JPH0797416A - Liquid resin and its production - Google Patents

Abstract

PURPOSE:To obtain a curable solventless liquid resin composition which does not emit any solvent even by the conventional film formation method, i.e., heat drying. CONSTITUTION:The title resin comprises 50-95wt.% monomer (A) represented by the general formula CH2=C(R<1>)COO(CnH2nO)mR<2> (wherein R<1> is hydrogen or CH3; R<2> is 1-5C alkyl; n is an integer of 1-3; and m is an integer of 4-25) 3-35wt.% polymerizable unsaturated carboxylic acid (B), 2-45wt.% polymerizable unsaturated hydroxylated or alkoxylated monomer (C) other than component A, and 0-20wt.% polymerizable vinyl compounds and has a number-average molecular weight of 10000-200000 and a viscosity of 500-30000cP 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 forming a coating film, a film forming material such as ink, an adhesive, etc., and a method for producing the same. Further, the liquid resin of the present invention is a compatibilizer, an interface modifier,
It can also be used as a pigment dispersant or the like.

[0002]

2. Description of the Related Art Conventionally, a resin system containing an organic solvent has been used for a film forming material such as a paint, an adhesive and an ink. It is known that this conventional resin system scatters 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 makes it difficult to obtain a hard cured product and that the plasticizer migrates. It has been pointed out that latex-based emulsions and hydrosols have problems such as non-uniformity of cured products and slow drying speed. 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]

As a result of intensive studies on various resin systems for solving the above problems, the present inventor has found that a specific (meth) acrylic acid ester, a polymerizable unsaturated carboxylic acid, an alkoxy group or a hydroxyl group is used. A polymerizable unsaturated monomer containing a, and a copolymer of a polymerizable vinyl compound having a high molecular weight, which has been conventionally used, can be formed by a roll coater or a knife coater, and a curing agent. The inventors have found that a solventless resin composition that can be cured by a conventional heating and drying method without using a resin is obtained, and the present invention has been completed.

[0005]

Means for Solving the Problems The present invention comprises 50 to 95% by weight of a monomer (A) represented by the following general formula, 3 to 35% by weight of a polymerizable unsaturated carboxylic acid (B), and the above monomer. A polymerizable unsaturated monomer (C) containing a hydroxyl group or an alkoxy group other than (A) (2 to 45% by weight) and another polymerizable vinyl compound (0 to 20% by weight) as a constituent component, and having a number average molecular weight of 10, 000 to 200,000 and a viscosity of 500
A liquid resin having a cps to 30,000 cps (50 ° C.). General ^{_{formula: CH 2 = C (R 1}} ) COO (C n H 2n O) m R 2 ( wherein, R ¹ represents a hydrogen atom or CH _3, R ² is C 1 -C
~ 5 alkyl group, n is an integer of 1 to 3, m is an integer of 4 to 25. Further, the present invention is characterized in that the radical polymerization of the liquid resin is carried out in a solvent such that the monomers (A) to (D) of the resin are good solvents and the resin is a poor solvent. The method for producing a liquid resin according to claim 1.

The monomer (A) represented by the above general formula in the present invention is used as a constituent component for making the copolymer in a liquid state. For example, tetraethylene glycol (meth) acrylate and 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, n-butoxytetrapropylene glycol (meth) acrylate, n-pentoxy Examples include tetrapropylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, and ethoxy polyethylene glycol (meth) acrylate. Four
The viscosity of the copolymer can be effectively reduced by using an acrylate having a polyoxyalkylene chain of -25, preferably 5-22, 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 does not easily 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 monomer (A) can be used in combination of two or more kinds. The amount of the component is 35 to 95% by weight, preferably 40% by weight, based on the liquid resin which is a copolymer.
When the amount of the monomer (A) in the copolymer is less than 40% by weight, particularly less than 35% by weight, the copolymer cannot maintain the low viscosity required for film formation, and conversely 85% by weight. %, Especially 95% by weight, it is not preferable because a hard film cannot be obtained.

The polymerizable unsaturated carboxylic acid (B) of the present invention is used for introducing a crosslinking component into the copolymer together with the component (C), and examples thereof include maleic acid, fumaric acid, itaconic acid, citraconic acid, or , These alkyl or alkenyl monoesters, phthalic acid β- (meth) acryloxyethyl monoester, isophthalic acid β- (meth)
Acryloxyethyl monoester, terephthalic acid β-
(Meth) acryloxyethyl monoester, succinic acid β
-(Meth) acryloxyethyl monoester, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, etc. may be mentioned.

