RU2487863C2 - Aldehydes having hydroxyl groups - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to novel aldehyde derivatives which contain hydroxyl groups. In formula (I):

R¹ and R² each independently denotes a univalent hydrocarbon residue with 1-12 carbon atoms; R³ is a hydrogen atom; R⁴ and R⁵ either independently denote a univalent aliphatic residue with 2-20 carbon atoms which may contain 1-2 hydroxyl groups, provided that R has at least one hydroxyl group, or together denote a divalent aliphatic residue with 4-20 carbon atoms, having at least one hydroxyl group and which is part of a substituted heterocyclic ring with 6 ring atoms, wherein said ring contains 2 heteroatoms in form of tertiary amine nitrogen.

EFFECT: invention also relates to a method of producing said aldehydes, a curable or cured composition containing said aldehydes and use of said compositions in gluing, sealing articles or coating an article.

17 cl, 2 tbl, 10 ex

Description

FIELD OF THE INVENTION

The present invention relates to the field of aldehydes and the field of polyurethanes.

State of the art

b-aminoalkylation of aldehydes with formaldehyde and primary or secondary aliphatic amines is disclosed by C. Mannich, for example, in US Pat. No. 1,824676. Thus, the resulting β-aminoaldehydes are also referred to as “Mannich bases”. As versatile components of the synthesis, they are widely used.

In the case of known applications, it would be preferable to have aldehydes with other functional groups. In particular, in the chemistry of polyurethanes, there is a need for aldehydes which possess functional groups reactive with isocyanate groups and, at the same time, can covalently integrate into the polyurethane polymer.

Description of the invention

The objective of the present invention, therefore, is to obtain new aldehydes having reactive functional groups that are available for the subsequent reactions.

It was unexpectedly found that this problem is solved by aldehydes according to claim 1. In this case, we are talking about mannich bases not yet described having hydroxyl groups. They are, in most cases, liquid compounds at room temperature that are barely odorless and which are prepared in a simple manner from readily available starting materials. They contain tertiary amino groups of relatively low basicity and can act catalytically in chemical reaction systems. Their hydroxyl groups are available for further reactions, for example, with isocyanate groups.

These aldehydes are suitable, for example, for the preparation of aldimines which can be used as hardeners in the case of curable compositions with amine-reactive groups, such as epoxy groups, anhydride groups or, in particular, isocyanate groups. In the compositions having isocyanate groups, the aldehydes released upon curing from the aldimines, through their hydroxyl groups, are covalently incorporated into the resulting polyurethane polymer and, thus, remain completely in the composition.

Another object of this invention are the aldehydes according to claim 9, which are the conversion products of the described aldehydes.

A further object of the present invention are curable compositions containing the described aldehydes according to claim 17.

Finally, the method for producing aldehydes according to claims 10 and 11 of the claims, the curable composition according to claims 24, the use according to claims 15, and the product according to claims 29 are further objects of the present invention.

Further aspects of this invention are the subject of other independent claims. Particularly preferred embodiments of the present invention are the subject of the dependent claims.

The ways of carrying out the invention

The object of this invention are aldehydes ALD of the formula (I):

,

,

Where

R ¹ and R ²

or, independently of each other, mean, respectively, a monovalent hydrocarbon residue with 1-12 carbon atoms,

or together they mean a divalent hydrocarbon residue with 4-12 carbon atoms, the part of which represents, if necessary, a substituted carbocycle with 5-8, preferably 6, carbon atoms;

R ³ means a hydrogen atom or an alkyl group or an arylalkyl group or an alkoxycarbonyl group, in particular with 1-12 carbon atoms;

and

R ⁴ and R ⁵

or, independently of each other, mean, respectively, a methyl group or a monovalent aliphatic, cycloaliphatic or arylaliphatic residue with 2-20 carbon atoms, which, if necessary, contains hydroxyl groups or aldehyde groups and which, if necessary, includes heteroatoms in ether oxygen or tertiary amine nitrogen, provided that R ⁴ has at least one hydroxyl group,

or together mean having at least one hydroxyl group a divalent aliphatic residue with 4-20 carbon atoms, a part of which, if necessary, is a substituted heterocycle with 5-8, preferably 6, atoms in the cycle, and this cycle, in if necessary, includes other heteroatoms in the form of ether oxygen or tertiary amine nitrogen and, if necessary, aldehyde groups.

R ¹ and R ² preferably mean, respectively, a methyl group.

R ³ preferably means a hydrogen atom.

R ⁴ and R ⁵ preferably mean, respectively, a 2-hydroxyethyl group or a 2-hydroxypropyl group.

Preferred ALD aldehydes of formula (I) according to one embodiment are those in which the radicals R ⁴ and R ⁵ together have at least two hydroxyl groups. These preferred ALD aldehydes of formula (I) are ALD1 aldehydes of formula (I '):

,

,

Where

R ^{4 '} and R ^5'

or, independently of each other, mean, respectively, a methyl group or a monovalent aliphatic, cycloaliphatic or arylaliphatic residue with 2-20 carbon atoms, which, if necessary, contains hydroxyl groups or aldehyde groups and which, if necessary, includes heteroatoms in ether oxygen or tertiary amine nitrogen,

provided that R ^{4 '} has at least one hydroxyl group and that R ^4' and R ^{5 '} together have at least two hydroxyl groups,

or together mean having at least two hydroxyl groups a divalent aliphatic residue with 4-20 carbon atoms, part of which, if necessary, is a substituted heterocycle with 5-8, preferably 6, atoms in the cycle, and this cycle, in if necessary, includes other heteroatoms in the form of ether oxygen or tertiary amine nitrogen and, if necessary, aldehyde groups;

and R ¹ , R ² and R ³ have the meanings already indicated.

Preferred ALD aldehydes of formula (I) according to a further embodiment are those in which R ⁴ and R ⁵ together have only one hydroxyl group. These preferred ALD aldehydes of formula (I) are ALD2 aldehydes of formula (I ”):

,

,

Where

R ^{4 ”} and R ^5”

or, independently of each other, mean, respectively, a methyl group or a monovalent aliphatic, cycloaliphatic or arylaliphatic residue with 2-20 carbon atoms, which, if necessary, contains hydroxyl groups or aldehyde groups and which, if necessary, includes heteroatoms in ether oxygen or tertiary amine nitrogen,

provided that R ^{4 ”} has one hydroxyl group and that R ^5” does not contain any hydroxyl group,

or together they mean a divalent aliphatic residue having one hydroxyl group with 4-20 carbon atoms, the part of which, if necessary, is a substituted heterocycle with 5-8, preferably 6, atoms in the cycle, and this cycle, if necessary, includes other heteroatoms in the form of ether oxygen or tertiary amine nitrogen and, if necessary, aldehyde groups;

and R ¹ , R ² and R ³ have the meanings already indicated.

Particularly preferred are at least two hydroxyl groups aldehydes ALD1 of the formula (I ').

In most cases, aldehydes ALD1 of formula (I ′) with two hydroxyl groups are preferred. These, in most cases preferred, ALD1 aldehydes of the formula (I ′), according to one embodiment, comprise an R ^{4 ′} residue with two hydroxyl groups and an R ^{5 ′} residue without a hydroxyl group; or, according to another embodiment, comprise a residue R ^{4 ′} with one hydroxyl group and a residue R ^{5 ′} with one hydroxyl group.

ALD aldehydes of the formula (I) are obtained, in particular, as a product of the Mannich reaction or a similar Mannich reaction of b-aminoalkylation, as is known from the literature; therefore, they can also be called the foundations of Mannich.

According to one embodiment, the aldehyde Y1 of the formula (II), the aldehyde Y2 of the formula (III) and a secondary aliphatic having at least one hydroxyl group, amine C of the formula (IV) are reacted by elimination of water to form the aldehyde ALD of the formula (I) )

This interaction can be carried out either using free reagents Y1, Y2 and C according to formulas (II), (III) and (IV), or the reagents can be used partially or fully in derivatized form. Thus, aldehyde Y1, for example, can be used in the form of an enolate, in the form of an ether of enol, in particular in the form of an ether of silylenol, or in the form of enamine. Aldehyde Y2 can be used, for example, in the form of an oligomer - in the case of formaldehyde, in particular in the form of 1,3,5-trioxane or in the form of paraformaldehyde - or in the form of a hydrate, semi-acetal, acetal, N, O-acetal, aminal or semi-aminal . The secondary aliphatic amine C can finally be used, for example, in the form of a salt, in particular in the form of an amine hydrochloride or in the form of an amine hydrosulfate, or in the form of silylamine. Part of the reagents can be used in free form and part of the reagents can be used in derivatized form or can only be derived from derivatized forms. When using reagents in a derivatized form, ALD aldehyde, under certain conditions, also forms in a derivatized form, for example, in the form of a salt; in this case, by suitable processing, it can be converted into free form according to formula (IV). Depending on the circumstances, it may be rational to use additional excipients such as Lewis acids or catalysts in such conversion reactions.

Further, the conversion reaction can be carried out as a one-step reaction, in which case all three reagents can simultaneously react with each other; or, however, a sequential course of action can be chosen in that two reactants are first reacted with each other and the thus obtained intermediate product is then reacted with a third reactant, the intermediate product being isolated or not isolated. Suitable intermediates are, in particular, the iminium salts, which are obtained by reacting the aldehyde Y2, in free or derivatized form, with a salt of the secondary aliphatic amine C and which can be reacted with the aldehyde Y1, in free or derivatized form, to give the corresponding aldehyde salts of ALD of formula (I). This kind of sequential course of action can have the advantage of making milder reaction conditions possible and at the same time leading to a higher yield of the product.

