JPH0848728A - Curable liquid resin, preparation thereof, and use thereof - Google Patents

Abstract

PURPOSE:To obtain a solvent-free curable liq. coating resin free of solvent escaping even when applied by a customary coating method and dried by heating. CONSTITUTION:A curable liq. resin comprises (A) 10-90wt.% units of CH2=C(R<1>) COO-R<2> (wherein R<1> is hydrogen or CH3; and R<2> is a 4-22C alkyl group) or CH2=C(R<1>)COO(CnH2nO)mR<3> (wherein R<1> is hydrogen or CH3; R<3> is a 1-5C alkyl group; n is an integer of 1 to 3; and m is an integer of 4 to 25); (B) 1-40wt.% units of CH2=C(R<4>)CONR<5>R<6> [wherein R<4> is hydrogen or CH3; and R<5> and R<6> are each hydrogen or CH2OR<7> (wherein R<7> is hydrogen or a 1-5C alkyl group), provided that R<5> and R<6> are not simultaneously hydrogen]; and (C) 0-40wt.% other polymerizable vinyl compd. The resin has a number-average mol.wt. of 10,000 to 200,000 and a viscosity of 500 to 30,000cp (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, the present invention provides a coating material which can be formed by a conventionally used film forming method, for example, a roll coater or a knife coater, and which does not dissipate the solvent even when the conventional heat drying is performed.

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. Further, the inventors have found a solvent-free coating forming composition that can be cured by conventional heating and drying without using a curing agent, and have reached the present invention.

[0006]

Means for Solving the Problems The present invention includes (A) a monomer represented by the following formula (1) or the following formula (2): 10 to 90 wt% CH₂= C (R¹) COO-R² (1) (In the formula, R¹Is a hydrogen atom or CH₃, R²Has 4 to 4 carbon atoms
22 represents an alkyl group. ) CH₂= C (R¹) COO (C_nH_2nO)_mR³ (2) (In the formula, R¹Is a hydrogen atom or CH₃, R³Has 1 to 1 carbon atoms
An alkyl group of 5, n is an integer of 1 to 3, m is an integer of 4 to 25
Represents each number. ) (B) Monomer represented by the following formula (3): 1 to 40% by weight CH₂= C (R^Four) CONR^FiveR⁶ (3) In the formula, R^FourIs a hydrogen atom or CH₃, R^Five, R⁶Is the hydrogen source
Child or CH₂OR⁷(R ⁷Is a hydrogen atom or 1 to 1 carbon atoms
5 represents an alkyl group. ) Respectively (however, R
^FiveAnd R⁶Are not both hydrogen atoms. ). And (C) other polymerizable vinyl compound 0 to 40% by weight, and having a number average molecular weight of 10,000 to 200,000.
0 and viscosity of 500 cps to 30,000 cps
s (50 ° C.) curable liquid resin. Further departure
It is clear that the monomer (A) is the same as R in the formula (1).²Is the carbon number
The above curable liquid which is a monomer having 8 to 20 alkyl groups
Resin. Further, the present invention provides the above (A) to
Radical (C) in a water-miscible solvent which may contain water
Of the above-mentioned curable liquid resin, which is characterized by undergoing cull polymerization
Regarding the manufacturing method. Furthermore, the present invention provides the above curable liquid resin
Substantially solvent-free, characterized by containing a curing catalyst
The present invention relates to a film forming material.