The amount of the polymerizable unsaturated carboxylic acid (B) used is 3 to 35% by weight, preferably 5 to 25% by weight, based on the liquid resin which is a copolymer. If the component) is less than 5% by weight, especially less than 3% by weight, it is difficult to obtain a hard film. On the other hand, if it exceeds 25% by weight, especially more than 35% by weight, the viscosity of the liquid resin becomes high and film formation becomes difficult, which is preferable. Absent. The film formation in the present invention means that a resin having a thickness of 0. is formed on a substrate made of paper, metal, plastic, ceramics or the like by a method such as printing and painting.
This means forming a film having a thickness of 1 to 100 μm.

The polymerizable unsaturated monomer (C) having a hydroxyl group or an alkoxy group of the present invention has, for example, a vinyl group
It is a compound in which a hydroxyl group or an alkoxy group is bonded to XYZ- as a bonding group. X is a direct bond or -CH
_{2 -, - Q-CH 2} -, - Q- represents, Q is may have a substituent such as an alkyl group, a phenylene group, an aromatic residue or cyclohexane and naphthalene group, decalin, norbornane, etc. Represents a residue such as an alicyclic compound. Y is a direct bond or -O-, -CO-,-.
COO -, - OCO -, - SO 2 - represents a.

Z is a direct bond or an alkylene group or polyalkyleneoxy group which may have a substituent such as an alkyl group or a hydroxyl group. Carbon number of alkylene group is 9
Below, preferably 4 or less, and the number of repeating units of the polyalkyleneoxy group is 3 or less, preferably 1, and when it is above the above range, it becomes difficult to obtain hardness after the curing reaction. Therefore, the styrene monomer (A) having a long-chain alkyleneoxy group represented by the above general formula is not preferable.

As the monomer (C) used in the present invention,
Specifically, allyl alcohol, methyl allyl ether, ethyl allyl ether, propyl allyl ether,
Allyl ether such as butyl allyl ether, 4-hydroxystyrene, 4-hydroxymethylstyrene, vinylphenyl methyl ether, vinylphenyl ethyl ether, isopropenylphenyl methyl ether, isopropenylphenyl ethyl ether, vinylphenylmethyl methyl ether, vinylphenylmethyl Styrene compounds such as ethyl ether, isopropenylphenylmethyl methyl ether, isopropenylphenylmethyl ethyl ether, vinylcyclohexyl methyl ether, vinylcyclohexyl ethyl ether, isopropenylcyclohexyl methyl ether,
Vinylcyclohexyl compounds such as isopropenylcyclohexyl ethyl ether, vinylcyclohexylmethyl methyl ether, vinylcyclohexylmethyl ethyl ether, isopropenylcyclohexylmethyl methyl ether, isopropenylcyclohexylmethyl ethyl ether,

2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2
-Hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-ethoxypropyl (meth ) Acrylate,
2-ethoxypropyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 3-propoxypropyl (meth) acrylate, 2-propoxypropyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 3-butoxypropyl ( (Meth) acrylate, 2-butoxypropyl (meth) acrylate, glycerol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, polyethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, (Meth) acrylates such as methoxy polyethylene glycol (meth) acrylate,
Methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, methyl isopropenyl ether, ethyl isopropenyl ether,
Vinyl ethers such as propyl isopropenyl ether and butyl isopropenyl ether may be used, and a plurality of them may be used from these groups.

The amount of the monomer (C) used is 2-45% by weight, preferably 5-40, based on the liquid resin which is a copolymer.
% Of the component (C) in the copolymerization is 5% by weight, especially 2
If the amount is less than 50% by weight, the liquid resin cannot be cured. Conversely, if the amount is more than 40% by weight, especially 45% by weight,
Water resistance is reduced, which is not preferable.

In the present invention, a polymerizable vinyl compound (D) other than the above may be used, if necessary, in order to adjust the water resistance and hardness of the cured film. For this purpose it is preferred to use non-functional vinyl compounds. Examples of such a non-functional compound (D) include aromatic vinyl compounds such as styrene, vinyltoluene and vinylpyridine, (meth) acrylates having an alkyl group having 3 or less carbon atoms such as methylmethacrylate and ethylmethacrylate, Vinyl carboxylates such as vinyl acetate and vinyl butyrate, N
-Vinylpyrrolidone, N-vinylcarbazole, diallyl phthalate, acrylonitrile, vinyl chloride and the like.

