KR910008621B1 - Hardening resin composition - Google Patents

Abstract

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Description

Curable Resin Composition

The present invention relates to a novel curable resin composition.

Curable resin compositions widely used for coating or other purposes up to now include those containing a hydroxyl group as a functional group, such as melamine resin, protected isocyanate and the like, and a resin containing a crosslinking agent capable of thermally reacting with the hydroxyl group. However, these compositions have the drawback that, when heat-cured, they produce by-products such as water and alcohol, which contaminate the interior of the drying furnace and adversely affect the appearance of the cured coating.

In addition, curable resin compositions comprising a resin containing an α, β-unsaturated carbonyl group and a polyamino compound are also known (US Patent No. 3975251). When heated, the composition is crosslinked and cured by Michael addition reaction of a polyamino compound with an α, β-unsaturated carbonyl group. However, this composition is likely to be accompanied by a drawback that the hardened film is easily discolored and the water resistance is impaired due to the polyamino compound remaining in the hardened film. In addition, the compositions have the drawback of reduced storage stability due to the gradual Michael addition reaction during storage.

It is an object of the present invention to provide a novel curable resin composition which overcomes the above drawbacks.

Another object of the present invention is to provide a novel curable resin composition which forms a film which is free of discoloration and excellent in water resistance when cured without producing by-products during heat-curing.

Another object of the present invention is to provide a novel curable resin composition having excellent storage stability.

These and other objects of the present invention will become more apparent from the following description.

The present invention provides a curable resin composition consisting essentially of the following (i) to (i).

(Iii) Resin (A) containing α, β-unsaturated carbonyl groups and primary and / or secondary hydroxy groups or (ii) Resin (B) containing α, β-unsaturated carbonyl groups and primary and / or secondary (C) alkali metal alkoxides, metal hydroxides, organic acid salts of metals, quaternary ammonium hydroxides, quaternary phosphonium hydroxides, tertiary sulfonium hydroxides and organic acid salts of these onium hydroxides At least one curing catalyst selected from the group consisting of.

The present inventors conducted extensive research to overcome the above drawbacks of known curable resin compositions and found the following facts.

(1) a resin containing (I) a specific curing catalyst and an α, β-unsaturated carbonyl group and a primary and / or secondary hydroxyl group, or (II) a resin containing a specific curing catalyst and a carbonyl group and a resin containing a hydroxyl group. Compositions comprising a mixture can be crosslinked at relatively low temperatures and have good storage stability.

(2) Since heat-curing mainly occurs by the addition reaction of hydroxy groups and unsaturated groups, the composition has almost no defects in forming discolored coatings during formation or curing of by-products. Furthermore, the composition provides a coating having excellent water resistance, surface smoothness, and the like.

The present invention has been accomplished based on this new finding.

The present invention provides a curable resin composition composed essentially of the component (A) and the curing catalyst as the component, and is essentially a component (ii) resin mixture and the curing catalyst as the component. It provides the curable resin composition comprised.

에 의해 나타내지며, 예를들면 아크릴로일, 메타크릴로일, 이타코노일, 말레오일, 푸마로일, 크로토노일, 신나모일, 아크릴아미도, 메타크릴아미도 등이다. 1차 및 2차 히드록시기중에서, 1차 히드록시기가 경화성의 측면에서 바람직하다.In resin (A) which is a component (iii) containing an alpha, (beta)-unsaturated carbonyl group and a primary and / or secondary hydroxyl group in this invention, an (alpha), (beta)-unsaturated carbonyl group is a general formula.

It is represented by, for example, acryloyl, methacryloyl, itaconoyl, maleoyl, fumaroyl, crotonoyl, cinnamoyl, acrylamido, methacrylic amido and the like. Among the primary and secondary hydroxy groups, primary hydroxy groups are preferred in terms of curability.

As long as the resin (A) has an α, β-unsaturated carbonyl group and a primary and / or secondary hydroxy group, the resin is not limited to a specific kind, but an acrylic resin, a polyester resin, a urethane resin, a polybutadiene resin, an alkyd resin, It may be any of the known resins including epoxy resins, phenol resins, polyether resins and polyamide resins. Furthermore, the resin (A) can be prepared by any of the known methods.

The molecular weight of the resin (A) is not particularly limited. Generally, the resin (A) has a highest molecular weight, as determined by gel permeation chromatography, preferably from about 250 to about 100000, more preferably from about 500 to about 20000, given the curability and solubility in the solvent. In view of the curability and water resistance of the coating, the resin (A) is from about 0.01 to about 20 moles, preferably from about 0.1 to about 5 moles of α, β-unsaturated carbonyl group and from about 0.01 to about 50 moles, per kg of resin, Preferably it contains about 0.1 to about 10 moles of hydroxy groups.

