JPH01129066A - Curable composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which is excellent in low-temperature curability and shelf stability and can give a cured product excellent in water resistance, impact resistance, overcoatability, staining resistance, etc., by mixing a mixture of a specified resin containing alkoxysilane group, etc., with a resin containing epoxy groups with a chelate compound as a crosslinking/curing agent. CONSTITUTION:A resin having at least one kind of functional groups selected from OCN, OH, epoxy, COOH and NH2 groups is reacted with a compound having a functional group complementarily reactive with the functional group of said resin and/or a hydroxyl group to obtain a resin (A) having an alkoxysilane group and/or a hydroxysilane group. Separately, a resin having at least one kind of functional groups selected from among OCN, NH2 and OH groups is reacted with a compound having a functional group complementarily reactive with the functional group of said resin and an epoxy group to obtain an epoxy group-containing resin (B). 100 pts.wt. mixture of 5-95wt.% resin A with 95-5wt.% resin B is mixed with 0.01-30 pts.wt. Al, Zr or Ti chelate compound (C) as a curing/crosslinking agent.

Description

[Detailed description of the invention] LlLefill! The present invention relates to novel curable compositions.

Ryomai Gokei 1 Conventionally, as a composition that can be crosslinked and cured at a relatively low temperature of room temperature to 100°C, a composition prepared by adding an acid, a base, an organometallic catalyst, etc. to an alkoxysilane-containing vinyl polymer is known0. For example, JP-A-60-67553 discloses a composition in which an aluminum chelate compound is blended with a vinyl polymer containing an alkoxysilane such as methacryloxypropyltrimethoxysilane.

However, in the conventional compositions described above, the only crosslinking functional group is the silanol group produced by hydrolysis of alkoxysilane, so a large amount of water is required for curing, and a large amount of by-products such as alcohol are produced during this hydrolysis. Therefore, the physical properties of the cured product cannot be said to be sufficient, and when the cured product is cured only with moisture in the air, it is hardened from the surface, making it difficult to harden the inside, causing the cured product to sag and become rough.

An object of the present invention is to provide a novel curable composition that eliminates the above-mentioned drawbacks.

□ As a result of extensive research to achieve the above object, the present inventors have discovered that silanol can be produced by adding a specific oxirane group to a vinyl polymer containing an alkoxysilane group and/or a hydroxysilane group. Since not only the group but also the oxirane group becomes a crosslinking functional group, it can be sufficiently cured by atmospheric moisture even at room temperature, and by-products such as alcohol are extremely
They discovered that the cured product has excellent physical properties because of the small amount, and that when it is cured with only moisture in the air, there is little difference in hardening between the surface and the inside, and no sagging occurs, leading to the completion of the present invention. .

That is, the present invention provides a resin (a) having one or more functional groups of an isocyanate group, a hydroxyl group, an epoxy group, a carboxyl group, and an amine group, and a functional group that reacts complementary to the functional group and an alkoxy group. A resin having an alkoxysilane group and/or a hydroxysilane group formed by reacting a compound having a silane group and/or a hydroxysilane group (
A) and a resin (b) having an isocyanate group or a hydroxyl group have an epoxy group formed by reacting the resin (b) with a compound having an epoxy group and a functional group that reacts complementary to the functional group of the resin (b). The present invention relates to a curable composition characterized in that a chelate compound is blended as a crosslinking reaction curing agent into a mixture of resin (B).

The resin (A) used in the curable composition of the present invention includes:
A resin (IL) having one or more functional groups of isocyanate group, hydroxyl group, epoxy group, carboxyl group, and amino group is added with a functional group that reacts complementary to the functional group and an alkoxysilane group and/or hydroxyl group. An alkoxysilane group obtained by reacting a compound having a silane group (hereinafter simply referred to as "compound (I)") and/or
Alternatively, a resin having a hydroxysilane group can be used.

