JPH08217946A - Liquid resin composition and its production - Google Patents

Abstract

PURPOSE: To obtain a nonsolvent liq. resin compsn. which can form a film by a conventional film-forming method and can be cured by thermal drying even without using a curative by compounding specific liq. resins. CONSTITUTION: This compsn. is prepd. by compounding 100 pts.wt. liq. resin with 40-900 pts.wt. another liq. resin. The first resin is a copolymer made from 30-95wt.% monomer component comprising a monomer represented by the formula: CH2 =C(CR<1> )COO(Cn H2n O)m R<2> (wherein R<1> is H or CH3 ; R<2> is H or 1-4C alkyl; n is 1-3; and m is 4-25) and/or a monomer represented by the formula: CH2 =C(R<1> )COOR<3> (wherein R<3> is 4-22C alkyl), 5-70wt.% monomer component comprising an epoxidized polymerizable vinyl monomer and/or a carboxylated polymerizable vinyl monomer, and 0-20wt.% other polymerizable vinyl monomer and has a number average mol.wt. of 10,000-200,000. The second resin is represented by the formula: R<4> O(Cn H2n O)m R<5> (wherein R<4> and R<5> are each H, 1-5C alkyl, aryl, or epoxy; n is 1-3; and m is 4-22).

Description

Detailed Description of the Invention

FIELD OF THE INVENTION The present invention relates to a liquid resin composition capable of forming a hard coating film by forming a film as a resin for a film forming material such as a paint or an ink or an adhesive, without using a solvent, and a liquid resin composition thereof. Regarding manufacturing method.

[0001]

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 can be 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 the cured product 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. In addition, most of the so-called solventless resin compositions use an organic solvent at the time of synthesis to remove the solvent content after the completion of the synthesis, and it takes extra time and solvent. This is not desirable for safety and hygiene, because the parts diffuse into the atmosphere.

[0003]

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 and a polymerizable unsaturated monomer containing a carboxyl group are used. A film forming method in which a resin composition in which a copolymer composed of a polymerizable unsaturated monomer containing an epoxy group and another polymerizable vinyl compound is mixed in a polyoxyalkylene having a terminal modified is conventionally used. It has been found that, for example, a solventless liquid resin composition can be formed by a roll coater or a knife coater, and can be cured by a conventional heat drying method without using a curing agent. Further, the inventors have found that this composition allows the polymerization reaction to proceed favorably without using an organic solvent during radical polymerization, and completed the present invention.

[0004]

The present invention provides the following general formula (A-
1) and / or the monomer (A) 30 represented by the general formula (A-2)
95 wt% Formula _{(A-1): CH 2} = C (R 1) COO (C n H 2n O) m
R ² (in the formula, R ¹ is a hydrogen atom or CH ₃ , R ² is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n is an integer of 1 to 3,
m represents an integer of 4 to 25. ) General formula (A-2):. CH 2 = C (R 1) COO-R 3 ( wherein, R ¹ represents a hydrogen atom or CH _3, R ³ represents an alkyl group having 4 to 22) in a molecule Polymerizable vinyl monomer (B) with epoxy group
And / or a polymerizable vinyl monomer having a carboxyl group in one molecule (C) 5 to 70% by weight and other polymerizable vinyl monomer (D)
Copolymerized from 0 to 20% by weight, the number average molecular weight is 10,000 to 20
The present invention relates to a liquid resin composition obtained by mixing 40 to 900 parts by weight of a liquid resin (E) represented by the following general formula (E-1) with 100 parts by weight of a liquid resin which is 10,000. Further, the present invention relates to a method for producing a liquid resin composition, characterized in that radical polymerization of the above resin is carried out without using another polymerization solvent.