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 monomer (B) of the present invention is a monomer represented by the following formula (3), in which an N-alkylol group is introduced into a copolymer, and a dealcoholization reaction is caused by heating to crosslink. , Imparts the function of curing the coating. ^{_{CH 2 = C (R 4)}} CONR 5 R 6 (3) as (wherein symbols are as defined above) monomer (B), specifically, N- methylol acrylamide, N- methylol methacrylamide, N-
(Methoxymethyl) acrylamide, N- (methoxymethyl) methacrylamide, N- (ethoxymethyl) acrylamide, N- (ethoxymethyl) methacrylamide, N- (propoxymethyl) acrylamide, N-
(Propoxymethyl) methacrylamide, N- (butoxymethyl) acrylamide, N- (butoxymethyl)
Monoalkylol (meth) acrylamides such as methacrylamide, N- (pentoxymethyl) acrylamide, N- (pentoxymethyl) methacrylamide,

N, N-di (methylol) acrylamide, N-methylol-N- (methoxymethyl) methacrylamide, 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-methoxymethyl-
There are dialkyrol (meth) acrylamides such as N- (pentoxymethyl) methacrylamide.

The monomers (B) can be used in combination of two or more kinds. The amount of the monomer (B) used is 1 to 40% by weight, preferably 3 to 25% by weight, based on the liquid resin which is a copolymer, and the amount of the component (B) in the copolymer is 3% by weight. %, Particularly less than 1% by weight, it becomes difficult to obtain a hard coating film, and conversely, if more than 25% by weight, especially 40% by 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 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 film-forming material using the liquid resin of the present invention comprises the liquid resin itself which is a copolymer of the above monomers and can be used as a substantially solvent-free type. Curing of the composition can be performed under heating at 120 ° C. to 230 ° C. for 0.5 minutes to 30 minutes. However, in order to accelerate the curing reaction of the composition, acidic compounds such as p-toluene sulfone and phosphoric acid as catalysts, and organic acid metals such as sodium acetate, zinc naphthenate, cobalt naphthenate, zinc octylate, and tin octylate. Lewis acids such as salts, stannous chloride, aluminum chloride, ferric chloride, titanium chloride, zinc chloride and antimony chloride, basic compounds such as butylamine, ethylenediamine, triethylamine and imidazole, amino acids such as glycine, aluminum acetylacetonate , Metal acetylacetonates such as chromium acetylacetonate, titania acetylacetonate and cobalt acetylacetonate, and tin compounds such as dibutyltin dilaurate, dibutyltin diacetate and dibutyltin oxide may be used. Among these catalysts, p-toluenesulfonic acid and dibutyltin dilaurate are suitable for the composition for a film forming material of the present invention.

A small amount of water or an organic solvent may be added in order to improve the coatability of the composition for forming a film.
The amount that can be blended is up to 5% by weight based on the liquid resin. Further, in order to enhance the curability of the coating, this composition contains
A curing agent resin such as an amino resin or a phenol resin may be blended. Further, in order to improve the film performance, known acrylic resins, epoxy resins, polyesters, polystyrene and the like may be added. 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 a 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 cured by heating. 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.

[0020]

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

Example 1 In a 500 ml four-necked round bottom flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a condenser, isopropyl alcohol (IPA) 150 ml water 100 ml n-lauryl methacrylate 45 g N- (methoxymethyl) Methacrylicamide 10 g AIBN 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 25,000 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 10,000 cps.

0.3% of dibutyltin laurate was added to the obtained liquid resin to prepare a coating composition. This coating composition was hung 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 this was baked at 180 ° C. for 30 minutes 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. Table 1 shows the results of performance tests of coating films obtained by the same operation as above except that p-toluenesulfonic acid was used instead of dibutyltin laurate in the above coating composition.

Comparative Example 1 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 150 ml water 100 ml N- (methoxymethyl) methacrylamide 45 g AIBN 0.5 g. 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 36,000 as measured by GPC (in terms of styrene), but it was solid at room temperature (25 ° C) and heated to 90 ° C. However, the viscosity could not be measured.

