MXPA01005588A - Substance for bonding, coating and sealing, consisting of cyanoacrylates and aldehyde or ketone condensation products - Google Patents

Abstract

Gel-forming condensation products of aldehydes or ketones can be used with polyols in cyanoacrylates to obtain dimensionally stable adhesives, coating and sealing substances. These are stable in storage and are especially suitable for bonding porous substrates such as paper or wood. They are particularly easy to handle when produced in the form of rub-off glue sticks.

Description

SUBSTANCE FOR ACCESSION, COATING AND SEALING, WHICH CONSISTS OF CYANOACRILATES AND THE PRODUCTS OF THE CONDENSATION OF ALDEHYDE OR CETONA This invention relates to a composition for adhesion, coating and sealing based on a mixture of A) cyanoacrylates and B) condensation products of aldehydes and ketones. Cyanoacrylate adhesives like these are known. Thus, DE 43 17 886 discloses a cyanoacrylate adhesive which, in order to reduce adhesion to the skin, contains 1 to 40% by weight of fatty derivatives in the form of certain aliphatic alcohols or certain esters of aliphatic carboxylic acids. Up to 100,000 ppm of an anionic polymerization accelerator is added to this mixture. A large number of substances are mentioned, which include, among others, condensation products of formaldehyde and acetaldehyde and ethers of polyalkylene oxides, for example with sorbitol as the hydroxyl-containing compound. The polyoxyethylene and polyoxyethylene sorbitan esters / sorbitol addition products are specifically mentioned. To make the cyanoacrylate - a more viscous or thixotropic low viscosity liquid - a thickener is dissolved or dispersed, for example, polymethyl methacrylate, acrylate rubber, cellulose derivative or silicate. According to the examples, the thickener is added in an amount of 0 to 10% by weight. The disadvantage of this composition is that, even with a high concentration of thickener, the cyanoacrylate adhesive is liquid and, consequently, can not be used as a sealing compound, for example, or is unsuitable for adhering porous substrates and, in general, It is difficult to apply. Contrary to the background of this prior art, the problem addressed by the present invention was to provide a cyanoacrylate composition with improved handling performance that can, of course, show performance properties, at least useful, if not outstanding, for adhesion, coating and sealing and, above all, adequate storage stability at room temperature. In addition, production must be simple. The solution provided by the invention is defined in the clauses and consists essentially in the use of a gel former based on a condensation product of aldehydes and ketones with polyols for cyanoacrylates in order to produce compositions that are dimensionally stable at 20 ° C. Dimensionally stable means that the composition does not change its shape for a period of 10 days at 20 ° C only under the effect of its own weight when the cylindrical composition is stored horizontally at 20 ° C in an open tube of 1.5 cm in diameter and cm in length; at least the bar then protrudes less than 10 mm and preferably less than 0.1 mm beyond the tube. On the other hand, however, the dimensional stability should be only so great that, when a slight external pressure is applied, the composition is rubbed on paper in the same way as the commercially available adhesive sticks. Suitable gel formers are certain condensation products of aldehydes and ketones with