Further, the interaction can be carried out using solvents, in particular polar solvents such as water or alcohols, or the interaction can be carried out without the use of solvents.

According to a preferred embodiment, the reaction is carried out using all the free-form reagents as a one-step reaction, and the ALD aldehyde after the reaction is carried out is purified by distillation. Preferably, no organic solvents are used.

Suitable aldehyde Y1 of the formula (II) are, for example, the following: isobutyraldehyde, 2-methylbutyraldehyde, 2-ethyl-butyraldehyde, 2-methylvaleraldehyde, 2-ethylcaprodealdehyde, cyclopentanecarboxaldehyde, cyclohexanecarboxaldehyde, 1,2,3,2 methyl 3-phenylpropionic aldehyde, 2-phenylpropionic aldehyde and diphenylacetaldehyde. Isobutyraldehyde is preferred.

Suitable aldehyde Y2 of the formula (III) are, for example, the following: formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, isobutyraldehyde, phenylacetaldehyde, benzaldehyde and substituted benzaldehydes, as well as glyoxylic acid esters, in particular glyoxylic acid ethyl ester. Formaldehyde is preferred.

As amine C of formula (IV), according to one embodiment, at least two hydroxyl groups of secondary aliphatic amines C1 are suitable.

As “primary amine”, respectively, “secondary amine”, respectively, “tertiary amine”, as used herein, are compounds containing primary, respectively, secondary, respectively, tertiary amino groups. The term "primary amino group" means an amino group in the form of an NH ₂ group that is bound to one organic residue. The term "secondary amino group" means an amino group in which a nitrogen atom is attached to two organic residues, which can also be a common part of the cycle. The term “tertiary amino group” means an amino group in which a nitrogen atom (= tertiary amine nitrogen) is bound to three organic residues, two of which can also be a common part of the cycle.

As “aliphatic,” as used herein, is meant an amine or amino group wherein the nitrogen atom is bonded exclusively to aliphatic, cycloaliphatic or arylaliphatic residues.

Suitable amines C1 with two hydroxyl groups, in particular, are selected from the group consisting of diethanolamine, dipropanolamine, diisopropanolamine, 3- (2-hydroxyethylamino) -1-propanol and 3- (2-hydroxypropylamino) -1-propanol, N-methyl -2,3-dihydroxypropylamine, 3,4-dihydroxypyrrolidine, 2,5-bis (hydroxymethyl) pyrrolidine, 2,6-bis (hydroxymethyl) piperidine, 3,4- or 3,5-dihydroxypiperidine, 2- (2,3 -dihydroxypropyl) pyrrolidine and 2- (2,3-dihydroxypropyl) piperidine, as well as products of the interaction of ammonia with two molecules that contain one epoxy hydrochloric group, particularly a group of the glycidyl ether.

Suitable amines C1 with more than two hydroxyl groups are, for example, the following: 2- (2,3-dihydroxypropylamino) ethanol, 3,4,5-trihydroxypiperidine, N, N-bis (2,3-dihydroxypropyl) amine, 2 5-bis (2,3-dihydroxypropyl) pyrrolidine; and 2,6-bis (2,3-dihydroxypropyl) piperidine.

The use of amines C1 in the preparation of ALD aldehydes leads, in particular, to the preferred ALD1 aldehydes of the formula (I ′).

As amine C of formula (IV), according to a further embodiment, suitable are secondary C2 amines having only one hydroxyl group, which are selected, in particular, from the group consisting of primary amine alkoxylates, such as 2- (N-methylamino) ethanol, 2 - (N-ethylamino) ethanol, 2- (N-propylamino) ethanol, 2- (N-isopropylamino) ethanol, 2- (N-butylamino) ethanol, 2- (N-cyclohexylamino) ethanol, 3- (N- methylamino) -2-propanol, 3- (N-ethylamino) -2-propanol, 3- (N-propylamino) -2-propanol, 3- (N-isopropylamino) -2-propanol, 3- (N-butylamino) -2-propanol, 3- (N-cyclohexylamino) -2-propanol, 2- (N-ethyl noetoksi) ethanol, and cycloaliphatic hydroxyamines such as 2-pyrrolidine-methanol, 3-hydroxypyrrolidine, 2-piperidinemethanol, 3- or 4-hydroxypiperidine and 1- (2-hydroxyethyl) piperazine.

The use of C2 amines in the preparation of ALD aldehydes leads, in particular, to the preferred ALD2 aldehydes of formula (I ”).

Suitable amines C of formula (IV) are further C3 amines with two secondary aliphatic amino groups and at least one hydroxyl group, such as, for example, 2-hydroxymethylpiperazine, 2- (2,3-dihydroxypropyl) piperazine, 2, 3- or 2,6-bis (hydroxymethyl) piperazine and N, N'-dimethipropylene-2-oldiamine. Amines C3 are reacted with, respectively, a double amount of aldehyde Y1 and aldehyde Y2. In this case, ALD aldehydes are formed in the form of hydroxyl groups of aldehydes of the formula (V):

,

,

Where

R ⁶ means a divalent aliphatic, cycloaliphatic or arylaliphatic residue with 2-20 carbon atoms, which, if necessary, has hydroxyl groups and which, if necessary, includes heteroatoms in the form of ether oxygen or tertiary amine nitrogen;

R ⁷ and R ⁸

or, independently of one another, mean, respectively, a methyl group or a monovalent aliphatic, cycloaliphatic or arylaliphatic residue with 2-20 carbon atoms, which, if necessary, has hydroxyl groups and which, if necessary, includes heteroatoms in the form of simple oxygen ether or tertiary amine nitrogen,

or together mean a divalent aliphatic residue containing at least one hydroxyl group with 4-20 carbon atoms, which together with NR ⁶ -N forms a heterocycle with 5-8, preferably 6, atoms in the cycle, and this cycle, in the case of optionally includes other heteroatoms in the form of ether oxygen or tertiary amine nitrogen,

with the proviso that at least one of the radicals R ⁶ , R ⁷ and R ⁸ has at least one hydroxyl group,

and R ¹ , R ² and R ³ have the meanings already indicated.

According to a further embodiment, the ALD aldehydes of formula (I) are also prepared using primary aliphatic, having at least one hydroxyl group, amines C 'of formula (IV'), in that they are reacted with aldehyde Y1 and aldehyde Y2 in a molar ratio of 1: 2: 2 when splitting off water. In this case, ALD aldehydes are formed in the form of aldehydes of the formula (VI):

Primary aliphatic amines with one or more hydroxyl groups, in particular those selected from the group consisting of aminoalkoxylates such as 2-aminoethanol, 3-amino-1-propanol, 1-, are suitable as the amine C 'of formula (IV'). amino-2-propanol, 2-amino-1-butanol, 3- (2-hydroxyethoxy) propylamine, 2- (2-aminoethoxy) ethanol, as well as 4- (2-aminoethyl) -2-hydroxyethylbenzene and 3-aminomethyl -3,5,5-trimethylcyclohexanol.

Preferred aldehydes of ALD1 are 3- (N-bis (2-hydroxyethyl) amino) -2,2-dimethylpropanal and 3- (N-bis (2-hydroxy-2-methylethyl) amino) -2,2-dimethylpropanal.

Preferred aldehydes of ALD2 are 2,2-dimethyl-3- (N- (2-hydroxyethyl) methylamino) propanal, 2,2-dimethyl-3- (N- (2-hydroxypropyl) methylamino) propanal, 2,2-dimethyl- 3- (N- (2-hydroxypropyl) ethylamino) propanal, 2,2-dimethyl-3- (N- (2-hydroxypropyl) isopropylamino) propanal, 2,2-dimethyl-3- (N- (2-hydroxypropyl) butylamino) propanal, 2,2-dimethyl-3- (N- (2-hydroxypropyl) cyclohexylamino) propanal and 2,2-dimethyl-3- (N- (N '- (2-hydroxyethyl) piperazino)) propanal.

ALD aldehydes of formula (I) can be prepared as described above from well-available starting materials using a simple method. They have a number of special properties. So, they have good thermal stability, since the carbon atom in the b-position to the aldehyde group does not carry any hydrogen atom and therefore it is impossible to eliminate the secondary amine during the formation of alkene. Further, they have unexpectedly good stability with respect to oxidation by atmospheric oxygen. Further, their basicity is unexpectedly distinctly lower than expected in the case of aliphatic amines of similar structure; pK _a, measured in the case of the conjugated acid ALD aldehyde amounts to approximately 2 units lower than that of the conjugate acid is used for preparation of this aldehyde ALD primary or secondary amine C. These unexpected properties are possibly associated with intramolecular 1,4-interaction between the amino group and the aldehyde group (orbital overlap between the free electron pair of nitrogen and the p-, respectively, p * orbital of carbonyl), as postulated by PY Johnson et al. (J. Org. Chem., 40, No. 19, 2710-2720 (1975) ) on the main The development of NMR and UV spectroscopic studies of b-aminoaldehydes.