The resin (L) has one or more functional groups selected from isocyanate groups, hydroxyl groups, epoxy groups, and amine groups in its molecules. However, in the case of having two or more types of functional groups, combinations of two types of functional groups that are highly reactive with each other, such as isocyanate group-epoxy group, hydroxyl group-7mino group, hydroxyl group-epoxy group, etc. Matching is preferred. As the resin (a) having these functional groups,
Conventionally known organic resins can be used, such as acrylic resins, polyester resins, polyester urethanes, polyether resins, polyether urethanes, aliphatic epoxy resins, and modified products thereof.

By reacting with the above resin C&), alkoxysilane groups and/or
Alternatively, the compound (1) for obtaining the resin (A) having a hydroxysilane group may contain a functional group that reacts complementary to the functional group in the resin (a), an alkoxysilane group that is less reactive with the functional group, and/or Or, it is a compound each having one or more hydroxysilane groups in one molecule. Further, the functional group of the compound (I) which reacts complementary to the functional group in the resin (L) described above may be an alkoxysilane group and/or a hydroxysilane group, which is complementary to the functional group of the resin (a). Examples of the functional group of the compound CI) that reacts with , include an isocyanate group, a hydroxyl group, an amino group, a carboxyl group, an epoxy group, a mercapto group, an alkoxysilane group, and a hydroxysilane group. Further, the combination of the functional group of the compound (I) which reacts complementarily with the functional group of the resin (a) is, for example, the isocyanate group of the resin (a) and the hydroxyl group, amine 7 group, carboxyl group, combination with mercapto group, combination of hydroxyl group of resin (a) with isocyanate group, carboxyl group, alkoxysilane group, or hydroxysilane group of compound (I), combination of epoxy group of resin (a) with compound (I) Examples include a combination of an amino group and a carboxyl group, a 7-mino group of resin (a) and an isocyanate group of compound (I), and an epoxy group.

Examples of the above-mentioned compound (I) include general formulas (I) to
(m) OR, OR.

(■) (■) R1 ■ R' -3i -0R2 R'' (II) In the formula, R□, R2, R, and R4 are each CLN12
represents an alkyl group or a cycloalkyl group, R' and R
"represents an alkyl group, cycloalkyl group, or phenyl group of 01 to 12, and R,, R2, R3, R', and R" may all be the same or partially or completely different, an alkoxysilane compound represented by or hydroxysilane compounds and condensates thereof obtained by hydrolyzing these in the presence of acid and water, general formula % formula % () where R1, R2, R3, R' and R'' are as above. They have the same meaning, and R represents a hydrocarbon group of C, ~, whose terminal is substituted with an isocyanate group or a hydroxyl group.

Examples include isocyanate group- or hydroxyl group-containing compounds represented by:

In the above formula, examples of the alkyl group or dichlorofurkyl group include methyl, ethyl, propyl, butyl, pentyl, and hexyl. Examples include heptyl, decyl, cyclopropyl, cyflobutyl, cyclohexyl groups, and formulas (I) to (
Among R-R4 in VI), lower alkyl groups of 01-@ are preferably used because they form a coating film with excellent curability. In addition, examples of CI) to (m) above include, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane,
Trimethoxymethylsilane, triethoxymethylsilane, tributoxymethylsilane, tributoxyethylsilane, trimethoxybutylsilane, triethoxycyclohexylsilane, dimethoxydimethylsilane, jetoxydimethylsilane, jetoxydiethylsilane, dipropoxydiethylsilane, etc. Also, general formula (IV) ~
An example of (Vl) is 0CNC3H,S i (OC2R5)3.0CNC
2H4S i (OCH3)s, 0CNCs Hs
S i (OC2H! )2, CR3 OCNC2H4S i C0CHs )2, CR3 OCNCH2S i (OC2R5)s, OCN CH
2S i (OCH3) s, 0CNCH2S f
(OC2R5)2 , ■ CR3 OCNCH2S i (OCH3)s , HOCH2
S i (OCH3),.

HOC2H4S i (OCH3)s , 0, HCR
3 HOCH2S f (OC2Hs )s , HOC2
Examples include H4S i (OC2R5) 2CR3. In addition, compounds having functional groups other than those listed above (
Examples of I) include epoxy group-containing silane compounds such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyljethoxysilane, and β-(3,4epoxycyclohexyl)ethyltrimethoxysilane;
Examples include amino group-containing silane compounds such as phenyl-γ-7minopropyltrimethoxysilane; mercapto group-containing silane compounds such as γ-mercaptopropyltrimethoxysilane.

