MX2008004208A - Reactive polyurethane-hot melt adhesive having a low isocyanate-monomer content - Google Patents

Abstract

The invention relates to relates to moisture-hardened hot melt adhesive which contains at least one polyurethane polymer of formula (I) which comprises aldimine groups and which is solid at room temperature, in addition to at least one polyurethane polymer P which comprises isocyanate groups, if q in formula (I) represents zero, or if X in formula (I) represents N-R8with R8as a substituent of formula (III). The compositions are characterised in that contain visibly less isocyanate monomers and are therefor particularly advantageous from a work-hygiene point of view.

Description

HOT FUSION ADHESIVES OF REAGENT POLYURETHANES WITH REDUCED CONTENT OF ISOCYANATE MONOMERS FIELD OF THE INVENTION The invention relates to the field of hot melt adhesives that harden with moisture. BACKGROUND OF THE INVENTION Hot melt adhesives (Hotmelts) are adhesives, which are based on thermoplastic polymers. These polymers are solid at room temperature, soften with heating to give a viscous liquid and can therefore be applied as melts. Contrary to the so-called warm melt adhesives (Warmmelts), which have a pasty consistency and are easily applied at elevated temperatures, typically in the area of 40 to 80 ° C, the application of hot melt adhesives is carried out at temperatures a from 85 ° C. When they cool down to room temperature, they harden, forming an adhesive force at the same time. Classic hot melt adhesives are non-reactive adhesives. With heating they soften or melt again with or which are not suitable for use at high temperatures. In addition, conventional hot melt adhesives often at temperatures well below the softening point tend to creep (river flow). These disadvantages are largely avoided in the case of reactive hot melt adhesives by the addition of reactive groups leading to crosslinking, in the polymer structure. In particular, the reactive polyurethane compositions are suitable as hot-melt adhesives. They are also called PUR-RHM abbreviated. They consist mostly of polyurethane polymers containing isocyanate groups, which are obtained by the reaction of suitable polyols with an excess of diisocyanate. After application, they quickly form a high adhesive strength by cooling and obtain their final properties, especially their resistance to heat and their resistance to environmental influences, by the subsequent cross-linking of the polyurethane polymer as a consequence of the reaction of the groups. isocyanate with moisture. Due to the distribution of the molar masses produced during the production of polyurethane polymers containing isocyanate, these PUR-RHM, however, contain very large amounts of unreacted monomeric diisocyanates, which at the application temperatures of 85 ° C at 200 ° C, typically from 120 ° C to 160 ° C common for hot melt adhesives, partially produce gases and as irritating, sensitizing or toxic materials can represent a danger to the health of workers. For this reason, different restrictions have been imposed to avoid the content of monomeric diisocyanates in reactive polyurethane compositions in general and especially in PUR-RHM. A similar proposal is the physical separation of the monomeric diisocyanate by means of distillation or extraction. These methods require multiple devices and therefore are expensive; furthermore, they are not applicable to all diisocyanates. Another proposal consists of the use of special diisocyanates with a group of different reactive isocyanates. For example, in document WO 03/033562 A1 the use of non-symmetrical MDl isomers, 2,4-diphenylmethyl diisocyanates, with which polyurethane polymers with a low content of monomeric diisocyanates with a low viscosity can be obtained in a simple manner. The disadvantage of this method is the insufficient availability of suitable diisocyanates on a technical scale, coupled with a high price. In addition, the losses in the crosslinking speed must be taken into account, since isocyanate groups with reduced reactivity are available for the crosslinking reaction. Finally, there is the proposal that during the reaction with polyols instead of using the monomeric diisocyanates use adducts or oligomers, to avoid humidity, described for example in DE 44 29 679 A1. Here the disadvantages of the viscosity and the reactivity of the products thus produced are presented. SUMMARY OF THE INVENTION The task of the present invention therefore consists in presenting polyurethane polymer compositions containing reactive isocyanate groups (PUR-RHM) which can be used as hot melt adhesives, which are obtained in a process simple from monomers and monomeric diisocyanates technically available, and having a low content of monomeric diisocyanates, are stable to storage and can be processed in an appropriate manner, and have a rapid crosslinking. Surprisingly it has been shown that the compositions according to claim 1 solve this task. They obtain at room temperature polyurethane polymers containing aldimino groups, which can be produced by means of the reaction of corresponding isocyanate groups with special compounds, which contain