Finally, ALD aldehydes, also at relatively low molecular weight, have no or only slight odor. This property of low odor intensity, unexpected for aldehydes, on the one hand, appears due to the fact that ALD aldehydes, based on available OH groups, are relatively low volatility. Further, a slight odor is probably favored by the aforementioned intramolecular 1,4-interaction and spatial difficulty of the aldehyde group, which is located at the tertiary carbon atom.

Aldehydes ALD of the formula (I) can be very widely used.

They can be used as catalysts in the case of chemical reaction systems, for example, in curable compositions having isocyanate groups, in particular, to reduce their curing time.

Their aldehyde groups and their hydroxyl groups enable sequential reactions to synthesize further functionalized ALD aldehyde reaction products. They can be reacted, for example, with compounds which are reactive with respect to hydroxyl groups to form reaction products having aldehyde groups. Suitable hydroxyl reactive compounds are, for example, isocyanates, epoxides, anhydrides and carboxylic acids. Thus, for example, compounds having isocyanate groups by reacting with hydroxyl groups aldehydes, ALD can be converted to compounds having aldehyde groups, for example, polyurethane polymers having aldehyde groups or polyisocyanates having aldehyde groups.

Further, the aldehyde groups of ALD aldehydes can be converted to ald-imines using compounds containing primary amino groups. Aldimines can be used as protected aldehyde groups and / or protected (“blocked”) amino groups. On the one hand, hydroxy-functional monoaldimines are thus obtained, which, on the other hand, can be reacted with compounds reactive with hydroxyl groups until further reaction products are formed. On the other hand, hydroxy-functional polyaldimines are thus obtained, which can be used, for example, in the chemistry of polyurethanes as hardeners. If polyaldimines are contacted with polyisocyanates in the presence of moisture, the primary amino groups formally released by hydrolysis of the aldimino groups react with the isocyanate groups when ALD aldehydes are released, while their hydroxyl groups also react with the isocyanate groups. The released ALD aldehydes are finally covalently incorporated into the polymer formed during curing, which is very favorable. Due to the integration of aldehydes, the latter in the composition do not cause any negative effects, such as increased shrinkage, penetration into the surrounding air, in particular, of unpleasant odors, or migratory effects, such as sweating; likewise, they do not adversely affect the mechanical properties of the composition, for example, in that they would act plasticizing or impair the stability of the composition with respect to environmental influences, such as heat or UV radiation. As already mentioned, aldehydes ALD1 are preferred, since they carry at least two hydroxyl groups and, thus, when curing the isocyanate-containing compositions as at least difunctional hardeners, when elongated or crosslinked, they are covalently incorporated into the resulting polymer . The indicated relatively low basicity of ALD aldehydes is favorable for such use, since strongly basic tertiary amines can excessively accelerate the direct reaction of isocyanate groups, in particular, with water, which can interfere with the curing of polyurethanes.

Further, ALD aldehydes can be used as initiator molecules for polyalkoxylation reactions. Thus, depending on the number of hydroxyl groups present in the ALD aldehyde used, monohydric alcohols or polyols containing aldehyde groups are obtained. Thus, polyols containing at least one aldehyde group are obtained by polyalkoxylation of the aldehyde ALD of formula (I).

Finally, ALD aldehydes can be used as a source of cationic compounds in that the tertiary amino groups are partially or completely protonated to form ammonium groups or alkylated to form quaternary ammonium groups. Aldehydes of formula (VII) are available due to the protonation or alkylation of ALD aldehydes of formula (I) :

,

,

Where

R ⁹ means a hydrogen atom or an alkyl, cycloalkyl or arylalkyl residue with 1-20 carbon atoms;

and R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the meanings already indicated.

Any Bronsted acid, such as hydrochloric acid, sulfuric acid, phosphoric acid, carboxylic acids, such as acetic acid or benzoic acid, and also sulfonic acids, such as methanesulfonic acid or p-toluenesulfonic acid, can be used to protonate the aldehydes of ALD of formula (I). Known alkylating agents, in particular methylating agents such as methyl iodide, dimethyl sulfate, dimethyl phosphonate, diazomethane, fluorosulfuric acid methyl ester or trimethyloxonium tetrafluoroborate, can be used to alkylate the ALD aldehydes of formula (I).

One skilled in the art will recognize that the cationic aldehyde of formula (VII) also contains an anion that compensates for the positive charge of the aldehyde.

The reaction products indicated in this context, obtained from the described ALD aldehydes of the formula (I), represent only a small selection of the possibilities of their useful conversion products and should in no way limit the use of ALD aldehydes.

A further object of the present invention are curable compositions comprising at least one polyisocyanate and at least one ALD aldehyde of the formula (I) or at least one aldehyde of the formula (VII).

The term "polyisocyanate" includes, as used herein, compounds with two or more isocyanate groups, regardless of whether they are monomeric diisocyanates, oligomeric polyisocyanates, or relatively high molecular weight polymers having isocyanate groups.

As the aldehyde ALD of the formula (I), in particular, the aldehydes ALD of the formula (I) described in detail above, respectively, their preferred form of implementation are suitable. Suitable aldehydes of formula (VII) are already described above.

Curable compositions comprising at least one polyisocyanate and at least one aldehyde ALD1 of formula (I ′) are preferred.

According to one embodiment, the curable composition is a single component.

As the term “one-component” is meant, according to this document, the curable composition, in which case all the constituent parts of the composition are stored mixed in the same container and which is stable when stored at room temperature for a longer period of time, therefore, in relation to its properties for use or consumption due to storage does not change or only slightly changes, and which after application is cured by exposure to moisture and / or heat.

The one-component curable composition includes at least one polyisocyanate, the isocyanate groups of which, in particular, are in the form of blocked isocyanate groups.

By “blocked isocyanate group”, as used herein, is meant an isocyanate group in which due to the prior introduction of the free isocinate group into a blocking agent known in the art, for example phenol, ketoxime, pyrazole or malonic acid diester, it is so reduced reactivity towards nucleophiles, that it is stable when stored together with suitable hardeners at room temperature and only when exposed to heat and / or moisture naet react with these hardeners, wherein the blocking means, depending on type, is released or not released.

Suitable isocyanate-blocked polyisocyanates are commercially available or can be prepared, if necessary, by reacting the polyisocyanates with suitable blocking agents.

The one-component curable composition may be moisture curing and / or thermoset.

By “thermosetting composition”, according to this document, is meant a composition with blocked isocyanate groups, in which case when heated to a suitable temperature, usually in the range from 120 ° C. to 200 ° C., in special cases already at temperatures starting from 80 ° C. , blocked isocyanate groups are activated so that crosslinking is possible with suitable hardeners and thus curing. This process is also referred to as hot drying and is usually carried out after application of the composition.

More typically, the complete curing of the described one-component composition occurs through exposure to a combination of moisture and heat.

According to a preferred embodiment, the curable composition is two-component.

As “two-component”, according to this document, is meant a curable composition, in which case the constituent parts of the composition are in the form of two different components that are stored in containers separated from each other and which, accordingly, are stable during storage. Both components are designated as component K1 and as component K2. Only shortly before or during application of the composition, both components are mixed with each other, after which the mixed composition is cured, and curing, under certain conditions, proceeds or is supplemented only by exposure to moisture and / or heat.

Particularly preferred are two-component curable compositions consisting of component K1 and component K2, wherein these compositions contain at least one polyisocyanate P and at least one aldehyde ALD1 of formula (I ′). When cured, the aldehyde ALD1, on the basis of at least two hydroxyl groups, acts as a hardener for polyisocyanate P and, when the chains are extended or crosslinked, is covalently incorporated into the resulting polymer.

Component K1 of a particularly preferred curable two-component composition contains at least one polyisocyanate P.

As the polyisocyanate P, according to one embodiment, PI polyisocyanate in the form of a monomeric di- or tri-isocyanate or oligomer of a monomeric diisocyanate or a derivative of a monomeric diisocyanate is suitable.

Suitable monomeric di- or triisocyanates are, for example, the following: 1,4-tetramethylene diisocyanate, 2-methylpentamethylene-1,5-diisocyanate, 1,6-hexamethylene diisocyanate (HDI), 2,2,4- and 2,4,4 trimethyl-1,6-hexamethylene diisocyanate (TMDI), 1,10-decamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, lysine diisocyanate and lysine ester diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate, 1-methyl -2,4- and -2,6-diisocyanatocyclohexane and any mixtures of these isomers (HTDI or H ₆ TDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (= isophorondiisocyanate or IPDI), perhydro-2 ,four'- and -4,4'-diphenylmethanediisocyanate (HMDI or H ₁₂ MDI), 1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI), 1,3- and 1,4-bis (isocyanatomethyl) cyclohexane, m- and p-xylylene diisocyanate (m- and p-XDI), m- and p-tetramethyl-1,3- and -1,4-xylylene diisocyanate (m- and p-TMXDI), bis (1-isocyanato-1-methylethyl) naphthalene, isocyanates of dimeric and trimeric fatty acids, such as 3,6-bis (9-isocyanatononyl) -4,5-di (1-heptenyl) cyclohexene (dimeryldiisocyanate), b, b, b ', b', b ”, b "-Hexamethyl-1,3,5-mesitylene triisocyanate, 2,4- and 2,6-toluene diisocyanate and any mixtures of these isomers (TDI), 4,4'-, 2,4'- and 2,2'-diphenylmethanediisocyanate and any laughs and these isomers (MDI), mixtures of MDI and MDI homologs (polymeric MDI or PMDI), 1,3- and 1,4-phenylenediisocyanate, 2,3,5,6-tetramethyl-1,4-diisocyanatobenzene, naphthalene 1,5-diisocyanate (NDI), 3,3'-dimethyl-4,4'-diisocyanatophenyl (TODI), dianisidinediisocyanate (DADI), 1,3,5-tris (isocyanatomethyl) benzene, tris (4-isocyanatophenyl) methane and tris (4-isocyanatophenyl) thiophosphate.