(식중 R₁은 수소원자 또는 메틸기이다)에 의하여 나타내지는 N-메틸롤 아크릴아미드 또는 메타크릴아미드와 이소시아네이트의 부가 생성물의 잔기를 갖고 1차 및/또는 2차 히드록시기를 갖는 우레탄 수지를 포함한다. 이들 수지는 아미드결합 및 우레탄 결합을 갖기 때문에 부착력이 우수한 피막을 제공하는데 이바지한다. 수지는 또한 한편으로는 수지의 고부착력 때문에, 다른 한편으로는 에스테르 결합등보다 가수분해하기가 쉽지 않은 아미드 및 우레탄 결합 때문에 끊는 물에 침지한 후에도 단단하게 부착되어 남아있는 피막을 제공한다.Preferred examples of the resin (A) are general formula (I)

N-methylol acrylamide or methacrylamide represented by the formula (wherein R ₁ is a hydrogen atom or a methyl group) and a urethane resin having residues of addition products of isocyanate and having primary and / or secondary hydroxy groups. Since these resins have amide bonds and urethane bonds, they contribute to providing a film having excellent adhesion. The resin also provides a film that remains firmly attached even after immersion in water, which is broken on the one hand because of the high adhesion of the resin and on the other hand because of the amide and urethane bonds, which are less prone to hydrolysis than ester bonds and the like.

The resin containing the functional group and hydroxy group represented by the general formula (I) may be, for example, 1 mole of N-methylol acrylamide or methacryl in the absence of a catalyst or in the presence of a basic catalyst at a temperature of about 20 to about 150 ° C. The amide is reacted with a mole of diisocyanate compound for about 1 to about 10 hours, and an addition product of the resulting isocyanate-containing N-methylol acrylamide or methacrylamide (hereinafter referred to as "addition product (a)") And hydroxyl-containing resins can be easily prepared by mixing the isocyanate group of the addition product (a) with the hydroxyl group portion of the hydroxyl-containing resin in an inert organic solvent in the presence of a catalyst member or a basic catalyst under the same reaction conditions as above. have.

Preferred examples of useful diisocyanate compounds are 2,4-tolylene diisocyanate, m-xylylene diisocyanate, methylcyclohexane-2,4-diisocyanate, 1,3-diisocyanate methyl cyclohexane, isophorone di Isocyanates and the like are those having two free isocyanate groups having different reactivity per molecule.

Examples of useful basic catalysts are tertiary amines such as triethylamine dimethyl ethanol, pyridine, tributylamine and the like.

Useful inert organic solvents are those in which the adduct (a) and the resin (C) can melt or disperse and are free of active hydrogen atoms that can react with the isocyanate groups of the adduct (a). However, examples of the solvents include aromatic hydrocarbons such as xylene and toluene, ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone and cyclohexanone, ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, methyl cellosolve Esters such as acetate, ethyl acetate, methyl acetate and the like.

Useful hydroxyl-containing resins are not limited to particular types and may be any of those known as long as the resin has at least 2.0 hydroxyl groups on average per molecule. Examples of such resins are kinds of acrylic polyols, polyester polyols, polyether polyols, alkyds, caprolactone polyols, epoxies, urethane polyols and the like.

에 의하여 나타내진다. 기의 예는 아크릴로일, 메타크릴로일, 이타코노일, 말레오일, 푸마로일, 크로토노일, 신나모일, 아크릴아미도, 메타크릴아미도 등이다. 1차 및/또는 2차 히드록시기를 갖는 수지(C)의 히드록시기 중에서, 1차 히드록시가 경화성의 측면에서 바람직하다.In the resin composition of the present invention consisting essentially of a resin mixture of component (ii) and a curing catalyst of component (ii), the α, β-unsaturated carbonyl group of the resin (B) is of the general formula

Is represented by. Examples of the group are acryloyl, methacryloyl, itaconoyl, maleoyl, fumaroyl, crotonoyl, cinnamoyl, acrylamido, methacrylicamido and the like. Of the hydroxyl groups of the resin (C) having primary and / or secondary hydroxy groups, primary hydroxy is preferred in terms of curability.

As long as the resin has an α, β-unsaturated carbonyl group, the type of resin (B) is not critical. The type of resin (C) is not particularly limited as long as the resin has primary and / or secondary hydroxyl groups. The resins (B) and (C) are not limited to specific types, and include acrylic resins, polyester resins, urethane resins, polybutadiene resins, alkyd resins, epoxy resins, phenol resins, polyether resins, polyamide resins, and the like. Any of the known resins may be used. Resin (B) and (C) can be manufactured by any of a well-known method.

