NO773601L - ARTIC RESIN COMPONENTS FOR THE MANUFACTURE OF BIOCIDE COATINGS - Google Patents

Abstract

Synthetic resin components for the production of biocidal coatings.

Description

A biocidal coating must emit a sufficient concentration of biocidal substances at the interface between the coating and the environment (seawater, fresh water, soil, air) which prevents attack or destruction of the objects that are sought to be protected from animal and vegetable organisms. However, it must be avoided that in the case of excessive concentrations of active substance on the surface of the coatings, which is due to a too high dissolution or release rate for the biocidal substances, the environment is too heavily burdened and that the effect of the coating is used up too early.

It is known to add copper or copper salts and organometallic compounds to paint and coating systems.

Thus, organotin compounds and especially triorganotin compounds such as tributyltin oxide or tributyltin fluoride are used on a large scale due to their excellent microbiocidal effect, e.g. in disinfectants, as a wood preservative and textile preservative, and in fungicidal and bactericidal coatings and paints, based on various binders.

One of the most important areas of application is currently the underwater protection of ships and sea structures against growth of marine organisms.

In ships, e.g. attack on the underwater hull with ballanids a sharp increase in water resistance which leads to increased fuel consumption, in many cases over ^ o%.

Certain marine organisms can attack the ship measurement and the convoy

is increased metal corrosion.

Removal of underwater coatings in docks is lengthy and expensive

and cause longer outage times.

The well-known and outstanding water resistance of epoxy resins, their extremely low water swelling and high mechanical strength led to these being used as underwater paints. With the addition of triorganotin compounds such as tributyltin fluoride, tributyltin oxide and tributyltin sulphide, very effective antifouling paints are obtained.

These systems do indeed exhibit good anti-germ properties, but also have certain disadvantages which limit their use. Certain triorganotin compounds such as tributyltin oxide are e.g. little f or en lic with epoxy resin mixing agents. They are released too quickly on the surface and the working life of such paints is therefore not satisfactory.

In other systems, sufficient water-soluble pigments, metal salts and inert fillers are added to the binders.

However, the dissolution or leaching process depends on so many and changeable factors (such as temperature, substrate, water salinity) that the process proceeds uncontrolled. As a rule, the surface concentration of biocidal substances for new measurements is far above the necessary limit and is therefore released too early into the environment, with the result that the biocidal effect is depleted relatively soon.

According to the invention, one has set himself the task of remedying these disadvantages and providing biocidal coatings and paints which are effective over a longer period of time.

The task is solved according to the invention by means of synthetic resin mixtures of

1. Glycidyl compounds of the type that are common for the preparation of polyadducts, characterized by groups of general formula

where R denotes an optionally substituted aliphatic,

cycloaliphatic or aromatic hydrocarbon residue with 1 to 10 C atoms, preferably 3 to 6 C atoms, and

II. amino group-containing hardeners for glycidyl compounds, containing at least two active amino hydrogen atoms, namely consisting of

a) 1. Reaction products of hydroxyl-group containing primary or secondary di- or polyamino compounds with

2. Triorganotin oxides or triorganotin alkoxides or

b) addition products of

1. di- or polyamino compounds on

2. stannyl ester - a, (3-unsaturated carboxylic acids

as well as possibly

III. common modifiers such as fillers, reinforcing agents, accelerators, pigments, for the production of biocidal coatings where the compounds mentioned under I and II can be replaced in whole or in part by corresponding organotin-free glycidyl compounds,

respectively hardeners.

Another object of the invention is mixture components for use according to claim 1, consisting of

1. I. Glycidyl compounds of the type usual for the preparation of polyadducts, characterized by groups of general formula - 0 - SnR^

where R denotes a possibly substituted aliphatic cycloaliphatic or aromatic hydrocarbon residue with 1 to 10 C atoms, preferably 3 to 6 C atoms, and

II. amino-group containing hardeners for glycidyl compounds, containing at least two active amino hydrogen atoms namely av

a) 1. turnover products of hydroxyl-group-containing, primary or secondary di- or

polyamino compounds with

2. triorganotin oxides or triorganotin alkoxides or

b) addition products of

1. di- or polyamino compounds on

2. stannyl esters and ,[3-unsaturated carboxylic acids.