one or more aldimino groups as well as an active hydrogen. Another aspect of the invention relates to a cured composition according to claim 14, as well as to the use of the composition as a hot melt adhesive and an adhesion process and an article resulting from that type of process. In a final aspect the invention relates to a process for reducing the content of monomeric diisocyanates in polyurethane polymers having isocyanate groups or in compositions containing polyurethane polymers having isocyanate groups, in which the polyurethane polymers having isocyanate groups they are reacted with special compounds containing one or more aldimino groups as well as an active hydrogen. DETAILED DESCRIPTION OF THE INVENTION The object of the invention are compositions, which include: a) at least one polyurethane polymer of the formula (I) containing aldimino groups, solid at room temperature in the formula (I): p represents an integer between 1 or 2, preferably 1; q is an integer between 0 and 1, preferably 1, with the proviso that the sum of p and q is 2; R1 is either a monovalent hydrocarbon radical with 6 to 30 carbon atoms, which optionally has at least one heteroatom, especially in the ether-oxygen form, or R1 is a substituent of the formula (II) wherein R6 is a bivalent hydrocarbon radical of 2 to 20 carbon atoms which optionally has a heteroatom, especially in the form of ether-oxygen and R7 is a monovalent hydrocarbon radical of 1 to 20 carbon atoms; In addition R2 and R3 represent two mutually independent substituents representing a monovalent hydrocarbon radical of 1 to 12 carbon atoms, or R2 and R3 together form a single substituent representing a bivalent hydrocarbon radical of 4 to 20 carbon atoms, which is a part of a carbocyclic ring of 5 to 8 carbon atoms, preferably 6 carbon atoms, wherein said carbocyclic ring may optionally be substituted; R 4 represents a bivalent hydrocarbon radical having 2 to 12 carbon atoms which optionally contains at least one heteroatom, in particular in the form of ether-oxygen, in particular in the form of ether-oxygen or tertiary-nitrogen amine; R5 represents a polyurethane polymer having solid isocyanate groups at room temperature after separation of (p + q) isocyanate groups; and further X is O, S or N-R8 where R8 represents either a monovalent hydrocarbon radical of 1 to 20 carbon atoms, which optionally has at least one ester group of carboxylic acid, nitrile, nitro, acid ester phosphonic, sulfone or sulfonic acid ester, or R8 is a substituent of formula (III), with the meanings for R1, R2, R3 and R4 already mentioned b) at least one polyurethane polymer P containing isocyanate groups, in the case that q in formula (I) means zero, or in cases of X in formula (I) represents N-R8 with R8 being a substituent of the formula (III). The dotted lines in the formulas in this document represent links between the substituents and the corresponding molecular radical. In particularly preferred embodiments R2 = R3 = methyl and R1 is a hydrocarbon radical with 11 to 30 carbon atoms. The compositions are suitable as reactive hot melt adhesive compositions, also called abbreviated "PUR-RHM". The concept "polymer" The concept "polymer" in this document covers both a collectivity of chemical units, which will be prepared in relation to the degree of polymerization, molar mass and chain length of the different macromolecules, which are produced by means of the poly-reaction (polymerization, poly-addition, poly-condensation). The concept also encompasses derivatives of this collectivity of macromolecules of the polyreactions, compounds that are obtained by means of the reactions, as for example the additions or substitutions of functional groups in certain macromolecules and which can be chemically uniform or chemically non-uniform. The concept also includes so-called prepolymers, that is oligomeric pre-adducts whose functional groups participate in the formation of macromolecules.

The term "polyurethane polymer" covers all polymers which are produced according to the diisocyanate polyaddition process. This also includes those polymers that are completely or almost completely free of urethane groups. Examples of polyurethane polymers are polyether polyurethanes, polyester polyurethanes, polyether polyureas, polyureas, polyester polyureas, polyisocyanurate and polycarbodiimides. "Room temperature" means a temperature of 25 ° C. The polyurethane polymer of the formula (I) containing aldimino groups, solid at room temperature, is produced by the reaction of at least one aldimine of the formula (XI) containing an active hydrogen, with at least one polyurethane polymer having isocyanate groups D. The reactive groups carrying active hydrogen of the aldimine of the formula (XI) react in an addition reaction with an isocyanate group of the polyurethane polymer D. The concept " "active hydrogen" herein denotes a deprotonated hydrogen atom attached at a nitrogen, oxygen or sulfur atom. The term "reactive group containing an active hydrogen" denotes a functional group containing an active hydrogen, especially a primary or secondary amino group, a hydroxyl group, a mercapto group or a urea group.