The molecular weight of resin (B) and (C) is not specifically limited. In general, the resins (B) and (C) have a peak of preferably about 250 to about 100000, more preferably about 500 to about 20000, as determined by gel permeation chromatography in terms of curability and solubility in solvents. Has a molecular weight. In view of the curability and water resistance of the coating, the resin (B) contains from about 0.01 to about 20 moles, preferably from about 0.1 to about 5 moles of α, β-unsaturated carbonyl groups per kg of resin and the resin (C) is a resin. It is preferred to contain about 0.01 to about 50 moles, preferably about 0.1 to about 10 moles of hydroxy groups per Kg.

Preferred examples of the resin (B) are urethane resins having a residue of an addition product of N-methylol acrylamide or methacrylamide and isocyanate represented by the general formula (I). These resins contribute to providing a coating with very good adhesion and resistance to boiling water.

The resin having a functional group of formula (I), for example, reacts the adduct (a) with all the hydroxy groups present in the resin having at least 1.0 hydroxy group on average per molecule, or under the conditions as described above, or N- It can be easily prepared by reacting methylol acrylamide or methacrylamide with isocyanate-containing resins. Examples of useful isocyanate-containing resins are homopolymers prepared by homopolymerizing unsaturated monomers such as isocyanate ethyl acrylate or methacrylate, α, β-dimethyl-m-isopropenylbenzyl isocyanate, or 1 mole of hydroxyl- Reaction product of a containing acrylate or methacrylate with 1 mole of diisocyanate compound, a copolymer prepared by copolymerizing the monomer with another radical polymerizable unsaturated monomer, and a hydroxyl-containing resin with the diisocyanate compound Resin produced by the reaction.

The mixing ratio of the resin (B) and the resin (C) in the resin mixture which is the component (ii) according to the present invention is preferably from about 99.99 to about 50% by weight, more preferably from about 99.9 to about It is about 70% by weight, and the resin (C) is preferably about 0.01 to about 50% by weight, more preferably about 0.1 to about 30% by weight.

The curing catalyst as a component in the present invention is a group consisting of alkali metal alkoxides, metal hydroxides, organic acid salts of metals, quaternary ammonium hydroxides, quaternary phosphonium hydroxides, tertiary sulfonium hydroxides and organic acid salts of these onium hydroxides. At least one selected from.

Representative metals of metal hydroxides are alkali metals, alkaline earth metals, cobalt, nickel, copper, molybdenum, lead, iron, chromium, manganese, zinc and the like.

Representative alkali metal alkoxides are sodium ethoxide, sodium methoxide, potassium methoxylated, potassium ethoxylated and the like.

Typical alkali metal hydroxides are sodium hydroxide, potassium hydroxide, lithium hydroxide and the like. Representative alkaline earth metal hydroxides are calcium hydroxide, magnesium hydroxide, barium hydroxide and the like.

Useful quaternary ammonium hydroxides, quaternary phosphonium hydroxides and tertiary sulfonium hydroxides include the hydroxides represented by formulas (II), (III) and (IV), respectively.

Wherein R ₁ , R ₂ , R ₃ and R ₄ are the same or different and each represents an organic group having a hydrogen atom or 1 to 14 carbon atoms, and at least one of R ₁ , R ₂ , and R ₃ groups has 1 to 14 carbon atoms It is an organic group, and R ₁ and R ₂ groups or R ₁ , R ₂ and R ₃ groups can form heterocyclic groups when taken together with the nitrogen atom, the person atom and the sulfur atom to which they are bonded.

The type of organic group represented by R ₁ , R ₂ , R ₃ and R ₄ and having 1 to 14 carbon atoms is not critical unless they actually interfere with the ionization of ammonium hydroxide, phosphonium hydroxide or sulfonium hydroxide. not. Generally usable with such organic groups are hydrocarbon groups of 1 to 14 carbon atoms which may contain heteroatoms such as oxygen atoms. Examples of organic groups containing oxygen atoms are hydrocarbon groups substituted with hydroxy or alkoxy groups.

Examples of such hydrocarbon groups are aliphatic, aliphatic ring or aromatic hydrocarbons such as alkyl, cycloalkyl, cycloalkylalkyl, aryl and aralkyl groups. Alkyl groups can be either straight or branched and can include those of up to 8 carbon atoms. Preferred alkyl groups are lower and include methyl, ethyl, n- or iso-propyl, n-, iso-, secondary- or tertiary-, butyl, pentyl, heptyl and octyl groups. Preferred examples of the cycloalkyl group or cycloalkylalkyl group are those having 5 to 8 carbon atoms such as cyclopentyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl and the like. Useful aryl groups are phenyl, tolyl, xylyl and the like. Benzyl groups are suitable as aralkyl groups.

Preferred examples of hydrocarbon groups containing hetero atoms such as oxygen atoms are hydroxyalkyl (particularly hydroxy-lower alkyl), particular examples being methoxymethyl, ethoxymethyl, ethoxyethyl, n-propoxyethyl, iso Hydroxymethyl such as propoxymethyl, n-butoxymethyl, iso-butoxyethyl, tert-butoxyethyl, hydroxyethyl, hydroxybutyl, hydroxypentyl, hydroxyheptyl, hydroxyoctyl, alkoxy Alkyl (especially lower alkoxy-lower alkyl).

