JPS6029726B2 - polymerizable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an epoxy-modified (meth)acrylate-based polymerizable composition, and its object is to provide an epoxy-modified (meth)acrylate-based polymerizable composition with improved touch resistance. is to provide.

Previously, some of the present inventors disclosed in Japanese Patent Application No. 50-125037 that at least one carboxyl group of an unsaturated alicyclic polybasic acid and (meth)acrylic acid in the presence of a nitrite or a nitrosamine compound. We have proposed a method for stably producing a (meth)acrylate polymerizable composition having a carboxyl group formed through an ester bond with a glycol having 2 to 4 carbon atoms.

Patent No. 50-25037 describes glycols having 2 to 4 carbon atoms [selected from the group consisting of alkyl groups, alnickel groups, cycloalkyl groups, cycloalkenyl groups, allyl groups, and aralkyl groups having at most 8 carbon atoms; may be substituted with a hydrocarbon group, a halogen atom, a hydroxyl group, an amino group or an ether bond, or a hydrocarbon group containing a halogen atom, a hydroxyl group, an amino group or an ether bond] (hereinafter referred to as a glycol having 2 to 4 carbon atoms) (abbreviated as ) things (
Epoxy-modified (meth)acrylate obtained by reacting a half ester of the unsaturated alicyclic polybasic acid or its anhydride with a polyepoxy compound having at least one epoxy group in the presence of a nitrite or a nitrosamine compound. The meta)acrylate-based polymerizable composition can be cured alone or as a solution of a polymerizable vinyl monomer in the presence of a catalyst or accelerator at room temperature or under heating, or it can be cured by irradiation with electron beams, d-rays, ultraviolet rays, etc. By quickly radically curing by irradiation with active radiation or actinic rays, it has excellent surface hardening properties even when cured in the air.
In particular, it provides a high-performance cured product with excellent adhesion even to metals, but on the other hand, its corrosion resistance, especially alkali resistance, is not always sufficient, perhaps because it has many ester bonds and hydroxyl groups in the molecule. There wasn't. In particular, when a diglycidyl ester compound such as a diglycidyl ester of phthalic acid, or a glycidyl ether compound of a polyol such as ethylene glycol or butanediol is used as a polyepoxy compound having two or more epoxy groups. The resulting polymerizable composition is extremely useful because it provides a cured product with low viscosity and excellent maneuverability and metal adhesion, but the alkali resistance of the cured product was not necessarily satisfactory. As a result of various studies on improving corrosion resistance, particularly alkalinity, the present inventors discovered that the polymerizable composition according to the present invention provides a cured product with excellent corrosion resistance, and arrived at the present invention.

That is, the gist of the present invention is to provide an epoxy-modified (meth)acrylate obtained by reacting a compound represented by the following general formula '1} with a polyepoxy compound having at least two epoxy groups in the molecule. The present invention relates to a polymerizable composition comprising the same and a polymerizable vinyl monomer.

[However, in the formula, R,, R2 is hydrogen or a methyl group; A is an alkylene group having 2 to 4 carbon atoms (at most 8 carbon atoms)
substituted with a hydrocarbon group selected from the group consisting of alkyl groups, alkenyl groups, cycloalkyl groups, cycloalkenyl groups, allyl groups and aralkyl groups, halogen atoms or ether bonds, or hydrocarbon groups containing halogen atoms. (also good); Z is Q. 8 Residue of an unsaturated alicyclic dibasic acid compound obtained by reacting a monounsaturated dibasic acid or its derivative with a gene compound; B
or R4, R3, R4 are hydrocarbon groups selected from the group consisting of hard alkyl groups, alkenyl groups, cycloalkyl groups, cycloalkenyl groups, allyl groups and aralkyl groups with a prime number of 6 to 2; Residues of basic acids] Compounds used in carrying out the present invention
1) is disclosed in Japanese Patent Application No. 1983-25037.
In the presence of a nitrite or a nitrosamine-based compound as described in the No. 1, {i is a half ester of a mono(meth)acrylate of a glycol having 2 to 4 carbon atoms and an unsaturated alicyclic dibasic acid, 'o' is reacted with a monoepoxy compound represented by general formula B, and then N is produced by reacting with a dibasic acid anhydride.