Comparative Example 2 IPA 150 ml Water 100 ml n-lauryl methacrylate 45 g N- (methoxymethyl) methacrylamide 2 g in a 500 ml four-necked round bottom flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and condenser. 0.5 g of AIBN 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 39,000 as measured by GPC (in terms of styrene). Viscosity was measured at 50 ° C.
s. 0.3% of dibutyltin laurate was added to the obtained liquid resin to prepare a coating composition. This coating composition was hung 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 this was left standing at 20 ° C. for 24 hours to obtain a smooth cured coating film. 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 a water charge of 50 ml and an IPA charge of 200 ml. The yield of the obtained resin was 97%, and the number average molecular weight was 27,000.
And the viscosity was 13,000 cps at 50 ° C. A coating composition obtained by adding 0.3% of dibutyltin laurate to this resin was operated in the same manner as in Example 1 and the results of the performance test of the coating film are shown in Table 1.

Example 3 In a 500 ml four-necked round bottom flask equipped with a stirrer, nitrogen introducing tube, temperature sensor, and condenser, IPA 150 ml water 100 ml n-lauryl methacrylate 45 g N-methylol acrylamide 10 g AIBN 0.5 g. And 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 30,000. When the viscosity was measured at 50 ° C., it showed 15,000 cps. A coating composition obtained by adding 0.3% of dibutyltin laurate to this resin was operated in the same manner as in Example 1 and the results of the performance test of the coating film are shown in Table 1.

Example 4 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 n-pentadecyl methacrylate 45 g N, N-di (methoxymethyl) ) Methacrylamide 10 g AIBN 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 27,000. When the viscosity was measured at 50 ° C., it was 18,000 cps. A coating composition obtained by adding 0.3% of dibutyl tin laurate to this resin is
The results of the performance test of the coating film obtained by operating in the same manner as in Example 1 are shown in Table 1.

Example 5 In a 500 ml four-necked round bottom flask equipped with a stirrer, nitrogen introducing tube, temperature sensor, dropping funnel and condenser, IPA 150 ml water 100 ml stearyl methacrylate 40 g N-methylol-N- (methoxymethyl) ) Acrylamide 10 g, styrene 3 g, AIBN 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 22,000. When the viscosity was measured at 50 ° C., it showed 15,000 cps. A coating composition obtained by adding 0.3% of dibutyltin laurate to this resin was operated in the same manner as in Example 1 and the results of the performance test of the coating film are shown in Table 1.

Example 6 IPA 150 ml Water 100 ml CH ₂ ═C (CH ₃ ) COO (CH ₂ CH ₂ O) Into a 500 ml four-necked round bottom flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and condenser. ₉ H 45 g N- (methoxymethyl) methacrylamide 10 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 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 22,000 as measured by GPC (in terms of styrene). A viscosity measurement showed 7,000 cps. A coating composition obtained by adding 0.3% of dibutyltin laurate to this resin was operated in the same manner as in Example 1 and the results of the performance test of the coating film are shown in Table 1.

Example 7 With the formulation of Example 6, the same reaction was carried out with 50 ml of water and 200 ml of IPA. The yield of the obtained resin was 97%, and the number average molecular weight was 25,000.
At 50 ° C., the viscosity was 10,000 cps. A coating composition obtained by adding 0.3% of dibutyltin laurate to this resin was operated in the same manner as in Example 1 and the results of the performance test of the coating film are shown in Table 1.

Example 8 IPA 150 ml Water 100 ml CH ₂ ═C (CH ₃ ) COO (CH ₂ CH ₂ O) In a 500 ml four-necked round bottom flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a condenser. ₉ H 45 g N-methylol acrylamide 10 g AIBN 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 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 27,000. When the viscosity was measured at 50 ° C., it showed 12,000 cps. A coating composition obtained by adding 0.3% of dibutyltin laurate to this resin was operated in the same manner as in Example 1 and the results of the performance test of the coating film are shown in Table 1.

Example 9 In a 500 ml four-necked 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 N- (methoxymethyl) acrylamide 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 23,000. When the viscosity was measured at 50 ° C., it was 14,500 cps. A coating composition obtained by adding 0.3% of dibutyl tin laurate to this resin is
The results of the performance test of the coating film obtained by operating in the same manner as in Example 1 are shown in Table 1.