Shown below are examples of heterocyclic groups formed by these groups when the R ₁ and R ₂ groups or R ₁ , R ₂ and R ₃ groups are taken together with the nitrogen atom, phosphorus atom or sulfur atom to which they are attached.

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

Curing catalysts useful in the present invention include organic acid salts of hydroxides of these alkali metals, alkaline earth metals and other metals and organic acid salts of the onium hydroxides.

Examples of organic acids useful for forming organic acid salts include formic acid, acetic acid, lactic acid, trimethylacetic acid, acrylic acid, methacrylic acid, chloroacetic acid, hydroxyacetic acid, crotonic acid, monomethyl maleate, monoethyl fumarate, monomethyl itacco Nate and the like. Among these organic acids, those having a dissociation constant (pKa value) of 1 × 10 ⁻⁵ or more are preferable, especially acetic acid, formic acid and acrylic acid.

Suitable amounts of curing catalyst useful as component (iii) are from about 0.001 to about 30 parts by weight per 100 parts of resin (A) or component (ii), a mixture of resin (B) and (C). The use of smaller amounts of curing catalysts is undesirable because they exhibit unsatisfactory curing. On the other hand, the use of a higher amount of curing catalyst is not preferred because the catalyst used tends to remain in the cured film, reducing water resistance. The preferred amount of curing catalyst is about 0.01 to about 20 parts by weight.

If necessary, the curable resin composition of the present invention consisting essentially of the resin component (i) or the component (ii) and the curing catalyst of the component (i) may be colored pigments, extender pigments, corrosion resistant pigments, leveling agents, antifoaming agents, sagging. It may contain additives such as an inhibitor and the like.

The curable resin composition of the present invention can be cured crosslinked by heating at a relatively low temperature. The composition is suitably heated at about 60 to 300 ° C., preferably about 100 to about 170 ° C., for about 5 to about 120 minutes, preferably about 10 to about 30 minutes.

According to the present invention, a resin (A) having an α, β-unsaturated carbonyl group and a primary and / or secondary hydroxyl group or a resin (B) having an α, β-unsaturated carbonyl group and a resin (C) having the above hydroxyl group By combining the mixture of with certain curing catalysts, the addition reaction of hydroxy groups and unsaturated groups is brought about at relatively low temperatures, and the addition reactions do not produce by-products and do not involve any discoloration of the cured coating. The composition of the present invention is also advantageous in that it is excellent in storage stability and forms a coating having excellent water resistance, surface smoothness, etc. at the time of curing, and thus is suitable for coating compositions, particularly for paint.

The composition of the present invention prepared using the functional group of the general formula (I) as the α, β-unsaturated carbonyl group can form a film having particularly high adhesion and hot water resistance.

The invention is described in more detail in the following Preparation Examples, Examples and Comparative Examples, in which both parts and percentages are by weight.

Preparation of Resin (A) Having α, β-unsaturated Carbonyl Group and Primary and / or Secondary Hydroxy Group

[Production Example 1]

Glycidyl methacrylate, part 142

2-hydroxyethyl acrylate 116 parts

n-butyl methacrylate 742 parts

25 parts of azobis isobutyronitrile

The mixture is added dropwise to 1000 parts of toluene in a 4-necked flask at 120 ° C. over 3 hours. It is then aged at 120 ° C. for 5 hours.

Methacrylic acid 86 parts

Hydroquinone0.2part

Tetraethyl ammonium bromide 1.0 part

Toluene Part 87

The above mixture is added and the resulting mixture is reacted at 120 ° C. When the acid value reaches 1 or less, the reaction is terminated to obtain an acrylic resin solution. The resin solution thus obtained had a nonvolatile matter content of 50.0% and a viscosity of M (determined by a Gardner-Holt bubble viscometer at 25 ° C., the same also below). The resin has a highest molecular weight of about 25000 as determined by gel permeation chromatography, and has a content of 0.92 mole of α, β-unsaturated carbonyl group, 0.92 mole of primary hydroxyl group content and 0.92 mole of secondary hydroxyl group content per kg of resin solids.

[Production Example 2]

"Epikoat ＃ 154" ( ^* 1) part 627

252 parts acrylic acid

Hydroquinone part1

Tributylamine3part

Ethylene Glycol Monobutyl Ether 883 Parts

The above mixture is charged into a four-necked flask and reacted at 100 ° C. When the acid value reaches zero, the reaction is terminated to obtain an epoxy resin solution. The resin solution thus obtained had a nonvolatile matter content of 49.7% and a viscosity of H. The resin has a highest molecular weight of about 1000 as determined by gel permeation chromatography, and has a content of 3.98 moles of α, β-unsaturated carbonyl group and a content of 3.98 moles of secondary hydroxy group per kg of resin solids.