The monomer (A) in the present invention is used as a constituent component for making the copolymer into a liquid, and has the above general formula (A
-1), for example, tetraethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, propoxytetraethylene glycol (meth) acrylate, n-butoxytetra Ethylene glycol (meth) acrylate, n-pentaxytetraethylene glycol (meth)
Alkoxy and other alkoxypolyethylene glycol (meth) acrylate, tetrapropylene glycol (meth) acrylate, methoxytetrapropylene glycol (meth) acrylate, ethoxytetrapropylene glycol (meth) acrylate, propoxytetrapropylene glycol (meth) acrylate, n-butoxytetra There are alkoxy polypropylene glycol (meth) acrylates such as propylene glycol (meth) acrylate and n-pentaxytetrapropylene glycol (meth) acrylate. Repeating unit is 4
The viscosity of the copolymer can be effectively lowered 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 the repeating unit is 26 or more, the degree of polymerization is hard to increase and the viscosity is too high, which is not preferable because a dedicated melting system is required at the time of film formation.

The compounds represented by the general formula (A-2) include, for example, butyl (meth) acrylate, pentyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate and 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, There are alkyl (meth) acrylates having 4 to 22 carbon atoms such as heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, icosyl (meth) acrylate, henicosyl (meth) acrylate, and docosyl (meth) acrylate. Among them, (meth) acrylate having an alkyl group having 8 to 20 carbon atoms is preferable. When the carbon number is 3 or less, it is difficult to obtain a liquid resin, and when the carbon number is 23 or more, it is difficult to increase the degree of polymerization and the viscosity is too high, which is not preferable because a dedicated melting system is required at the time of film formation.

The monomer (A) can be used in combination of two or more kinds. The amount of the component is 30 to 95% by weight, preferably 35 to 95% by weight based on the liquid resin which is a copolymer.
85%, 35% by weight of the monomer (A) in the copolymer,
Particularly when it is less than 30% by weight, the liquid resin composition cannot maintain the low viscosity required for film formation, and conversely 85% by weight,
Particularly, if it exceeds 95% by weight, a hard coating film cannot be obtained, which is not preferable.

The monomer (B) and the monomer (C) of the present invention are both used to introduce a crosslinking component into the liquid resin composition,
As the monomer (B), maleic acid, fumaric acid, itaconic acid, citraconic acid, or their alkyl or alkenyl monoesters, phthalic acid β- (meth) acryloxyethyl monoester, isophthalic acid β- (meth)
Acryloxyethyl monoester, terephthalic acid β-
(Meth) acryloxyethyl monoester, succinic acid β
-(Meth) acryloxyethyl monoester, polymerizable unsaturated carboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, etc. As a monomer (C), glycidyl (meth) acrylate, glycidyl cinnamate, allyl Examples thereof include polymerizable unsaturated glycidyl such as glycidyl ether, vinylcyclohexene monoepoxide, and 1,3-butadiene monoepoxide.

The amount of the monomer (B) and the monomer (C) used is 5 to 70% by weight, preferably 10 to 60% by weight, based on the liquid resin which is a copolymer. (B) and /
Or, if the component (C) is less than 10% by weight, especially less than 5% by weight, it becomes difficult to obtain a hard coating film, and conversely 60% by weight,
In particular, if it exceeds 70% by weight, the viscosity of the liquid resin becomes high and film formation becomes difficult, which is not preferable. The film formation in the present invention means that a resin is formed into a coating 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. Say.

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, hardness, adhesion and the like of the cured coating film. Examples of such a monomer (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, and vinyl acetate. ,
There are vinyl carboxylates such as vinyl butyrate, N-vinylpyrrolidone, N-vinylcarbazole, diallyl phthalate, acrylonitrile and vinyl chloride.

