DE3838185A1 - HAUNDBARE COMPOSITION AND A METHOD FOR HARDENING THE SAME - Google Patents

Abstract

A curable composition comprises: (i) a resin (I) having an alkoxysilane and/or hydroxysilane group and oxirane group and obtained by reacting a resin (A) having a group selected from an isocyanate, hydroxyl, oxirane, carboxyl and amino group with a compound (a) having a group reactive with the functional group of the resin (A), and an alkoxysilane and/or hydroxysilane group and with a compound (b) having a group reactive with the functional group of the resin (A) and oxirane group, or (ii) a mixture of a resin (II) having an alkoxysilane group and/or hydroxysilane group and obtained by reading the resin (A) with the compound (a) and a resin (III) having oxirane group and obtained by reacting a resin (B) having a group selected from an isocyanate, hydroxyl, carboxyl and amino group with the compound (b), and (iii) a chelate compound, as a crosslinking curing agent. The composition is curable at a temperature of up to 100 DEG C in the presence of water.

Description

The present invention relates to novel curable Compositions and a method for curing the same.

There are already known compositions which by mixing an acid, base, an organometallic catalyst, etc. with an alkoxysilane group-containing vinyl polymer are prepared and by crosslinking at a relatively low temperature d. H. at room temperature to 100 ° C, can be cured. So describes z. For example, the unaudited JA patent publication SHO 60-67 553 a composition containing an alkoxysilane group-containing Vinyl polymer, e.g. Methacryloxypropyltrimethoxysilane, and an aluminum chelate compound mixed with the polymer includes.

However, the usual compositions have disadvantages. Because the hydroxysilane group formed by the hydrolysis of the alkoxysilane group the only cross-linking, functional group is, The compositions require a large amount of water for Curing. Therefore, lend the large quantities By-products, such as alcohols derived from hydrolysis, the cured product has degraded properties. If the composition only in the presence of water The air is cured, it is only at the air hardened in contact surface, wherein the Inner remains almost uncured, so the different Curing degree between surface and interior during curing possibly leads to a shrunken product.

The aim of the present invention is the creation of a new one Composition containing a small amount of water completely can be cured, and a method of curing the Compositions.

Another object of the invention is to provide a new one Composition containing a cured product with excellent Provides properties, and a method for  Curing the same.

Another object of the invention is to provide a new composition, with only the water in the air is curable, with the difference in the degree of cure between surface and interior is reduced and none Shrinkage occurs, and a method of curing the Composition.

These and other objects are achieved by the present invention with a curable composition characterized is that it includes:

• (i) a resin (I) containing an alkoxysilane group and / or hydroxysilane group and oxirane group and has been obtained by Reaction of a resin (A) containing at least one functional Group selected from an isocyanate group, hydroxyl group, Oxirane group, carboxyl group and amino group, with a compound (a) which is a functional group used to functional group of the resin (A) complementary and with this is reactive, and an alkoxysilane group and / or Hydroxysilane group, and with a compound (b), the one functional group that belongs to the functional group of the resin (A) is complementary and reactive with it, and an oxirane group, or
• (ii) a mixture of a resin (II) containing an alkoxysilane group and / or hydroxysilane group and has been obtained by reacting a resin (A) with the compound (a), and a resin (III) having an oxirane group and obtained is by reacting a resin (B), which is at least one functional group selected from an isocyanate group, Hydroxyl group, carboxyl group and amino group, with the compound (b) and
• (iii) a chelate compound used as a crosslinking curing agent serves and with the resin (I) or the mixture mixed.

The invention also provides a curing process, characterized in that the composition at a temperature of up to 100 ° C in the presence of Water is cured.

According to the invention, intensive research was conducted to the disadvantages of the known, in the above publication overcome the above composition was determined.

• (1) The presence of the resin with an alkoxysilane group and / or hydroxysilane group and oxirane group does not matter only the hydroxysilane group, but also the oxirane group usable as a crosslinking, functional group, so that the composition in the presence of a small amount of water is completely curable.
• (2) The composition gives only a considerable amount when cured reduced amounts of alcohol and similar by-products and gives a cured product with excellent, almost undisturbed Properties.
• (3) If the composition is only in the presence of water is cured in air, subject to the hydroxysilane group at the surface in contact with the air the composition of a crosslinking reaction, which causes that the oxirane groups in a chain-like manner throughout Interiors undergo a crosslinking reaction, due the smaller difference in degree of cure between the surface and the interior is thereby caused no shrinkage.

The present invention is based on these new findings.

There are 2 types of curable compositions according to the invention: one comprises component (i) and a chelate compound, which serves as a crosslinking curing agent and with  this is mixed and the other comprises the component (ii) and the chelate compound.

Component (i) of the former, curable Composition, d. H. the resin (I) has an alkoxysilane group and / or hydroxysilane group and oxirane group and was obtained by reacting a resin (A) containing at least a functional group selected from an isocyanate group, Hydroxyl group, oxirane group, carboxyl group and amino group, with a compound (a) having a functional group belonging to the functional group of the resin (A) is complementary and reactive with it, and one Alkoxysilane group and / or hydroxysilane group, and with a compound (b) containing a functional group, the to the functional group of the resin (A) complementary and is reactive with this and has an oxirane group.

The term "functional group responsible for the functional Group of the resin (A) complementary and reactive with this is "used here means that this Groups can be implemented and connected with each other.

Combinations of such complementary functional groups according to the invention are z. B. hydroxyl / isocyanate, hydroxyl / Alkoxysilane, hydroxy / hydroxysilane, hydroxyl / carboxyl, Isocyanate / amino, isocyanate / mercapto, isocyanate / carboxyl, Oxirane / carboxyl, oxirane / amino, etc.