2. Another object of the present invention is a method for producing glycidyl compounds according to claim 1 I, characterized in that hydroxyl group-containing glycidyl compounds are reacted with triorganotin compounds. 3. Another object of the invention is a method for producing amino group-containing hardeners for glycidyl compounds as stated in claim 1 II, characterized in that

a) 1. Hydroxyl group-containing primary or secondary di- or polyamino compounds are reacted with

2. triorganotin oxides or triorganotin alkoxides

or

b) 1. di- or polyamino compounds are added

2. stannyl ester a,b-unsaturated carboxylic acids.

By chemically binding organotin residues according to the present invention, either via the hardener and/or via the epoxy resin, the effect of said paints can be significantly extended. The chemical binding of the organotin residues causes a slow and regulated release of the active organotin compound, since the organotin residues that are built into the polymer must first be split off during hydrolysis, because these residues can come to the surface of the paint by diffusion and dissolution processes and exert the biocidal effect on the surface . In this way, an extended release time of active substance is achieved, with a consequent extended working time for the paint.

Coatings and paints according to the invention also have the advantage compared to those to which triorganotin compounds have been added in the usual mixture that they smell less. For this reason, the paints can also be used in bactericidal and fungicidal coatings and interior paints.

For the conversion with triorganotin oxides or triorganotin alkoxides to organotin-containing epoxy resins according to the invention, all hydroxyl-group-containing epoxy compounds that can be cured with amino group-containing hardeners at room temperature or a slightly elevated temperature can be used.

Examples are ordinary epoxy resins which are converted according to

to the following general equation:

where R has the above meaning, but in particular denotes a butyl residue, R"'" denotes an optionally branched aliphatic hydrocarbon residue with

1 - 6 C atoms, n is equal to o,l to 20. CH~

and can also be 1,1 bis-C+-hydroxyphenyl)-ethane, bis-C+-hydroxyphenyl)-methane, bis-C+-hydroxyphenyl)-sulfone, resorcin, hydroquinone or novolaks. An extensive list of suitable di- or polyphenols can be found in the handbook "Epoxidverbindungen und Epoxidharze" (Epoxy compounds and epoxy resins) by A.M. Paquin, Springer Verlag Berlin/Gottingen/Heidelberg, 1958. X-^and X^ can

and other residues of aliphatic, cycloaliphatic or aromatic dicarboxylic acids. You can use epoxy resins where X^= J.^or X-^ is different from X^.

In the reaction of aliphatic polyols with epichlorohydrin to aliphatic glycidyl ethers, products containing hydroxyl groups are formed under certain reaction conditions.

The hydroxyl groups can be converted with R^SnOR^" or (R^Sn^O) into epoxy resins according to the invention. Glycerol, pentaerythritol, trimethylolpropane or erythritol etc. can be used as polyols.

Glycidyl ethers of hydroxyalkylated and preferably hydroxymethylated di- or polyphenols can also be suitably used as starting compounds on the epoxy resin side for the production of biocidal coatings. Examples include: 2^-bis-Chydroxymethyl-^-hydroxyphenyl)-propane

2-(3-hydroxymethyl-1+-hydroxyphenyl)-2-(1+-hydroxyphenyl)-propane 2-(hydroxymethyl)-1,^-dihydroxybenzol

2,6-di-hydroxymethyl-1,<>>+-dihydroxybenzene

Mono-hydroxymethyl-^- , h 1 -dihydroxyphenyl ether

bis-C hydroxymethyl-^-hydroxyphenyl)-methane

hydroxymethylated fluoro-formaldehyde resins.

The aforementioned compounds can be prepared in a known manner, as the phenols are reacted in the presence of alkali at ho to r/o°C with aqueous formaldehyde solution. Other usable di- or polyphenols can be found in the aforementioned literature (A.M. Paquin).

The conversion of hydroxyalkylated phenols to hydroxyalkylated phenylglycidyl ethers takes place in a known manner by reaction with an excess of epichlorohydrin (relative to equivalent phenolic OH groups) and equimolar amounts of alkali.

The glycidyl ether produced is reacted in an organic solvent with (R^Sn)^O or R^SnOR"<1>" so that per mol of hydroxymethyl there are 0.01 - 1.0 mol of R^Sn groups.

Mono-functional glycidyl compounds can also be used as carriers for the R^Sn residues. Examples are mono-, di- or trihydroxymethyl-phenylglycidyl ethers or mixtures of these, mono- or dihydroxymethylated alkyl-substituted phenylglycidyl ethers where the alkyl group can contain 1 - 9 C atoms. Compounds of this type are added to tin-containing or tin-free diglycidyl ethers or esters after the reaction with trialkyltin oxides or trialkyltin alkoxides, as for a reactive diluent.