Specific examples of the monomer (D) include allyl ethers such as allyl alcohol, methyl allyl ether, ethyl allyl ether, propyl allyl ether and butyl allyl ether, 4-hydroxystyrene, 4-hydroxymethylstyrene, Styrene such as vinyl phenyl methyl ether, vinyl phenyl ethyl ether, isopropenyl phenyl methyl ether, isopropenyl phenyl ethyl ether, vinyl phenyl methyl methyl ether, vinyl phenyl methyl ethyl ether, isopropenyl phenyl methyl methyl ether, isopropenyl phenyl methyl ethyl ether Compounds, vinyl cyclohexyl methyl ether, vinyl cyclohexyl ethyl ether, isopropenyl cyclohexyl methyl ether, iso Lope sulfonyl cyclohexyl ethyl ether, vinyl cyclohexyl methyl ether, vinyl cyclohexyl methyl ether, isopropenyl cyclohexyl methyl ether, isopropenyl cyclohexylmethyl
There are vinylcyclohexyl compounds such as ethyl ether.

As the monomer (D), for example, a compound having a vinyl group, a —X—Y—Z— bonding group and a hydroxyl group or an alkoxy group bonded thereto can also be used. X is a direct bond or _{-CH 2 -, - Q-CH} 2 -, - Q- represents, Q
Represents an aromatic residue such as a phenylene group or a naphthalene group which may have a substituent such as an alkyl group or a residue such as an alicyclic compound such as cyclohexane, decalin or norbornane. 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. The number of carbon atoms in the alkylene group is 3
Below, preferably 2 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 a hard coating film. Therefore, the above general formula (A-1), a monomer having a long-chain alkyl group or alkyleneoxy group as represented by (A-2) (A)
Is not preferable.

Specific examples include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate and 3-hydroxyethyl (meth) acrylate.
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 (Meth), such as diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, polyethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate
A vinyl ether such as acrylate, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, methyl isopropenyl ether, ethyl isopropenyl ether, propyl isopropenyl ether, butyl isopropenyl ether, etc., and a plurality of them may be used.

The amount of the monomer (D) used is 0 to 20% by weight, preferably 0 to 1 based on the liquid resin which is a copolymer.
It is 5% by weight. When the amount used is 20% by weight or more, the curability is deteriorated and the viscosity is increased, which makes it difficult to form a film, which is not preferable.

The liquid resin (E) in the present invention is a constituent component for imparting an appropriate fluidity to the liquid resin composition of the present invention and facilitating the polymerization reaction without adding an organic solvent as a polymerization solvent. Further, it is hardened together with the copolymer of the monomers (A) to (D) during curing and does not deteriorate the physical properties of the coating film. For this, 4-22,
By using a compound in which a polyoxyalkylene chain which is a repeating unit of 6 to 20 is modified, the viscosity of the liquid resin composition can be effectively lowered and the curability can be imparted. When the repeating unit is 3 or less, the compatibility with the monomers (A) to (D) becomes poor, and when it is 22 or more, the viscosity is too high and the degree of polymerization is difficult to increase, which is not preferable. Both ends are modified with a hydrogen atom, as well as an alkyl group having 1 to 5 carbon atoms, an epoxy group, and an allyl group.

The amount of the liquid resin (E) used is 50 to 700 parts by weight, preferably 100 to 400 parts by weight, based on 100 parts by weight of the liquid resin which is a copolymer. If the amount used is 50 parts by weight or less, the reaction proceeds excessively during the polymerization and gelation occurs. Further, if it is 700 parts by weight or more, the curability is deteriorated and a hard coating film cannot be obtained, which is not preferable.

Examples of the compound used as the liquid resin (E) include polyethylene glycol, polyethylene glycol monoglycidyl ether, polyethylene glycol methyl glycidyl ether, polyethylene glycol diglycidyl ether, polyethylene glycol ethyl glycidyl ether, polyethylene glycol butyl glycidyl ether, polyethylene glycol. Propyl glycidyl ether, polyethylene glycol hexaglycidyl ether, polyethylene glycol monoallyl ether, polyethylene glycol methyl allyl ether, polyethylene glycol diallyl ether, polyethylene glycol ethyl allyl ether, polyethylene glycol butyl allyl ether, polyethylene glycol propyl allyl ether Tell, polyethylene glycol hexaallyl ether, polyethylene glycol monomethyl ether, polyethylene glycol monoallyl ether, polyethylene glycol dimethyl ether, polyethylene glycol methyl allyl ether, polyethylene glycol monoethyl ether, polyethylene glycol diethyl ether, polyethylene glycol ethyl allyl ether, polyethylene glycol methyl ethyl Polyethylene glycols such as ether, polyethylene glycol dipropyl ether, polyethylene glycol dibutyl ether, polyethylene glycol dipentyl ether,