Preferred combinations of the functional group of Resin (A) / functional group of the compound (a) or (b), which are complementary to each other and give the resin (I), are z. B: hydroxyl / alkoxysilane, hydroxy / hydroxysilane, Hydroxyl / isocyanate, isocyanate / hydroxyl, etc.

Typically, the resin (I) z. B. produced, by

• (1) a hydroxyl group-containing resin with a compound  the one alkoxysilane group and / or hydroxysilane group contains, or an isocyanate group-containing alkoxysilane as compound (a) and an isocyanate group-containing Oxirane compound is reacted as compound (b),
• (2) an isocyanate group-containing resin having a hydroxyl group-containing Alkoxysilane compound as compound (a) and a hydroxyl group-containing oxirane compound as Reacting compound (b),
• (3) an isocyanate group-containing resin having a hydroxyl group-containing Oxirane compound as compound (b) to Forming an oxirane-containing urethane resin, some of the oxirane groups of the resin of a ring cleavage subjected with an alcohol to a hydroxyl group in the resin and the product obtained with a A compound which has an alkoxysilane group and / or a Hydroxysilane contains as compound (a).

According to these methods (1) to (3), resins are obtained which have a urethane bond and in the alkoxysilane group and / or hydroxysilane group or the oxirane group introduced by the urethane bond.

The "hydroxyl group-containing" to be used in these methods (1) to (3) Resin "is a well-known resin that has a Hydroxyl group containing the alkoxysilane group and / or Hydroxysilane group and isocyanate group is reactive. Such resins are for. Acrylic resin, polyesters, polyethers, polyurethanes, Polyether urethanes, polyester urethanes, etc.

The "isocyanate group-containing resins" are z. B. an adduct of the hydroxyl-containing resin with a diisocyanate compound, preferably z. Tolylene diisocyanate, xylylene diisocyanate, hydrogenated products such as diisocyanates or isophorone diisocyanate in the ratio of 1 mole of diisocyanate compound per mole of hydroxyl group; Homopolymers of an isocyanate group-containing, unsaturated monomer, eg. B. an equimolar adduct of isophorone diisocyanate or tolylene diisocyanate with a hydroxyalkyl (meth) acrylate, for. 2-hydroxyethyl (meth) acrylate, m-isopropenyl- α , α- dimethylbenzyl isocyanate or isocyanoethyl (meth) acrylate, or a copolymer of the monomer and an aromatic vinyl monomer, alkyl (meth) acrylate, etc.

"Compounds containing an alkoxysilane group and / or hydroxysilane group for example, those containing an alkoxysilane group and / or hydroxysilane group containing the Hydroxyl group of the hydroxyl-containing resin reactive is hydroxysilane group-containing compounds by hydrolysis of an alkoxysilane-containing compound in the presence of an acid or water as catalyst, low condensation products of such compounds, etc. Suitable alkoxysilane-containing compounds are z. B. represented by the following formulas.

wherein R₁, R₂, R₃ and R₄ are the same or different and each a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms are; R₅ and R₆ are the same or different and each an alkyl group having 1 to 12 carbon atoms, a Cycloalkyl group having 3 to 12 carbon atoms or phenyl are.  

"Isocyanate-containing alkoxysilane" are z. B. represented by the following formulas:

wherein R₅ and R₆ are as defined above, R₇ is a hydrocarbon group with 1 to 12 carbon atoms and with one Isocyanate group substituted or isocyanate group, and R₈, R₉ and R₁₀ are the same or different and each one Alkyl group having 1 to 12 carbon atoms or a cycloalkyl group with 3 to 12 carbon atoms.

Alkyl groups or cycloalkyl groups in the above formulas are z. Methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, Decyl, undecyl, dodecyl, cyclopropyl, cyclobutyl, cyclohexyl etc. R₁ to R₄ and R₈ to R₁₀, which in the formulas (I) to (V) are bonded to the oxygen atom are preferably Lower alkyl having 1 to 6 carbon atoms, since then a strong curable coating can be obtained.

Compounds of formulas (I) to (III) are z. Tetramethoxysilane, Tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, Trimethoxymethylsilane, triethoxymethylsilane, tributoxymethylsilane, Tributoxyethylsilane, trimethoxybutylsilane, Triethoxycyclohexylsilane, dimethoxydimethylsilane, diethoxydimethylsilane, Diethoxydiethylsilane, dipropoxydiethylsilane, Diethyldihydroxysilane, dihexyldihydroxysilane, methyltrihydroxysilane,  Phenyltrihydroxysilane, tetrahydroxysilane, etc.

Compounds of formulas (IV) to (VI) are for. B.

etc.

The "isocyanate group-containing oxirane compound" is an oxirane compound with an isocyanate group having the hydroxyl group the hydroxyl-containing resin is reactive. Such compounds have z. For example, the following formulas:

wherein R₈ is as defined above, R₁₁ is a hydrogen atom or methyl, R₁₂ is a hydrocarbon group having 1 to 12 carbon atoms and the groups R₁₂ are the same or different and n is an integer of 1 to 10. The hydrocarbon groups represented by R₁₂ having 1 to 12 carbon atoms correspond to z. As the above-mentioned alkyl groups having 1 to 12 carbon atoms, but have a smaller by 1 number of hydrogen atoms. More specific compounds of formulas (VII) to (XV) are represented by the following formulas:

The "hydroxyl-containing alkoxysilane compound" is a those with an alcoholic, with an isocyanate group reactive hydroxyl group. Such compounds are z. B .:  

wherein R₈, R₉ and R₁₀ are as defined above, R₁₃ is a hydrocarbon group with 1 to 12 carbon atoms and with Hydroxyl is substituted. The hydrocarbon group represented by R₁₃ with 1 to 12 carbon atoms is the same as mentioned above. More specific examples Compounds of formulas (XVI) to (XVIII) are as follows:

The "hydroxyl-containing oxirane compound" is one such with an alcoholic, isocyanate-reactive Hydroxyl group. Such compounds are z. B. by the following formulas are shown:

wherein R₈, R₁₁, R₁₂ and n are as defined above.