This group also includes the trialkyltin glycidyl ethers which can be prepared from glycidol and related compounds with trialkyltin oxides or alkoxides.

For the production of suitable organotin-containing hardeners can

one reacts hydroxylalkylamines with triorganotin oxides or triorganotin alkoxides. Suitable hydroxyalkylamines are formed by

reaction of mono- or diepoxy compounds with di- or polyamines to p-hydroxyalkylamines according to_ the general equation

This turnover is known under the term adduction.

Examples of usable amines are: Ammonia, polyethylene polyamines,

and polypropyleneamines such as diethylenetriamine and dipropylenetriamine, cycloaliphatic diamines such as l-amino-3-aminomethyl-3,5,5-trimethyl-cyclohexane, also called isophoronediamine, 3>3'-dimethyl-h., h 1diamino-dicyclohexyl-methane, heterocyclic amines such as N-amino-ethyl-piperazine, long-chain polyetheramines such as 1,12-diamino-^,8-di-oxadodecane, aromatic amines such as phenylenediamine, diamino-diphenyl-methane, polyaminoamides, i.e. condensation products of natural or synthetic higher monomeric or dimerized fatty acids with an excess of polyamines.

Examples of a monoepoxy compound are ethylene oxide, propylene oxide, styrene oxide or glycidyl ethers such as butyl glycidyl ether, cresyl glycidyl ether or glycidyl esters such as glycidyl methacrylate. As a diepoxy compound you can also use glycyldyl ethers of the aforementioned diphenols, preferably bisphenol-A-diglycidyl ether, as well as glycidyl ethers of diols such as ethylene glycol, butanediol or hexanediol and glycyldyl esters of dicarboxylic acids such as phthalic acids, hexahydrophthalic acids and dimerized fatty acids.

The term "dimerized fatty acid" generally applies to polymerized acids which are produced from "fatty acids". The term "fatty acid" includes unsaturated, natural or synthetic monobasic aliphatic acids with 12 to 22 C atoms, preferably 18 C atoms. These fatty acids can be polymerized in a known manner (see DT-OS 1 kh^ 938?DT-OS 1 1+1+3 -968, DT-PS 2 118 702 and DT-PS 1 280 852).

Typical polymeric fatty acids in the trade have approximately the following composition:

monomeric acids (Mo) 5 - 15 percent by weight

dimeric acids (Di) 60 - 80 percent by weight

trimer acids (Tri) 10 - 35 percent by weight

The content of dimer acid can be increased by generally known distillation processes up to 10% by weight.

The conversion to organotin-containing adducts takes place by splitting off HOR-^, where R^ is hydrogen (when using (R^Sn^O)) or alkyl (when using R^SnOR1).

The molar ratio between the R^Sn residue and the OH group in the adduct used can be between 0.01:1 and 1:1. A molar ratio of 0.1:1 to 1:1 is preferably chosen.

Condensation products of phenols, aldehydes and polyamines, so-called rnannich bases, can also be used as starting compounds for organotin-containing hardeners.

The applicable rnannich bases can be simply described by

where the symbols have the following meaning:

m = 0, 1, 2

R 1 H, CH 3 , C 2 H 5 , C 3 H 2 , ChE 9 or C 2 .

R 3 = H, CH 3 , C(CH 3 ) 3 , Nonyl. ■

R^1 corresponds to the residue of one of the described polyamines.

For the production of organotin-containing hardeners according to the invention, the Mannich base is reacted with triorganotin oxides or -alkoxides while splitting off HOR^, where R^ has the indicated meaning.

The molar ratio between the R^Sn residue and the phenolic OH group is between 0.01:1 and 1:1, preferably 0.8 - 1:1.

Suitable tin-containing hardeners can further be prepared by adding di- or polyamine, respectively polyaminoamides to the activated double bond in a,B-unsaturated mono- or dicarboxylic acid trialkyl tin esters: As amines, the aforementioned compounds can be used. Examples of unsaturated carboxylic acids whose trialkyl tin esters can be used are: Acrylic acid and α- or |3-alkyl substituted acrylic acids of the type methacrylic acid or crotonic acid, maleic acid, itaconic acid, citraconic acid or alkylidenemalonic acids with the general formula

7 8

where R' has the meaning H, CH^ , phenyl and R has the meaning H, CH^ C2H? or C 1^.

Di- or polyamine and the unsaturated trialkyl tin ester are reacted in a ratio of 1:1 or with a deficit of trialkyl tin ester.