The composition amount of the polymerizable vinyl compound (D) is 0 to 20% by weight, preferably 15% by weight or less, and more than 20% by weight based on the liquid resin (A) which is a copolymer. The viscosity of the liquid resin (A) becomes high and it becomes difficult to form a film, which is not preferable. The liquid resin of the present invention has a number average molecular weight (polystyrene conversion) value of 10,000 to 200,0 measured by a GPC method (gel permeation chromatograph) by adjusting the blending amount of the initiator.
00, preferably 10,000 to 150,000. 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 mechanical properties such as flexibility are deteriorated, and the physical properties of the cured film such as solvent resistance and boiling water resistance. Is not preferable, and when the value is larger than the above value, the resin cannot maintain a viscosity capable of forming a film, which is not preferable.

The liquid resin of the present invention can be produced by a solution method or a dispersion method of radical polymerization using a known radical polymerization initiator. As the solvent to be used, ethyl acetate, methyl ethyl ketone, toluene, benzene, dioxane, tetrahydrofuran, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, methyl cellosolve, butyl cellosolve, methyl carbitol, Examples thereof include ethyl carbitol, methyl cellosolve acetate, ethyl cellosolve acetate, and diacetone alcohol.

Since the solubility parameter (sp value) of the liquid resin is 8.0 to 10.0 (cal / cm ³ ) ^1/2 , isopropanol, n-propanol, methanol, ethanol, allyl alcohol, ethylene glycol, Propylene glycol, methyl cellosolve, etc., sp
The value is 10.0 (cal / cm ³ ) ^1/2 or more, preferably 1
If a solvent of 1.5 (cal / cm ³ ) ^1/2 or more is used, only the polymer which has reached a preferable degree of polymerization will be separated from the reaction solution, so that it is only necessary to remove the supernatant to isolate the resin component. Therefore, it is preferable. When a water-miscible solvent such as dioxane, isopropanol, n-propanol, methanol, tetrahydrofuran, methyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol is used, water may be added to isolate the resin component. Therefore, it is preferable.

The radical polymerization initiator is not particularly limited, but examples thereof include peroxides such as benzoyl peroxide, t-butyl peroxide, cumene hydroperoxide and lauroyl peroxide, azobisisobutyronitrile and azo. An azo initiator such as biscyclohexanenitrile, a persulfate initiator such as potassium persulfate or ammonium persulfate, and the like can be used. The blending amount of such radical polymerization initiator is
The content is preferably 0.01 to 5% by weight, more preferably 0.1 to 3% by weight, based on the total amount of the monomers. The viscosity of the obtained resin is 500 to 30,000 cps, preferably 800 to 20,000 cps at 50 ° C. measured by a rotary vibration viscometer.

The curable liquid resin composition of the present invention comprises the liquid resin itself which is a copolymer of the above monomers and can be used as a substantially solventless resin. However,
A small amount of water or an organic solvent may be added to improve the film-forming property. The amount that can be blended is up to 5% by weight based on the liquid resin. The curable liquid resin composition of the present invention may contain a curing agent resin such as an amino resin or a phenol resin in order to enhance the curability. Further, titanium white, colorants such as various pigments, lubricants and the like may be added.

A curing catalyst generally used for improving the curing characteristics of the curable liquid resin composition of the present invention can be used. As an example of a typical curing catalyst, p
-Toluenesulfonic acid, phthalic anhydride, benzoic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid formic acid, acetic acid, itaconic acid, oxalic acid, maleic acid, and their ammonium salts, lower amine salts, polyvalent metal salts, etc. . The curable liquid resin composition of the present invention has a resin 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.
It can be cured by forming a film with a thickness of m and heating at 150 to 260 ° C. for 1 to 30 minutes.