In the processes (1) to (3), the reaction of the hydroxyl group with the alkoxysilane and / or hydroxysilane and isocyanate group (Process (1)) and the reaction of the isocyanate group with the hydroxyl group (methods (2) and (3)) be carried out known methods. These reactions can z. B. by dissolving or dispersing the mixtures of Compounds with said functional groups in an organic solvent such as xylene, toluene, ethyl acetate, Propyl acetate, methyl ethyl ketone, methyl isobutyl ketone or heptane, and reaction of the solution or dispersion, usually at about 40 to about 150 ° C for about 1 to about 10 hours respectively.

From the standpoint of the properties of the available, cured Product is the resin (I), which after one of the procedures (1) to (4) for use in the method of the present invention has been, preferably one in which an alkoxysilane group and / or hydroxysilane group or oxirane group a urethane bond was introduced.

The oxirane group of the resin (I) for use in the invention is preferably an alicyclic oxirane group, since the oxirane group then undergoes a ring-split polymerization reaction is subjected to high reactivity is what leads to faster curing and after the curing provides improved properties of the coating.

The resin (I) to be used in the present invention may be about 0.01 to about 10 moles of alkoxysilane and / or hydroxysilane groups and about 0.1 to about 10 moles of oxirane groups per kg of the resin as functional groups. If less than about 0.01 mol alkoxysilane and / or hydroxysilane present  are, results in a reduced hardenability, which It becomes impossible to get a coating with excellent physical and to obtain chemical properties. If On the other hand, the amount is over about 10 mol, the composition against the influence of water in the air sensitive, does not harden uniformly and gives a bad Surface texture of the coating. In the presence of less as 0.1 mole of oxirane groups, the coating may shrink and shows deteriorated properties; thus is he undesirable. On the other hand, it is technically difficult to do more than introduce about 10 moles of oxirane groups in the resin, which also affects the hardenability.

The molecular weight of the resin (I) associated with the type of Resin varies, may suitably according to the required Properties of the coating to be formed and may usually be about 1000 to about 100,000, preferably from about 2,000 to about 20,000 (GPC peak molecular weight) be.

Now, the resins (II) and (III) described in U.S. Pat curable compositions of the invention are used and component (ii), as well as the mixed, as a crosslinking curing agent serving chelate compound.

The resin (II) for use in the present composition is a resin having an alkoxysilane group and / or Hydroxysilane group obtained by reaction of the resin (A) with the compound (a).

Preferred combinations of the functional groups of Resin (A) / functional groups of compound (a) used together are complementary and give the resin (II), z. B. Hydroxyl / isocyanate, hydroxyl / carboxyl, hydroxyl / alkoxysilane, Hydroxyl / hydroxysilane, isocyanate / hydroxyl, isocyanate / mercapto, Isocyanate / carboxyl, isocyanate / amino, oxirane / carboxyl, Oxirane / amino, carboxyl / isocyanate, carboxyl / hydroxyl,  Carboxyl / oxirane, amino / isocyanate, amino / oxirane, etc.

Typically, the resin (II) z. B. are produced by

• (1) Reaction of a hydroxyl-containing resin with the above-mentioned compound which is an alkoxysilane and / or Contains hydroxysilane group,
• (2) Reaction of a hydroxyl group-containing resin with a isocyanate group-containing alkoxysilane compound,
• (3) reaction of an isocyanate group-containing resin with the above-mentioned hydroxyl-containing alkoxysilane compound,
• (4) reacting an isocyanate group-containing resin with at least one amino group-containing alkoxysilane compound (eg, N-phenyl- γ- aminopropyltrimethoxysilane) and a mercapto group-containing alkoxysilane compound (eg, γ- mercaptopropyltrimethoxysilane),
• (5) reaction of an oxirane group-containing resin with at least one of the above amino group-containing alkoxysilane compounds, a carboxyl group-containing alkoxysilane compound (e.g., trimethoxysilylbenzoic acid) and the above mercapto group-containing alkoxysilane compound,
• (6) reacting a carboxyl group-containing resin with at least one glycidyl group-containing alkoxysilane compound (e.g., γ- glycidoxypropyltrimethoxysilane, γ- glycidoxypropyldiethoxysilane or β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane), the above hydroxylated alkoxysilane compound and the above isocyanate group-containing alkoxysilane compound,
• (7) Reaction of an amino group-containing resin with at least one of the above isocyanate group-containing alkoxysilane compounds and the above glycidyl group-containing Alkoxysilane compounds, etc.

The methods (2) or (3) give a urethane group-containing Resin.  

The "hydroxyl-containing resin" and the "isocyanate group-containing Resin "for use in these processes (1) to (7) may be the same resins that have already been mentioned. The "oxirane group-containing resin" is z. B. a polymer that is in Substantially from an unsaturated monomer, such as glycidyl (meth) acrylate consists. Examples of carboxyl-containing Resins "are polymers consisting essentially of a carboxyl group-containing, unsaturated monomer, such as (meth) acrylic acid or maleic acid, and a polyester resin by esterification of polybasic acids (such as phthalic acid, isophthalic acid or terephthalic acid) with a polyvalent Alcohol (such as ethylene glycol, polyethylene glycol, neopentyl glycol, 1,6-hexanediol or trimethylolpropane). The "amino-containing resin" is z. As a resin produced by reacting the above polybasic acid with an amino group-containing acid Compound such as propanolamine, monoethanolamine, Diethanolamine, ethylenediamine, etc.