Note: ( ^* 1) "Epikoat ＃ 154": Trade name, Yuka Shell Epoxy Co., Ltd. Product, phenol-novolac type epoxy resin, number average molecular weight of about 500, epoxy equivalent of about 174.

[Manufacture example 3]

Ethylene glycol 496 parts

Fumaric Acid 1044

240 parts of trimethylolpropane

The above mixture is filled into a four-necked flask and subjected to condensation reaction at 200 ° C. When the acid value reaches 10 or less, the reaction is terminated. Thereafter, 1456 parts of butyl acetate are added to obtain a polyester resin solution. The resin solution thus obtained had a nonvolatile matter content of 50.4% and a viscosity of G. The resin has a highest molecular weight of about 5000, as determined by gel permeation chromatography, and has a content of 6.18 moles of α, β-unsaturated carbonyl group and a content of 2.34 moles of primary hydroxy group per kg of resin solids.

[Production Example 4]

"Placcel 308" ( ^* 2) 1000 copies

Isophorone diisocyanate 444 parts

Metal ethyl ketone 1444 parts

The mixture is placed in a four-necked flask and reacted at 70 ° C. When the NCO value reaches 30, the reaction is terminated.

232 parts of 2-hydroxyethyl acrylate

Hydroquinone part1

Methyl ethyl ketone 233 parts

The above mixture is added and the resulting mixture is reacted at 80 ° C. When the NCO value reaches 1 or less, the reaction is terminated to obtain a urethane resin solution. The resin solution thus obtained has a nonvolatile matter content of 50.0% and a viscosity of X. The resin has a highest molecular weight of about 2000, as determined by gel permeation chromatography, and has a content of 1.19 mol of α, β-unsaturated carbonyl group and 0.89 mol of primary hydroxyl group per kilogram of resin solids.

Note: ( ^* 2) "Placcel ＃ 308": Trade name, Daicel chemical Industries, Ltd. Product, ε-caprolactone type trifunctional polycaprolactone polyol, number average molecular weight of about 1280, hydroxyl value of 198.

Production Example 5

Isophorone diisocyanate 444 parts

232 parts of 2-hydroxyethyl acrylate

Methyl ethyl ketone 290 parts

The mixture was charged into a four-necked flask and reacted at 80 ° C. until the NCO value reached 87 to obtain an isocyanate-containing unsaturated monomer solution.

"Epicoat ＃ 1002" ( ^* 3) 1256 copies

Diethanolamine 210 parts

Methyl ethyl ketone 628 parts

Apart from the above process, the mixture is charged into a four-necked flask and reacted at 80 ° C. over 3 hours to obtain a hydroxyl-containing resin solution.

2094 parts of the monomer solution (966 parts) and the hydroxyl-containing resin solution were mixed and reacted at 80 ° C. for 10 hours to obtain an epoxy urethane resin solution. The resin solution thus obtained had a nonvolatile matter content of 70.0% and a viscosity of X. The resin has a highest molecular weight of about 2300 determined by gel permeation chromatography, and has a content of 0.93 mole of α, β-unsaturated carbonyl group and 0.93 mole of primary hydroxyl group per kg of resin solids.

Note: ( ^* 3) "Epicot ＃ 1002": Trade name, Yuka Shell Epoxy Co., Ltd. Product, bisphenol A epoxy resin, number average molecular weight of about 1256, epoxy equivalent of about 630.

[Examples 1 to 17]

The curable resin composition of the present invention is prepared by uniformly mixing the resin solution and the curing catalyst obtained in Preparation Example shown in Table 1 in the amounts shown in Table 1.

TABLE 1a

TABLE 1b

Note: ( ^* 4) Compound A

It is a compound represented by.

( ^* 5) Compound B is

It is a compound represented by.

Each composition prepared in Examples 1-17 is applied to a glass plate to form a layer having a thickness of about 20 μm on drying.

The layer deposited on the glass plate is baked in the oven and cured. The coated glass plates were examined for water resistance and gel fraction ratio. The composition is also tested for storage stability. Firing is carried out under the following conditions and the test is carried out by the method described below.

[Firing Conditions]

The coated glass plates were used for 30 minutes at 140 ° C. in Examples 1 to 5 and 17, for 100 minutes at 100% in Example 6, for 10 minutes at 120 ° C. for Examples 7 and 8, and 140 for Examples 9 to 16. Firing at 10 ° C. for 10 minutes.

[Water resistance]

The appearance of the coated glass plate was irradiated with hot water at 40 ° C. for 7 days.

[Gel fraction ratio]

The layer formed and cured on the glass plate is peeled off and placed in a container of 300-mesh stainless steel mesh. This layer is extracted with a Soxhlet extractor for 6 hours using a mixture of acetone and methanol of the same weight. The gel fraction ratio is calculated by the following equation.