Particularly suitable as PI polyisocyanate are oligomers or derivatives of monomeric diisocyanates, in particular HDI, IPDI, TDI and MDI. Commercially available types are, in particular, HDI-biurets, such as Desmodur ^® N 100 and N 3200 (Bayer), Tolonate ^® HDB and HDB-LV (Rhodia) and Duranate ^® 24A-100 (Asahi Kasei); HDI-isocyanurates, such as Desmodur ^® N 3300, N 3600 and N 3790 BA (all manufactured by ^{Bayer), Tolonate ® HDT, HDT} -LV and HDT-LV2 (Rhodia), Duranate ® TPA- 100 and THA-100 ( Asahi Kasei) and Coronate ^® HX (Nippon Polyurethane); HDI-uretdiones, for example as Desmodur ^® N 3400 (Bayer); HDI-iminooksadiazindiony, for example as Desmodur ^® XP 2410 (Bayer); HDI-allophanates, such as Desmodur ^® VP LS 2102 (Bayer); IPDI-isocyanurates, e.g., in solution as Desmodur ^® Z 4470 (Bayer), or in solid form as Vestanat ^® T1890 / 100 (Degussa); TDI oligomers, for example, as Desmodur ^® IL (Bayer), as well as mixed TDI / HDI-based isocyanurates, for example, as Desmodur ^® HL (Bayer). Further, MDI forms (so called “modified MDI”) which are mixtures of MDI with MDI derivatives, such as, for example, MDI carbodiimides, respectively MDI uretonimines or MDI urethanes known for example under the trade names Desmodur ^® CD, Desmodur ^® PF, Desmodur ^® PC (all manufactured by Bayer), as well as mixtures of MDI and MDI homologs (polymer MDI or PMDI), sold under the trade names like Desmodur ^® VL, Desmodur ^® VL50, Desmodur ^® VL R10, Desmodur ^® VL R20 and Desmodur ^® VKS 20F (all available from Bayer), Isonate ^® M 309, Voranate ^® M 229 and Voranate M ^® 580 (all available from Dow) or Lupranat ^® M 10 R (available from BASF).

The above oligomeric PI polyisocyanates in practice are usually mixtures of substances with different degrees of oligomerization and / or chemical structures. Preferably, they have an average NCO functionality of 2.1 to 4.0 and, in particular, contain isocyanurate, iminooxadiazinedione, urethdione, urethane, biuret, allofanate, carbodiimide, uretonimine or oxadiazintrione groups. These oligomers preferably have a low content of monomeric diisocyanates.

As the PI polyisocyanate, liquid MDI forms at room temperature are preferred, as well as HDI, IPDI and TDI oligomers, in particular isocyanurates.

As a polyisocyanate P, according to a further embodiment, a polyurethane polymer PUP containing isocyanate groups is suitable.

The term "polymer" includes, according to this document, on the one hand, a set of chemically uniform, however, differing in terms of degree of polymerization, molecular weight and chain length of macromolecules, which is obtained by polyreaction (polymerization, polyaddition, polycondensation). The concept also includes, on the other hand, derivatives of such a combination of macromolecules obtained by polyreaction, therefore, compounds which are obtained by introducing into the interaction, such as, for example, addition or substitution reactions, functional groups of the above macromolecules and which may be chemically uniform or chemically not uniform. The concept further includes also the so-called prepolymers, that is, reactive oligomeric prepolymers whose functional groups are involved in the synthesis of macromolecules.

The term "polyurethane polymer" includes all polymers that are obtained by the so-called method of diisocyanate polyaddition. This concept also includes such polymers that are almost or completely devoid of urethane groups. Examples of polyurethane polymers are polyether polyurethanes, polyester polyurethanes, polyether polycarbamides, polycarbamides, polyester polycarbamides, polyisocyanurates and polycarbodiimides.

A suitable isocyanate-containing polyurethane PUP polymer is prepared by reacting at least one polyol with at least one polyisocyanate.

As polyols for obtaining the polyurethane polymer PUP, for example, the following polyols or mixtures thereof can be used:

polyether polyols, also referred to as polyoxyalkylene polyols or oligoetherols, which are polymerization products of ethylene oxide, 1,2-propylene oxide, 1,2- or 2,3-butylene oxide, tetrahydrofuran or mixtures thereof, possibly polymerizable using an initiating molecule, such as, for example , water, ammonia, 1,2-ethanediol, 1,2- and 1,3-propanediol, neopentyl glycol, diethylene glycol, isomeric dipropylene glycols and tripropylene glycol, diethylene glycol, triethylene glycol, isomeric dipropylene glycols and tripropylene glycols, isomeric butanides ntanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecandiols, 1,3- and 1,4-cyclohexanedimethanol, bisphenol-A, hydrogenated bisphenol-A, 1,1,1-trimethylol ethane, 1,1,1-trimethylolpropane, glycerin, aniline, as well as mixtures of the above compounds. Can be used as polyoxyalkylene polyols that have a low degree of unsaturation (determined according to ASTM D-2849-69 and indicated in milliquivalents of unsaturation per gram of polyol (meq / g)), obtained, for example, using so-called catalysts based on a double metal cyanide complex ( DMC catalysts), as well as higher unsaturation polyoxyalkylene polyols obtained, for example, using anionic catalysts such as NaOH, KOH, CsOH or alkali metal alkoxides.

Particularly suitable as polyether polyols are polyoxyalkylenediols and β-triols, in particular polyoxyalkylenediols. Particularly suitable polyoxyalkylene di and triols are polyoxyethylene di and triols, as well as polyoxypropylene di and triols.

Particularly suitable are polyoxypropylenediols and β-triols with a degree of unsaturation lower than 0.02 meq / g and a molecular weight ranging from 1000 g / mol to 30,000 g / mol, as well as polyoxypropylene diols and β-triols with a molecular weight of 400 g / mol to 8000 g / mol. The term "molecular weight" or "molecular weight" is always understood, according to this document, the average (number average) molecular weight M _n . Polyoxypropylenediols with a degree of unsaturation lower than 0.02 meq / g and a molecular weight in the range from 1000 g / mol to 12000 g / mol, in particular from 1000 g / mol to 8000 g / mol are particularly suitable. These polyether polyols are available, e.g., under the trademark Acclaim ^® by the company Bayer.

Especially suitable are so-called “blocked by terminal EO groups” (blocked by terminal ethylene oxide groups) polyoxypropylenediols and triols. The latter are special polyoxypropylene polyoxyethylene polyols, which, for example, are obtained by the fact that pure polyoxypropylene polyols, after the completion of polypropoxylation, are alkoxylated with ethylene oxide and, therefore, have primary hydroxyl groups;

styrene-acrylonitrile- or acrylonitrile-methyl methacrylate-grafted polyether polyols;

polyester polyols, also referred to as oligoesters, obtained by known methods, in particular by the polycondensation reaction of hydroxycarboxylic acids or the polycondensation reaction of aliphatic and / or aromatic polycarboxylic acids with dihydric or polyhydric alcohols.

Particularly suitable are polyester polyols which are derived from dihydric to trihydric, in particular dihydric, alcohols, such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl -1,5-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecandiol, 1,12-hydroxystearyl alcohol, 1,4-cyclohexanedimethanol, dimer fatty acid diol (dimerdiol ), neopentyl glycol ester of hydroxypivalic acid, glycerin, 1,1,1-trimethylolpropane or mixtures of the above alcohols with organic di- or tricarboxylic acids, in particular dicarboxylic acids or their anhydrides or esters, such as, for example, succinic acid, glutaric acid, adipic acid, trimethyladipic acid, cork acid, azelaic acid, sebacic acid, dodecandicarboxylic acid, maleic acid, fumaric acid, dimeric fatty acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, dimethyl terephthalic acid, hexahydrophthalic acid, trimel itovaya acid and trimellitic acid anhydride or mixtures of the aforementioned acids, and also polyester polyols from lactones such as, for example, e-caprolactone, initiators and, as the above di- or trihydric alcohols.

Particularly suitable polyester polyols are polyester diols;

polycarbonate polyols, which are prepared by reacting, for example, the above - used for the synthesis of polyester polyols - alcohols with dialkyl carbonates, like dimethyl carbonate, diaryl carbonates, like diphenyl carbonate, or phosgene.