The resin (II) can be prepared by adding the resin (A) and the compound (a) with their respective functional Groups of a known reaction, for. B. ring splitting, addition or condensation, subject.

The thus-obtained resin (II) may be about 0.01 to about 10 mol Alkoxy and / or hydroxysilane groups per kg of the resin. Are less than about 0.01 mole of alkoxysilane and / or Hydroxysilane present, resulting in a reduced Cure, which does not coat with excellent chemical Features. With more than 10 moles of alkoxysilane and / or hydroxysilane groups, the resin (II) has a reduced Compatibility with the oxirane-containing resin (III), which results in a lower stability of the mixture.

The resin (III) for use in the curable invention Composition is a resin with an oxirane group, obtained by reacting a resin (B) which is at least an isocyanate, hydroxy, carboxyl or amino group as  having functional group, with the compound (b).

Typically, the resin (III) z. B. are produced by:

• (1) Reaction of the above isocyanate group-containing Resin with the above hydroxyl-containing oxirane compound;
• (2) Reaction of the above hydroxyl group-containing resin with the above isocyanate group-containing oxirane compound,
• (3) Reaction of the above amino group-containing resin with the above isocyanate group-containing oxirane compound or similar procedures.

The methods (1) or (2) give a urethane group-containing Resin.

Preferred combinations of the functional group of the resin (B) / functional group of the compound (b) related to each other are complementary and give the resin (III), z. B. isocyanate / Hydroxy, amino / isocyanate, hydroxyl / isocyanate, carboxyl / Oxirane, etc.

In the preparation of the resin (III), it is appropriate to a To use compound with an alicyclic oxirane group because the oxirane group is extremely reactive, to an accelerated one Curing leads and improved after curing Properties of the coating results.

The resin (III) can be prepared by adding the resin (B) and the compound (b) with their respective functional Groups a known method of addition reaction subjects.

The thus-obtained resin (III) may be about 0.1 to about 10 mol Oxirane groups per kg of resin. In the presence of Less than about 0.1 mole of oxirane groups can have poor properties while in the presence of more than 10 mol  Oxirane groups may impair hardenability becomes. Next, it can be difficult to get such a large amount Introduce oxirane groups into the resin.

An epoxy resin, such as bisphenol A, bisphenol F or a novolak Epoxy resin according to the invention optionally instead of Resin (III) is of low compatibility with the resin (II) and gives no coatings with excellent Surface texture and good weather resistance.

The molecular weight of the resin (II) and the resin (III) is usually 500 to 100,000, preferably 750 to 30,000, as the number average molecular weight, although Changes in the type of resin and the properties of the resin Depend on the coating to be formed.

The amounts of resin (II) and (III), based on the combined amount is 5 to 95 wt .-%, preferably 20 to 80% by weight, resin (II) and 95 to 5% by weight, preferably 80 to 20 wt .-%, resin (III). If less than 5% by weight Resin (II) with more than 95 wt .-% resin (III) can be used results in a reduced hardenability, with more as 95% by weight of resin (II) with less than 5% by weight of resin (III) a reduced hardenability results, resulting in a hardened Product with bad characteristics results and therefore is undesirable.

According to the invention, a chelate compound is used as crosslinking Curing agent used. It is appropriate as a connection at least one aluminum, titanium or zirconium chelate Connection to use. From these chelate compounds preferred are those which contain a compound a keto-enol tautomer as a stable chelate ring containing forming ligands.

Suitable compounds which can form a keto-enol tautomer are e.g. Β- diketones (e.g., acetylacetone), acetoacetic acid esters (e.g., methyl acetoacetate), malonic esters (e.g., ethyl malonate), ketones having a hydroxyl group in the β- position (e.g., diacetone alcohol), aldehydes having a Hydroxyl group in β- position (eg salicylaldehyde), esters with a hydroxyl group in β- position (eg methyl salicylate), etc. Particularly good results are obtained when using acetoacetates and β- diketones.

The aluminum chelate compound can be prepared by one z. For example, the compound that forms a keto-enol tautomer can, with an aluminum alcoholate of the formula

wherein R₁₄ may be the same or different and alkyl with 1 to 20 carbon atoms or alkenyl, usually in a ratio of up to 3 moles of the former compound per mole of the latter compound mixes and the Mixture heated as needed.

Examples of alkyl groups having 1 to 20 carbon atoms are the abovementioned alkyl groups having 1 to 12 carbon atoms, Tridecyl, tetradecyl, octadecyl, etc. alkenyl groups are z. As vinyl, allyl, etc.

Aluminum alcoholates of the formula (XXV) are z. B. aluminum trimethoxide, Aluminum triethoxide, aluminum tri-n-propoxide, Aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum triisobutoxide, Aluminum tri-sec-butoxide, aluminum tri-t butoxide, etc. Particularly useful is the use of Aluminum triisopropoxide, aluminum tri-sec-butoxide and Aluminum tri-n-butoxide.

The titanium chelate compound can be prepared with advantage by z. For example, the compound that forms a keto-enol tautomer can, with a titanate of the formula  

wherein m is an integer of 0 to 10 and R₁₅ may be the same or different and is alkyl having 1 to 20 carbon atoms or alkenyl, usually in the ratio of up to about 4 moles of the former compound per mole of Ti in the titanate, and then as needed heated. Examples of the alkyl groups having 1 to 20 carbon atoms and the alkenyl groups are the same ones as mentioned above.

Titanates of the formula (XXVI) wherein m = 0 are e.g. As tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-t-butyl titanate, tetra-n-pentyl titanate. Tetra-n-hexyl titanate, tetraisooctyl titanate. Tetra-n-lauryl titanate, etc. Favorable results are obtained, for. Example, using tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate and tetra-t-butyl titanate. Of the titanates in which m = 1 or greater, the dimers to hende camers ( m = 1 to 10 in formula (XXVI)) of tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate and tetra-t-butyl titanate give good results.