polyols. Compounds containing at least one acetal or ketal group are used as gel formers. Such compounds can be obtained by condensation reactions and are also commonly prepared, for example, by partial or complete dehydration of polyols with aldehydes and ketones in a ratio (OH: = C = 0) of 1: 0.5 to 1: 0.01 and of Preference 1: 0.5 to 1: 0.1, for example, in the presence of an acid as a catalyst. The acetals and ketals according to the invention can also be prepared by the reaction of polyols with aldehyde or ketone derivatives, for example, by the reaction of geminal dichlorides with the emission of hydrogen chloride or acetals or ketals with the elimination of alcohol. Suitable compounds have a melting point of at least 50 ° C, more particularly of at least 100 ° C and preferably at least 150 ° C. Mixtures of the acetals and ketals can also be used. Suitable polyols contain at least one group 1, 2-diol, 1,3-diol or 1,4-diol. Other functional groups, for example, ether, acid, ester, amide, cyano, hemiacetal and halide groups, may also be present. Examples of such polyols are ethane-1,2-diol, propane-1,3-diol, propane-1,2-diol, butane-2,3-diol, butane-1,4-diol, 2,2-dimethylpropane. -l, 3-diol, 2,2-bis- (hydroxymethyl) -propane-1,3-diol, 2- (bromomethyl) -2- (hydroxymethyl) -propane-1,3-diol, butane-1, 3 , 4-diol, 1-phenylpropane-1,2,3-triol, hexane-1,2-diol, neopentyl glycol, 1-bishydroxymethyl cyclohexane, 2-methylpropane-1,3-diol, hexane-1, 2, 6-triol, 2- (2-hydroxyethoxy) -butane-1,4-triol, glycerol, di- and polyglycerol, diglycerol diacetate, trimethylol propane, di- (trimethylolpropane), trimethylol ethane, pentaerythritol, bicyclo [2.2.1] heptane-2, 3, 5, 6-tetrol, 2,2,3,3-tetrahydroxybutanediic acid, dipentaerythritol, sorbitol, formitol, xylitol, inositol, glucitol, glucose, sucrose, starch, cellulose, ascorbic acid, partial polyvinyl acetate or fully hydrolyzed, 9, 10-dihydroxystearic acid methyl ester, diacetyl sorbitol and methyl glycoside. Preferred polyols are sorbitol, xylitol and mannitol, more particularly sorbitol. Suitable aldehydes or ketones contain at least one substituted or unsubstituted aromatic, heteroaromatic or alicyclic ring. Other functional groups may also be present, for example ether, ester, amide, cyano and halide groups. Examples of suitable ketones are cyclopentanone, cyclohexanone, cycloheptanone, 1- (3, 3-dimethylcyclohexyl) -ethanone, 1-cyclopropyletanone, 3-methyl-5-propylcyclohex-2-en-1-one, dicyclopropylmethanone, 4-tert-butyl cyclohexanone, dicyclohexyl methanone, 4-methylcyclohexanone, 1- (1-methylcyclopropyl) -ethanone, (4-chlorophenyl) cyclopropyl methanone, 1- (lH-pyrrol-2-yl) -ethanone, 1- (2, 4, β -trimethylphenyl) -ethanone, 1- (2-furanyl-2-propanone, 1- (2-naphthalenyl) ethanone, 1- (2-thienyl) -1-propanone, 1- (4-bromophenyl) -ethanone, 1- (4-methoxyphenyl) -ethanone, 1- (naphthalenyl) -ethanone, 1, 1-diphenyl-2-propanone, 1,2-diphenyl ethanone, 1,3-diphenyl-2-propanone, 1-phenyl-1-butanone, 1-phenyl-1-decanone, 1-phenyl-1-dodecanone, 1-phenyl-1-hexanone, 1 -phenyl-l-octanone, 1-phenyl-l-pentanone, l-phenyl-l-penten-3-one, 1-phenyl-l-tetradecanone, l-phenyl-2-butanone, l-phenyl-2-propanone , 1-pyrazinyl ethanone, 2, 2, 2-trifluoro-1-phenyl-ethanone, 1- (2-furanyl) -ethanone, 1- (2-pyridinyl) -ethanone, 1- (2-thienyl) -ethanone, -chloro-l- (4-fluorophenyl) -1-butanone, 4-phenyl-2-butanone, 1-phenyl-ethanone, bis- (2-hydroxyphenyl-methanone, bis- (4-chlorophenyl) -methanone, cyclopentyl-phenyl-methanone, cyclopropyl) - (4-methoxyphenyl) -methanone, cyclopropyl- (4-methylphenyl) -methanone, cyclopropyl-2-thienyl