The reaction between the resin (a) and the compound (1) includes a ring-opening reaction, which is known per se, in each combination of functional groups.
It can be produced according to methods such as addition reaction and condensation reaction.

The resin (A) thus obtained contains about 0.01 alkoxy group and/or hydroxysilane group per 1 kg of resin (A).
~1O mol. Nucleus is about 0.01
If the amount is less than 1 mole, the curability will decrease and a coating film with excellent physical and chemical properties will not be obtained, while if the amount is more than 10 moles, the compatibility with the oxirane group-containing resin (B) will decrease, resulting in the stability of the mixed solution. Sexuality decreases.

The resin (B) used in the cured composition of the present invention includes a resin (b) having functional groups such as an isocyanate group, an amino group, and a hydroxyl group, and a functional group that reacts complementary to the functional group and an epoxy group. (hereinafter simply referred to as "compound (II) J"), a resin having an epoxy group can be used.

As the resin (b), the same isocyanate group- or hydroxyl group-containing resin as described in the resin (a) can be used.

A resin (B) having an epoxy group is produced by reacting with the resin (b).
Examples of the functional group of compound (II) for obtaining ) include an isocyanate group and a hydroxyl group. resin(
The combination of the functional group of compound (II) that reacts complementary with the functional group of resin (b) is, for example, a combination of the isocyanate group of resin (b) and the hydroxyl group or amino group of compound (II), ) and the isocyanate group of compound (II).

As the above-mentioned compound (II), for example, the general formula % formula %
Isocyanate group-containing compounds such as () ([) (No change in content) (XI[) Examples include hydroxyl group-containing compounds such as Vl) (X■) (XIX). The above general formula (
In) to (XIX), R1 represents the same meaning as above, R5 is a hydrogen atom or a methyl group, and R6 is 01 to +2
Examples of the compound represented by the above-mentioned general formula, where n represents a hydrocarbon group and n represents an integer of 1 to 10, include the following. Among the above compounds, it is preferable to use a compound having an alicyclic epoxy group because the epoxy group has a high reactivity in ring-opening polymerization, so it cures quickly, and the physical properties of the cured coating film are further improved. It is.

The reaction between the resin (b) and the compound (II) can be carried out in accordance with a known addition reaction method in each combination of functional groups.

The resin (B) thus obtained can contain about 0.1 to 5 moles of epoxy groups per 1 kg of the resin (B).

If the number of epoxy groups is less than about 0.1, the physical properties will deteriorate, while if the number of epoxy groups is more than about 5 moles, the curability tends to decrease, and it is technically difficult to introduce them.

In the present invention, even if an epoxy resin such as bisphenol A type, bisphenol F type epoxy resin, or novolac type epoxy resin is used instead of the resin (B),
The compatibility with the resin (A) is insufficient, and a coating film with excellent finishing properties cannot be obtained, and the weather resistance of the coating film is also poor.

In addition, the molecular weight of the resins (A) and (B) described above varies depending on the type of resin and the required performance, but is usually 500.
A number average molecular weight of ~ioo, 000, preferably 750 to 30,000 can be used.

The blending ratio of resin (A) and resin (B) is in the range of 5 to 95% by weight of polymer (A), preferably 20 to 80% by weight, based on the total amount of both; )9
If the amount of polymer (A) in the range of 5 to 5% by weight, preferably 80 to 20% by weight is less than 5% by weight, or if the amount of polymer (B) is more than 95% by weight, the curability decreases. , on the other hand, the polymer (A) is more than 95% by weight, or the polymer (B
) is less than 5% by weight, which is not preferable because the curability decreases and the resulting cured product has poor physical properties.

The curable composition of the present invention is obtained by blending a chelate compound into a mixture of resin (A) and resin (B).

As the chelate compound used in the present invention, aluminum chelate compounds, titanium chelate compounds, and zirconium chelate compounds are preferable. Among these chelate compounds, compounds that can constitute a ketone enol tautomer are used as stable compounds. A chelate compound containing as a ligand forming a chelate ring is preferred.