Polypropylene glycol, polypropylene glycol monoglycidyl ether, polypropylene glycol methyl glycidyl ether, polypropylene glycol diglycidyl ether, polypropylene glycol ethyl glycidyl ether, polypropylene glycol butyl glycidyl ether, polypropylene glycol propyl glycidyl ether, polypropylene glycol hexaglycidyl ether, polypropylene glycol Monoallyl ether, polypropylene glycol methyl allyl ether, polypropylene glycol diallyl ether, polypropylene glycol ethyl allyl ether, polypropylene glycol butyl allyl ether, polypropylene glycol propyl allyl ether, polypropylene Glycol glycol allyl ether, polypropylene glycol monomethyl ether, polypropylene glycol monoallyl ether, polypropylene glycol dimethyl ether, polypropylene glycol methyl allyl ether, polypropylene glycol monoethyl ether, polypropylene glycol diethyl ether, polypropylene glycol ethyl allyl ether, polypropylene glycol methyl ethyl ether, Examples thereof include polypropylene glycols such as polypropylene glycol dipropyl ether, polypropylene glycol dibutyl ether and polypropylene glycol dipentyl ether.

Since the liquid resin composition of the present invention has an appropriate fluidity from the start of the polymerization to the end of the polymerization, the monomers (A) to (D) and the liquid resin (E) are mixed to obtain a known radical polymerization. Polymerization can easily proceed by heating and stirring with an initiator to produce a liquid resin composition. On this occasion,
The liquid resin (E) remains unreacted during polymerization, but is cured by heating at 130 ° C to 250 ° C after film formation,
A sufficiently hard coating film can be obtained.

As a radical polymerization initiator by copolymerization,
Although not particularly limited, for example, peroxides such as benzoyl peroxide, t-butyl peroxide, cumene hydroperoxide and lauroyl peroxide, azo initiators such as azobisisobutyronitrile and azobiscyclohexanenitrile, and peroxides Persulfate initiators such as potassium sulfate and ammonium persulfate can be used. The blending amount of such radical polymerization initiator is 0.01 to 5% by weight based on the total blending amount of the monomers.
Is preferable, and more preferably 0.1 to 3% by weight. GPC of high molecular weight component in the obtained liquid resin composition
The number average molecular weight (converted to styrene) was 10,000.
It becomes 0 to 200,000.

The liquid resin composition of the present invention comprises the copolymer of the monomers (A) to (D) and the liquid resin (E), and can be used as a substantially solventless resin. However, a small amount of water or an organic solvent may be added in order to improve the film-forming property. The amount that can be compounded is 5 with respect to the liquid resin.
Up to weight%. The liquid resin composition of the present invention may be mixed with a curable resin such as an amino resin, a phenol resin or an acrylic oligomer in order to enhance 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 liquid resin composition of the present invention can be used. Examples of typical curing catalysts include p-toluenesulfonic acid, phthalic anhydride, benzoic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, formic acid, acetic acid,
Itaconic acid, oxalic acid, phosphoric acid, maleic acid, and their ammonium salts, lower amine salts, polyvalent metal salts and the like. The liquid resin composition of the present invention is formed into a 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, A hard coating film can be obtained by heating at ~ 260 ° C for 1 to 30 minutes. The liquid resin composition of the present invention can be used as a compatibilizer, an interfacial modifier, a pigment dispersant, etc., as well as a coating, a film forming material such as an ink, a resin such as an adhesive.