The zirconium chelate compound can be produced cheaply by z. For example, the compound that is a keto-enol tautomer can form with a zirconate of the formula

wherein m is an integer of 0 to 10 and R₁₆ may be the same or different and is alkyl having 1 to 20 carbon atoms or alkenyl, usually in the ratio of up to about 4 moles of the former compound per mole of Zr in the zirconate and then as needed heated. Examples of the alkyl groups having 1 to 20 carbon atoms and alkenyl groups are the same as those already illustrated above.

The zirconates represented by formula (XXVII) in which m = 0 are e.g. B. Tetraethylzirconat, tetra-n-propylzirconate, tetraisopropylzirconate, tetra-n-butylzirconate, tetra-sec-butylzirconate, tetra-t-butylzirconate, tetra-n-pentylzirconate, tetra-t-pentylzirconate, tetra-t-hexylzirconate, tetra-t-butylzirconate n-heptylzirconate, tetra-n-octylzirconate, tetra-n-stearylzirconate, etc. Particularly good results can be obtained by using tetraisopropylzirconate, tetra-n-propylzirconate, tetraisobutylzirconate, tetra-n-butylzirconate, tetra-sec-butylzirconate and tetra-t-mono- butylzirconate can be obtained. Of the zirconates in which m = 1 or more, the dimers to hende camers ( m = 1 to 10 in formula (XXVII)) give tetraisopropylzirconate, tetra-n-propylzirconate, tetra-n-butylzirconate, tetraisobutylzirconate, tetra-sec- Butylzirconate and tetra-t-butylzirconate give good results. The chelate compound may contain structural units in which such zirconates are bonded together.

Examples of particularly preferred chelate compounds for the invention Use are aluminum chelate compounds, such as diisopropoxy-ethylacetoacetate-aluminum, tris (ethylacetoacetate) aluminum, Tris (n-propylacetoacetate) aluminum, Tris (isopropyl acetoacetate) aluminum, tris (n-butyl acetoacetate) aluminum, Isopropoxy-bis (ethylacetoacetate) aluminum, Isopropoxy-bis (propionylacetonate) aluminum, tris (acetylacetonate) aluminum, Tris (propylacetoacetate) aluminum, tris (propionylacetonate) aluminum, Acetylacetonate-bis (ethylacetoacetate) aluminum, Ethyl bis (acetylacetonate) aluminum, Tris (isopropionylacetonate) aluminum, tris (sec. butyrylacetonat) aluminum, [Bis (isopropionylacetonat) -sek- butyrylacetonate] aluminum and tris (butylacetoacetate) aluminum; Titanium chelate compounds such as diisopropoxy bis (ethylacetoacetate) titanate, Diisopropoxy-bis titanate (acetylacetonate)  and isopropoxy-tris (propionylacetonate) titanate; and zirconium chelate compounds, such as tetrakis (acetylacetonate) zirconium, Tetrakis (n-propylacetoacetate) zirconium, tetrakis (propionylacetonate) zirconium and tetrakis (ethylacetoacetate) zirconium.

According to the invention, one of the aluminum, zirconium and Titanchelatverbindungen be used, or at least 2 Types of these compounds can be combined appropriately be used. It is convenient to use the crosslinking curing agent in an amount of about 0.01 to about 30 wt. Parts per 100 parts by weight of the resin component (i) or (ii), calculated as solids, to use. Quantities outside this area are not desirable; if the crowd is lower, results in a reduced crosslinking curability, while when used in larger quantities the Curing agent remains in the cured product and possibly leads to a reduced water resistance. The amount is preferably 0.1 to 10 parts by weight, especially 1 to 5 parts by weight.

If necessary, the curable composition of the invention stretching pigments, coloring pigments, dyes etc. are incorporated. If necessary, it is also possible, the composition mono- or polyfunctional Epoxy compounds, low molecular weight silane compounds, such as triphenylmethoxysilane and diphenyldimethoxysilane, conventional alkoxysilane-containing silicone resins and others Incorporate resins. For improved storage stability it is still possible the composition Add compounds, the ligands for the chelate compound deliver, such as As the above compounds, the capable of forming a keto-enol tautomer.

The curable composition of the invention may, for. B. as a coating, adhesive, ink, etc. are used.  

The composition of the invention is crosslinked at low temperatures up to 100 ° C in the presence of Water easily curable. The composition of the invention In particular, in general, in about 8 hours to about 7 days without any heating, simply by adding water to Composition and subsequent application of the composition or Applying the composition and exposure of the coating to air completely be cured. Alternatively, the composition by heating, for. B. at 40 to 100 ° C, in about 5 min curable to about 3 hours. Water is used for curing in such small amounts that the moisture content the air is enough. If water is the composition before the application is added, then give about 0.1 to about 1% by weight of water usually gives satisfactory results.

The resin composition of the present invention is crosslinked at low temperature in the presence of a small amount Water probably curable easily for the following reason. In the presence of z. B. the Zirkoniumchelatverbindung hydrolyze the alkoxy groups in the resin in the first stage in the presence of water under the catalytic action of Zirconium chelate compound to form hydroxysilane groups. In the next, second stage are subject to the Hydroxysilane groups of a dehydration condensation with crosslinking or react with the zirconium chelate compound formation of

for networking. In the third Stage is a coordination of

and others Hydroxysilane groups, and the latter are polarized, whereupon the polarized groups are ring-split polymerization effect the oxirane groups in the resin.

The known curable composition of the same type as the composition of the invention cures only by the reaction of the second stage, while it in the Resin component of the composition according to the invention introduced Oxirane groups allow the reactions of the second and the third stage simultaneously in a chain-like manner  proceed, whereby the composition cross-linked with curing becomes. The composition of the invention is presumed for this reason, favorably at low temperature curable in the presence of a small amount of water.