Gel fraction ratio (%) = (weight of layer after extraction / weight of layer before extraction) × 100

[Storage Stability]

Into a sealed can having an internal volume of 250 cc is filled 200 g of each composition obtained in the examples and the comparative examples. The composition is investigated after storage for 30 days at 50 ° C. Compositions with no significant increase in viscosity and no gelation are indicated by the symbol "A".

[Discoloration resistance]

The layer formed and cured on the glass plate is visually observed for the degree of discoloration. The layer without color change is represented by A and the layer turned yellow is represented by B.

Table 2 shows the test results.

TABLE 2

[Hot water resistance]

The hot water resistance of each composition is investigated by the following method.

The composition is applied to a steel sheet treated with zinc phosphate to form a layer having a thickness of 20 탆 upon drying. The coated plate was calcined and then immersed in boiling water for 1 hour or 2 hours and recovered to evaluate the appearance and adhesion of the layer.

(Iii) Appearance of coating layer

The coating layer is examined for cracks, peeling and blister formation.

(Ii) adhesion

The coated plate was cut crosswise with respect to the substrate to prepare 100 squares having a 1-mm face, a cellophane adhesive tape was attached, and the tape-covered face was uniformly pressed with a uniform force, followed by peeling. Count the number of squares that remain attached.

Table 3 below shows the results.

TABLE 3

Preparation of Resin (B) Having an α, β-unsaturated Carbonyl Group

[Manufacture example 6]

Glycidyl methacrylate, part 142

n-butyl methacrylate 858 parts

25 parts of azobisisobutyronitrile

The mixture is added dropwise to 1000 parts of toluene in a four-necked flask at 120 ° C. over 3 hours. The resulting mixture is aged at 120 ° C. for 5 hours.

Methacrylic acid 86 parts

Hydroquinone0.2part

Tetraethyl ammonium bromide 1.0 part

Toluene Part 87

The above mixture is added and the resulting mixture is reacted at 120 ° C. When the acid value reaches 1 or less, the reaction is terminated to obtain an acrylic resin solution. The resin solution has a nonvolatile matter content of 50.0% and a viscosity of H. The resin has a highest molecular weight of about 25000, as determined by gel permeation chromatography, and has an α, β-unsaturated carbonyl group content of 0.92 mol and a secondary hydroxyl group content of 0.92 mol per kilogram of resin solids.

[Manufacture example 7]

"Epicot ＃ 154" Part 627

252 parts acrylic acid

Hydroquinone part1

Tributylamine3part

883 parts of ethylene glycol monobutyl ether

The above mixture is charged into a four-necked flask and reacted at 100 ° C. When the acid value reaches zero, the reaction is terminated to obtain an epoxy resin solution. The resin solution thus obtained has a nonvolatile matter content of 49.7% and a viscosity of H. The resin has a highest molecular weight of about 1000, as determined by gel permeation chromatography, and has a content of 3.96 mol of α, β-unsaturated carbonyl group and a content of 3.96 mol of secondary hydroxy group per kilogram of resin solids.

[Manufacture example 8]

Ethylene glycol 496 parts

Fumaric Acid 1044

The mixture was put in a four-neck flask and subjected to condensation reaction at 200 ° C. The reaction is terminated when dehydration is complete. Then 1252 parts of butyl acetate are added to the reaction mixture to obtain a polyester resin solution. The resin solution has a nonvolatile matter content of 50.2% and a viscosity of Q. The resin has a highest molecular weight of about 3500, as determined by gel permeation chromatography, and has an alpha, beta -unsaturated carbonyl group content of 7.19 moles per kilogram of resin solids, but no hydroxy group.

[Manufacture example 9]

"Plasel ＃ 308 1000

Isoprone diisocyanate 666 parts

Methyl ethyl ketone 1666 parts

The above mixture is charged into a four-necked flask and reacted at 70 ° C. When the NCO value reaches 38, the reaction is terminated.

2-hydroxyethyl acrylate 348 parts

Hydroquinone1.5parts

350 parts methyl ethyl ketone

The above mixture is added and the final mixture is reacted at 80 ° C. When the NCO value reaches 1 or less, the reaction is terminated to obtain a urethane resin solution. The resin solution thus obtained has a nonvolatile matter content of 49.8% and a viscosity of Z. The resin has a highest molecular weight of about 2000, as determined by gel permeation chromatography, and has an alpha, beta -unsaturated carbonyl group content of 1.49 moles per kg of resin solids, but no hydroxy group. Preparation of Resin (C) Having Primary and / or Secondary Hydroxy Groups

[Production Example 10]

2-hydroxyethyl acrylate 116 parts

n-butyl methacrylate 884 parts

25 parts of azobisisobutyronitrile

The mixture is added dropwise to 1000 parts of toluene in a four-necked flask at 120 ° C. over 3 hours. Thereafter, aging was performed at 120 DEG C for 5 hours to obtain an acrylic resin solution. The resin solution thus obtained has a nonvolatile matter content of 50.0% and a viscosity of zero.