In the formula (XI) R \ R2, R3, R4 and X have the meanings given for the compound of the formula (I). The aldimine of the formula (XI) is produced when at least one aliphatic aldehyde A is tightly hindered and at least one aliphatic amine B, corresponding to the formula H2N-R4-XH, which in addition to one or more primary amino groups also contains minus another reactive group containing an active hydrogen. The reaction between aldehyde A and amine B is carried out in a condensation reaction under the dissociation of water. These condensation reactions are well known and described, for example in Houben-Weyl, "Methoden der organischen Chemie", Vol. XI / 2, page 73 onwards. The aldehyde A is used in a stoichiometric or stoichiometric excess amount relative to the primary amine groups B. For production of the aldimine of the formula (XI) at least one spherically hindered aliphatic aldehyde A of the formula (IV) is used. in formula (IV) R1, R2 and R3 have the same meanings as indicated for formula (I). The aldehyde A is odorless. Under an "odor-free" substance is meant a substance that has such a low odor that it is not detectable to most humans, that is, it can not be felt with the nose. The aldehyde A for example is produced from a carboxylic acid R1-COOH and a β-hydroxyaldehyde of the formula (V) in an esterification reaction. This esterification can be carried out according to known methods, described for example in HoubeN-Weyl, "Methoden der organischen Chemie", Vol. VIII, pages 516-528. The β-hydroxyaldehyde of the formula (V), for example, is obtained by means of a cross-addition of aldol from formaldehyde (or oligomeric formaldehyde forms, such as paraformaldehyde or 1,3,5-trioxane) and an aldehyde from the formula (VI).

In formulas (V) and (VI) R2 and R3 have the same meaning as described for formula (I). As the carboxylic acids R1-COOH suitable for esterification with the β-hydroxyaldehydes of the formula (V), the following examples can be mentioned: saturated aliphatic carboxylic acids such as: oenanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, laurinic acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margarine acid, stearinic acid, nonadecanoic acid, araquinic acid; simple unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, erucic acid; polyunsaturated aliphatic carboxylic acids such as linolic acid, linoleic acid, elaeostearinic acid, arachidonic acid; cycloaliphatic carboxylic acid such as cyclohexanecarboxylic; arylaliphatic carboxylic acids such as phenylacetic acid; aromatic carboxylic acid such as benzoic acid, naphthoic acid, toluyl acid, anisic acid; isomers of those acids; mixtures of fatty acids obtained from the technical saponification of natural oils and fats such as, for example, rapeseed oil, sunflower oil, linseed oil, olive oil, coconut oil, palm kernel oil, palm oil; as well as monoalkyl- and aryl dicarboxylic acid ester, such as that obtained from the simple esterification of dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, bicarbonate 1, 12- docecanic, maleic acid, fumaric acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydrotherphthalic acid, 3,6,9-trioxaundecanic acid and similar polyethylene glycol derivatives, with alcohols such as methanol, ethanol, propanol, butanol, homologs and isomers of these alcohols. Preferred are caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linolic acid, linoleic acid, the isomers of those acids as well as the technical mixtures of fatty acids, which contain those acids. Especially preferred is lauric acid. Suitable aldehydes of the formula (VI) for the reaction with formaldehyde to β-hydroxyaldehydes of the formula (V) are, for example, isobutyraldehyde, 2-methylbutyraldehyde, 2-ethylbutyraldehyde, 2-methylvaleraldehyde, 2-ethylcapronaldehyde, cyclopentanecarboxaldehyde, cyclohexanecarboxaldehyde, 1, 2,3,6-tetrahydrobenzaldehyde, 2-methyl-3-phenylpropionaldehyde, 2-phenylpropionaldehyde and diphenyl-acetaldehyde. Isobutyraldehyde is preferred. Suitable ß-hydroxyaldehydes of the formula (V) are, for example, the products of the reaction of formaldehyde with the aforementioned aldehydes as suitable for the formula (VI). 