methanone, cyclopropyl phenyl methanone, 1,5-diphenyl-1,4-pentadien-3-one, phenyl-2- pyridinyl methanone, 2-bromo-l- (4-nitrophenyl) ethanone, 2-naphthalenyl phenyl methanone, 3-chloro-1-phenyl-l-propanone, 4- (4-hydroxyphenyl) -2-butanone, 4- (4 -methoxyphenyl) -3-buten-2-one, 1- (4-pyridinyl) -ethanone, 1- (4-hydroxyphenyltetanone, 1-phenyl-1-propanone, 4-phenyl) l-3-buten-2-one, diphenyl methanone, l-phenyl-2-butanone, 1-phenyl-2-buten-l-one, bis- (4-methylphenyl) -methanone, 2-methyl-1-phenyl -l-propanone, 2-chloro-1-phenyl-ethanone, cyclopropyl- (4-fluorophenyl) -methanone, 1- (p-methoxyphenyl) -2-propanone, cyclohexyl phenyl methanone and phenyl- (2-thienyl) -methanone . Examples of suitable aldehydes are benzaldehyde, 3-chlorobenzaldehyde, 4-chlorobenzaldehyde, 2,6-dichlorobenzaldehyde, 2,4-dinitrobenzaldehyde, 3,4-dichlorobenzaldehyde, 3-fluorobenzaldehyde, 4-bromobenzaldehyde, 2-methyltetrahydrobenzaldehyde, tetrahydrobenzaldehyde, 2 -methyl-5-isopropylcyclopenten-1-aldehyde, 2,2, 4-trimethylcyclohexa-4, β-diene-1-aldehyde, 3 (4) -methyl-1-propyl-cyclohexen-3-aldehyde, 1,3 (4) -dimethylcyclohexen-3-aldehyde, 2-methyl-l-propylcyclohexen-3-aldehyde, 3-cyclohexen-l-aldehyde, 2,3,4,5,6-pentafluorobenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 4-tolyl acetaldehyde, 2-methylbenzaldehyde, 4-hydroxybenzaldehyde, 3-methylbenzaldehyde, 2-hydroxy-1-naphthaldehyde, 4-methylbenzaldehyde, 3, 5-dimethoxy-4-hydroxybenzaldehyde, cinnamaldehyde, 3-nitrobenzaldehyde, 2-pentylancinamaldehyde, 4-diethylaminobenzaldehyde, 4-methoxybenzaldehyde, 2-phenylpropionaldehyde, 2-methoxycinnamaldehyde, 4-methylbenzaldehyde, phenoxyacetaldehyde, methylpyrrole-2-aldehyde, 2,5-dimethoxytetrahydrofuran-3 -aldehyde, 2,5-dipropyl-3,4-dihydropyran-2-aldehyde, 2,5-diethyl-3,4-dihydropyran-2-aldehyde, 2,5-diisopropyl-3,4-dihydropyran-2-aldehyde , 2, 5-dimethyl-3, 4-dihydropyran-2-aldehyde, 2,5-dibutyl-3,4-dihydropyran-2-aldehyde, thiophen-3-aldehyde, indole-3-aldehyde, thiophen-3-aldehyde [sic], pyridine-3-aldehyde, pyridin-4-aldehyde and N-methylpyrrole-2-aldehyde. Preferred aldehydes are benzaldehyde, 3-chlorobenzaldehyde and 3-fluorobenzaldehyde, more particularly benzaldehyde. Examples of acetals and ketals according to the invention are di-O-benzylidene mannitol, di-O- (2-chlorobenzylidene) -mannitol, di-O- (4-nitrobenzylidene) -mannitol, di-O- (3- fluorobenzylidene) -mannitol, 0-benzylidene sorbitol di-O-benzylidene, sorbital diacetate, di-O- (2-chlorobenzylidene) -sorbitan diacetate, tri-0- (4-chlorobenzyldene) -sorbitol, O-benzylidene, threitol, 0-benzylidene tartaric acid dimethylester, 0-cyclohexylidene glycerol, O-cyclohexylidene ascorbic acid and 0-benzylidene-9, 10-dihydroxystearic acid methyl ester. The preferred acetals and ketals are di-O-benzylidene mannitol, di-O- (3-fluorobenzylidene) -mannitol and di-O-benzylidene sorbitol, more particularly, di-O-benzylidene sorbitol. The content percentage of the aldehyde or ketone condensation products is 0.1 to 10% by weight, preferably 0.4 to 6% by weight and more particularly 1 to 3% by weight, based on the cyanoacrylate composition. The cyanoacrylate composition is based essentially on common cyanoacrylates, that is, on monoacrylates and / or biscyanoacrylates. Its content percentage is at least 29.5% by weight and preferably at least 50% by weight, based on the cyanoacrylate compositions as a whole.