Compounds that can constitute keto-enol tautomers include β-diketones (acetylacetone, etc.), acetoacetic esters (methyl acetoacetate, etc.), malonic acid esters (ethyl malonate, etc.), and Ketones having a hydroxyl group (such as diaheptone alcohol), aldehydes having a hydroxyl group at the β position (such as salicylaldehyde), esters having a hydroxyl group at the β position (methyl salicylate), and the like can be used. In particular, acetoacetic acid esters, β
- Favorable results are obtained using diketones.

The aluminum chelate compound is, for example, the above-mentioned ketone compound per mole of the aluminum alcoholade represented by the general formula % (in which R7 represents an alkyl group or an alkenyl group having 1 to 20 carbon atoms). - It can be suitably prepared by mixing compounds that can constitute an enol tautomer at a molar ratio of usually about 3 moles or less, and heating if necessary.

As the alkyl group having 1 to 20 carbon atoms, the above-mentioned carbon number I
In addition to the alkyl group of N10, undecyl, dodecyl,
Examples of the alkenyl group include tridecyl, tetradecyl, and octadecyl groups, and examples of the alkenyl group include vinyl and allyl groups.

Examples of the aluminum alcoholades represented by the general formula (XX) include aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum triisobutoxide, aluminum aluminum tri-5ec-butoxide, aluminum tri-tert-butoxide, etc., especially aluminum triisopropoxide, aluminum tri-5ec-butoxide, etc.
Preferably, eQ-butoxide, aluminumtri-n-butoxide, etc. are used.

A titanium chelate compound is, for example, based on 1 mol of Ti in a titanate represented by the general formula [where m is an integer of θ to 10, and R6 represents an alkyl group or alkenyl group having 1 to 20 carbon atoms].
It can be suitably prepared by mixing the compounds that can constitute the ketone enol tautomer at a molar ratio of usually about 4 moles or less, and heating if necessary. Carbon number 1
The alkyl group and alkenyl group of ~20 are the same as above.

Titanates represented by general formula (XXI) include:
When m is 1, tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetra-isopropyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, tetra-ter
Examples include t-butyl titanate, tetra-n-pentyl titanate, tetra-n-hexyl titanate, tetraisooctyl titanate, tetra-n-lauryl titanate, and especially tetraisopropyl titanate, tetra-n
-butyl titanate, tetraisobutyl titanate, tetra-tert-butyl titanate, etc. are used to give suitable results. In addition, for those where n is 1 or more, tetra-n-butyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, tetra-ter
Dimer to monomer of t-butyl titanate (general formula (
m=1 to 10) in XX[) gives preferable results.

The zirconium chelate compound is, for example, per 1 mole of Zr in the zirconates represented by the general formula [wherein m is an integer of 0 to 10, and R9 represents an alkyl group or alkenyl group having 1 to 20 carbon atoms]. It can be suitably prepared by mixing compounds that can constitute the above-mentioned keto-enol tautomer at a molar ratio of usually about 4 moles or less, and heating if necessary. The alkyl group and alkenyl group having 1 to 20 carbon atoms are the same as described above.

Zirconates represented by the general formula (XX[[) include tetraethylzirconate, tetra-n-propylzirconate, tetraisopropylzirconate, tetra-n-butylzirconate, tetra-5ea-butylzirconate, tetra- tert-butyl zirconate, tetra-n-pentyl zirconate, tetra-ter
t-pentyl zirconate, tetra-tjrt-hexyl zirconate, tetra-n-hebutyl zirconate,
Tetra-n-octylzirconate, tetra-n-stearylzirconate, etc., especially tetraisopropylzirconate, tetra-n-propylzirconate, tetraisobutylzirconate, tetra-n-butylzirconate, tetra-5ec- Suitable results are obtained using butyl zirconate, tetra-tert-butyl zirconate, and the like. In addition, for those where m is 1 or more, tetraisopropyl zirconate, tetra-n-propyl zirconate, tetra-n-butyl zirconate,
Tetraisobutylzirconate, tetra-3eC-butylzirconate, tetra-tert-butylzirconate dimer to monomer (m= in general formula (X■)
1 to 10) give suitable results. Further, it may contain a structural unit in which these zirconates are associated.