The resin has a highest molecular weight of about 30000 determined by gel permeation chromatography and has 1.00 mole of primary hydroxyl groups per kg of resin solids but no α, β-unsaturated carbonyl groups.

[Production Example 11]

"Epicot ＃ 154" Part 627

Ethanolamine 245 parts

Ethylene Glycol Monobutyl Ether 872 parts

The mixture was charged in a four-necked flask and reacted at 100 ° C for 1 hour to obtain an epoxy resin solution.

The resin solution has a nonvolatile content of 49.7% and a viscosity of V. The resin has a highest molecular weight of about 1000 as determined by gel permeation chromatography. The resin has a content of 5.45 mol of primary hydroxyl group and 2.73 mol of secondary hydroxyl group per kg of resin solids, but no α, β-unsaturated carbonyl group.

[Manufacture example 12]

Ethylene Glycol 496 Parts

Phthalic Acid 1332

240 parts of trimethylolpropane

The mixture is charged in a four-necked flask and condensed at 200 ° C. When the acid value reaches 10 or less, the reaction is terminated. 1906 parts of butyl acetate are added thereto to obtain a polyester resin solution. The resin solution has a nonvolatile content of 50.5% and a viscosity of M. The resin has a highest molecular weight of about 5000 as determined by gel permeation chromatography. The resin does not have an α, β-unsaturated carbonyl group but has a primary hydroxyl group content of 1.78 moles per kilogram of resin solids.

[Examples 18 to 30 and Comparative Examples 1 to 3]

The curable resin composition and comparative curable resin composition of this invention are manufactured by mixing the resin solution obtained by the manufacture example shown in Table 4 below, and a curing catalyst uniformly in the quantity shown in Table 4.

TABLE 4

Each composition prepared in Examples 18-30 and Comparative Examples 1-3 was applied to a glass plate to form a layer having a thickness of about 20 μm when dried. The layer deposited on the glass plate is baked in the oven and cured. The cured cladding plates were examined for water resistance and gel fraction ratio. The composition is also tested for storage stability. The coated glass plates were subjected to 30 minutes at 140 ° C. in Examples 18, 19 and 27 to 30 and Comparative Examples 1 to 3, 10 minutes at 140 ° C. in Examples 20 to 22, and 30 ° at 120 ° C. in Examples 23 and 24. Firing for minutes, and in Examples 25 and 26 for 10 minutes at 100 ° C.

The results are shown in Table 5 below.

Each composition was examined for hot water resistance by the same method as above.

The results are shown in Table 6 below.

TABLE 5

TABLE 6

Example which demonstrates curable resin composition containing the (alpha), (beta)-unsaturated carbonyl group as a functional group of general formula (I).

Example 31

"Epikoute # 1002 Part 1256

Diethanolamine 210 parts

Methyl ethyl ketone 628 parts

The mixture was charged in a four-necked flask and reacted at 80 ° C. for 3 hours to obtain a hydroxyl-containing resin solution.

Isophorone diisocyanate 444 parts

202 parts of N-methylol acrylamide

Methyl ethyl ketone277 parts

Apart from the above process, the mixture is placed in a four-necked flask and reacted at 80 ° C until the NCO value reaches 91 to obtain an isocyanate-containing unsaturated monomer solution.

The hydroxyl-containing resin solution (2094 parts) is mixed with 923 parts of isocyanate-containing unsaturated monomer. The mixture is reacted at 80 ° C. for 10 hours to obtain an epoxy urethane resin solution. The resin solution has a solids content of 70% and a viscosity of Z ₅ . The resin has a highest molecular weight of about 2200, as determined by gel permeation chromatography, and has an α, β-unsaturated carbonyl group content of 0.95 mol and a primary hydroxyl group content of 0.95 mol per kilogram of resin solids. One part cobalt acetate is added to 100 parts of resin solution (as a solid content), these are mixed, and the curable resin composition of this invention is obtained.

Example 32

A curable resin composition of the present invention was obtained in the same manner as in Example 31 except that the same amount of calcium acetate was used instead of cobalt acetate.

Example 33

The curable resin composition of the present invention was produced in the same manner as in Example 31 except that 0.5 part of trimethylsulfonium acetate was used instead of cobalt acetate.

Example 34

A curable resin composition of the present invention was obtained in the same manner as in Example 31 except that 0.2 part of sodium formate was used instead of cobalt acetate.