"Common onocyanoacrylic acid esters" in the context of the invention are understood as compounds corresponding to the general formula (I): H2C = C (CN) -CO-0-R (I! where R is an alkyl, alkenyl, cycloalkyl, aryl, alkoxyalkyl, aralkyl or haloalkyl group with up to 2 conjugated CC double bonds, with a cycloaliphatic ring of 6C, with an aromatic nucleus derived from benzene or preferably with Br or Cl as halogen and containing 1 to 18, and preferably 2, 3 or 4 carbon atoms, more especially a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, cyclohexyl, heptyl, 2-ethylhexyl group, n-octyl, n-nonyl, oxononyl, n-decyl, d-dodecyl, 2,2,2-trifluoroethyl, hexafluoroisopropyl, allyl, methallyl, crotyl, propargyl, benzyl, phenyl, cresyl, 2-chloroethyl, 3-chloropropyl, 2-chlorobutyl, tetrahydrofurfuryl, 2-methoxyethyl, butoxyethoxyethyl, 3-methoxybutyl and 2-ethoxyethyl. The aforementioned cyanoacrylates are known to experts in adhesives, cf. Ullmann's Encyclopedia of Industrial Chemistry, Vol. Al, page 240, Verlag Chemie Weinheim (1985), US-PS 3,254,111. Preferred monomers are allyl, methoxyethyl, ethoxyethyl, methyl, ethyl, propyl, isopropyl or butyl esters of 2-cyanoacrylic acid. "The biscyanoacrylates" are compounds corresponding to the general formula (II): [H2C = C (CN) -CO-0] 2R1 n: where R1 is a branched or unbranched bifunctional alkane group containing 2 to 18, more particularly 6 to 12 carbon atoms which may also contain heteroatoms, such as halogens and oxygen, or aliphatic or aromatic rings. However, R1 is preferably a pure hydrocarbon. It is important that the biscyanoacrylates are particularly pure. This requirement is satisfied, for example, by the following production and purification methods: essentially, the monocyanoacrylates are transesterified with diols and the reaction mixtures are subsequently worked by fractional crystallization. Consequently, the process suitable for the production of biscyanoacrylates comprises the transesterification of the 2-cyanoacrylic acid or alkyl ester thereof corresponding to the general formula (III): H2C = C (CN) -CO-0-R2 (III) where R is a branched or unbranched alkyl group containing 1 to 6"carbon atoms, with diols corresponding to the general formula (IV): [HO zR1 (IV) where R1 is a branched or unbranched difunctional alkane group containing 2 to 18 carbon atoms, which may also contain heteroatoms, such as halogens and oxygen, or aliphatic or aromatic rings to form biscyanoacrylates corresponding to general formula II and then purifying the reaction mixture by fractional crystallization. Accordingly, a starting product is a monofunctional cyanoacrylic acid corresponding to formula III or an alkyl ester thereof. The alkyl group should be selected so that the alcohol formed can be easily removed. Suitable possibilities are known to the person skilled in the art from the general trans-esterification reaction. The alcohol is preferably removed by distillation. Consequently, R2 is a branched or unbranched alcohol radical containing 1 to 6 carbon atoms, preferably 1 or 2 carbon atoms. The monofunctional cyanoacrylate is stabilized in the usual way. The diols (formula IV) are primary or secondary dihydric alcohols, preferably primary alcohols. The hydroxyl groups can be in any position one of another, although these are preferably in the alpha / omega position. The diols contain 2 to 18 carbon atoms and preferably 6 to 12 atoms. These can be in a branched or cyclic linear array. The aliphatic radical may also contain an aromatic group or, in addition to hydrogen and carbon atoms, heteroatoms such as, for example, chlorine or oxygen atoms, preferably in the form of polyethylene or polypropylene glycol units. Hexanediol, octanediol, decanediol and dodecanediol are specifically mentioned as diols. The cyanoacrylate is used in excess. Consequently, the molar ratio of monofunctional cyanoacrylate to diol is at least 2.0: 1.0, preferably 2.5: 1.0 and, more preferably, 2.2: 1.0. The trans-esterification is catalyzed by strong acids, more specifically, sulfonic acids and preferably aromatic sulfonic acids such as, for example, p-toluenesulfonic acid. However, naphthalenesulfonic acid, benzenesulfonic acid and acid ion exchangers can also