[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. (Prototype Examples-1 to 11) A 500 ml four-necked round bottom flask equipped with a stirrer, a nitrogen introduction tube, a temperature sensor, and a condenser was charged with the following monomers and compounds, and the temperature in the flask in a hot water bath. Was heated to 65 ° C. and the reaction was continued for 6 hours. The liquid resin composition thus obtained was measured by GPC, and the number average molecular weight (in terms of styrene) of the obtained polymer component and the viscosity at 25 ° C. were measured using a rotational viscometer (RFS-II, manufactured by Rheometrics). The measured values are shown in Table 1.

(Prototype Example-1) Polyethylene glycol dimethyl ether 400 g (average molecular weight 350, n = 2, m = 6 to 7) Methoxytetraoxyethylene methacrylate 40 g Succinic acid β-methacryloxyethyl monoester 10 g Glycidyl methacrylate 50 g Azo Bisisobutyronitrile (AIBN) 1g

(Prototype Example-2) Polyethylene glycol dimethyl ether 100 g (average molecular weight 250, n = 2, m = 4 to 5) Methoxynonaoxyethylene methacrylate 85 g Succinic acid β-methacryloxyethyl monoester 15 g AIBN 1 g

(Prototype Example-3) Polyethylene glycol dimethyl ether 200 g (average molecular weight 350, n = 2, m = 6 to 7) Methoxynonaoxyethylene methacrylate 60 g Succinic acid β-acryloxyethyl monoester 25 g Methyl methacrylate 15 g AIBN 1 g

(Prototype Example-4) Polyethylene glycol dimethyl ether 400 g (average molecular weight 400, n = 2, m = 8) Methoxynonaoxyethylene methacrylate 40 g Glycidyl methacrylate 45 g Methoxydiethylene glycol methacrylate 15 g AIBN 1 g

(Prototype Example-5) Polyethylene glycol dimethyl ether 200 g (average molecular weight 350, n = 2, m = 6 to 7) n-butyl methacrylate 80 g Succinic acid β-methacryloxyethyl monoester 20 g AIBN 1 g

(Prototype Example-6) Polyethylene glycol dimethyl ether 200 g (average molecular weight 350, n = 2, m = 6 to 7) Methoxynonaoxyethylene methacrylate 50 g Lauryl methacrylate 30 g Succinic acid β-methacryloxyethyl monoester 20 g AIBN 1.2 g

(Prototype Example-7) Polyethylene glycol dimethyl ether 200 g (average molecular weight 350, n = 2, m = 6 to 7) methoxynonaoxyethylene methacrylate 60 g succinic acid β-methacryloxyethyl monoester 20 g methoxydiethylene glycol methacrylate 20g AIBN 1g

(Prototype Example-8) Polyethylene glycol dimethyl ether 200 g (average molecular weight 350, n = 2, m = 6 to 7) methoxynonaoxyethylene methacrylate 80 g methacrylic acid 10 g methyl methacrylate 10 g AIBN 1 g

(Prototype Example-9) Polyethylene glycol methylallyl ether 200 g (average molecular weight 350, n = 2, m = 6 to 7) Methoxytricosoxyethylene methacrylate 80 g Succinic acid β-methacryloxyethyl monoester 20 g AIBN 1 g

(Prototype Example-10) Polyethylene glycol diallyl ether 200 g (average molecular weight 450, n = 2, m = 8 to 9) Icosyl methacrylate 80 g Glycidyl methacrylate 20 g AIBN 1 g

(Prototype Example-11) Polyethylene glycol diglycidyl ether 200 g (average molecular weight 400, n = 2, m = 6 to 7) Methoxynonaoxyethylene methacrylate 80 g Succinic acid β-methacryloxyethyl monoester 20 g AIBN 1 g

(Comparative Example-1) 50 equipped with a stirrer, a nitrogen introducing tube, a temperature sensor, a dropping funnel and a condenser
In a 0 ml four-neck round bottom flask, polyethylene glycol methyl allyl ether 200 g (average molecular weight 400, n = 2, m = 6 to 7) methoxynonaoxyethylene methacrylate 20 g succinic acid β- (meth) acryloxyethyl monoester 80 g When 1 g of AIBN was charged and the temperature in the flask was raised to 65 ° C. in a hot water bath to cause a reaction, gelation occurred after 1 hour.