[0022]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention thereto. (Prototype example-1) Stirrer, nitrogen introduction tube, temperature sensor,
Into a 500 ml four-necked round bottom flask equipped with a condenser, isopropyl alcohol (IPA) 280 ml methoxytetraoxyethylene methacrylate 100 g succinic acid β-methacryloxyethyl monoester 10 g methoxydiethylene glycol methacrylate 8 g AIBN 1.2 g, Increase the temperature inside the flask to 65 ° C in a hot water bath.
The reaction continued for an hour. The resulting polymer solution is cooled with ice water to precipitate the resin. When settling started, while swirling, transfer the contents of the flask to a 500 ml beaker, remove the upper layer liquid, wash with ether several times, and then
It was dried under reduced pressure at 0 ° C overnight. The yield of the obtained resin is 95.
% Average molecular weight measured by GPC (in terms of styrene)
Was 32,000. Rotational viscometer (VM-1
00, manufactured by Yamaichi Denki Co., Ltd., the viscosity was measured at 50 ° C., and it was 10,250 cps.

(Prototype Example-2) 50 equipped with a stirrer, nitrogen introducing tube, temperature sensor, dropping funnel and condenser
A 0 ml four-neck round bottom flask is charged with isopropyl alcohol 260 ml methoxynonaoxyethylene methacrylate 100 g succinic acid β- (meth) acryloxyethyl monoester 6 g methoxydiethylene glycol methacrylate 5 g AIBN 1.1 g. Raise the temperature in the flask to 65 ° C in a hot water bath,
The reaction was continued for 4 hours. The resulting polymer solution is cooled with ice water to precipitate the resin. When settling started, the contents of the flask were transferred to a 500 ml beaker while swirling, the upper layer liquid was removed, and the mixture was washed several times with ether, and then 50
It was dried under reduced pressure at 0 ° C overnight. The yield of the obtained resin is 97.
%, Number average molecular weight is 25,000 and viscosity is 50 ° C.
It was 4,110 cps.

(Prototype Example-3) 50 equipped with a stirrer, nitrogen introducing tube, temperature sensor, dropping funnel and condenser
A 0 ml four-necked round bottom flask is charged with isopropyl alcohol 300 ml methoxynonaoxyethylene methacrylate 100 g succinic acid β- (meth) acryloxyethyl monoester 16.4 g methoxydiethylene glycol methacrylate 13.5 g AIBN 1.3 g. Raise the temperature in the flask to 65 ° C in a hot water bath,
The reaction was continued for 4 hours. The resulting polymer solution is cooled with ice water to precipitate the resin. When settling started, the contents of the flask were transferred to a 500 ml beaker while swirling, the upper layer liquid was removed, and the mixture was washed several times with ether, and then 50
It was dried under reduced pressure at 0 ° C overnight. The yield of the obtained resin is 97.
%, Number average molecular weight is 29,000 and viscosity is 50 ° C.
It was 6,140 cps.

(Prototype Example-4) 50 equipped with a stirrer, a nitrogen introducing tube, a temperature sensor, a dropping funnel and a condenser
A 0 ml four-neck round bottom flask is charged with isopropyl alcohol 200 ml methoxynonaoxyethylene methacrylate 50 g succinic acid β- (meth) acryloxyethyl monoester 18.4 g methoxydiethylene glycol methacrylate 15.2 g AIBN 0.84 g. Raise the temperature in the flask to 65 ° C in a hot water bath,
The reaction was continued for 4 hours. The resulting polymer solution is cooled with ice water to precipitate the resin. When settling started, the contents of the flask were transferred to a 500 ml beaker while swirling, the upper layer liquid was removed, and the mixture was washed several times with ether, and then 50
It was dried under reduced pressure at 0 ° C overnight. The yield of the obtained resin is 97.
%, Number average molecular weight is 33,000 and viscosity is 50 ° C.
It was 9,200 cps.

(Prototype Example-5) 50 equipped with a stirrer, a nitrogen introducing pipe, a temperature sensor, a dropping funnel and a condenser
In a 0 ml four-necked round bottom flask, isopropyl alcohol 265 ml methoxytricosoxyethylene glycol (meth) acrylate 100 g succinic acid β- (meth) acryloxyethyl monoester 7.2 g methoxydiethylene glycol methacrylate 6.0 g AIBN 1.13 g. Prepare. Raise the temperature in the flask to 65 ° C in a hot water bath,
The reaction was continued for 4 hours. The resulting polymer solution is cooled with ice water and the resin is allowed to settle. When the sedimentation started, the contents of the flask were transferred to a 500 ml beaker while swirling, the upper layer liquid was removed, and after washing several times with ethanol, vacuum drying was carried out at 50 ° C. overnight. The number average molecular weight of the obtained resin was 18,000. Although it was a waxy solid at room temperature, it was 5,300 cps when the viscosity was measured at 50 ° C. with a viscous liquid.