be used. The concentration of the transesterification catalyst should be between 1 and 20% by weight, based on the monofunctional cyanoacrylate. The trans-esterification reaction is carried out in solution, as is normally the case. Suitable solvents are aromatic hydrocarbons and halogenated hydrocarbons. The preferred solvents are toluene and xylene. The concentration of the solution is 10 to 50% and preferably 10 to 20%. The monohydric alcohol formed and the water formed are removed in a known manner and preferably distilled with solvent. The conversion of the transesterification reaction is verified, for example, by NMR spectrum. The reaction takes several hours, as is usually the case. Where toluene is used as the solvent and para-toluenesulfonic acid as the catalyst, the reaction ends after 10 to 15 hours when there is no more separation of alcohol. The work of the reaction mixture is very important. Where acidic ion exchangers are used as the catalyst, they can be simply filtered. Where soluble sulfonic acids are used, for example p-toluenesulfonic acid as the catalyst, these are removed by solvent substitution: toluene is replaced by a mixture of hexane, heptane or decane. Pure biscyanoacrylate is obtained after two fractional crystallisations. According to the NMR spectrum, it has a purity of more than 99%. The biscyanoacrylate obtained is stable in storage with the usual stabilizers and in normal concentrations, that is, any change in its melting point after storage for 6 months at 20 ° C is difficult. However, the obtained bis-cyanoacrylates polymerize very rapidly in the presence of bases, preferably at substantially the same rate as the corresponding monocyanoacrylates. As with monofunctional cyanoacrylate, traces of water are sufficient. A three-dimensional crosslinked polymer with relatively good thermal properties is formed. Therefore, according to the invention, known cyanoacrylate adhesives are used in an amount of 0.5 to 50% by weight, preferably 1 to 10% by weight and more preferably 2 to 5% by weight, based on the cyanoacrylate composition as a total. It is known that cyanoacrylates are susceptible to anionic polymerization and radical chain, for this it is advisable to protect the ester compositions against both types of polymerization to prevent premature hardening of the ester, thereby avoiding storage difficulties. To prevent anionic polymerization, an anionic polymerization inhibitor can be added to the adhesives according to the invention. Any anionic polymerization inhibitor of the type used to date in cyanoacrylate adhesives are suitable for this purpose. For example, the anionic polymerization inhibitor can be an acid gas, a protonic acid or an anhydride thereof. The anionic polymerization inhibitor for the adhesives according to the invention is sulfur dioxide, preferably in an amount of 0.001 to 0.5%, based on the adhesive. Other suitable anionic polymerization inhibitors are dinitrogen monoxide, florhydric acid, hydrochloric acid, sulfuric acid, phosphoric acid, organic sulfonic and carboxylic acids and anhydrides thereof, phosphorus pentoxide and acid chlorides. In a preferred embodiment, a radical chain polymerization inhibitor is also added to the adhesives according to the invention in an amount of 0.01 to 0.05% by weight. This radical chain polymerization inhibitor can also be any of the known radical chain polymerization inhibitors for cyanoacrylate compositions. Normally phenolic compounds are used, for example, hydroquinone, t-butylcatequinone, pyrocatechol and p-methoxyphenol. The aforementioned ethyl-2-cyanoacrylate preparations, commercially available, are already stabilized. If it were necessary to adjust the concentration of stabilizer where these commercially available preparations are used, this will not present difficulties for the expert. In another preferred embodiment, the polymers are also added to the cyanoacrylate compositions according to the invention, for example, to increase their viscosity (thickener) or to vary the adhesive properties. The polymers can also be used in an amount of 1 to 60% by weight, more particularly, 10 to 50% by weight and preferably 10 to 30% by weight, based on the formulation as a whole. Suitable