(Comparative Example-2) 50 equipped with a stirrer, a nitrogen introducing tube, a temperature sensor, a dropping funnel and a condenser.
In a 0 ml four-necked round bottom flask, polyethylene glycol dimethyl ether 200 g (average molecular weight 350, n = 2, m = 6 to 7) methoxynonaoxyethylene methacrylate 97 g succinic acid β- (meth) acryloxyethyl monoester 3 g AIBN 1 g Was charged, the temperature in the flask was raised to 65 ° C. in a hot water bath, and the reaction was carried out for 6 hours. The obtained liquid resin composition is GP
The number average molecular weight (converted to styrene) of the obtained polymer component measured by C and the viscosity measurement value at 25 ° C. using a rotational viscometer (RFS-II, manufactured by Rheometrics) are shown in Table 1.
Shown in

(Comparative Example-3) 50 equipped with a stirrer, a nitrogen introducing tube, a temperature sensor, a dropping funnel and a condenser.
In a 0 ml four-necked round bottom flask, polyethylene glycol dimethyl ether 200 g (average molecular weight 350, n = 2, m = 6 to 7) methoxynonaoxyethylene methacrylate 40 g succinic acid β- (meth) acryloxyethyl monoester 30 g methyl methacrylate 30 g AIBN 1 g was charged, the temperature in the flask was raised to 65 ° C. in a water bath, and the reaction was continued for 6 hours. The number average molecular weight (in terms of styrene) of the obtained liquid resin measured by GPC was 32,000,
The viscosity at 25 ° C was above the measurement range of a rotational viscometer (RFS-II, manufactured by Rheometrics Co.) and could not be measured.
Also, the viscosity was too high to be applied with an applicator of 0.5 mil.

(Comparative Example-4) 50 equipped with a stirrer, a nitrogen introducing tube, a temperature sensor, a dropping funnel and a condenser.
In a 0 ml four-necked round bottom flask, polyethylene glycol dimethyl ether 40 g (average molecular weight 350, n = 2, m = 6 to 7) methoxynonaoxyethylene methacrylate 60 g succinic acid β- (meth) acryloxyethyl monoester 40 g AIBN 1 g Was charged, the temperature inside the flask was raised to 65 ° C. in a hot water bath, and a reaction was carried out. After 30 minutes, gelation occurred.

(Comparative Example-5) 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 was charged with polyethylene glycol dimethyl ether 800 g (average molecular weight 350, n = 2, m = 6 to 7) methoxynonaoxyethylene methacrylate 80 g glycidyl methacrylate 20 g AIBN 1 g, and the inside of the flask was heated in a water bath. The temperature was raised to 65 ° C. and the reaction was continued for 6 hours. The number average molecular weight (in terms of styrene) of the obtained liquid resin measured by GPC was 18,000,
The viscosity at 25 ° C. measured using a rotational viscometer (RFS-II, manufactured by Rheometrics) was 200 cps.

Table 1 Number average molecular weight of liquid resin and viscosity of composition ──────────────────────────── Prototype number average molecular weight viscosity (Cps) ──────────────────────────── 1 21000 130 2 23000 3000 3 22000 20000 4 33000 650 5 22000 8000 6 35000 2400 7 28000 2400 8 24000 3300 9 23000 900 10 24000 2800 11 25000 2100 Comparative Example 2 22000 90 Comparative Example 3 19000 Unmeasurable Comparative Example 5 23000 40 ──────────────────── ───────