The organotin-containing binders according to the present invention have a broad spectrum of action. They are effective against a wide variety of fungi and bacteria and thereby provide protected substrates such as metal, wood, plastic etc. a high and long-lasting protection.

The content of biocidal compounds in the coating mass depends on the application and can be regulated in different ways, e.g. through

1) the type of epoxy resin used and further by the ratio

OH to R^Sn groups.

2) The organotin-containing amine hardener used

3) the combinations of

a) epoxy resin according to the invention containing organotin-free epoxy resin, b) epoxy resin according to the invention with organotin-free amine hardener, c) organotin-free epoxy resin with amine hardener according to the invention. h) The addition of the usual modifying agents such as fillers, reinforcing agents, accelerators, pigments

etc.

Meaning of abbreviations in the following examples:

TBTO, = Tributyltin oxide

BPA = Bisphenol-A

EDA = Ethylenediamine

AT = Amine number

THF = Tetrahydrofuran

EP = Epoxy

Production examples of the epoxy resin and hardeners according to the invention.

Example 1.

A solution of 100 g bisphenol-A epoxy resin (epoxy number 0.21^-, hydroxyl number 0.239), 6)+.3 g (0.108 mol) tributyltin oxide and 90 ml toluene is refluxed. In the course of 5 hours, 1.6 ml... (8h% of theoretical) water is secreted. After distilling off the toluene, 163 g (99% of theoretical) of high-viscosity resin remains

(Sn content 15.8%).

Example 2.

100 g of glycerol glycidyl ether (hydroxide number 0.185) is added to 55.3 g (0.093 mol) of tributyltin oxide in toluene solution under azeotropic water separation for 5 hours. 1.5 ml (88%

of theoretical) water. You get a low cost. product (Sn content 13.5%), which, according to the IR spectrum, contains no more OH groups.

Example 3.

100 g of methylol-substituted diglycidyl ether of BPA (epoxy number. 0.38, hydroxyl number 0.17<*>0) is added to 51.8 g (0.087 mol) of tributyltin oxide in toluene at 120 C under azeotropic water separation. After 6 hours, 1.7 ml have separated (90% of theoretical). The toluene is distilled off. A highly viscous resin is obtained (Sn content 13.If%).'

Example h.

To 32.0 g (0.1 mol) of tributyltin methoxide in MeOH is added a solution of 18.0 g (0.1 mol) of p-hydroxymethyl-phenylglycidyl ether in 1,100 ml of toluene. After 1 hour at room temperature, the solvent is distilled off at a bath temperature of up to h5° C. ^-3 g of crystalline product is obtained (Sn content 25.5%), which, according to the IR spectrum, no longer contains OH bands.

Example 5.

A solid epoxy resin on a bisphenol-A basis (epoxy number 0.215) is reacted with an excess of ethylenediamine to diglycidyl ether-ethylenediamine adduct. 100 g of the remaining adduct after distilling off excess EDA (OH number 0.<1>+1) is heated with llh g (0.19 mol) of tributyltin oxide in toluene for 5 hours under azeotropic water separation. The toluene is then distilled off. A viscous product with a Sn content equal to 21.k% is obtained.

Example 6.

50 g of a 1:1 adduct of diethylenetriamine and propylene oxide (OH number 0.62) is reacted with 92.5 g (0.155 mol) of tributyltin oxide in toluene under azeotropic separation of water. After 6 hours, 2.!+ ml of water has been secreted (86% of theoretical). After distilling off the solvent, a low-viscosity product is obtained (Sn content equal to 25.9%) which, according to the IR spectrum, no longer contains OH groups.

Example 7.

Phenol, formaldehyde and trimethyl-hexamethylenediamine are converted in a molar ratio of 1:1:1 to a Mannich base with a hydroxyl number of 0.376. 130 g of this base is reacted with 138 g (0.232 mol) TBT0

in 80 g of toluene under azeotropic water separation. The product formed (Sn content equal to 20.8%) is, according to the IR spectrum, free of OH groups.

Example 8.

Hydroquinone, formaldehyde and diethylenetriamine are reacted in a molar ratio of 1:1:1 to a Mannich base with an amine number equal to 738

and a phenol number equal to 1+50. 100 g (OH number 0.*f) of the Mannich base is reacted with 120 g (0.2 mol) TBT0 in 80 g toluene under azeotropic water separation. After 5 hours, 3 A ml of water has been formed (9h%

of theoretical). After distilling off the toluene, a product with a Sn content equal to 21.8% is obtained.