polymers are, above all, polymers based on vinyl ethers, vinyl esters, esters of acrylic acid and methacrylic acid containing 1 to 22 carbon atoms in the alcohol component, styrene co- and styrene ter-polymers with ethene, butadiene. Copolymers of vinyl chloride / vinyl acetate with a vinyl chloride content of 50 to 95% by weight are preferred. The polymers can be present in liquid form, resin-like or even in solid form. It is particularly important that the polymers do not contain impurities from the polymerization process that could inhibit the curing of the cyanoacrylate. If polymers have a high water content, they can be dried. The molecular weight (Mw) of the polymers can be spread over a wide range, but it should be at least 1500 and at most 1,000,000 because otherwise the final viscosity of the adhesive formulation could be too high. Mixtures of the aforementioned polymers can also be used. More particularly, a combination of low molecular weight and high molecular weight products has particular advantages in relation to the final viscosity of the adhesive formulation. Examples of suitable polymers based on vinyl acetate include the Mowillith types 20, 30 and 60 and the types Vinnapas B1.5, B100, B17, B5, B500 / 20VL, B60, U10, UW1, UW30, UW4 and UW50. Examples of suitable acrylate-based polymers are Acronal 4F and Laromer types 8912, PE55F and P033F. Examples of suitable polymers based on methylacrylate include Elvacite 2042, Neocril B 724, B999 731, B 735, B 811, B 813, B 817 and B722, Plexidon MW 134, Plexigu types M 825, M 527, N 742, N 80 , P 24, P28 and PQ 610. An example of suitable polymers based on vinyl ether is Lutonal A25. The cellulose and silica gel derivatives can also be used for thickening. The addition of polycyanoacrylates is particularly emphasized. In addition, the cyanoacrylate composition according to the invention may contain other auxiliaries to obtain certain effects in proportion to the contemplated application. These other auxiliaries include, in particular, the polymerization accelerators described in DE 43 17 886, that is to say, polyalkylene oxides and derivatives thereof, particularly esters and ethers. Other polymerization accelerators are crown ethers and derivatives thereof, compounds capped with silica and cyclo-sulfur compounds. It is known that these polymerization accelerators are added in an amount of 10 to 100,000 ppm and more particularly in an amount of 30 to 10,000 ppm, based on the cyanoacrylate composition. Another accelerator is cyclodextrin. The fatty derivatives described in DE 197 52 893 and DE 43 17 886 can also be used as plasticizers. These are fats and fatty derivatives, more particularly aliphatic alcohols, aliphatic carboxylic acid esters and carboxylic acid esters of a carbocyclic compound. Additional information can be found in the aforementioned patents. The usual plasticizers, for example phthalates, citric acid esters, chloroparaffin and trimellitic acid esters, can also be used. It is also possible to add solvents, in particular to increase the solubility of the condensation product of aldehyde or ketone or to facilitate that this product is more easily incorporated in the form of a solution. Suitable organic solvents are, for example, alcohols, ethers, ketones, and low molecular weight alkyl esters. Particularly suitable organic solvents are isopropanol, methoxypropanol, ethoxypropanol, ethoxyethanol, propoxyethanol, butoxyethanol, methyl ethyl ketone and N-methyl-2-pyrrolidone. However, the content of solvents in the cyanoacrylate composition must be low so as not to jeopardize dimensional stability and is preferably less than 20% by weight. Other auxiliaries are activators, dyes, pigments, fragrances, preservatives, antiseptics and fillers. The cyanoacrylate composition according to the invention is produced essentially by dissolving the cyanoacrylates and condensation products of aldehyde or ketone with a polyol by heating and then hardening the resulting solution by cooling. In general, a stabilized cyanoacrylate composition is first prepared from an acrylate and an anionic polymerization inhibitor under nitrogen as an inert gas and then heated to 50 to 90 ° C. The required components are