Particularly preferred chelate compounds in the present invention include aluminum diisopropylate ethyl acetoacetate, tris(ethyl acetoacetate) aluminum, tris(n-propylacetoacetate) aluminum, tris(isopropylacetoacetate) aluminum, tris( n-butylacetoacetate) aluminum, isopropoxybisethylacetoacetate aluminum, diisopropoxyethylacetoacetate aluminum, tris(acetylacetonato)aluminum, tris(ethylacetonato)aluminum, diisopropylate ethylacetonatoaluminum, monoacetyl Acetonate bis(ethylacetonato)aluminum, monoethylacetoacetate bis(acetylacetonato)aluminum, tris(impropylate)aluminum, tris(sec-butyrate)aluminum, diisopropylate mono-5ee
-butoxyaluminum, tris(acetylacetone)
Aluminum chelate compounds such as aluminum; titanium chelate compounds such as diisopropoxy bis(ethylacetoacetate) titanate, diisopropoxy bis(acetylacetate) titanate, diisopropoxy bis(acetylacetone) titanate; tetrakis(acetylacetone) zirconium , tetrakis (n
Zirconium chelate compounds such as -propylacetoacetate) zirconium, tetrakis (acetylacetonate) zirconium, and tetrakis (ethylacetoacetate) zirconium can be mentioned.

In the present invention, any one of aluminum chelate compounds, zirconium chelate compounds, and titanium chelate compounds may be used as the crosslinking reaction curing agent;
The blending amount of the crosslinking reaction curing agent, which may be used in combination as appropriate, is 0.01 to 30 parts by weight per 100 parts by weight of the copolymer.
Approximately 1 part by weight is appropriate. If it is less than this range, the crosslinking curability tends to decrease, and if it is more than this range, it tends to remain in the cured product and reduce the water resistance, which is not preferable.The preferred blending amount is 0.1 to 10% by weight. The more preferred amount is 1 to 5 parts by weight.

The curable composition of the present invention may optionally include an extender pigment,
Color pigments, dyes, etc. can be added. In addition, if necessary, other materials such as -functional or polyfunctional epoxy compounds, low molecular weight silane compounds such as triphenylmethoxysilane and diphenyldimethoxysilane, and silicone resins having general alkoxysilane groups may be used. Resins can also be added.

The curable composition of the present invention can be suitably used in, for example, paints, adhesives, inks, and the like.

The curable composition of the present invention can be easily crosslinked and cured at a low temperature of 100°C or lower. That is, according to the present invention, the composition can be sufficiently cured in about 8 hours to 7 days by simply exposing it to room air after application and without any heating. In addition, when heated to 4f40-100°C, it can be sufficiently cured in about 5 minutes to 3 hours. Furthermore, a small amount of moisture, comparable to that in the air, is sufficient for curing at room temperature.

Taking the case where a zirconium chelate compound is used as an example, the reason why the curable composition of the present invention is easily crosslinked and cured at low temperatures is considered as follows.

That is, in the -stage reaction, the alkoxysilane group in the resin is hydrolyzed in the presence of a trace amount of water using the zirconium chelate compound as a catalyst to produce a silanol group. Crosslinking occurs due to dehydration condensation of comrades or by reaction with the zirconium chelate compound. Furthermore, as a third step reaction, the silanol groups are polarized. This polarized silanol group reacts with the epoxy group in the resin to form an oxonium salt.Then, the hydroxyl group and alkoxysilane group formed by the oxonium salt are crosslinked to form an ether, or crosslinked by ionic polymerization of epoxy molecules by oxonium salt. happens.