The curable composition of the invention comprises a Resin component comprising an alkoxysilane and / or hydroxysilane group and oxirane group, and a chelate compound as a crosslinking curing agent, so that the composition the following exceptional benefits having:

• (1) The composition can be cured easily at low Temperature up to 100 ° C in the presence of a low Amount of water, z. As the moisture in the air, be networked.
• (2) Crosslinking by the above-mentioned condensation reaction etc. and crosslinking by the ring-cleavage reaction run at the same time, causing the difference in Degree of cure between surface and interior reduced and shrinkage is avoided.
• (3) Due to reduced amounts of alcohol and others By-products provides the composition cured Products with excellent properties, in particular Resistance to water, weather and shock, they can be applied as a top coat and shows flexibility and resistance to discoloration.
• (4) The composition has high storage stability and stays stable for at least 1 year in the absence of water.
• (5) If the resin used has a urethane bond, then shows the obtained cured product excellent Impact resistance, elongation and other properties.

The present invention will be described with reference to the following Preparation Examples, Examples and Comparative Examples explained in which, unless otherwise stated, all parts and percentages are by weight.  

Preparation of resin (I) with alkoxysilane and / or hydroxysilane groups and oxirane group Production Example I-1

phthalic anhydride 1480 parts neopentylglycol 1155 parts

These compounds were used in a four-necked flask against and at 220 ° C subjected to a Dehydratationskondensationsreaktion. When the acid number of the mixture is reduced to at most 3 was, the reaction was stopped, whereupon the reaction mixture diluted with 2455 parts of toluene to a resin solution has been. The solution had a non-volatile content Components of 50.0% and a Gardner viscosity (at 25 ° C, as in the following) of P.

To the resin solution was added 444 parts of isophorone diisocyanate and 444 Parts of toluene were added and the mixture was at 110 ° C for 3 h implemented. Subsequently, 192 parts

added and the mixture was added for 2 h 110 ° C reacted. With the addition of 31 parts of ethylene glycol the mixture was reacted at 110 ° C for a further 4 h. As the NCO number of the mixture was reduced to a maximum of 5 was the reaction ends. The reaction mixture was then 99 Parts of phenyltrimethoxysilane and 0.1 part of p-toluenesulfonic acid added. The mixture was heated for about 5 h until their temperature reached 110 ° C to remove methanol. Subsequently, toluene (275 parts) was added to the reaction mixture added to give Resin Solution I containing a content of non-volatile constituents of 49.7% and a Gardner Had viscosity of X. The solution had 0.47 moles of oxirane groups and 0.31 mole of methoxysilane groups per kg of resin solids and had a GPC peak molecular weight of 3200.

Production Example I-2

A four-necked flask was charged with 850 parts of "Placcel # 208 "® (Product of Daicel Ltd., polycaprolactone with terminal Hydroxyl group, MW 850), 555 parts of isophorone diisocyanate and Added 1400 parts of xylene and the mixture was allowed to stand for 1 h  Heated to 130 ° C. The obtained resin solution had a content non-volatile components of 50.3% and a Gardner Viscosity of H. To the solution were added 148 parts of glycidol and 148 parts of xylene was added, then reacted at 130 ° C for 5 h, which gave Reaction Mixture A. With the addition of 31 parts Ethylene glycol, the mixture was reacted at 130 ° C for 3 h. After further addition of 68 parts of methyl trimethoxysilane and 0.1 part of tris (acetylacetonate) aluminum became the mixture reacted to remove methanol for about 3 hours until its Temperature had reached 140 ° C. Subsequently, 52 parts n-propanol was added to the reaction mixture, giving the resin solution II yielded a content of non-volatile constituents of 50.0%, a Gardner viscosity of L and a GPC peak Molecular weight of 2000 and 1.2 moles of oxirane groups and 0.6 mole of methoxysilane groups per kg of resin solids.

Production Example I-3

2-hydroxyethyl methacrylate 130 parts n-butyl methacrylate 870 parts Azo-bis-isobutyronitrile 30 parts

The above mixture was added to 667 parts of butyl acetate in one Four-necked flask was added dropwise at 120 ° C. over a period of 3 h, Thereafter, the resulting mixture was kept at 120 ° C for 3 h, which is a resin solution containing non-volatile Components of 60.5% and a Gardner viscosity of G resulted. To the solution were added the following compounds:

The mixture was reacted at 120 ° C for 5 hours. The reaction mixture had a non-volatile content of 60.2% and a Gardner viscosity of Q.

Then the following compounds were added to the mixture:  

The mixture was reacted for about 5 hours to remove ethanol, until their temperature reached 120 ° C, which is the Resin solution III, which contains a non-volatile content Components of 61.0%, a Gardner viscosity of Q and had a GPC peak molecular weight of 20,000 and 0.5 mol Oxirane groups and 0.05 mole ethoxysilane groups per kg of resin solids contained.

Production Example I-4

Tolylene diisocyanate (522 parts) and 2000 parts of polypropylene glycol with terminal hydroxyl group (MW 500) were in a four-necked flask and reacted at 80 ° C for 3 h, which is a resin solution containing non-volatile Components of 100% and a Gardner viscosity of Z₂ revealed. To the solution was added 216 parts of the following compound added

The mixture was heated to 180 ° C until the removed Amount of water had reached 18 parts. The reaction mixture had a nonvolatile content of 100% and a Gardner viscosity of Z₃.

With the addition of 480 parts of the compound

The mixture was further reacted until its NCO number had decreased to at most 5, giving Resin Solution IV. The solution had a nonvolatile content  of 99.8%, a Gardner viscosity of Z₅ and a GPC Peak molecular weight of 3200 and contained 0.3 mole of oxirane groups and 0.3 moles of hydroxysilane groups per kg of resin solids.