Polycarbonate diols are particularly suitable;

block polymers containing at least two hydroxyl groups which have at least two different blocks with the structure of a polyester, polyester and / or polycarbonate of the kind described above are also suitable as polyols;

polyacrylate and polymethacrylapolyols;

polyhydroxyfunctional fats and oils, for example, natural fats and oils, in particular castor oil; or obtained by chemical modification of natural fats and oils - the so-called oleochemical - polyols, for example, obtained by epoxidation of unsaturated oils and the subsequent opening of the cycle with carboxylic acids, respectively alcohols, epoxy polyesters, respectively, epoxy polyesters, or obtained by hydroformylation and hydrogenation of unsaturated polyol oils; or obtained from natural fats and oils by a cleavage process, such as alcoholysis or ozonolysis, and subsequent chemical binding, for example, by transesterification or dimerization of the thus obtained cleavage products or their derivatives, polyols. Suitable breakdown products of natural fats and oils are, in particular, fatty acids and fatty alcohols, as well as fatty acid esters, in particular methyl esters (FAME), which, for example, can be derivatized by hydroformylation and hydrogenation to form fatty hydroxy acid esters;

polyhydrocarbon polyols, also referred to as oligohydrocarbonols, such as, for example, polyhydroxy functional polyolefins, polyisobutylene, polyisoprene; polyhydroxy-functional copolymers of ethylene and propylene, ethylene and butylene or ethylene, propylene and diene, which, for example, are manufactured by Kraton Polymers; polyhydroxy-functional polymers of dienes, in particular 1,3-butadiene, which, in particular, can also be obtained by anionic polymerization; polyhydroxy-functional copolymers of dienes, such as 1,3-butadiene, or mixtures of dienes, and vinyl monomers, such as styrene, acrylonitrile, vinyl chloride, vinyl acetate, vinyl alcohol, isobutylene and isoprene, for example, polyhydroxy-functional copolymers of acrylonitrile and butadiene, for example, copolymers of butadiene and acrylonitrile with terminal carboxyl groups (commercially available under the name of Hycar ^® CTBN; manufactured by Noveon) and epoxides or aminoalcohols; as well as hydrogenated polyhydroxy functional polymers or diene copolymers.

These said polyols preferably have an average molecular weight of 250-30000 g / mol, in particular 400-20000 g / mol, and preferably have an average OH functionality in the range of 1.6 to 3.

In addition to these polyols, in the preparation of the PUP polyurethane polymer, small amounts of low molecular weight di- or polyhydric alcohols can be used together, such as, for example, 1,2-ethanediol, 1,2- and 1,3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, isomeric dipropylene glycols and tripropylene glycols, isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecandiols, 1,3- and 1,4-cyclohexanedimethanol, hydrogenated bisphenols, for example, fatty bisphenols, ols dimeric fatty acid, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerol, pentaerythritol, low molecular weight alkoxylation products of the aforementioned di- and polyhydric alcohols, and mixtures of the above alcohols.

Aliphatic, cycloaliphatic or aromatic polyisocyanates, in particular diisocyanates, such as, for example, monomeric diisocyanates, which have already been indicated as suitable PI polyisocyanates, as well as oligomers and polymers of these monomeric diisocyanates, as well as any mixtures of these isocyanates. Monomeric diisocyanates, in particular MDI, TDI, HDI and IPDI, are preferred.

The preparation of the PUP polyurethane polymer is carried out in a known manner directly from polyisocyanates and polyols or by gradual addition processes, which are also known as chain extension reactions.

According to a preferred embodiment, the PUP polyurethane polymer is prepared by reacting at least one polyisocyanate and at least one polyol, the isocyanate groups with respect to the hydroxyl groups being in stoichiometric excess. The ratio between isocyanate and hydroxyl groups is preferably from 1.3 to 10, in particular from 1.5 to 5.

The reaction is preferably carried out at a temperature at which the polyols, polyisocyanates and the resulting polyurethane polymer are in a liquid state.

The polyurethane polymer PUP has a molecular weight, preferably above 500 g / mol, in particular from 1000 g / mol to 30,000 g / mol.

Further, the PUP polyurethane polymer preferably has an average NCO functionality in the range of 1.8 to 3.

Finally, mixtures containing PUP polyurethane polymer and PI polyisocyanate, in particular mixtures containing MDI-based PUR polyurethane polymer and monomeric and / or polymeric MDI, as well as mixtures containing IPDI, are also suitable as polyisocyanate P; PUP polyurethane polymer; and monomeric and / or oligomeric IPDI.

Component K2 of a particularly preferred curable two-component composition comprises at least one aldehyde ALD1 of formula (I ′). Suitable for this are the above-described aldehydes ALD1 of the formula (I '), respectively, preferred for this form of execution, which are already described in detail. Aldehydes ALD1 of formula (I ′) with residues R ^{4 ′} and R ^{5 ′} , which together contain two hydroxyl groups, are particularly suitable.

If necessary, component K2 contains other compounds which are reactive with respect to isocyanate groups, such as polyols, polyamines, aminoalcohols, polythiols or blocked amines.

Suitable polyols in the case of component K2 are the same polyols that are already indicated as suitable for the preparation of the PUP polyurethane polymer, as well as the same low molecular weight di- or polyhydric alcohols, which are indicated above as suitable for sharing in the preparation of the PUP polyurethane polymer.

Suitable polyamines for component K2 are standard aliphatic or aromatic polyamines with primary and / or secondary amino groups, which are usually used in two-component polyurethane compositions, such as, for example, 1,5-diamino-2-methylpentane (MPMD), 1,3- xylylenediamine (MXDA), N, N'-dibutylethylenediamine, 3,5-diethyl-2,4 (6) -diaminotoluene (DETDA), 3,5-dimethylthio-2,4 (6) -diaminotoluene (Ethacure ^® 300; Albemarle ) as well as primary and secondary polyoxyalkylene diamines, which are produced, for example, under the name Jeffamine ^® (Huntsman Chemicals company).

Suitable amino alcohols in the case of component K2 are compounds which include at least one primary or secondary amino group and at least one hydroxyl group, such as, for example, 2-aminoethanol, 2-methylaminoethanol, 1-amino-2- propanol and diethanolamine.

Suitable polythiols in the case of component K2 are, for example, liquid mercapto-terminated polymers known under the trade name Thiokol ^® as well as thiocarboxylic acid polyesters.

As available, if necessary, in the component K2 blocked amines are suitable, for example, ketimines, oxazolidines, enamines and aldimines. Particularly suitable blocked amines are polyaldimines, which are obtained by reacting polyamines with two or more primary amino groups and aldehydes ALD1 of the formula (I ′). Further, particularly suitable blocked amines are polyaldimines, which are obtained by reacting polyamines with two or more primary amino groups and products resulting from the esterification of carboxylic acids, which are described in International Application WO-2004/013088-A1, in particular, products obtained by the esterification of lauric acid with 3-hydroxypivalaldehyde.

According to one embodiment, component K2 contains water.

A particularly preferred curable two-component composition contains, if necessary, other components, in particular, auxiliary substances and additives commonly used in polyurethane compositions, for example, the following:

plasticizers, for example, carboxylic acid esters, such as phthalates, for example dioctyl phthalate, diisononyl phthalate or diisodecyl phthalate, adipates, for example dioctyl adipate, azelates and sebacinates, organic esters of phosphoric acid and sulfonic acids or polybutenes;

non-reactive thermoplastic polymers, such as, for example, homo- and copolymers of unsaturated monomers, in particular from the group consisting of ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate and alkyl (meth) acrylates, in particular polyethylene (PE), polypropylene (PP), polyisobutylene, copolymers of ethylene and vinyl acetate (EVA) and atactic poly-b-olefins (ARAO);

solvents;

inorganic and organic fillers, for example, ground or precipitated calcium carbonates, which, if necessary, are coated with fatty acids, in particular stearates, barite (BaSO ₄ , also called barium sulfate), silica flour, calcined kaolins, aluminum oxides, aluminum hydroxides silicic acids, in particular finely divided silicic acids from pyrolysis processes, carbon black, in particular industrial carbon black (referred to as “carbon black” in the following context), polyvinyl chloride powders or hollow iki;

fibers, for example, of polyethylene;

pigments, for example, titanium dioxide or iron oxides;

catalysts that accelerate the hydrolysis of blocked amino groups, in particular acids, for example, organic carboxylic acids like benzoic acid, salicylic acid or 2-nitrobenzoic acid, organic carboxylic acid anhydrides like phthalic anhydride, hexahydrophthalic anhydride and hexahydromethylphthalic anhydride, esters of organic carboxylic acids, organic sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid or 4-dodecylbenzenesulfonic acid, sulfonic acid esters, etc. Gia organic or inorganic acid or mixtures of the aforementioned acids and acid esters;

catalysts that accelerate the reaction of isocyanate groups, for example, organotin compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dibutyltin diacetylacetonate and dioctyltin dilaurate, bismuth compounds like bismuth trioxide and trisamide dimorpholino diethyl ether and 1,4-diazabicyclo [2.2.2] octane;

rheology modifiers, such as thickeners or thixotropic agents, for example, urea compounds, polyamide waxes, bentonites or pyrogenic silicic acids;

reactive diluents and crosslinking agents, for example, monomeric diisocyanates, as well as oligomers and derivatives of these polyisocyanates, adducts of monomeric polyisocyanates with short chain polyols, as well as adipic acid dihydrazide and other dihydrazides, as well as polyisocyanates with blocked isocyanate groups indicated above;

blocked amines, for example, in the form of ketimines, oxazolidines, enamines or aldimines;

drying agents, such as molecular sieves, calcium oxide, highly reactive isocyanates, such as p-tosyl isocyanate, orthoformate esters, tetraalkoxysilanes, such as tetraethoxysilane;

organoalkoxysilanes, hereinafter also referred to as "silanes", such as, for example, epoxysilanes, (meth) acrylsilanes, isocyanatosilanes, vinylsilanes, carbamatosilanes, alkylsilanes, S- (alkylcarbonyl) mercaptosilanes and aldiminosilanes, as well as oligomeric forms of these silanes;

stabilizers against exposure to heat, light and UV radiation;

flame retardant substances;

surfactants, such as wetting agents, spreading agents, deaerating agents or anti-foaming agents;

biocides, such as, for example, algicides, fungicides or mushroom growth inhibiting substances.