Compared to the conventional case, in the conventional curable composition of this type, crosslinking and curing was performed only in the second step reaction, whereas in the curable composition of the present invention, the epoxy group is particularly contained in the resin. By introducing the above, the second-stage reaction and the third-stage reaction occur in parallel in a chain, resulting in crosslinking and curing. In these chain reactions, the alkoxysilane groups in the composition are hydrolyzed by moisture and converted into silanol groups, and the silanol groups further cause crosslinking to proceed with the above-mentioned chain reaction that does not require moisture. Therefore, the reaction proceeds in a chain manner with the minimum amount of moisture required to hydrolyze the alkoxysilane group, so that moisture in the air is sufficient as the moisture. Furthermore, by using a silanol group-containing composition, it can be cured at low temperatures even in a moisture-free environment (two-component type).

&1 Shitoasha According to the curable composition of the present invention, a resin containing an alkoxysilane group and/or a hydroxysilane group and an epoxy group is used as a resin component, and a chelate compound is used as a crosslinking reaction curing agent. By incorporating these, the following particularly remarkable effects can be achieved.

(1) It can be easily crosslinked and cured at a low temperature of 100° C. or lower in the presence of a small amount of moisture, for example, moisture in the air.

(2) Since the crosslinking by the condensation reaction etc. and the crosslinking by the ring-opening polymerization reaction occur in parallel, there is little difference in hardenability between the surface and the inside, and no distortion occurs.

(3) Since there are few by-products such as alcohol, a cured product with excellent physical properties can be obtained. In particular, it has excellent physical properties such as water resistance, weather resistance, impact resistance, suitability for overcoating, flexibility, and stain resistance.

(4) It has excellent storage stability and is stable for more than one year in a moisture-free state.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. In Examples and Comparative Examples, "1 part" or "1%" is based on weight.

Production Example A-1 Monophthalic anhydride 148 parts Trimethylolpropane 27 parts Neopentyl glycol 114 parts The above mixture was charged into a reaction vessel equipped with a rectification column, and the mixture was gradually reduced to 230% over 2 hours.
After raising the temperature to ℃, it was heated at the same temperature for 7 hours to perform a dehydration condensation reaction to obtain a reaction product. Next, this was added to a mixed solvent of xylene/butyl acetate = 1/1 (weight ratio). A polyester solution having a solid content of 50% (the amount of hydroxyl groups in 500 parts of the solution was 0.73 mol) was obtained.

Next, the following mixture, 500 parts of the above 50% solids polyester solution, 100 parts of phenyltrimethoxysilane, and 0.5 parts of tris(acetylacetonate)aluminum, was charged into a reaction vessel equipped with a rectification column, and heated at 80°C to 100°C for 500 parts. The reaction was carried out by heating for an hour while distilling off the by-product methanol.
00) was obtained.

Production Example A-2 Butyl acetate 60 parts Toluene 60 parts Tetraisopropyl titanate 0.2 parts The above mixture was charged into a reaction vessel equipped with a rectification column and heated at 80°C to 100°C for 3 hours to remove methanol as a by-product. After the reaction was carried out while distilling out 4.0 parts of deionized water and 0.001 part of 88% formic acid, the by-produced methanol was further distilled off at 80°C for 3 hours, and the solid content was 50% Resin A-2 (Resin A-2). 3.8 moles of flukoxysilane and hydroxysilane groups and a number average molecular weight of about 900 were obtained in 1 kg of solid content.

Production Example A-3 0CNC2H4S i (OCH3) s 10 parts The above mixture was reacted at 80 to 100°C, and infrared analysis showed 2
After confirming that the absorption of isocyanate groups around 250 cm-' had disappeared, resin A-3 with a solid content of 55% (1.5 mol of methoxysilane groups in 1 kg of resin solid content, number average molecular weight of about 25,000) was added. Obtained.

Production Example A-4 HOC2H4Si (OC2H5)3 0.5 parts After heating the above mixture at 80°C for 5 hours, n-butanol 1
Add 6 parts and heat to 80°C to 100°C, and infrared analysis shows 22
It was confirmed that the absorption of isocyanate groups around 50 cm''1 had disappeared, and the solid content was 50% resin A-4 (resin solid content 1
0.15 mol of ethoxysilane group per kg and a number average molecular weight of 16.000) were obtained.