Example 35

α, α-dimethyl-m-isopropenyl

Benzyl Isocyanate 210 Parts

n-butyl acrylate part 649

Styrene, part 150

20 parts of azobisisobutyronitrile

1000 parts of toluene is charged into a four-necked flask and heated to 120 ° C. with stirring, and then the mixture is added dropwise over 3 hours. The resulting mixture is aged at the same temperature for 2 hours to give an isocyanate-containing acrylic resin solution having a solid content of 50% and a viscosity p.

101 parts of N-methylol acrylamide

Methyl ethyl ketone 101 parts

Hydroquinone0.1part

The mixture was added dropwise to 1029 parts of a resin solution and the resulting mixture was reacted for 5 hours until the NCO value reached 1 or less to obtain an acrylic urethane resin solution. The resin solution has a solid content of 50% and a viscosity of Z. The resin has a highest molecular weight of about 26000 determined by gel permeation chromatography and has an α, β-unsaturated carbonyl group content of 0.90 mol per kilogram of resin solids.

232 parts of 2-hydroxyethyl acrylate

768 parts n-butyl methacrylate

20 parts of azobisisobutyronitrile

Apart from the above process, 1000 parts of toluene is charged into a four-necked flask and heated to 120 ° C. with stirring. The mixture is added dropwise over 3 hours, and the resulting mixture is aged for 2 hours at the same temperature to obtain an acrylic resin solution. The resin solution has a solid content of 50% and a viscosity of H. The resin has a highest molecular weight of about 2400 determined by gel permeation chromatography and has a primary hydroxyl group content of 2.00 moles per kilogram of resin solids.

Tetramethylammonium hydroxide (0.5 parts) is mixed with 100 parts of a mixture of 50 parts of an acrylic urethane resin solution (as a solid) and 50 parts of an acrylic resin solution (as a solid) to obtain a curable resin composition of the present invention.

Example 36

A curable resin composition of the present invention was prepared in the same manner as in Example 35, except that tetramethylammonium hydroxide was used in another amount, that is, 1.0 part.

Example 37

A curable resin composition of the present invention was prepared in the same manner as in Example 35 except that 1.0 part of cobalt acetate was used instead of tetramethylammonium hydroxide.

Example 38

A curable resin composition of the present invention was prepared in the same manner as in Example 35 except that 0.5 part of sodium formate was used instead of tetramethylammonium hydroxide.

Each composition obtained in Examples 31 to 38 was applied to a glass plate to form a layer having a thickness of about 20 μm when dried. The layer deposited on the glass plate is cured by baking in a dryer. The coated plates are examined for water resistance and gel fraction ratio. The composition is also tested for storage stability. Firing is carried out in the same manner as described above, wherein Examples 31 to 33, 35 and 37 are carried out at 140 ° C. for 30 minutes, and Examples 34, 36 and 38 are carried out at 130 ° C. for 30 minutes. Table 7 below shows the results.

Hot water resistance was investigated by the same method as the above of each composition, and the result is shown in following Table 8.

TABLE 7

TABLE 8

Claims (7)

Essentially (i) a resin containing an α, β-unsaturated carbonyl group and a primary and / or secondary hydroxy group, or (ii) a resin (B) containing an α, β-unsaturated carbonyl group and a primary and / Or mixtures of resins (C) containing secondary hydroxy groups, and (iii) alkali metal alkoxides, metal hydroxides, organic acid salts of metals, quaternary ammonium hydroxides, quaternary phosphonium hydroxides, tertiary sulfonium hydroxides and these oniums Curable resin composition consisting of at least one curing catalyst selected from the group consisting of organic acid salts of hydroxides. The resin of claim 1 wherein the resin (A) is of general formula

A composition wherein N-methylol acrylamide or methacrylamide and an isocyanate product of an isocyanate and a hydroxy group are represented by R ₁ represents a hydrogen atom or a methyl group. The resin according to claim 1, wherein the resin (B) is a general formula

A composition having a residue of an adduct of N-methylol acrylamide or methacrylamide and isocyanate represented by (wherein R ₁ is a hydrogen atom or a methyl group). The composition of claim 1, wherein the resin (A) is a resin having from about 0.01 to about 20 moles of an α, β-unsaturated carbonyl group and from about 0.01 to about 50 moles of hydroxyl group per kg of resin. The resin of claim 1 wherein resin (B) has from about 0.01 to about 20 moles of α, β-unsaturated carbonyl groups per kg of resin, and resin (C) has from about 0.01 to about 50 moles of hydroxyl groups per kg of resin Composition. The composition of claim 1 wherein the resin mixture as component (ii) consists of about 99.99 to about 50 weight percent of resin (B) and about 0.01 to about 50 weight percent of resin (C). The method according to claim 1, wherein the amount of the curing catalyst as component (i) is from about 0.001 to about 30 per 100 parts by weight of the mixture of resin (A) or component (ii) as component (ii) or resin (B) and resin (C). Parts by weight.