This is expressed by the following formula. General formula '1},'
Glycol monos with 2 to 4 carbon atoms used in
Half esters of meth)acrylate unsaturated alicyclic basic acids are polyvalent esters such as ethylene glycol monoacrylate, ethylene glycol monomethacrylate, propylene glycol monoacrylate, propylene glycol monomethacrylate, glycerin diacrylate and glycerin dimethacrylate. Substituted acrylate or methacrylate and 1,4-butylene glycol, 1,3-butylene glycol, dimethylolethane,
2-chloromethyl-ethylene glycol, 2-chloro-1
, 3-propylene glycol, 2-frommethyl-ethylene glycol, 2-bromo-1,3-propylene glycol, 2-chloromethyl-1,3-propylene glycol, 2-bromomethyl-1,3-propylene glycol, 4-chloro-1,2 -butylene glycol, 4-1
, 2-butylene glycol, 1,2-butylene glycol, glycerin monophenyl ether, 2-vinylethylene glycol, glycerin monotrile ether, styrene glycol, glycerin monoaryl ether, 1,2-cyclohexane diol , monoacrylates or methacrylates of glycols having 2 to 4 carbon atoms or their derivatives, such as glycerin monobutyl ether and dicyclobentadiene monohydrate, and tetrahydrophthalic anhydride, tetrahydrophthalic acid,
Methyltetrahydrophthalic anhydride, methyltrahydrophthalic acid, 1-methyl-2,3,6-trihydrophthalic anhydride, 1-methyl-2,3,6-trihydrophthalic acid,
1,2-dimethyl-3,6-dihydrophthalic anhydride, 1
, 2-dimethyl-3,6-dihydrophthalic acid, 4,5-dimethyltetrahydrophthalic anhydride, 4,5-dimethyltetrahydrophthalic acid, 4,5-dimethoxytetrahydrophthalic anhydride, 1,2-dichloro-3,6-dihydrophthalic anhydride , 1,2-dihydro-3,6-dihydrophthalic acid, 1,2-dihydro-3,6-dichlorophthalic anhydride, 1,2-dihydro-3,6-dichlorophthalic acid,
1,2-dihydrodiphenyl phthalic anhydride and 1,2
-dihydro-3,6-diphenylphthalic acid, 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride, 3,6-endomethylene-1,2,3,6-tetrahydrophthalic acid, 3,6-endomethylene -1,2-
Dimethyl-3,6-dihydro-phthalic anhydride, 3,6-endomethylene-1,2-dimethyl-3,6-dihydrophthalic acid, Q-terbinene monohydric maleic acid adduct, furan monohydric maleic acid adduct, 8-Hydroxyfuran-maleic anhydride adduct, isobenzofuran-maleic anhydride adduct, thiophene-maleic anhydride adduct, and 2
, 5-dimethyl-3,4-diphenylcyclobentachene monohydric maleic acid adduct, and other half-esters of unsaturated alicyclic dibasic acids.

Also'.

The monoepoxy compound used in ' is the general formula (however,
In the formula, R2 is hydrogen or a methyl group; B is or R4, R3
, R4 is a hydrocarbon group selected from the group consisting of a hard alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group, allyl group, and aralkyl group having 6 to 2 carbon atoms)
Typical examples are glycidyl ether compounds having one epoxy group and glycidyl ester compounds having one epoxy group. Examples of glycidyl ether type compounds include epichlorohydrin or B-methylepichlorohydrin and compounds of the general formula H
O-R4 (wherein R4 is a hydrocarbon group selected from the group consisting of a hard alkyl group having 6 to 2 carbon atoms, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an allyl group, and an aralkyl group) It can be obtained by reacting with a hydroxy compound, and representative examples thereof include hexyl glycidyl ether and hexyl B-methyl glycidyl ether (hereinafter referred to as methyl glycidyl ether). omitted) 2-methyloctyl glycidyl ether, lauryl glycidyl ether,
Examples include cyclohexyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, and oleyl glycidyl ether.