then dissolved or suspended with vigorous stirring until a homogeneous mixture is obtained. The condensation product is then added in portions at 80 to 95 ° C and is largely dissolved at 90 to 95 ° C. The mixture is then cooled, preferably to around 80 ° C, and emptied into the required molds. After about one hour, the composition is generally hard and, after about 24 hours, is dimensionally stable enough for use as a stick. Despite its dimensional stability, the cyanoacrylate composition can be rubbed under light pressure onto a substrate, for example, paper. By virtue of its dimensional stability, the cyanoacrylate composition is suitable for conversion into geometric form, especially in a bar. The adhesive sticks are preferably produced in cylindrical form. The particular form of preference is adapted for the contemplated application. However, any shape is possible, particularly the geometric shapes with at least one plane or axis of symmetry, for example spheres, squares, pyramids, cones, cylinders, bars, ribbons, flakes, films and "pads". The shape is preferably smaller in two dimensions than in the third. Such forms are, for example, bars (hot melt bars) or "fillings" in the form of wax bars. The base or the geometric element can be angular, especially triangular, rectangular or hexagonal, or round (for example, circular or elliptical). The diameter can be from 2 to 100 mm and the length up to 150 mm. Consequently, the form and quantity of the cyanoacrylate compositions according to the invention is highly variable and determines them broadly what is convenient for the particular application contemplated. Liquid compositions of cyanoacrylate with high thixotropic properties can be produced by cutting the ready-to-use cyanoacrylate composition at high rotational speed. The cyanoacrylate compositions according to the invention are suitable for bonding, coating and sealing, more particularly for bonding porous substrates such as, for example, leather, textiles, paper, cardboard, thick cardboard, wood and leather. By virtue of its bar shape, the cyanoacrylate compositions according to the invention can be used with particular advantages as a shoe repair adhesive, for PVC pipes and for artificial nails. The "gluing" of wounds, particularly where relatively long chain cyanoacrylates are used, is also possible. Together with the primers, for example, aliphatic amines, the polyolefins can also be firmly attached. The primers can also be converted into the bar shape with the gel formers according to the invention. Correction bars and dyes can be produced by the addition of pigments and / or coating dyes. Due to the absence of solvents, such bars are particularly favorable to the environment. In portioned form, the cyanoacrylate compositions according to the invention can be used as filling material to fill fractures and holes in various materials. Both substrates are preferably coated with the adhesive, for example by rubbing with an adhesive stick. Joints filling gaps are also possible. Where cyanoacrylate compositions are used to seal, their rapid curing speed is worth mentioning. Surprisingly, the cyanoacrylate composition according to the invention is extremely stable in storage. For example, in conventional stick bar tubes, it could be stored and handled for many weeks at room temperature without any reduction in adhesive strength. Other advantages of the cyanoacrylate composition according to the invention include simple application, safe handling (not splashing, for example in the eyes or on the skin), application over large areas, bonding of vertical substrates. The invention is illustrated by the following examples.

After 6 months at 2 to 5 ° C, the adhesive sticks were still usable, that is, their consistency and adhesive properties were good. After 9 months at -18 ° C, the adhesive sticks were again still usable, i.e. no destruction of the gel structure or polymer formation was observed. After heating to 20 ° C, the closed lids were easily removed from the tubes. In tests with paper, the hardening time and the adhesive strength were virtually unchanged (tearing the paper). Storage stability at -18 ° C over 9 months is important especially for medical applications.