3-hydroxypivaldehyde is preferred. Amine B is an aliphatic amine, which in addition to one or more primary amino groups contains at least one other reactive group, which contains an active hydrogen. The term "primary amino group" in the present document represents an NH2 group, which is linked to an organic radical, while the term "secondary amino group" designates an NH group, which is bonded in two organic radicals. The term "aliphatic amine" designates compounds "which at least contain an amino group, which is attached to an aliphatic, cycloaliphatic or arylaliphatic radical.They differ from aromatic amines in which the amino group is directly attached to an aromatic radical, such as for example in aniline or 2-aminopyridine: As amine B, the following compounds are suitable, for example: aliphatic hydroxyamines, such as 2-aminoethanol, 2-methylaminoethanol, 1-amino-2-propanol, 3-amino-1-propanol, 4-amino-1-butanol, 4-amino-2-butanol, 2-amino-2-methylpropanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 7-amino-1-heptanol, 8- amino-1-octanol, 10-amino-1-decanol, 12-amino-1-dodecanol, 4- (2-aminoethyl) -2-hydroxyethylbenzene, 3-aminomethyl-3,5,5-trimethyl-cyclohexanol; a derivative carrier of a primary amino group of glycols such as diethylene glycol, dipropylene glycol, dibutylene glycol and oligomers and polymers of those glycols, for example 2- (2-aminoethoxy) -ethanol, triethylene glycol monoamine, s- (2-hydroxymethylethyl) -? - (2- aminomethyl ethoxy) -poly (oxy (methyl-1,2-ethanediyl)); a hydroxyl group and derivatives carrying a primary amino group of trivalent or poly-alkoxylated alcohols or polyalkoxyethylated diamines; products of the simple cyanoethylation and subsequent hydration of glycols, for example 3- (2-hydroxyethoxy) -piOpylamine, 3- (2- (2-hydroxyethoxy) -ethoxy) -propylamine, 3- (6-hydroxyhexyloxy) -propylamine; - aliphatic mercaptoamines such as 2-aminoethiol (cystamine), 3-aminopropantiol, 4-amino-1-butantiol, 6-amino-1-hexantiol, 8-amino-1-octantiol, 10-amino-1-decantiol, 12-amino -1-dodecantiol; aminothioglucose such as 2-amino-2-deoxy-6-thioglucose; - bi- or polyvalent aliphatic amines which, in addition to one or more primary amino groups, carry a secondary amino group such as N-methyl-1,2-ethanediamine, N-ethyl-1,2-ethanediamine, N-butyl-1, 2 -etandiamine, N-hexyl-1, 2-ethanediamine, N- (2-ethylhexyl) -1, 2-ethanediamine, N-cyclohexyl-1,2-ethanediamine, 4-aminomethyl-piperidine, 3- (4-aminobutyl) -piperidine, N-amino-ethylpiperazine, diethylenetriamine (DETA), bis-hexamethylenetriamine (BHMT); di- and triamine of the cyanoethylation or cyanobutylation of mono- and diamines, for example N-methyl-1,3-propanediamine, N-ethyl-1,3-propanediamine, N-butyl-1,3-propanediamine, N-hexyl -1,3-propanediamine, N- (2-ethylhexyl) -1,3-propanediamine, N-dodecyl-1,3-propanediamine, N-cyclohexyl-1, 3-propanediamine, 3-methylamino-1-pentylamine, 3 -ethylamino-1-pentylamine, 3-butylamino-1-pentylamine, 3-hexylamino-1-pentylamine, 3- (2-ethylhexyl) amino-1-pentylamine, 3-dodecylamino-1 -pentylamine, 3-cyclohexylamino-1- pentylamine, dipropylenetriamine (DPTA), N3- (3-aminopentyl) -1, 3-pentanediamine, N5- (3-amino-propyl) -2-methyl-1,5-pentanediamine, N5- (3-amino-1- ethylpropyl) -2-methyl-1,5-pentanediamine and fatty diamines such as N-cocoalkyl-1,3-propanediamine, N-oleyl-1,3-propanediamine, N-soyaalkyl-1,3-propanediamine, N-tallowalkyl- 1,3-propanediamine or N- (C? 6-22-alkyl) -1,3-propanediamine, which is obtained under the trade name