When using these other constituents, it is preferable to pay attention to the fact that they do not greatly impair the storage stability of the respective components K1 and K2 of the composition. If such additives are available as an integral part of component K1, care must be taken to ensure that these additives do not cause significant cross-linking of isocyanate groups during storage. In particular, this means that the additives used in this way should not contain any water or contain at most trace amounts of water. It may be rational to chemically or physically dry the known additives before introducing into component K1.

In the case of component K2, along with these additives, further auxiliary substances and additives are additionally possible that are not capable or only briefly able to be stored together with free isocyanate groups. In particular, these are other catalysts, in particular, tertiary amines and metal compounds.

Obtaining both components K1 and K2 is carried out separately from each other, in the case of component K1 with the exception of moisture. Both components K1 and K2 are separately stable during storage, that is, they, each, in a suitable packaging or device, such as a barrel, bucket, bag, cartouche or bottle, can be stored for a period of time before use, for example, for several months, without changing them, to the extent relevant to their use, in relation to their respective properties.

For applying a two-component composition, both components K1 and K2 are mixed with each other. It should be noted that the ratio of the components of the mixture is chosen so that the components reactive with respect to the isocyanate groups are in a suitable ratio to the isocyanate groups of the component K1. In particular, the ratio is from 0.1 to 1.1, preferably from 0.5 to 0.95, particularly preferably from 0.6 to 0.9, the equivalent of the sum of the available hydroxyl groups, amino groups, mercapto groups and protected amino groups per equivalent of isocyanate groups, the protected amino groups being doubled in the form of oxazolidine groups. During curing, excess isocyanate groups react with moisture, in particular with air moisture.

The mixing of both components K1 and K2 is carried out using a suitable method, for example, in a static mixer. Mixing can be carried out continuously or intermittently. The mixed composition is then applied to the substrate, if necessary, using a suitable means for applying. In this case, it must be ensured that between mixing the components and the application does not take too much time, since due to too strong preliminary reaction of the components of the mixed composition before application, the function of the cured composition may be impaired, for example, by the fact that adhesion to the substrate is obtained only unsatisfactory or delayed. The maximum period of time during which a mixed composition is to be applied is called “vitality”.

After mixing the components K1 and K2, curing begins. In this case, the groups of component K1, which are reactive with respect to the isocyanate groups — hydroxyl groups, primary and secondary amino groups, and mercapto groups — react with isocyanate groups. If the composition contains blocked amines, then they also react with isocyanate groups, provided that their blocked amino groups come in contact with moisture, for example, moisture from the air. Finally, excess isocyanate groups react directly with water, in particular with moisture from the air. As a result of these reactions, the composition cures to form a solid material; this process is also referred to as crosslinking.

The described curable composition has several advantages.

The aldehyde ALD1 of the formula (I ′) contains one tertiary amino group. Such aldehydes can therefore have a catalytic effect on the reaction of isocyanate groups and thus accelerate curing. Moreover, it is preferable that its basicity is relatively low, since strongly basic tertiary amines can disrupt the hydrolysis of existing, if necessary, aldimino groups and / or can excessively accelerate the direct reaction of isocyanate groups, in particular, with water, which may result in incomplete or uncontrolled curing.

Further, the aldehyde ALD1 of the formula (I ′) acts as a hardener for the polyisocyanates, since in the residues R ^{4 ′} and R ^{5 ′ it} together contains at least two hydroxyl groups and therefore reacts with the isocyanate groups by chain extension or crosslinking of the corresponding polymer and does not lead to chain breaks.

By incorporating the aldehyde ALD1 into the cured polymer, also potentially catalytically tertiary amino groups are covalently incorporated into the resulting polymer. After incorporation into the polymer, the catalytic activity of the tertiary amino group due to its limited mobility is significantly reduced, which may be an advantage for the strength of the material.

Aldehyde groups are preserved during curing and are also incorporated into the cured material. They can be used, if desired, for the subsequent reactions.

Another advantage of the compositions described is the relatively low odor of ALD1 aldehydes. Due to this, the compositions before, during and after curing hardly have a smell, which certainly cannot be expected in the presence of aldehydes.

Preferred applications of the described curable compositions are adhesives, sealants, grouting materials, coatings, flooring, paints, varnishes, primers or foams.

A further aspect of the present invention relates to a method for bonding a substrate S1 to a substrate S2, which comprises the steps of:

i) applying the above curable composition to a substrate S1;

ii) contacting the applied composition with the substrate S2 for an unlimited time connection;

or

i ') applying the above composition to the substrate S1 and to the substrate S2;

ii ') contacting the applied composition with each other for an unlimited connection time;

moreover, the substrate S2 consists of the same material as the substrate S1, or another material.

A further aspect of the present invention relates to a sealing method. It includes a stage:

i ”) applying the above curable composition between the substrate S1 and the substrate S2, so that the composition is in contact with the substrate S1 and the substrate S2;

moreover, the substrate S2 consists of the same material as the substrate S1, or another material.

Usually the sealant is pressed into the so-called joint.

A further aspect of the present invention relates to a method for coating a substrate S1. It includes a stage:

i '”) applying the above curable composition to the substrate S1 for an unlimited connection time.

In the case of these three methods, suitable substrates S1 and / or S2 are, for example, inorganic substrates such as glass, glass ceramics, concrete, mortar, brick, tile, gypsum and natural stones such as granite or marble; metals or alloys such as aluminum, steel, non-ferrous metals, galvanized metals; organic substrates such as leather, fabrics, paper, wood, resin-bonded wood materials, resin-textile composite materials, plastics, such as polyvinyl chloride (unplasticized and plasticized PVC), copolymers of acrylonitrile, butadiene and styrene (ABS), SMC (sheet molded materials) , polycarbonate (PC), polyamide (PA), polyesters, PMMA (polymethyl methacrylate), epoxies, polyurethanes (PUR), polyoxymethylene (POM), polyolefins (PO), in particular, treated on the surface with plasma, corona discharge or flame and polyethylene (PE) or polypropylene (PP), copolymers of ethylene and propylene (EPM) and ternary copolymers of ethylene, propylene and diene (EPDM); coated substrates, such as powder coated metals or alloys; as well as paints and varnishes, in particular automotive varnishes.

The substrates, if necessary, can be pretreated before applying the composition. Such pretreatments include, in particular, physical and / or chemical cleaning methods, such as, for example, grinding, sandblasting, brushing or the like, or treatment with cleaners or solvents or applying an adhesion enhancing agent, an adhesion enhancing agent solution, or primer coating.

Application of the curable composition can be carried out in a wide range of temperatures. For example, the composition can be applied at room temperature, however, it can also be applied at lower, as well as at higher temperatures.

After applying the described compositions as an adhesive, sealant, pouring compound, coating, flooring, paint, varnish, primer or foam, the product is obtained. This product is, in particular, a structure, in particular, a construction of an overhead or underground structure, or an industrial product or consumer product, in particular a window, a household machine, or a vehicle, in particular a water or land vehicle, preferably a car, a bus, truck or ship, or an assembly part of a vehicle, or a product of the furniture, textile or packaging industry.

Examples

1. Description of measurement methods

Viscosity is measured using a Physica UM thermostatic cone-plane viscometer (cone diameter 20 mm, cone angle 1 °, distance between cone apex and plane 0.05 mm, shear rate 10-1000 s ^-1 ).

The amine content, that is, the total content of amino groups and, if any, blocked amino groups (aldimino groups) in the obtained compounds, is determined titrometrically (using 0.1N HClO ₄ in glacial acetic acid with respect to crystalline violet) and always indicate in mmol N / g

The pK _a value in the case of conjugated acid of Mannich base is determined approximately by the potential of incomplete neutralization by potentiometric titration of approximately 1 mmol of Mannich base in 50 ml of water with 0.1 N. HCl.

Infrared spectra were recorded on a FT-IR 1600 Perkin-Elmer instrument in the form of undiluted films on a horizontal unified ATR measuring unit using a ZnSe crystal; absorption bands are indicated in wave numbers (cm ^-1 ) (measurement range: 4000-650 cm ^-1 ); the addition of sh (shoulder) indicates a band appearing in the form of a shoulder, the addition of br (ears.) indicates a broad band.

GC / MS (gas chromatography / mass spectrometry) is carried out using the following conditions: Optima-5-MS column, 30 m × 0.25 mm, film thickness 0.5 μm; the heating rate of 15 ° C / min from 60 ° C to 320 ° C, then incubated for 15 minutes at a temperature of 320 ° C; carrier gas: helium (He), 14 lbs / ^in2; flow division: 15 ml / min; EI ⁺ ionization method (electron impact ionization method with the formation of positive ions). In the case of a gas chromatogram, the retention time of the product signal (t _R ) is indicated. In the case of the mass spectrum, only the largest peak (in the form m / z) is indicated; relative intensity (in%) and, when possible, the estimated location of the molecular fragment is indicated in parentheses.