In addition, as glycidyl ester compounds, for example, epichlorohydrin or 8-methylepichlorohydrin and the general formula (wherein R3 is a hard alkyl group having 6 to 2 carbon atoms, an alkenyl group,
It can be obtained by reacting with a monobasic acid represented by a hydrocarbon group selected from the group consisting of a cycloalkyl group, a cycloalkenyl group, an allyl group, and an aralkyl group, and representative examples thereof Examples include hebutanoic acid glycidyl ester, hebutanoic acid-8-methylglycidyl ester (hereinafter, examples of B-methylglycidyl ester are omitted), n-undecylenic acid glycidyl ester, stearic acid glycidyl ester.n -Henicosan glycidyl ester, oleic acid glycidyl ester, linoleic acid glycidyl ester, linoleic acid glycidyl ester, benzoic acid glycidyl ester, methylbenzoic acid glycidyl ester, versatic acid glycidyl ester, and the like.

R4 of the glycidyl ether compound represented by the general formula and R3 of the glycidyl ester compound represented by the general formula R3 each have 6 to 2 carbon atoms.
It is a solid hydrocarbon group.

When the number of carbon atoms in the hydrocarbon group is 6 or less, the insect resistance of the cured product is not sufficient, probably because the protective effect on the ester bond adjacent to R3 and R4 in the compound of the general formula u is small. , and those having carbon atoms of 20 or more have little practical significance in terms of raw material availability. Furthermore, [mouth]
As the dibasic acid anhydride used in the above, both saturated and unsaturated dibasic acid anhydrides can be used, but representative examples thereof include:
Examples include succinic anhydride, glutaric anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, maleic anhydride, itaconic anhydride, citrolaconic anhydride, and the like.

Furthermore, as polyepoxide compounds having at least two epoxy groups to be reacted with compound {1), glycidyl ether compounds containing substituted or unsubstituted glycidyl ether groups in the molecule and substituted or unsubstituted glycidyl ether groups can be used. A typical example is a glycidyl ester compound containing a glycidyl ester group in the molecule.

A glycidyl ether compound can be obtained by reacting a dihydroxy compound or a polyhydroxy compound with an epoxy compound.

Typical examples thereof include ethylene glycol glycidyl ether, diethylene glycol glycidyl ether, butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neobentyl glycol diglycidyl ether, glycerin di- and triglycidyl ether, Ethers, trimethylolpropane di- and triglycidyl ethers and epoxy compounds (e.g. epichlorohydrin, methylepichlorohydrin) and 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) or its homologues. Namely, glycidyl ethers of bisphenol A, diglycidyl ethers of bisphenol F and their polymers, and polyglycidyl ethers of novolac resins such as phenol and cresol can be mentioned. On the other hand, typical examples of glycidyl ester compounds include epoxy compounds such as epichlorohydrin and methylepichlorohydrin, dicarboxylic acids or polycarboxylic acids such as adipic acid, isophthalic acid, and phthalic acid, or their Examples include those obtained by reacting carboxylic acid anhydrides, copolymers of glycidyl (meth)acrylate, triglycidyl isocyanurate, glycidyl hydantoin, and the like. In carrying out the present invention, the reaction ratio of carboxyl group to 1 mole of epoxy group is generally 0.6 to 1.
The amount is 1.8 mol, particularly 0.8 to 1.2 mol is optimal. If the reaction ratio of carboxyl group to 1 mole of epoxy group is 0.6 mole or less, a compound having an unreacted excess of epoxy group will be present in the polymerizable composition.
On the other hand, if the amount is 1.8 mol or more, an excess of the terminally reacted compound without carboxyl groups will be present in the polymerizable composition. In either case, it is necessary to remove these unreacted compounds by some method, and even if it is not necessary to remove them, they may adversely affect the physical properties of the cured product of the polymerizable composition. Further, the proportion of (meth)acryloyl groups in the (meth)acrylate polymerizable composition to be produced is not particularly limited, but in particular, those with a molecular weight of 200 to 2000 per mole of (meth)acryloyl groups This is desirable because it yields a polymerizable composition that provides a cured product with excellent air drying properties and metal adhesion.