Epoxy B Production Example B-1 Tolylene diisocyanate 174 parts Butyl acetate 242 parts To the above solution, 74 parts of glycidol was gradually added dropwise over 2 hours at 25 to 30°C, and the mixture was kept for an additional 3 hours to obtain an isocyanate with a solid content of 50%. A base-containing epoxy compound (4.0 mol of isocyanate groups in 1 kg of compound solid content) was obtained.

Next, a mixture of 0.05 parts of dibutyltin dilaurate described below was reacted at 75 to 80°C until there was no absorption around 2250 crl in infrared analysis.
(11.6 moles of epoxy and a number average molecular weight of 4,500 were obtained in 1 kg of resin solid content.

Production Example B-2 222 parts of inphorone diisocyanate 223 parts of 445 parts of butyl acetate were added dropwise over 2 hours, and the mixture was maintained for an additional 3 hours. #The reaction temperature was 50 to 55°C. An epoxy compound containing isocyanate groups with a solid content of 50% (2.2 mol of isocyanate groups in 1 kg of compound solid content) was obtained.

Next, 0.01 part of dibutyltin diacetate (described below) was reacted at 75 to 80°C until there was no absorption near 2250 cm' in infrared analysis, and a solid content of 50% resin B-
2 (0.11 mol of epoxy group in 1 kg of resin solid content, number average molecular weight 22.000) was obtained.

Production Example B-3 The 50% acrylic resin used in Production Example A-4 90 parts Methyl isobutyl ketone 10 parts Dibutyltin dilaurate 0.10 parts The mixture was analyzed by infrared analysis at 80 to 100°C. The reaction was carried out until the absorption near 250C '' disappeared, and the solid content was 50% Resin B-3 (resin solid content 1
0.8 mol of epoxy group per kg, number average molecular weight 19.0
00) was obtained.

Examples 1 to 6 Table 1 was prepared using the resins of Production Examples A-1 to A-4 and B-1 to B-3.
Examples 1 to 6
A curable composition was obtained.

Comparative Examples 1 to 3 Compositions of comparative examples were obtained using the resin of Production Example A-3 and having the formulations shown in Table-1.

Next, the following tests were conducted.

[Coating film performance test 1 Each of the compositions of Examples 1 to 6 and Comparative Examples 1 to 3 had a dry film thickness of 1
00μ (However, water resistance and weather resistance were tested at 50μ).

) and then dried under the drying conditions listed in Table 1 and used for testing.

Appearance: The appearance was observed and abnormalities such as gloss, distortion, and cracking were visually evaluated.

Pencil hardness: Measured according to JIS K-5400.

Gel fraction: The dried coating film was peeled off from the glass plate and extracted in a Soxhlet extractor at reflux temperature using amethane for 6 hours, and the remaining content of the coating film was expressed in %.

Impact resistance: The material used is mild steel plate. Using a DuPont impact tester, a 500g weight was dropped onto the painted surface to detect cracks in the paint film.

Maximum drop distance (CM) without peeling Examined.

Water resistance: The material used is mild steel plate. Place the test piece in warm water (40℃
) for 60 days.

After that, check whether there are any abnormalities in the condition of the painted surface. Ta.

Weather resistance: The material used is aluminum plate. Q manufactured by SuQ Panel Co., Ltd.
Irradiation (1
After repeating the cycle of 5 minutes) and dew condensation (15 minutes) for 2000 hours, the degree of paint film deterioration was observed.

The test results are summarized in Table-2.

Procedural amendment (formality) March 2, 1986

Claims (1)

[Claims] 1. The resin (a) has one or more functional groups selected from isocyanate groups, hydroxyl groups, epoxy groups, carboxyl groups, and amino groups, and a functional group that reacts complementary to the functional groups. and a resin having an alkoxysilane group and/or a hydroxysilane group (A) obtained by reacting a compound having an alkoxysilane group and/or a hydroxysilane group, and one or more of isocyanate groups, amino groups, and hydroxyl groups. Crosslinking with a mixture of resin (B) having an epoxy group, which is obtained by reacting the resin (b) having a functional group with a compound having a functional group and an epoxy group that react complementary to the functional group of the resin (b). A curable composition comprising a chelate compound as a reactive curing agent. 2. The curable composition according to claim 1, wherein the resin (B) is a resin having an alicyclic epoxy group.