2. Obtaining aldehydes

Example 1: Aldehyde ALD-1

3- (N-bis (2-Hydroxyethyl) amino) -2,2-dimethylpropanal

83.4 g (1.00 mol) of a 36% aqueous solution of formaldehyde and 75.7 g (1.05 mol) of isobutyraldehyde are introduced into a round-bottom flask under nitrogen atmosphere. With good stirring and ice-cooling, 105.1 g (1.00 mol) of diethanolamine are slowly added dropwise from a dropping funnel, and it is important that the temperature of the reaction mixture does not rise above 20 ° C. Upon completion of the addition, leave to mix for one hour at room temperature. The resulting clear, colorless reaction mixture was stirred in an oil bath under reflux at 80 ° C for 2 hours, cooled to room temperature and the volatile constituents were distilled off at a temperature of 80 ° C in a vacuum of a water-jet pump. 181.2 g (96% of theory) of the crude product are obtained in the form of a clear yellowish oil having an amine content of 5.40 mmol N / g and a viscosity of 23.7 Pa · s at a temperature of 20 ° C. The crude product, along with 3- (N-bis (2-hydroxyethyl) amino) -2,2-dimethylpropanal, contains smaller amounts of 3-hydroxy-2,2-dimethylpropanal, N- (2-hydroxyethyl) oxazolidine and N- (2-hydroxyethyl) -2-isopropyl-oxazolidine (according to the GC / MS study).

pK _a is approximately 7.1.

IR: 3358 ears. (OH), 2950, 2929 (shoulder), 2913, 2870, 2830, 2719 (shoulder, ears) (ССО), 1721 (С = О), 1464, 1391, 1359, 1302 ears, 1206, 1147, 1078 (shoulder), 1037, 966, 940, 920, 883, 786.

GC / MS: t _R = 10.3 min.

Mass spectrum: 189 (2, [M] ⁺ ), 172 (3, [M-OH] ^- ), 158 (11, [M-CH ₂ OH] ⁺ ), 128 (4), 118 (100, [ MC (CH ₃ ) ₂ CHO] ⁺ ), 116 (15), 102 (6), 98 (5), 88 (2, [118-CHOH] ⁺ ), 88 (21), 74 (50), 56 ( 51).

Example 2: Aldehyde ALD-2

3- (N-bis (2-Hydroxy-2-methylethyl) amino) -2,2-dimethylpropanal

Under similar conditions, as described in Example 1, 83.4 g (1.00 mol) of a 36% aqueous solution of formaldehyde are reacted with 75.7 g (1.05 mol) of isobutyraldehyde and 133.2 g (1, 00 mol) of diisopropanolamine and treated. 199.4 g (92% of theory) of the crude product are obtained in the form of a clear yellowish oil having an amine content of 4.87 mmol N / g and a viscosity of 8.2 Pa · s at a temperature of 20 ° C. The crude product, along with 3- (N-bis (2-hydroxy-2-methylethyl) amino) -2,2-dimethylpropanal, contains smaller amounts of 3-hydroxy-2,2-dimethylpropanal, N- (2-hydroxy- 2-methylethyl) oxazolidine and N- (2-hydroxy-2-methylethyl) -2-isopropyl-oxazolidine (according to the GC / MS study).

pK _a is approximately 7.1.

IR: 3392 ears. (OH), 2966, 2933, 2872, 2818, 2719 (shoulder, ears) (ССО), 1722 (С = О), 1461, 1409, 1375, 1328, 1274, 1209, 1158, 1130, 1090 (shoulder) , 1055, 1028 (shoulder), 978, 945, 914, 891, 864, 839, 818, 786.

GC / MS: t _R = 10.3 min.

Mass spectrum: 217 (3, [M] ⁺ ), 172 (30, [M-CH (CH ₃ ) OH] ⁺ ), 146 (44, [MC (CH ₃ ) ₂ CHO] ⁺ ), 144 (21 ), 130 (6), 126 (6), 116 (7), 114 (10), 102 (100, [146-C (CH ₃ ) OH] ⁺ ), 100 (18), 88 (16), 70 (38).

Example 3: Aldehyde ALD-3

3- (1- (4- (2-Hydroxyethyl) piperazino)) - 2,2-dimethylpropanal

Under similar conditions, as described in Example 1, 32.0 g (0.38 mol) of a 36% aqueous formaldehyde solution are reacted with 29.1 g (0.40 mol) of isobutyraldehyde and 50.0 g (0, 38 mol) of 1- (2-hydroxyethyl) piperazine and treated. 81.4 g (99% of theory) of the crude product are obtained in the form of a clear, viscous, orange-colored oil with an amine content of 9.17 mmol N / g.

IR: 3395 ears. (OH), 2944, 2869, 2806, 2768 (shoulder), 2695 (ССО), 1723 (С = О), 1458, 1402 (shoulder), 1374, 1361 (shoulder), 1349, 1336, 1318, 1294, 1276 , 1153, 1120, 1096, 1085 (shoulder), 1052, 1011, 974 (shoulder), 942, 913, 877, 834, 815, 771.

3. The use of aldehydes as hardeners in polyurethane compositions

Examples 4 and 5 and Comparative Examples 6 and 7:

Two-component casting masses

In the case of each example, the corresponding component parts of component K2 according to Table 1 in the indicated mass parts are weighed without preliminary drying in a polyethylene glass with a screw lock and using a centrifugal mixer (SpeedMixer ^TM DAC 150, FkackTek Inc .; 2 minutes at a speed of 3000 rpm ) mix until a homogeneous cream is formed. The mass parts of PMDI indicated in Table 1 are added to it as component K1 and mixed (30 seconds at a speed of 3000 rpm). The ratio between the isocyanate groups of component K1 and the hydroxyl groups of component K2 is always 1.1.

Table 1
The composition of two-component casting masses Example four 5 6
(comparison) 7
(comparison) component K1 PMDI ^a 38,0 37,2 37.7 29.7 component K2 castor oil ^b 22.5 22.5 22.5 22.5 diol of a dimeric fatty acid ^with 17.5 17.5 17.5 22.5 triol ^d 4.75 4.75 4.75 4.75 diol ^e ALD-1
5,0 ALD-2
5,0 TPG
5,0 - acid catalyst ^f 0.25 0.25 0.25 0.25 molecular sieve ^g 2.0 2.0 2.0 2.0 chalk ^h 48.0 48.0 48.0 48.0 ^a Desmodur ^® VKS 20 F, Bayer; NCO content = 30.0% of the mass;
^b Fluka; OH number = 165 mg KOH / g;
^with Sovermol ^® 908, Cognis; OH number = 200 mg KOH / g;
^d Desmophen ^® 4011 T, Bayer; OH number = 550 mg KOH / g;
^{e the} aldehydes ALD-1 from Example 1 and ALD-2 from Example 2 and TPG = tripropylene glycol, OH number = 583 mg KOH / g are used as diols.
^f salicylic acid (5% wt. in dioctyl adipate).
^{g Purmol ® 4ST, CU Chemie Uetikon} ; pore size 4 E.
^h Omyocarb ^® 5-GU, Omya.

The casting masses thus obtained are tested with respect to cure speed and mechanical properties. An indication of the curing rate is obtained, firstly, by determining the time until the stickiness (time until the tack disappears) of the casting mass immediately after mixing the components K1 and K2. To do this, the mixed composition is applied to cardboard with a layer thickness of about 2 mm and under normal climatic conditions (temperature 23 ° C ± 1 ° C, relative humidity 50% ± 5%), the time is determined, which lasts until, with a light touch of the surface coatings using a low density polyethylene (LDPE) pipette for the first time no more residues remain on the pipette. Secondly, the further course of curing is monitored by periodic measurements of shore hardness D according to DIN 53505.

In order to test the mechanical properties, the casting mass is poured in the form of a film with a layer thickness of about 2 mm onto a flat form of polytetrafluoroethylene, the film is cured for 7 days under normal climatic conditions and tested according to DIN EN 53504 for tensile strength, elongation at break and E-module (tensile by 0.5-3.0%; tensile speed: 10 mm / min).

The results of these tests are presented in Table 2.

table 2
Properties of two-component casting masses Example four 5 6
(comparison) 7
(comparison) lack of stickiness (min) ^and 34 27 108 48 shore hardness D after 1 day 83 89 71 60 shore hardness D after 3 days 93 94 84 75

Shore D hardness after 7 days 95 96 85 82 shore hardness D; annealed ^b 96 96 94 88 tensile strength (MPa) 14.8 30,4 9.6 8.1 elongation at break (%) 6 3,5 thirty 60 E-module (MPa) 370 770 175 one hundred ^{and the} time until the lack of stickiness (time to the disappearance of tack) in minutes;
^b 4 hours at 105 ° C, test samples cured for 7 days under normal climatic conditions.

4. The use of aldehydes to obtain aldimines

Example 8: Dialdimine Derived from ALD-1 Aldehyde

68.2 g of polyether diamine (polyoxypropylene diamine with an average molecular weight of about 240 g / mol; Jeffamine ^® D-230; Huntsman; amine content of 8.29 mmol N / g) and 117.6 g are introduced into a round bottom flask under nitrogen atmosphere. ALD-1 aldehyde from Example 1 and the mixture was stirred for one hour at room temperature. Then the volatile constituents are removed in vacuo (10 mbar, temperature 80 ° C). Yield: 177.1 g of a transparent yellow oil with an amine content of 6.78 mmol N / g and a viscosity of 9.8 Pa · s at a temperature of 20 ° C.