Duomeen® from Akzo Nobel; the products of the Michael addition of di- or primary aliphatic polyamines with acrylonitrile, diesters of maleic or fumaric acid, diesters of citraconic acid, esters of acrylic and methacrylic acids and diester of itaconic acid, used in a 1: 1 molar ratio; - trisubstituted ureas bearing one or more primary amino groups, such as N- (2-aminoethyl) -ethyleneurea, N- (2-aminoethyl) -propyleneurea or N- (2-aminoethyl-N'-methylurea) Hydroxy- and mercaptoamines Particularly suitable aliphatics are those in which the primary amino groups of the hydroxyl or mercapto group are separated by a chain of at least 5 atoms, or by means of a ring, such as, for example, 5-amino-1-pentanol, 6-amino -1-hexanol, 7-amino-1-heptanol, 8-amino-1-octanol, 10-amino-1-decanol, 12-amino-1-dodecanol, 4- (2-aminoethyl) -2-hydroxyethylbenzene, 3 -aminomethyl-3, 5, 5-trimethyl-cyclohexanol, 2- (2-aminoethoxy-ethanol, triethylene glycol-monoamine, s- (2-hydroxymethylethyl) -? - (2-aminomethylethoxy) -poly (oxy (methyl-1, 2-ethanediyl)), 3- (2-hydroxyethoxy) -propylamine, 3- (2- (2-hydroxyethoxy) -ethoxy) -propylamine, 3- (6-hydroxyhexyloxy) -propylamine, 6-amino-1-hexantiol, 8-amino-1-octantiol, 10-amino-1-decantiol and 12-amino-1-dodecantiol As amines B, alkylamines are preferred. bivalent or polyvalent, which in addition to one or several primary amino groups carry a secondary amino group, especially N-methyl-1,2-ethanediamine, N-ethyl-1,2-ethanediamine, N-cyclohexyl-1, 2-ethanediamine, N-methyl-1,3-propanediamine, N-ethyl-1,3-propanediamine, N-butyl-1,3-propanediamine, N-cyclohexyl-1,3-propanediamine, 4-aminomethyl-piperidine, 3- (4-aminobutyl) -piperidine, DETA, DPTA, BHMT and fatty diamines such as N-cocoa-alkyl-1, 3-propanediamine, N-oleyl-1,3-propanediamine, N-soya-alkyl-1,3-propanediamine and N-tallowalkyl-1,3-propanediamine. Preferred are aliphatic hydroxy- and mercaptoamine in which the primary amino groups of the hydroxy or mercapto group are separated by a chain of at least 5 atoms, or by means of a ring, such as for example 5-a non-1-pentanol , 6-amino-1-hexanol and its superior analogs 4- (2-aminoethyl) -2-hydroxyethylbenzene, 3-aminomethyl-3,5,5-trimethyl-cyclohexanol, 2- (2-aminoethoxy) -ethanol, triethylene glycol- monoamine and its oligo- and polymers, 3- (2-hydroxyethoxy) -propylamine, 3- (2- (2-hydroxyethoxy) -ethoxy) -propylamine as well as 3- (6-hydroxyhexyloxy) -propylamine. The reaction between an aldehyde A and an amine B leads to a hydroxyaldimines, when hydroxyamine is used as amine B; to mercaptoaldimine when mercaptoamine is used as amine B; to aminoaldimines, when, as amine B, a bivalent or polyvalent amine is used, which in addition to one or several primary amino groups carries one or more secondary amino groups, or to urea aldimines when, as amine B, a trisubstituted urea is used, which carries one or several amino groups. As amine B, hydroxyamines and mines with one or two primary amino groups and a secondary amino group are preferred. In one embodiment the aldimines of the formula (XI) have a substituent N-R8 as substituents of X. That type of aldimines of the formula (XI) can be produced because the spherically hindered aliphatic aldehyde A of the formula (IV) is react with at least one aliphatic primary bi- or polyvalent amine of the formula H2N-R4-NH2 in a first step to produce an intermediate of the formula (VII), in addition to one or more aldimine groups still have at least one , preferably a primary amino group, and this intermediate product then in a second step in an addition reaction with a Michael receptor of the formula (VIII) is reacted in a ratio of the number of double bonds: number of NH2 = groups eleven. Thus an aminoaldimine is formed, which in addition to one or more aldimine groups still contains at least one, preferably a secondary amino group.