Examples 1. Production of cyanoacrylate compositions Stabilized cyanoacrylate was introduced under nitrogen into a three-necked flask and polymethacrylate was added in portions with vigorous stirring. 50 ° C. After 10 minutes, the solution was clear and homogeneous. To form a gel, the temperature was increased to 85 ° C and sorbital dibenzylidene was added in portions to avoid the formation of lumps. After 10 minutes, the gelling agent was almost dissolved. After cooling to about 80 ° C, the undissolved particles were removed by filtration. The solution was emptied still hot in conventional stick bar tubes and then cooled. After about an hour, the consistency was solid. The next day, the stick was ready to use and remained stable for several weeks despite repeated opening and closing. 2. Tests a) To test the stability in storage, a cyanoacrylate composition in a stick bar tube was tested for weeks for its adhesiveness on paper at 23 ° C / 50% relative humidity. b) To determine the application time, the cyanoacrylate composition was applied to one side of a paper strip 30 cm long and, immediately after, a second paper strip was applied and pressed down. The time elapsed before the paper was torn in the separation of the adhesive bond was measured. c) To determine the tensile strength of longitudinal joints, a) two drops of adhesive liquid were applied to the substrate of 10 x 25 mm area or b) a comparable amount was applied on one side by rubbing with the stick. Immediately after, the second substrate was lightly pressed on it. After 2 days at 23 ° C / 50% relative humidity, the beech wood and non-wood specimens were tested for tensile strength (speed: 10 mm / min). According to EN 205. The results were expressed as the average of 5 measurements.

The substrates were previously treated as follows: - beech wood, untreated - PMMA: degreased - ABS plastic: degreased - PVC: degreased and - Alu: cleaned by sandblasting and degreased. 3. Results The results of the test are mentioned in the Table 1. These show that useful resistances were obtained in each case, exceeding the resistances of the conventional cyanoacrylate adhesives in the case of beech wood.

Table 1. Composition (in parts by weight) and properties of cyanoacrylate compositions Ta = material rupture MF = material failure Part. MF = material failure in some test specimens.

Claims (1)

1. CLAIMS A composition of adhesive cyanoacrylate, coating and sealant based on a mixture of: A) at least one cyanoacrylate and B) at least one condensation product of aldehyde or ketone with a polyol. The composition as recited in claim 1, characterized by at least one substance from the following group of aldehydes or ketones: benzaldehyde, 3-chlorobenzaldehyde, and 3-fluorobenzaldehyde, more particularly benzaldehyde. The composition as recited in claim 1, characterized by at least one substance from the following group of polyols: sorbitol, xylitol and mannitol, more particularly sorbitol. The composition as recited in claim 1, characterized by at least one substance from the following group of condensation products of aldehyde or ketone with polyols: di-O-benzylidene mannitol, di-O- (3-fluorobenzylidene) -mannitol and di-O-benzylidene sorbitol, more particularly di-O-benzylidene sorbitol. The composition as recited in claim 1, characterized by the following composition (based on the cyanoacrylate composition as a whole): A) 99.8 to 29.5% by weight of at least one cyanoacrylate and B) 0.1 to 10% by weight of at least one condensation product of aldehyde or ketone with a polyol and C) 0.001 up to 0.5% by weight of stabilizers, D) 0 to 60% by weight of thickeners, solvents, plasticizers, fillers and other auxiliaries. The composition as mentioned in the claim 1, which is characterized by a geometric shape, more particularly a bar shape. A process for the production of the claimed composition in at least one of claims 1 to 6, characterized in that the solution is first prepared from the components A) and B) by heating and then cooled. The use of the compositions claimed in at least one of claims 1 to 6 for joining, coating and sealing. The use claimed in claim 8 for bonding porous substrates.