitening (solvent resistance, boiling water resistance) Note 2) Shows the coating film residual rate in the cellophane tape peeling test.

[0043]

The composition for film-forming material using the liquid resin of the present invention does not contain a solvent, so that it is possible to suppress the scattering of the solvent and the monomer at the time of coating and not only improve the working environment. , Now it is possible to make paints that do not release solvents into the atmosphere. Further, since it is oxidatively polymerized by oxygen in the air, it is possible to obtain a coating that does not require energy for curing and that can be cured at room temperature.

Claims (5)

[Claims] 1. (A) The following formula (1) or the following formula (2)
10 to 90 wt% CH ₂ = C (R ¹ ) COO-R ² (1) (in the formula, R ¹ is a hydrogen atom or CH ₃ , and R ² has 4 to 4 carbon atoms).
22 represents an alkyl group. ^{_{) CH 2 = C (R 3}} ) COO (C n H 2n O) m R 4 (2) ( wherein, R ³ is a hydrogen atom or CH _3, R ⁴ is 1 to carbon atoms
5, an alkyl group of 5, n is an integer of 1 to 3, and m is an integer of 4 to 25. (B) Epoxide (a) having an ethylenically unsaturated double bond and R ⁵ COOH (in the formula, R ⁵ is an unsaturated aliphatic hydrocarbon group having at least one double bond having 3 to 30 carbon atoms). 5 to 90% by weight of a macromonomer obtained by reacting with a fatty acid (b) represented by), and (C) other polymerizable vinyl compound 0 to 40% by weight, and having a number average molecular weight of 10,000 to 200, 000 and a viscosity of 500 cps to 30,000 cps (5
Curable liquid resin which is 0 ° C.). 2. The monomer (A) is the same as R ² in the formula (1).
The curable liquid resin according to claim 1, wherein is a monomer having an alkyl group having 8 to 20 carbon atoms. 3. The fatty acid (b), wherein R ⁵ has 16 to 2 carbon atoms.
The curable liquid resin according to claim 1 or 2, which is a fatty acid which is an unsaturated aliphatic hydrocarbon group having at least one double bond. 4. The method for producing a curable liquid resin according to claim 1, wherein the components (A) to (C) are radically polymerized in a water-miscible solvent which may contain water. 5. A composition for a film-forming material, which is obtained by adding a metal salt dryer to the curable liquid resin according to claim 1.