When the present invention is carried out in the presence of catalysts such as tertiary aminos, Lewis acids and their salts, and quaternary ammonium salts, the proportion of catalyst used is at most 5.0% relative to the total amount of each of the reaction components. Weight%. 5. If a catalyst is used in an amount exceeding There is also.

In the present invention, the reaction temperature varies depending on the types of the compounds used and their reaction ratios, the presence or absence of catalysts and their types, the types of nitrites and their usage ratios, and other reaction conditions, but generally it is room temperature to 200 qo, particularly preferably 50 to 150 qo.

When the reaction temperature is below room temperature, the reaction rate is slow and the reaction requires a long time. On the other hand, at 200 qo or more, gelation due to thermal polymerization often occurs. Although the present invention can be carried out in the absence of a solvent, it may also be carried out in the presence of an organic solvent inert to these reactions (eg, benzene, toluene, xylene, chloroform).

The polymerizable composition of the present invention can be used as it is, but by mixing it with a known polymerizable vinyl monomer,
It can also be used by adjusting the viscosity to a desired value.

This monomer is preferably liquid at room temperature, and examples thereof include styrene, acrylonitrile, methacrylonitrile, vinyltoluene, acrylic ester, methacrylic ester, divinylbenzene, vinylpyridine, vinyl acetate, and diallylphthalene. - can be mentioned. When the polymerizable composition obtained by the present invention is dissolved in this monomer and used as a solution, the suitable ratio of the monomer to the polymerizable composition is determined depending on the viscosity of the polymerizable composition and the purpose of use of the solution. However, the amount of monomer that is generally used in the field in which the polymerizable composition is used may be used, and there is no particular limitation.

The polymerizable composition obtained according to the present invention or a solution dissolved in the monomer thereof can be applied to a coating material and cured by a commonly used curing method such as an ultraviolet curing method or an electron beam curing method. can be cured and used as molding materials, laminated materials, coating materials and adhesive materials.

When a polymerizable composition or a solution thereof is cured by an ultraviolet curing method according to the present invention, generally known penzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl,
Photosensitizers such as diphenyl disulfide, tetolmethyluramonosulfide, diacel, azobisisobutyronitrile, 2-methylanthraquinone, 2-ethylanthraquinone, and 2-tert-butylanthraquinone are added to the polymerizable composition or By adding to those solutions,
The curing time can be further shortened.

Generally, the amount of photosensitizer added is at most 5% by weight based on the polymerizable composition or solution thereof. Further, when curing by a thermosetting method, curing can be simplified by adding a radical polymerization initiator such as an organic peroxide to shorten the curing time.

The proportion of the radical polymerization initiator added is generally at most 5% by weight, based on the polymerizable composition. When adding (mixing) this radical polymerization initiator, if the viscosity of the polymerizable composition is high, it may be dissolved in the monomer and then mixed with the polymerizable composition. Regardless of the mixing method, if the mixing temperature is high, the radical polymerization opening agent will decompose and the polymerizable composition will crosslink, producing a cured product before thermosetting, causing problems such as stopping the foundation during mixing. may occur.
From the above, it is preferable that the mixing temperature be as low as possible. "A (meth)acrylate polymerizable composition, a mixture thereof with a photosensitizer or a radical initiator, or a solution of a single star thereof" obtained by the present invention (hereinafter referred to as "
As a method for coating a material containing a polymerizable composition on the surface of a shaped object (object to be coated), there are commonly used methods such as a roll coater, a bar coater, and a curtain flow coater. After application by a coating device or commonly applied coating methods such as brushing and spray coating methods, it can be easily cured by the curing method described above.

When used as an adhesive, methods for interposing the polymerizable composition-containing material between adherends include methods of spraying or coating the polymerizable composition-containing material on the surface of the adherend, or methods of interposing the polymerizable composition-containing material between adherends. One example is a method of soaking the polymerizable composition-containing material in the body.