(Prototype Example-6) 50 equipped with a stirrer, a nitrogen introducing tube, a temperature sensor, a dropping funnel and a condenser
A 0 ml four-necked round bottom flask is charged with 280 ml of isopropyl alcohol methoxynonaoxyethylene methacrylate 100 g methyl methacrylate 7.1 g methoxydiethylene glycol methacrylate 13.5 g AIBN 1.2 g. Raise the temperature in the flask to 65 ° C in a hot water bath,
The reaction was continued for 4 hours. The resulting polymer solution is cooled with ice water to precipitate the resin. When settling started, the contents of the flask were transferred to a 500 ml beaker while swirling, the upper layer liquid was removed, and the mixture was washed several times with ether, and then 50
It was dried under reduced pressure at 0 ° C overnight. The yield of the obtained resin is 97.
%, Number average molecular weight is 29,000 and viscosity is 50 ° C.
It was 5,470 cps.

(Prototype Example-7) 50 equipped with a stirrer, a nitrogen introducing tube, a temperature sensor, a dropping funnel and a condenser
A 0 ml four-necked round bottom flask is charged with 280 ml of isopropyl alcohol methoxynonaoxyethylene methacrylate 100 g methyl methacrylate 7.1 g diethylene glycol methacrylate 12.5 g AIBN 1.2 g. Raise the temperature in the flask to 65 ° C in a hot water bath,
The reaction was continued for 4 hours. The resulting polymer solution is cooled with ice water to precipitate the resin. When settling started, the contents of the flask were transferred to a 500 ml beaker while swirling, the upper layer liquid was removed, and the mixture was washed several times with ether, and then 50
It was dried under reduced pressure at 0 ° C overnight. The yield of the obtained resin is 97.
%, Number average molecular weight is 35,000 and viscosity is 50 ° C.
It was 6,200 cps.

Comparative Example-1 A 500 ml four-neck round bottom flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a condenser was charged with isopropyl alcohol (IPA) 165 ml methoxynonaoxyethylene methacrylate 25 g succinic acid β-. (Meth) acryloxyethyl monoester 25 g methoxydiethylene glycol methacrylate 20 g AIBN 0.7 g are charged. Raise the temperature in the flask to 65 ° C in a hot water bath,
The reaction was continued for 4 hours. The resulting polymer solution is cooled with ice water to precipitate the resin. When settling started, the contents of the flask were transferred to a 500 ml beaker while swirling, the upper layer liquid was removed, and the mixture was washed several times with ether, and then 50
It was dried under reduced pressure at 0 ° C overnight. The obtained resin was a rubber-like solid and did not become a liquid whose viscosity could be measured even when heated to 50 ° C.

(Comparative Example-2) 50 equipped with a stirrer, a nitrogen introducing tube, a temperature sensor, a dropping funnel and a condenser.
A 0 ml four-neck round bottom flask is charged with isopropyl alcohol 260 ml methoxynonaoxyethylene methacrylate 100 g succinic acid β- (meth) acryloxyethyl monoester 12.5 g methoxydiethylene glycol methacrylate 0.9 g AIBN 11.3 g. Raise the temperature in the flask to 65 ° C in a hot water bath,
The reaction was continued for 4 hours. This polymer solution was added dropwise to water, but the resin component did not settle. Therefore, the solvent was removed by an evaporator to obtain a liquid resin component. The obtained liquid resin had a monomer odor and was slightly yellowed. Then, when this was analyzed by GPC, the number average molecular weight was 5,000.
And a peak was also seen in the low molecular weight region with a number average molecular weight of several hundred. The viscosity at 50 ° C. was 2000 cps.

(Exemplary Formulation Examples-1 to 8) The liquid resins synthesized in Prototype Examples-1 to 7 and Comparative Example-2 were dropped on a hard aluminum plate kept at 60 ° C. on a hot plate, and a 0.5 mil applicator was used. Was used to form a film. This was placed in an electric oven at 200 ° C. and heated for 15 minutes to obtain a cured film. Table 1
The physical properties of the cured film prepared by using the liquid resin synthesized according to each trial production example and comparative example are shown in FIG.