(Examples of formulation-1 to 11, comparative examples 2 and 3,
5) The liquid resin compositions synthesized in Prototype Examples-1 to 11 and Comparative Examples 2 and 5 were dropped on a hard aluminum 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 15 minutes to obtain a hard coating film. Table 2 shows the measured physical properties of the coating films produced using the liquid resin compositions of the respective prototype examples. The surface condition of the tack was confirmed by touching with fingers, and the solvent resistance and the boiling water resistance were visually confirmed after immersion in methyl ethyl ketone and boiling water for 10 minutes. In addition, the adhesiveness shows the film residual rate in the scoring tape test with cellophane tape. Table 2 Results of prescription examples 1 to 8 ────────────────────────────── Example resin tack solvent resistance solvent boiling resistance Adhesiveness /% ────────────────────────────── 1 Trial 1 ○ ○ ○ 100 2 Trial 2 ○ ○ ○ 100 3 Trial 3 ○ ○ ○ 100 4 Prototype 4 ○ ○ ○ 100 5 Prototype 5 ○ ○ ○ 100 6 Prototype 6 ○ ○ ○ 100 7 Prototype 7 ○ ○ ○ 100 8 Prototype 8 ○ ○ ○ 100 9 Prototype 9 ○ ○ ○ 100 10 Prototype 10 ○ ○ ○ 100 11 Prototype 11 ○ ○ ○ 100 Comparative Example 2 △ × ○ 30 Comparative Example 5 △ × △ 70 ────────────────────────── ─────

(Explanation of symbols) ○: No tack (tack), no whitening (solvent resistance, boiling water resistance) △: Some tack (tack), whitening (solvent resistance, boiling water resistance) ×: Tack Yes (tack), floating or peeling (solvent resistance, boiling water resistance)

[0044]

EFFECT OF THE INVENTION A curable resin composition comprising a conventional liquid resin having a molecular weight in the oligomer region and a liquid resin having a relatively low molecular weight can be formed into a film at room temperature, and the solvent does not scatter during baking. Further, since the synthesis reaction proceeds even without a solvent, the step of removing the solvent can be omitted, and the working environment is greatly improved.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C08L 71/02 LQE C08L 71/02 LQE C09D 133/06 C09D 133/06 133/14 PGF 133/14 PGF 163/00 PJA 163/00 PJA 171/02 PLQ 171/02 PLQ C09J 133/06 C09J 133/06 133/14 JDD 133/14 JDD 163/00 JFM 163/00 JFM JFP JFP 171/02 JFW 171/02 JFW (72) Inventor Miki Kawashima 2-33 Kyobashi, Chuo-ku, Tokyo Toyo Inki Manufacturing Co., Ltd.

Claims (2)

[Claims] 1. The following general formula (A-1) and / or general formula
Monomer (A) represented by (A-2)
30-95 wt% formula _{(A-1): CH 2} = C (R 1) COO (C n H 2n O) m
R ² (in the formula, R ¹ is a hydrogen atom or CH ₃ , R ² is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n is an integer of 1 to 3,
m represents an integer of 4 to 25. ) General formula (A-2):. CH 2 = C (R 1) COO-R 3 ( wherein, R ¹ represents a hydrogen atom or CH _3, R ³ represents an alkyl group having 4 to 22) in a molecule Polymerizable vinyl monomer (B) with epoxy group
And / or a polymerizable vinyl monomer having a carboxyl group in one molecule (C) 5 to 70% by weight and other polymerizable vinyl monomer (D)
Copolymerized from 0 to 20% by weight, the number average molecular weight is 10,000 to 20
A liquid resin composition obtained by mixing 40 to 900 parts by weight of a liquid resin (E) represented by the following general formula (E-1) with 100 parts by weight of a liquid resin of 20,000. Formula (E-1): in ^{_{R 4 O (C n H 2n}} O) m R 5 ( wherein, R ^4, R ⁵ are each a hydrogen atom, carbon atoms 5
, An alkyl group, an allyl group, an epoxy group, n is an integer of 1 to 3, and m is an integer of 4 to 22. ) 2. The method for producing a liquid resin composition according to claim 1, wherein radical polymerization of the monomers (A) to (D) is carried out in the liquid resin (E).