Example 10 In a 500 ml four-necked round bottom flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, dropping funnel and condenser, IPA 150 ml water 100 ml CH ₂ = C (CH ₃ ) COO (CH ₂ CH ₂ O) ₄ H 40 g N-methylol-N- (methoxymethyl) acrylamide 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 15,000. When the viscosity was measured at 50 ° C., it showed 20,000 cps. A coating composition obtained by adding 0.3% of dibutyltin laurate to this resin was operated in the same manner as in Example 1 and the results of the performance test of the coating film 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 N- (methoxymethyl) methacrylamide 2 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 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 35,000 as measured by GPC (in terms of styrene). Viscosity was measured at 50 ° C. and found to be 2,000 cp.
s. Dibutyltin laurate 0.3% in this resin
Table 1 shows the results of the performance test of the coating film obtained by operating the coating composition to which was added in the same manner as in Example 1.

Example 11 In a 500 ml four-necked 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 40 g N- (methoxymethyl) methacrylamide 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 obtained by adding 0.3% of dibutyltin laurate to this resin was operated in the same manner as in Example 1 and the results of the performance test of the coating film are shown in Table 1.

Table 1 ────────────────────────────────── Liquid resin Curing catalyst Tack Solvent resistance Solvent boiling water Adhesion Property (%) ────────────────────────────────── Example 1 Dibutyltin dilaurate ○ Note 1) ○ ○ 100 Note 2) Example 1 p-toluenesulfonic acid ○ ○ ○ 100 Example 2 dibutyltin dilaurate ○ ○ ○ 100 Example 3 dibutyltin dilaurate ○ ○ ○ 100 Example 4 dibutyltin dilaurate ○ ○ △ 90 Example 5 dibutyl Tin dilaurate ○ △ △ 80 Comparative Example 2 Dibutyltin dilaurate × × △ 70 Example 6 Dibutyltin dilaurate ○ ○ ○ 100 Example 6 p-toluenesulfonic acid ○ ○ ○ 100 Example 7 Dibutyltin dilaurate ○ ○ ○ 1 0 Example 8 Dibutyltin dilaurate ○ ○ ○ 100 Example 9 Dibutyltin dilaurate ○ ○ △ 90 Example 10 Dibutyltin dilaurate ○ △ △ 80 Comparative Example 3 Dibutyltin dilaurate × × △ 70 Example 11 Dibutyltin dilaurate ○ ○ ○ 100 ────────────────────────────────── Note 1) ○: No tack (tack), no whitening ( Solvent resistance, boiling water resistance) △: Some tack (tack), slightly cloudy (solvent resistance, boiling water resistance) ×: Tack (tack), whitening (solvent resistance, boiling water resistance) Note 2) Cellophane The coating film residual rate in the tape peeling test is shown.

[0037]

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.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C09D 133/26 PFW

Claims (4)

[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 1}} ) COO (C n H 2n O) m R 3 (2) ( wherein, R ¹ represents a hydrogen atom or CH _3, R ³ 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) below the monomer 1 to 40 wt% of formula _{(3) CH 2 = C (} R 4) CONR 5 R 6 (3) ( wherein, R ⁴ is a hydrogen atom or CH _3, R ⁵ , R ⁶ is a hydrogen atom or CH ₂ OR ⁷ (R ⁷ is a hydrogen atom or a carbon number 1
Represents an alkyl group of ~ 5. ) Respectively (however,
R ⁵ and R ⁶ are not both hydrogen atoms. ). And (C) other polymerizable vinyl compound 0 to 40% by weight, and having a number average molecular weight of 10,000 to 200,000.
0 and viscosity of 500 cps to 30,000 cps
A curable liquid resin that is s (50 ° 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 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. . 4. A substantially solvent-free film-forming material comprising the curable liquid resin according to claim 1 or 2 mixed with a curing catalyst.