Table 1 Results of Prescription Examples 1 to 8 ──────────────────────────── Example Resin Tack Solvent Resistance Boiled Water Resistance Properties Adhesiveness /% ──────────────────────────── 1 Trial 1 ○ ○ ○ 90 2 Trial 2 ○ ○ △ 95 3 Trial 3 ○ ○ ○ 100 4 Prototype 4 ○ ○ ○ 100 5 Prototype 5 ○ △ △ 90 6 Prototype 6 ○ ○ ○ 100 7 Prototype 7 ○ ○ ○ 100 8 Comparison 2 ○ × △ 70 ──────────── ─────────────────

(Explanation of Codes) ◯: No tack (tack), no whitening (solvent resistance, boiling water resistance) Δ: Some tack (tack), slightly cloudy (solvent resistance,
Water resistance (boiling resistance) ×: With tack (tack), whitening (solvent resistance, resistance to boiling water) The numerical value in the adhesive column in the table indicates the film remaining rate in the cellophane tape peeling test.

(Exemplary Prescription Examples-9 to 17) Prototype Examples-3 and 6
A fixed amount of para-toluenesulfonic acid was added as a catalyst to the liquid resin synthesized in 1., and the mixture was heated and stirred at 50 ° C. to prepare a transparent liquid curable solventless resin composition. this,
It was hung on a hard aluminum plate kept at 50 ° C. on a hot plate, and a film was formed using a 0.5 mil applicator. This was placed in an electric oven at 200 ° C. and heated for a certain period of time to obtain a cured film. Table 2 shows the physical properties of the cured film prepared by changing the amount of catalyst and the heating time.

Table 2 Results of Prescription Examples 9 to 14 ──────────────────────────────────── Examples Liquid catalyst amount Heating time Pencil tack Resistance to solvent boiling water resistance Resin (wt%) (min) Hardness (%) ──────────────────────── ──────────── 9 Trial 3 0.1 20 H ○ ○ ○ 90 10 Trial 3 0.3 5 4B ○ × △ 40 11 Trial 3 0.3 10 B ○ △ △ 60 12 Trial 3 0.3 15 2H ○○○ 95 13 Prototype 3 0.3 20 3H ○○○ 100 14 Prototype 3 0.6 15 2H ○○○ 100 15 Prototype 6 0.3 5 2B ○ × △ 60 16 Prototype 6 0 3 15 H ○ ○ ○ 100 17 Prototype 6 0.3 20 3 H ○ ○ ○ 100 ──────────────────────────────── ────

(Explanation of symbols) ◯: No tack (tack), no whitening (solvent resistance, boiling water resistance) Δ: Some tack (tack), some cloudiness (solvent resistance,
Water resistance (boiling resistance) ×: With tack (tack), whitening (solvent resistance, resistance to boiling water) The numerical value in the adhesive column in the table indicates the film remaining rate in the cellophane tape peeling test. The pencil hardness is JIS-K-54.
It measured according to 40.

[0037]

EFFECTS OF THE INVENTION A conventional curable resin composition having a molecular weight in an oligomer region can be formed into a film without solvent, and residual low-molecular weight monomers are removed at the resin synthesis stage. Scattering can be suppressed,
The working environment is improved.

Claims (2)

[Claims] 1. A monomer (A) 50 represented by the following general formula:
~ 95% by weight, polymerizable unsaturated carboxylic acid (B) 3 to 35
% By weight, 2 to 45% by weight of a polymerizable unsaturated monomer (C) containing a hydroxyl group or an alkoxy group other than the monomer (A),
And other polymerizable vinyl compounds as a constituent component in an amount of 0 to 20% by weight and a number average molecular weight of 10,000 to 200,0.
00 with a viscosity of 500 cps to 30,000 cps
Liquid resin characterized by being s (50 ° C.). General ^{_{formula: CH 2 = C (R 1}} ) COO (C n H 2n O) m R 2 ( wherein, R ¹ represents a hydrogen atom or CH _3, R ² is C 1 -C
~ 5 alkyl group, n is an integer of 1 to 3, m is an integer of 4 to 25. ) 2. The radical polymerization of the liquid resin is carried out in a solvent in which the monomers (A) to (D) of the resin are good solvents and the resin is a poor solvent. Item 1
The method for producing a liquid resin of.