Coatings and adherends include metals such as aluminium, copper, chromium, iron, lead, zinc, tin, nickel and precious metals and their alloys (e.g. brass, stainless steel, bronze), wood, paper and Celluloses such as cotton, polyethylene, polypropylene, polyvinyl chloride, polyacrylonitrile, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene resin (
synthetic resins such as polyamide resins, unsaturated polyester resins, phenolic resins, melamine resins, urea resins, and blends thereof, polybutadiene rubber, styrene-butadiene copolymer rubber (
SBR), ethylene-propylene copolymer rubber (EPR)
, ethylene-propylene-gene ternary copolymer rubber (EP
DM), polychloroprene, acrionitrile-butadiene copolymer rubber (NBR), chlorinated polyethylene and natural rubber, glass, gypsum, and inorganic compounds such as cement (including concrete). Moreover, the shapes thereof include powder, film, sheet, foil, pipe, rod, sphere, fiber, fabric, and other complex shapes. Hereinafter, the present invention will be explained in more detail with reference to Examples.

The performance of the coating films in Examples and Comparative Examples was determined according to the following. Pencil hardness was measured according to JISK-5401 using a Mitsubishi Juni pencil scratch tester.

Adhesion (cross-cut test) The obtained coating film was crossed at right angles with a safety razor blade, cut with 11 straight lines with an interval of 1 skin, 100 cross-cuts were drawn, and cellophane tape was applied to the cross-cuts. I put this cellophane tape on it and used acupressure to completely adhere it.

When the adhesive cellophane tape was peeled off, the number of goblets that were peeled off was determined. (100/100 means that no peeling occurred) Using a bending paint film bending tester (manufactured by Daisuke Kizai Co., Ltd.), the sample was bent 1800 degrees and the presence or absence of abnormalities in the paint film was measured.

Rub the paint film with a cloth soaked in M Old K Love Methyl Ethyl Ketone.
The number of times the coating was rubbed until it peeled off was expressed.

An alkali-resistant coated plate was immersed in a 5% NaOH aqueous solution at room temperature, and the evaluation was based on the time it took for a part of the coating film (thickness 10 to 20 mm) to dissolve.

[Production example of polymerizable composition]

(1) Production of Polymerizable Composition A 3. Into a four-necked flask equipped with a flask, a thermometer, a nitrogen inlet tube, and a condenser, 100 pieces of 2-hydroxyethyl acrylate (8.62 mol) and 1431 g of Methyltetrahydrophthalic anhydride (8.62 mol), 9.2
6 g of N,N-jetylcyclohexylamine and 1.
2 of sodium nitrite was charged, and the reaction was carried out for 5 hours at a temperature of 60 to 82.5 degrees Celsius under a nitrogen stream with a light on, to obtain a light brown liquid semi-esterified product.

This half-esterified product is hereinafter referred to as a reaction product. The acid value of this reaction product [I] determined from a water-acetone solution was 197.

The reaction product [I}85 obtained above, glycidyl ester of Vasatic acid as a monoepoxide resin (manufactured by Shell Chemical Co., Ltd., trade name Cardura E, epoxy equivalent weight 245) 75 female, N,N-diethylcyclohexy , Reamin 1. Put the key and 0.3 g of sodium nitrite into three four-necked flasks similar to the above, and boil for 10 minutes under a nitrogen stream.
The reaction was carried out at 115°C for 3 and a half hours. The acid value of the obtained reaction product was 8. The flask was temporarily cooled, and when the temperature of the contents reached 0, 49% of methyltetrahydrophthalic anhydride was further added and the mixture was heated to 100 to 108% under a nitrogen stream.
When the mixture was heated and reacted for 1.5 hours at midnight, a pale brown viscous liquid product was obtained. The acid value of this product is 83.
It was 9. This product is hereinafter referred to as the reaction product'. }. Next, 1 liter of the reaction product was placed in a 500 mm four-necked flask equipped with a thermometer, a nitrogen inlet tube, and a condensing tube.
3 cranes, neobentyl glycol diglycidyl ether epoxy resin (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd., trade name: Eporite 150 State P, epoxy equivalent: 150) 3 females, N, N-
0.5 g of dimethylcyclohexylamine and 0.1 g of sodium nitrite were charged, and heated under a light frame for 3 hours at a temperature of 100 to 115 oo in a nitrogen stream to obtain a yellowish brown, extremely viscous product. .