IR: 3391 ears. (OH), 2964, 2926, 2868, 1662 (C = N), 1469, 1456 (shoulder), 1392 (shoulder), 1373, 1294, 1106 (shoulder), 1049, 1004 (shoulder), 926, 903, 877 .

Example 9: Dialdimine Derived from ALD-2 Aldehyde

Under similar conditions, as described in Example 8, 27.2 g of isophorondiamine (Vestamin ^® IPD, Degussa; amine content of 11.67 mmol N / g) and 71.8 g of ALD-2 aldehyde from Example 2 are reacted. Yield: 93.2 g of a clear yellow "honey" with an amine content of 7.66 mmol N / g and a viscosity of 150 Pa · s at a temperature of 20 ° C.

IR: 3393 ears. (OH), 2962, 2926, 2868, 2837, 2818, 1662 (C = N), 1459, 1408, 1373, 1364, 1333, 1273, 1159, 1133, 1116 (shoulder), 1058, 1003, 976 (shoulder) 945, 909, 891 (shoulder), 864, 838.

Example 10: Dialdimine Derived from ALD-2 Aldehyde

Under similar conditions as described in Example 8 is reacted simple poliefirodiamina 37.7 g (polyoxypropylenediamine with a mean molecular weight of about 240 g / mol; Jeffamine ^® D-230; Huntsman; amine content of 8.29 mmol N / g) and 70.6 g of ALD-2 aldehyde from Example 2. Yield: 103.4 g of a brownish-yellow clear oil with an amine content of 6.26 mmol N / g and a viscosity of 4.0 Pa · s at a temperature of 20 ° C.

IR: 3419 ears. (OH), 2965, 2925, 2918, 2868, 2822 (shoulder), 1662 (C = N), 1457, 1408 (shoulder), 1373, 1331, 1274, 1196 (shoulder), 1106, 1089, 1059, 1019, 1002, 977, 944, 865, 838.

Example 11: Monoaldimine Derived from ALD-1 Aldehyde

Under similar conditions as described in Example 8 is reacted 6.55 g of 2- (2-aminoethoxy) ethanol ^{(DGA; Diglycol-amine ® Agent} , Huntsman; amine content of 9.39 mmol N / g) and 13.36 g of aldehyde ALD-1 from Example 1. Yield: 16.25 g of a clear yellow oil with an amine content of 7.18 mmol N / g and a viscosity of 3.4, Pa · s at a temperature of 20 ° C.

IR: 3358 ears. (OH), 2928, 2865, 2716 (shoulder), 1963 br., 1663 (C = N), 1467, 1459, 1391, 1358, 1285, 1238, 1123, 1044, 1003 (shoulder), 940 (shoulder), 924 (shoulder), 890, 815, 785, 770.

Claims (17)

1. Aldehyde ALD of the formula (I)

where R ¹ and R ² each independently of each other represents a monovalent hydrocarbon residue with 1-12 carbon atoms;
R ³ represents a hydrogen atom;
R ⁴ and R ⁵ either independently represent a monovalent aliphatic residue with 2-20 carbon atoms, which possibly contains 1-2 hydroxyl groups, provided that R ⁴ has at least one hydroxyl group, or
together they represent at least one hydroxyl group of a divalent aliphatic residue with 4-20 carbon atoms, which is part of a substituted heterocycle with 6 atoms in the cycle, and this cycle includes 2 heteroatoms in the form of tertiary amine nitrogen. 2. The aldehyde according to claim 1, characterized in that R ¹ and R ² respectively represent a methyl group. 3. The aldehyde according to claim 1 or 2, characterized in that the aldehyde ALD is the aldehyde ALD1 of the formula (I ′)

where R ¹ , R ² and R ³ are the substituents according to claim 1, and
R ^{4 ′} and R ^{5 ′} either independently represent a monovalent aliphatic residue with 2-20 carbon atoms that contains 1-2 hydroxyl groups, provided that R ^{4 ′} has at least one hydroxyl group and R ^{4 ′} and R ^{5 ′} together have at least two hydroxyl groups,
or together they represent at least two hydroxyl groups a divalent aliphatic residue with 4-20 carbon atoms, which is part of a substituted heterocycle with 6 atoms in the cycle, and this cycle includes two heteroatoms in the form of tertiary amine nitrogen. 4. The aldehyde according to claim 1 or 2, characterized in that R ⁴ and R ⁵ respectively represent a 2-hydroxyethyl group or a 2-hydroxypropyl group. 5. The method of producing an aldehyde according to any one of claims 1 to 4, characterized in that the aldehyde Y1 of the formula (II), the aldehyde Y2 of the formula (III) and a secondary aliphatic having at least one hydroxyl group amine C of the formula (IV) are reacted with cleavage of water to form the aldehyde ALD of formula (I)

where R ¹ and R ² each independently of each other represents a monovalent hydrocarbon residue with 1-12 carbon atoms;
R ³ represents a hydrogen atom;
R ⁴ and R ⁵ either independently represent a monovalent aliphatic residue with 2-20 carbon atoms, which possibly contains 1-2 hydroxyl groups, provided that R ⁴ has at least one hydroxyl group, or
together they represent at least one hydroxyl group of a divalent aliphatic residue with 4-20 carbon atoms, which is part of a substituted heterocycle with 6 atoms in the cycle, and this cycle includes 2 heteroatoms in the form of tertiary amine nitrogen. 6. The method according to claim 5, characterized in that the amine C is an amine C1, which has at least two hydroxyl groups and which is selected from the group consisting of diethanolamine, dipropanolamine, diisopropanolamine, 3- (2-hydroxyethylamino) -1- propanol and 3- (2-hydroxypropylamino) -1-propanol, N-methyl-2,3-dihydroxypropylamine, as well as the products of the interaction of ammonia with two molecules, each of which contains one epoxy group, in particular, a glycidyl ether group. 7. The method according to claim 5, characterized in that the amine C is a secondary amine C2, which has one hydroxyl group and which is selected from the group consisting of alkoxylates of primary amines, such as 2- (N-methylamino) ethanol, 2- (N -ethylamino) ethanol, 2- (N-propylamino) ethanol, 2- (N-isopropylamino) ethanol, 2- (N-butylamino) ethanol, 2- (N-cyclohexylamino) ethanol, 3- (N-methylamino) - 2-propanol, 3- (N-ethylamino) -2-propanol, 3- (N-propylamino) -2-propanol, 3- (N-isopropylamino) -2- propanol, 3- (N-butylamino) -2- propanol, 3- (N-cyclohexylamino) -2-propanol, 2- (N-ethylaminoethoxy) ethanol, as well as cycloaliph ble hydroxyamines such as 1- (2-hydroxyethyl) piperazine. 8. Curable composition containing at least one polyisocyanate and at least one aldehyde ALD of formula (I) according to any one of claims 1 to 4, possibly a catalyst and other auxiliary substances and additives, and the ratio of isocyanate groups to hydroxyl groups is in the range from 0.1 to 1.1. 9. A curable composition containing at least one polyisocyanate and at least one aldehyde ALD1 of the formula (I ′) according to any one of claims 3, 4, possibly a catalyst and other auxiliary substances and additives, the ratio of isocyanate groups to hydroxyl groups being a range from 0.1 to 1.1. 10. Curable composition according to claim 9, characterized in that the isocyanate groups of said at least one polyisocyanate are in the form of blocked isocyanate groups. 11. Curable composition according to claim 9, characterized in that it is a two-component composition consisting of component K1 and component K2, contained separately from each other, and component K1 is a polyisocyanate P selected from the group comprising PI polyisocyanate in the form monomeric di- or triisocyanate or oligomer of monomeric diisocyanate or a derivative of monomeric diisocyanate, in particular 1,6-hexamethylene diisocyanate (HDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (= isophorondiisocyanate il and IPDI), 2,4- and 2,6-toluene diisocyanate and any mixtures of these isomers (TDI) or 4,4′-, 2,4′- and 2,2′-diphenylmethanediisocyanate and any mixtures of these isomers (MDI), and component K2 is the aldehyde ALD1 of formula (I ') according to any one of claims 3, 4. 12. Curable composition according to claim 11, characterized in that the polyisocyanate P is an isocyanate-group PUP polyurethane polymer, which is obtained by reacting at least one polyol with at least one polyisocyanate, in particular monomeric diisocyanate. 13. Curable composition according to any one of paragraphs.11, 12, characterized in that the component K2 further comprises water. 14. The cured composition obtained by reacting the curable composition according to any one of claims 8 to 13 and water. 15. The cured composition according to 14, characterized in that the water is moisture in the air. 16. The use of a composition according to any one of paragraphs.8-15 for bonding, sealing products or coating the product. 17. The application of clause 16, wherein the product is a structure, in particular a construction of an above-ground or underground structure, or an industrial product or consumer product, in particular a window, a household machine, or a vehicle, in particular a water or land vehicle, preferably a car, bus, truck or ship, or an assembly part of a vehicle, or a product of the furniture, textile or packaging industry.