In the formula (VII), R1, R2, R3 and R4 have the same meanings described for the formula (I).

Thus, aldimines of the formula (XI) are formed, in which X represents the radical N-R8, and R8 represents a monovalent hydrocarbon radical of the formula (IX) or (IX). In formulas (VIII), (IX) and (IX) R9 represents a radical which is selected from the group consisting of -COOR13, -CN, -NO2, -PO (OR13) 2, -SO2R13 and -SO2OR13 and R10 is a hydrogen atom or a radical of the group consisting of -R13, -COOR13 and -CH2COOR13 and R11 and R12 independently of each other independently represent hydrogen atoms or a radical of the group consisting of -R13, -COOR13 and -CN, wherein R13 is a monovalent radical of 1 to 20 carbon atoms. The amine C is an aliphatic amine with at least two primary amino groups. Examples of suitable C-amines are aliphatic diamines such as ethylene diamine, 1,2- and 1,3-propanediamine, 2-methyl-1,2-propanediamine, 2,2-di-methyl-1,3-propanediamine, 1, 3- and 1,4-butanediamine, 1,3- and 1,5-pentanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,6-hexamethylenediamine (HMDA), 2, 2, 4 and 2, 4, 4-trimethylhexamethylenediamine and its mixtures (TMD), 1,7-heptanediamine, 1,8-octanediamine, 2,4-dimethyl-1,8-octanediamine, 4-amino-methyl-1,8-octanediamine, 1 9-nonanediamine, 2-methyl-1, 9-nonanediamine, 5-methyl-1, 9-nonanediamine, 1, 10-decanediamine, isodecanediamine, 1,1-undecanediamine, 1, 12-dodecandiamine, methyl-bis- (3 -aminopropyl) amine, 1, 5-diamino-2-methylpentane (MPMD), 1,3-diaminopentan (DAMP), 2,5-dimethyl-1,6-hexamethylenediamine, cycloaliphatic diamines such as 1, 2-, 1,3 - and 1, 4-diaminocyclohexane, bis- (4-aminocyclohexyl) -methane (H12MDA), bis- (4-amino-3-methylcyclohexyl) -methane, bis- (4-amino-3-ethylcyclohexyl) -methane, bis - (4-amino-3,5-dimethylcyclohexyl) -methane, bi s- (4-amino-3-ethyl-5-methylcyclohexyl) -methane (M-MECA), 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (= isophoronediamine or IPDA), 2- and 4- methyl-1, 3-diaminocyclohexane and its mixtures, 1, 3- and 1,4-bis- (aminomethyl) cyclohexane, 1-cyclohexylamino-3-aminopropan, 2,5 (2,6) -bis- (aminomethyl) - bicyclo [2.2.1] heptane (NBDA, produced by Mitsui Chemicals), 3 (4), 8 (9) -bis- (aminomethyl) -trichloride [5.2.1.02,6] decane, 1,4-diamino-2, 2,6-trimethylcyclohexane (TMCDA), 3,9-bis- (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, arylaliphatic diamines such as 1,3-xylylenediamine (MXDA), 1,4-xylylenediamine (PXDA) , aliphatic polyamines containing ether groups such as bis- (2-aminoethyl) ether, 4,7-dioxadecan-1, 10-diamine, 4,9-dioxadodecan-1, 12-diamine and their higher oligomers, polyoxyalkylene diamines which can obtained for example under the name Jeffamine® (produced by Huntsman Chemicals). Diamines are preferred, in which the primary amino groups are separated by a chain of at least 5 atoms, or by means of a ring, such as, in particular, 1,5-diamino-2-methylpentane, 1,6-hexamethylene and the like. amine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine and their mixtures, 1,10-decanediamine, 1, 12-dodecanediamine, 1,3-and 1,4-diaminocyclohexane, bis- (4-aminociclohexyl) -methane, bis- (4-amino-3-methylcyclohexyl) -methane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 1,3- and 1,4-bis- (aminomethyl) cyclohexane, , 5 (2,6) -bis- (aminomethyl) -bicyclo [2.2.1] heptane, 3 (4), 8 (9) -bis- (aminomethyl) -trichyclo- [5.2.1.02'6] decane, 1 , 4-diamino-2,2,6-trimethylcyclohexane (TMCDA), 3,9-bis- (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, 1, 3 and 1, 4 -xylylenediamine, as well as polyoxyalkylene diamines obtainable, for example, under the name Jeffamine® (produced by Huntsman Chemicals). Examples of suitable Michael receptors of the formula (VIII) are maleic or fumaric acid diester such as dimethyl maleinate, diethyl maleinate, dibutyl maleinate, diethyl fumarate; diester