The acid value of the product was 9. ■ Production of polymerizable composition B (comparative example) Into a 500' flask similar to that used in 'm', 285 g of the reaction product synthesized in {1'} and the neobentyl glycol diglycidyl gel used in '11 were added. -ether epoxy resin 150g, N,N-jetyl dichlorohexylamine 0. Add 0.1 liter of sodium nitrite and heat under nitrogen stream for 1 hour.
The reaction was carried out by heating at 10 to 120 qO for 6 hours under the ocean to obtain a yellow-brown sticky liquid product.

The acid value of this product was 11. {3} Manufacture of polymerizable composition C.
In the four-necked flask, the reaction product synthesized in step 0 {o
} 68 Akebono, methyltetrahydrophthalate diglycidyl ester epoxy resin (manufactured by Showa Denko, trade name Shodine 531, epoxy equivalent: 170) 10, 1,6-hexanediol diglycidyl ether epoxy resin (
Kyoeisha Yushi Kogyo Co., Ltd., trade name: Eporite 1600, epoxy equivalent: 160) 6-cycle, N,N-jeltylcyclohexylamine 1. Acid, sodium nitrite 0. A key was charged and subjected to temporary reaction by heating at 100 to 115° C. for 4 hours under a nitrogen stream to obtain a pale brown viscous liquid product.

The acid value of the obtained product was 10. '4' Production of polymerizable composition D (comparative example) In (2), in place of the four-necked flask, a four-necked flask was equipped with a Takazusa machine, a thermometer, a nitrogen introduction tube, and a reflux condenser. The reaction was carried out in the same manner as in '3' except that 285 g of the reaction product {i} synthesized in '11 was used instead of the reaction product 'o).

The obtained reaction product was light brown in color and sticky, and had an acid value of 12. [5] Production of polymerizable composition E {Into two four-necked flasks similar to those used in 31, '1
}The reaction product synthesized in
Diglycidyl ether epoxy resin (manufactured by Showa Denko,
(Product name: Shodyne 428, epoxy equivalent: 190) Approximately, N,N-jetylcyclohexylamine and 1 g of sodium nitrite were charged and heated at 110 to 120°C under a nitrogen stream.
The reaction was carried out under heating for half an hour, yielding an extremely viscous brown Iso-Z oily product.

The acid value of the obtained product was 7.7. {6' Production of Polymerizable Composition F 2 Into the same four-necked flask as used in '31, [1'
The reaction product synthesized in [E-712. Tow, Phoenix Z
Lycidyl ether (epoxy equivalent 150) 37 chicks, N,
N-diethylcyclohexylamine 2.5g, sodium nitrite 0. A heat reaction was carried out under a nitrogen stream while stirring at a temperature of 100 to 11 degrees for 3 and a half hours.

After the reaction was completed, the flask was cooled and the contents were allowed to fall to 26°C. The acid value of the reaction product at this time was 7. Next, 415 g of methyltetrahydrophthalic anhydride was further added to this reaction system, and the reaction was heated at 114 to 12,000 for 2 hours under a nitrogen stream, resulting in a pale brown, sticky liquid product with an acid value of 98. Obtained [reaction product (c)
]. The above reaction product was then added to a flask equipped with a lamp, thermometer, nitrogen inlet tube and reflux condenser.
2. 150 g of neobentyl glycol diglycidyl ether similar to that used in '1), N,N-diethylcyclohexylamine2. Acid, sodium nitrite 0. A boat was prepared and the mixture was heated and reacted at 10°C to 118°C for 3 and a half hours while crossing the ocean under a nitrogen stream. A pale brown, sticky resin with an acid value of 10 was obtained.