Example 9.

131.6 g of hexahydrophthalic acid glycidyl ester (epoxy number 0.5*+) is reacted with 38.*+ g bisphenol-A in the presence of 0.07 g of anhydro-succinylidene-triphenyl-phosphorane at 120° C to a product with an epoxy number equal to 0 ,19 (theoretical 0.22) and an OH number of 202. 50,And

.is reacted with 53.9g (0.093 mol) tributyltin oxide in the presence of

50 g toluene for k hours under reflux. 1.3 ml of water is secreted (81.3% of theoretical). According to the infrared spectrum, the product formed is free of 0H groups.

Example 10.

109 g (1.0 mol) of o-aminophenol and 298 g (0.5 mol) of tributyltin oxide are heated in toluene for 2 hours under azeotropic separation of water. 8.3 ml (95% of theoretical) water is secreted. After distilling off the solvent, a product is obtained (Sn content equal to 29.<*>+%) which is without OH groups.

Example 11.

70.8 g (0.1 mol) of itaconic acid di(tributyltin ester) is heated with 19.0 g (0.12 mol) of trimethylhexamethyleridiamine in THF at room temperature. After 20 hours, the solvent is distilled off and the excess of amine is distilled off in a vacuum. You get a tough, yellow product with AT 115 and a Sn content of 26.6%.

Example 12.

72.2 g (0.2 mol) of tributyltin acrylate in THF are added dropwise over the course of 2 hours to a solution of 15.0 g (0.25 mol) of ethylenediamine in THF. An exothermic reaction occurs. After the addition is complete, stir for 20 hours at room temperature. The solvent and the excess amine are then distilled off. The product formed has an amine number equal to 2>+8, Sn content equal to 27.7%.

Example 13.

72.2 g' (0.2 mol) of tributyl tin acrylate are dissolved in THF, added over the course of 2 hours to 31.6 g (0.2 mol) of trimethylhexamethylenediamine. Stir for 20 hours at room temperature and distill off THF at normal pressure and unreacted amine (0.<*>+ g) at oil pump vacuum.

You get a product with AT equal to 250, Sn content 20.8%.

Production of paints.

The organotin-containing glycidyl compounds or hardeners according to the invention, in order to obtain a better basis for comparison, were set to a tin content equal to 1% by adding organotin-free glycidyl compounds or hardeners, the specified percentage calculated on the basis of the dry weight of the coating.

Example 1^-.

h-, 7 g of adduct hardener according to example 5 is mixed with 90.9 g of a 75% xylene solution of solid epoxy resin on a bisphenol A basis (epoxy number 0.215) and ^-9.3 g of a 55% solution of isolated ethylenediamine bisphenol-A epoxy resin adduct (amine number 210). A paper filter with a diameter of 55 mm was coated with 0.5 g of this mixture.

Example 15.

2.3 g of a compound according to example 12 was added to 78.8 g of a 75% xylene solution of a solid epoxy resin on a bisphenol-A basis (Ep number = 0.215) and 1.6 g of ethylenediamine was mixed in after which paint was stroked out on filter paper as under example 1<*>+.

Example 16.

8.3 g of epoxy compound according to example 1 and 69.6 g of a 75% solution of solid epoxy.harp.Lks were mixed as in example 15 with ^358 g of a 55% solution of isolated ethylenediamine-epoxy resin-

adduct (amine number 210) and a paper filter coated as in example lh.

Example 17.

'3 58 g of compound according to example. 11 was mixed with 120 g of a 75% solution of solid epoxy resin according to example 15? and mixed with 6.5 g of trimethylhexamethylenediamine, on which a paper filter was coated as in example 1^.

Example 18.

2.2 g of the compound according to claim 7 was mixed with 2.9 g of Mannich base of trimethylhexamethylenediamine, formaldehyde and phenol in the ratio 1 : 1 : 1 and ^+3.9 75% solution of solid epoxy resin as in example 155 and a paper filter coated according to example 1^.

Comparative example.

20 g of 75% xylé-n solution of epoxy resin according to the example

15 and 12 g of a 55% solution of isolated ethylenediamine epoxy resin adduct (AT 210) were mixed. A paper filter as in example Ih- was coated with this mixture.

Examination of the biocidal effect.

To carry out the biocide experiments, nutrient agar was poured into Petri dishes with a diameter of 10 cm. After the agar had solidified, the paper tubes were placed on and sprinkled with slurries of prebiotic bacteria and fungi.