Production Example I-5

2-hydroxyethyl methacrylate 130 parts glycidyl 142 parts n-butyl methacrylate 728 parts Azo-bis-isobutyronitrile 30 parts

The above mixture was added to 667 parts of butyl acetate in one Four-necked flask was added dropwise at 120 ° C over 3 h, then The resulting mixture was kept at 120 ° C for 3 h. The Resin solution obtained had a non-volatile content Components of 60.3% and a Gardner viscosity of P.

The above compounds were added to the solution, and the Mixture was reacted to remove ethanol for about 5 hours, until its temperature had increased to 120 ° C, causing the resin solution V was obtained. This solution had a salary of non-volatile constituents of 63.0%, one Gardner viscosity of Q and a GPC peak molecular weight of 20,000 and contained 0.79 moles of oxirane groups and 0.79 moles Ethoxysilane groups per kg of resin solids.

Production Example I-6

Methyltrimethoxysilane (68 parts) became cold with 3100 parts the reaction mixture A from Preparation Example I-2 mixed and gave the resin solution VI.

 Examples 1 to 8 and Comparative Examples 1 to 3

From the resins and metal chelate compounds listed in Table 1 Compositions were prepared in which the Amount of chelate compound in parts / 100 parts of solids in Resin is specified.  

Table 1

The following tests were performed:

Tests for coating properties

The compositions of Examples 1 to 8 and the comparative examples 1 to 3 were placed on plates on a dry Thickness of 100 microns (or 50 microns to determine the water and Weather resistance) and below the in Table 2 conditions dried and then tested.

• *) Appearance:
  The appearance of the coating was observed by the naked eye on gloss and flaws, e.g. As shrinkage, cracking, etc., examined.
• *) Gel fraction ratio:
  the dried coating on the (glass) plate was separated therefrom and subjected to extraction with acetone for 6 hours at reflux temperature by means of a Soxhlet extractor, after which it was examined for the ratio of the residue (%).
• *) Impact resistance:
  a 500 g weight was dropped onto the coated surface of the plate (soft steel plate) by DuPont Impact Tester to determine the maximum drop distance (cm) at which the coating remained free of cracking or flaking
• *) Water resistance:
  the coated plate (soft steel plate) was immersed in hot (40 ° C) water for 60 days and then examined for changes in the coating.
• *) Weather resistance:
  the coated plate (aluminum plate) was repeatedly subjected to one cycle of irradiation for 2000 hours using a QUV weathering device (product "Q panel", UV fluorescent lamp "No. QFS-40, UV-B", wavelength 320-280 nm) Subjected to light at a temperature of 40 to 70 ° C (for 15 min) and condensation (15 min) and then examined for decomposition of the coating.
• *) Strain:
  Using TENSILON UTM-II (Toyo Baldwin Co. Ltd.), the coating (5 mm in width, 20 mm in length and 50-100 μm in thickness) was peeled off at a rate of 2 cm / min. to increase the elongation achieved determine (length when tearing - initial length). The elongation (%) is calculated as follows:

Table 2 shows the results.  

Table 2

Table 2 (continued)

Resin (II) with alkoxysilane and / or hydroxysilane groups Preparation Example II-1

phthalic anhydride 148 parts trimethylolpropane 27 parts neopentylglycol 114 parts

The above mixture was placed in a rectification column Reactor, gradually, over 2 h to a temperature heated from 230 ° C and then 7 h for dehydration condensation reaction kept at this temperature. The Reaction mixture was in a solvent mixture Xylene and butyl acetate (weight ratio 1: 1) dissolved, giving a 50% solids polyester solution (containing 0.73 mol Hydroxyl groups per 500 parts of solution).

The above polyester solution (50% solids) 500 parts phenyltrimethoxysilane 100 parts Tris (acetylacetonate) aluminum 0.5 part

Then the above mixture was placed in a rectification column added reactor and heated at 80 to 100 ° C for 5 h, wherein the by-produced methanol distilled off has been; this gave Resin II-1 at 57% solids (and 3.0 Mol of methoxysilane groups per kg of resin solids; number average of molecular weight: 3500).

Production Example II-2

"Placcel 208" (product of Daicel Ltd., polycaprolactone with terminal hydroxyl group, MW 830) 95 parts butyl 60 parts toluene 60 parts tetramethoxysilane 180 parts tetraisopropyl 0.2 part

The above mixture was placed in a reactor with rectification column given and heated to 80 to 100 ° C for 3 h while Methanol was distilled off as a by-product. Under the addition of 4.0 parts deionized water and 0.01 part 88% Formic acid was added to the mixture for an additional 3 h  by-product, d. H. Methanol, distilled at 80 ° C, giving the Resin II-2 gave (containing 3.8 moles of alkoxysilane and hydroxysilane groups per kg of resin solids; Number average molecular weight: about 900).

Preparation Example II-3

50% of acrylic resin (styrene / methyl methacrylate / n-butyl acrylate / 2-hydroxyethyl acrylate = 20 parts / 30 parts / 15 parts / 35 parts, dissolved in butyl acetate / toluene (1: 1 by weight); number average molecular weight: 20,000) 90 parts OCNC₂H₄Si (OCH₃) ₃ 10 parts

The above mixture was reacted at 80 to 100 ° C. According to IR analysis, when the absorption at about 2250 cm ^-1 disappeared due to the isocyanate group, the 55% solid content of resin II-3 (and 1.5 moles of methoxysilane groups per kg resin solids, number average molecular weight, about 25,000) was obtained.