'7} Polymerizable composition G production 1 equipped with a light frame machine, a thermometer, a throat introduction pipe and a reflux condenser
Into the flask, put the reaction product synthesized in step 01 at 28
Tow, 2-ethylhexyl glycidyl ether (manufactured by NOF Corporation, trade name Epiol EH, epoxy equivalent 186) 1
86g, N,N-jethylcyclohexylamine 1g,
Sodium nitrite 0. Prepare miscellaneous ingredients, 6 with 102-124q○
Heat the reaction under a nitrogen stream for an hour, and the acid value is 1.
A product No. 2 was obtained [reaction product (d)].

At this point, the flask was cooled once, and when the content reached 370 g, 166 g of methyltetrahydrophthalic anhydride was added.
was added, and the reaction was carried out by heating under a nitrogen stream for 3 hours at a temperature of 100 to 11, to obtain a light brown viscous liquid product with an acid value of 95 [reaction product (e)]. Then, the flask was cooled again, and when the temperature of the contents reached 30 oo,
In addition to this flask were 200.1 g of the same pisphenol A diglycidyl ether epoxy resin (Shoudyn 428) used in ①, and 5. N,N-diethylcyclohexylamine. Addition of 1.0 ml of sodium nitrite was carried out in the same manner under a nitrogen stream at 105 to 12 0,000 ml under a rope for 3 and a half hours to give a very viscous resin with an acid value of 7.3. (2) Preparation of Polymerizable Composition A reaction product (D') was synthesized using the same components as in '7-' in the same 1. flask used in '7-' (however, the final acid value was 10).

Except that 100.1 g of succinic anhydride was used instead of methyltetrahydrophthalic anhydride used in {7} below.
A reaction similar to 7) was carried out to obtain a reddish-brown viscous resin.

'9} Into a similar flask used in the production of polymerizable composition 1 {7), the reaction product synthesized in {1}) 28 base, lauryl glycidyl ether (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd., Product name: Eporite M-120
0, epoxy equivalent 300) 300g, N,N-jetylcyclohexylamine 1g, sodium nitrite 0. A male was prepared and heated to react at 100 to 11,500 ℃ for 8 hours under a nitrogen stream.

When the acid value reached 12, 166 g of methyltetrahydrophthalic anhydride was added to the flask to give an acid value of 100 to 11.
Heat reaction with a fly pestle under a nitrogen stream at 40○ for 4 and a half hours,
A reddish viscous liquid product with an acid value of 76.6 was obtained (reaction product). Next, the above reaction product N146. warm, bisphenol A diglycidyl ether (Shodine 428) 3 ropes, N,N-jetylcyclohexylamine 0. He added 0.0 ml of sodium nitrite and heated the reaction mixture at 110 to 125 qo for 5 hours under a nitrogen stream while stirring, and an extremely viscous light-colored resin with an acid value of 14 was obtained. OQ Production of polymerizable composition J {Into a 500' flask similar to that used in 91, the reaction product N146. synthesized in ① was placed. Crab, 1,6-hexamethylene glycol diglycidyl ether epoxy resin (
Kyoeisha Yushi Kagaku Kogyo Co., Ltd., trade name: Evolite 1600, epoxy equivalent: 150) 3 females, 0.2 g of N,N-diethylcyclohexylamine, 0.0 g of sodium nitrate,
The reaction was carried out by heating at 110 to 130 q○ for 5 hours and a half under a nitrogen stream with a light on, to obtain a viscous reddish-brown liquid product with an acid value of 9.

(11) Production of polymerizable composition K' t9) except that maleic anhydride of 9 keys was used in place of methyltetrahydrophthalic anhydride used to synthesize the reaction product. The reaction was carried out in exactly the same manner to synthesize the reaction product.