The concentration of presox bacteria and fungi was photometrically tested in a 1 cm thick cuvette.

The extinction figure of the slurry was measured in the Zeiss PMQ 2 spectrophotometer. At <1>+20yu., the following extinction figure was obtained against water as a reference:

The fungi were then allowed to grow for 3 weeks at 30°C and the bacteria for 37 days at 37<0>C.

The assessment of the biocidal effect was carried out 1. according to the strength of the fouling and the size of the zone of inhibition around the test disks.

Examination of the anti-fouling effect.

Sandblasted and primer-painted steel sheets measuring 15 x 10 cm were coated twice on both sides with trial paints that were pigmented with rutile in a weight ratio of 1:1 on a dry basis. Resins and hardeners were dissolved in common solvents for these components and adjusted to a solids content that ensured smooth processing and mixed in a stoichiometric ratio.

After drying, the trial plates were tested in a fresh water test station in Cuxhaven with regard to fouling with fresh water organisms.

Example 19.

Tin-containing hardeners according to example 5 reacted with solid epoxy resin on a BPA basis (Ep number = 0.215), tin content = 5.1%

in the dry film.

Example 20.

Tin-containing epoxy resins according to example 1, reacted with an isolated ethylenediamine-epoxy resin adduct (solid Ep resin on a BPA basis, Ep number = 0.215), tin content in the dry film = 6.3%.

Example 21.

Tin-containing epoxy resins according to example 1, reacted with tin-containing hardeners according to example 5, dry film dry content = 8.9%.

Example 22.

Tin-containing hardener according to example 7, reacted with tin-containing epoxy resin according to example 1, tin content of the dry film = 8.1$.

Example 23.

Tin-containing hardener according to example 5, reacted with a mixture of diglycidyl ester of dimerized tall oil fatty acid (Ep number - 0.25) and liquid bisphenol-A epoxy resin (Ep number = Q.53) in a weight ratio of 1/1, tin content for the dry film = 6.7%.

Comparative example.

Solid bisphenol-A epoxy resin (Ep number = 0.215) reacted with isolated ethylenediamine adduct of the same epoxy resin with an amine number equal to 210.

Claims (3)

1. Application of artificial resin mixtures of I. gylcidyl compounds of the type common to o": '-preparation of polyadducts and character sert v e. d groups with general formula - 0 - SnR^ where R denotes an optionally substituted aliphatic, cycloaliphatic or aromatic hydrocarbon residue with 1 to 10 carbon atoms, preferably 3 to 6 carbon atoms, and II. amino-group containing hardeners for the gylcidyl compounds, containing at least 2 active amino hydrogen atoms, namely av a) 1. Reaction products of hydroxyl-group containing primary or secondary di- or polyamino compounds with 2. triorganotin oxides or triorganotin alkoxides or b) addition products of 1. di- or polyamino compounds on 2. stannyl ester a,b-unsaturated carboxylic acids and■possibly III..common modifiers such as fillers, for- strengthening agents, accelerators, pigments for the production of biocidal coatings where the compounds mentioned under I and II can be wholly or partially replaced by corresponding organotin-free glycidyl compounds or hardeners. 2. components for mixtures which, according to claim 1, are used for the production of biocidal coatings, consisting of I. gylcidyl compounds of the type that are common for the production of polyadducts, characterized by , . groups of general formula 0 - SnR^ where R denotes a possibly substituted, aliphatic, cycloaliphatic or aromatic hydrocarbon residue with 1 to 10 C atoms, preferably 3 to 6 C atoms, and II. amino group-containing hardeners for the glycidyl compounds, containing at least 2 active amino hydrogen atoms, namely av a) 1. reaction products of hydroxyl-group containing primary or secondary di- or polyamino compounds with b) addition products of 1. di- or polyamino compounds on 2. Stannyl ester a,B-unsaturated carboxylic acids. 3. Process for the production of glycidyl compounds according to claim II, characterized in that glycidyl compounds containing hydroxyl groups are reacted with triorganotin compounds. h. Process for the production of amino group-containing hardeners for glycidyl compounds according to claim 1 II, characterized in that a) 1. Reaction products of primary or secondary di- or polyamino compounds containing hydroxyl groups are reacted with 2. triorganotin oxides or triorganotin alcohols oxides or b) addition products of 1. di- or polyamino compounds are added 2. stannyl ester a,B-unsaturated carboxylic acids.