Preparation Example II-4

60% acrylic resin (styrene (methyl methacrylate / n-butyl acrylate / m-isopropenyl- α , α- dimethylbenzyl isocyanate = 20 parts / 20 parts / 40 parts / 20 parts, in butyl acetate / toluene (1/1) by weight); MG 16,000 80 parts HOC₂H₄Si (OC₂H₅) ₃ 0.5 part

The above mixture was heated to 80 ° C for 5 hours and then heated to 80-100 ° C with the addition of 16 parts of n-butanol until the IR analysis indicated disappearance of absorbance at about 2250 cm ^-1 due to the isocyanate group; this gave Resin II-4 at 50% solids (and 0.15 mole ethoxysilane groups per kg resin solids, number average molecular weight: 16,000).

Oxirane group-containing resin (III) Production Example III-1

tolylenediisocyanate 174 parts butyl 242 parts

Glycidol (74 parts) became the above solution at 25 to 30 ° C added dropwise over 2 h, then the mixture was 3 h on the maintained at the same temperature, which is an isocyanate group-containing Oxirane compound of 50% solids (and 4.0 mol Isocyanate groups per kg of solids).

Polyester solution used in Preparation II-1 (50% solids) 500 parts the above isocyanate group-containing oxirane compound (50% solids) 350 parts dibutyltindilaurate 0.05 part

The mixture was reacted at 75 to 80 ° C until the IR analysis indicated disappearance of absorbance at about 2250 cm ^-1 , giving resin III-1 having a solids content of 50% (and 1.6 moles of oxirane groups per kg of resin solids and a number average molecular weight of 4500).

Production Example III-2

isophorone 222 parts butyl 445 parts

The connection

(223 parts) was dripped into the above solution within 2 h at 50 to 55 ° C, Thereafter, the mixture was at the same temperature for 3 hours which is an isocyanate group-containing oxirane compound with a solids content of 50% (and 2.2 moles of isocyanate groups per kg of solids).

The above isocyanate group-containing oxirane compound (50% solids) 5 parts 50% acrylic resin used in Production Example II-3 95 parts dibutyltin 0.01 part

The above mixture was reacted at 75 to 80 ° C until IR analysis indicated disappearance of absorbance at about 2250 cm ^-1 , giving resin III-2 with a solids content of 50% (and 0.11 moles of oxirane groups per kg Resin solids; number average molecular weight 22,000).

Production Example III-3

The above mixture was reacted at 80 to 100 ° C until IR analysis indicated disappearance of absorbance at about 2250 cm ^-1 , giving resin III-3 with a solids content of 50% (and 0.8 moles of oxirane groups per kg Resin solids, number average molecular weight: 19,000).

Examples 9 to 14

The resins of Preparation Examples II-1 to -4 and III-1 to -3 were in the combinations shown in Table 3 and amounts (calculated as solids) together with the used in Table 3 chelate compounds according to the invention to give curable compositions.

Comparative Examples 4 to 6

The resin of Production Example II-3 was used for production the comparison compositions listed in Table 3 used.  

Table 3

Table 3 (continued)

Tests for coating properties

The compositions of Examples 9 to 14 and Comparative Examples 4 to 6 were applied to plates to a dry thickness of 100 μm (or 50 μm for the determination of water and weather resistance) applied, below those in Table 4 dried conditions and appearance, gel fraction ratio, Impact resistance, water and weather resistance tested in the manner described above.

The coatings are further tested for pencil hardness in accordance with JIS K-5400.  

Table 4

Table 4 (continued)

Claims (10)

A curable composition characterized in that it comprises

• (i) a resin (I) having an alkoxysilane group and / or hydroxysilane group and oxirane group and obtained by reacting a resin (A) having at least one functional group selected from an isocyanate group, hydroxyl group, oxirane group, carboxyl group and amino group, having a compound (a) having a functional group complementary to and reactive with the functional group of the resin (A) and an alkoxysilane group and / or hydroxysilane group, and a compound (b) having a functional group A group which is complementary to and reactive with the functional group of the resin (A) and has an oxirane group, or
• (ii) a mixture of a resin (II) having an alkoxysilane group and / or hydroxysilane group and obtained by reacting the resin (A) with the compound (a) and a resin (III) having and having an oxirane group has been prepared by reacting a resin (B) having at least one functional group selected from an isocyanate group, hydroxyl group, carboxyl group and amino group, with the compound (b), and
• (iii) a chelate compound serving as a crosslinking curing agent mixed with the resin (I) or the mixture.

2. A curable composition according to claim 1, characterized in that the resin (I) contains a urethane bond Resin is. 3. A curable composition according to claim 1-2, characterized at least one of the resins (II) and (III) is a urethane bond-containing resin.   4. A curable composition according to claims 1-3, characterized that the resin (I) is a resin which has a urethane bond contains and as functional groups about 0.01 to about 10 moles of alkoxysilane and / or hydroxysilane and about 0.1 to about 10 moles of oxirane per kg of resin. 5. A curable composition according to claims 1-4, characterized that the resin (II) is a resin that has a urethane bond contains and as functional group (s) about 0.01 to about 10 moles of alkoxysilane and / or hydroxysilane per kg of resin having. 6. A curable composition according to claims 1-5, characterized that the resin (III) is a resin which has a urethane bond contains and as a functional group about 0.1 to about 10 moles of oxirane group per kg of resin. 7. A curable composition according to claims 1-6, characterized that the resin (I) or (III) is a resin having an alicyclic Is oxirane group. 8. A curable composition according to claims 1-7, characterized that the chelate compound in an amount of about 0.01 to about 30 parts by weight per 100 parts by weight of the resin component (i) or (ii), calculated as solids, present is. 9. A curable composition according to claims 1-8, characterized that the chelate compound at least one, from the Group: Aluminum chelate compound, zirconium chelate Compound and Titanium Chelate Compound is. 10. A method for curing the composition according to Claims 1-9, characterized in that the composition at a temperature of up to 100 ° C in the presence of water is cured.