The reaction product was a reddish brown, sticky resin with an acid value of 76.3. This reaction product [7] is further added to a hexahydrophthalic acid diglycidyl ester epoxy resin (manufactured by Showa Denko K.K., trade name Shodine 540, epoxy equivalent: 1
52) 15 He,N,N-jetylcyclohexylamine 1
g, sodium nitrite 0. When the mixture was heated and reacted at 103 to 124°C for 4 hours under a nitrogen stream, a reddish brown viscous resin with an acid value of 8 was obtained. Examples 1 to 9, Comparative Examples 1 to 2 Each polymerizable composition chick synthesized in the production example of a polymerizable composition,
1 g of acetone and 0.2-ethylanthraquinone. and prepared a resin solution.

Bar coater M is applied to this resin liquid on an aluminum plate with a skin thickness of 0.3.
．． 4 to a film thickness of 10A to 20AI, and high-pressure mercury lamp (manufactured by Matsushita Electric Co., Ltd., HIOOOTQ, IKW x 4)
Ultraviolet rays were irradiated for 3 seconds at a distance of 15 skin below the book. The back side was treated in the same way. All of the resulting coating films were completely cured, and no stickiness was observed. The performance of the coating film is shown in Table 1. As is clear from the comparisons between Example 1 and Comparative Example 1 in Table 1, and between Example 2 and Comparative Example 2, polymerizable compositions A and C in which a monoepoxide-based compound is reacted are polymerizable compositions in which a monoepoxide-based compound is not reacted. Although the coating film is softer than compositions B and D, it has better alkali resistance.

Examples 10 to 13 Four kinds of solutions of 'C'O}, Shi1 and 0 as shown below were prepared and coated with a bar coater to a mild steel plate (JIS, G3141) that had been sanded and MEK treated.
When the coating was applied to a thickness of ~40 mm and heated and cured at 130° C. for 20 minutes, a cured coating film with no surface stickiness was obtained.

Claims (1)

[Claims] 1. An epoxy-modified (meth)acrylate polymer obtained by reacting a compound represented by the following general formula (1) with a polyepoxy compound having at least two epoxy groups in the molecule. Sexual composition ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [However, in the formula, R_1 and R_2 are hydrogen or methyl groups; A is an alkylene group with 2 to 4 carbon atoms (an alkyl group with at most 8 carbon atoms) a hydrocarbon group selected from the group consisting of a group consisting of an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an allyl group and an aralkyl group, a halogen atom or an ether bond, or a hydrocarbon group containing a halogen atom. Good); Z is α. Residue of unsaturated alicyclic dibasic acid compound obtained by reacting β-unsaturated dibasic acid or its derivative with diene compound; B is ▲ mathematical formula, chemical formula, table, etc. ▼ or - R_4, R_3, and R_4 are hydrocarbon groups selected from the group consisting of alkyl groups, alkenyl groups, cycloalkyl groups, cycloalkenyl groups, allyl groups, and aralkyl groups having 6 to 20 carbon atoms; D is the residue of a dibasic acid; [Group] 2 An epoxy-modified (meth)acrylate polymerizable composition obtained by reacting a compound represented by the following general formula (1) with a polyexy compound having at least two epoxy groups in the molecule. A polymerizable composition comprising a polymerizable vinyl monomer. ▲There are mathematical formulas, chemical formulas, tables, etc.▼[However, in the formula, R_
1, R_2 is hydrogen or methyl group; A has 2 to 4 carbon atoms
alkylene groups (hydrocarbon groups selected from the group consisting of alkyl groups, alkenyl groups, cycloalkyl groups, cycloalkenyl groups, allyl groups and aralkyl groups having at most 8 carbon atoms, halogen atoms or ether bonds, or halogen Z may be substituted by the hydrocarbon group containing α. Residue of unsaturated alicyclic dibasic acid compound obtained by reacting β-unsaturated dibasic acid or its derivative with diene compound; B is ▲ mathematical formula, chemical formula, table, etc. ▼ or - R_4, R_3, and R_4 are hydrocarbon groups selected from the group consisting of alkyl groups, alkenyl groups, cycloalkyl groups, cycloalkenyl groups, allyl groups, and aralkyl groups having 6 to 20 carbon atoms; D is the residue of a dibasic acid; base]