of citraconic acid such as dimethyl citraconate; acrylic or methacrylic acid ester such as methyl (meth) acrylate, ethyl (meta) acrylate, butyl (meta) acrylate, lauryl (meta) acrylate, stearyl (meta) acrylate, tetrahydrofuranyl (meta) acrylate, ( meta) isobomyl acrylate; diester of itaconic acid such as edimethyl itaconate; cinnamic acid ester such as methyl cinnamate; diester of vinylphosphonic acid, such as vinylphosphonic acid dimethyl ester, vinylsulfonic acid ester, especially vinyl sulfonic acid ester; vinylsulfones; vinyl nitriles such as acrylonitrile, 2-pentenenitrile or fumaronitrile; 1-nitroethylene as ß-nitrostyrene and Knoevenagel condensation products, such as those made from malonic acid esters and aldehydes such as formaldehyde, acetaldehyde or benzaldehyde. Preferred are maleic acid diester, acrylic acid ester, phosphonic acid diester and vinyl nitriles. The reaction of aldehyde A with amine C to produce the intermediate of formula (VII) is carried out in a damnation reaction under the dissociation of water, as described above for the reaction of aldehyde A with amine B. The stoichiometry between the aldehyde A and the amine C is selected such that it contains m mol of aldehyde A per 1 mol of amine C. A solvent-free production process in which the water formed during the condensation is removed from the mixture is preferred. of reaction by means of the application of vacuum.

The reaction of the intermediate of the formula (VII) with the Michael receptor of the formula (VIII) is carried out, for example, because the intermediate is mixed with a stoichiometric or slightly over-stoichiometric amount of the Michael receptor of the formula (VIII). ) and the mixture is heated to temperatures of 20 to 100 ° C until complete transformation of the intermediate to aldimine of the formula (XI). The reaction is preferably carried out without the use of solvents. The aldimines of the formula (XI) may optionally be in equilibrium with the cyclic forms, such as those exemplified in formula (X). These cyclic forms in the case of aminoalimines are cyclic aminals for example imidazolidines or tetrahydropyrimidine; in the case of hydroxyaldimines they are cyclic aminoacetates, for example oxazolidines or tetrahydrooxazines, in the case of mercaptoaldimines they are cyclic thioamines such as for example triazolidines or tetrahydrothiazines.

In formula (X) R1, R2, R3, R4 and X have the same meanings as indicated for formula (I). Surprisingly, most of the aldimines of the formula (XI) do not tend to cyclization. Especially for the amidoaldimines it can be shown by means of Rl and NMR spectroscopic methods that these compounds are mostly in the form of open-chain aldimine, whereas the cyclic form, that is, the aminal form, is not present or only in footprints This contradicts the behavior of the aminoaldimines according to the state of the art which for example are described in US 4,404,379 and US 6,136,942, each of which is mainly in the form of cycloaminal. Also the hydroxy or mercaptoamines, in which the primary amino groups of the hydroxyl or mercapto group are separated by a chain of at least 5 atoms, or by means of a ring, show little cyclization. The constant absence of cyclic structures in which are aldimines of the formula (XI), are advantageous especially in view of their use with isocyanate-containing compositions, since the aldimines are constantly free of the basic nitrogen atoms present in aminals, oxazolidines and thioaminals, which can reduce the storage stability of the isocyanate-containing composition. The aldimines of the formula (XI) are odorless. Under the right conditions, they are stable to storage especially under the exclusion of moisture. In the case of moisture entry the aldimino groups of the aldimines can be formally hydrolyzed to amino groups through intermediate stages, where the aldehyde A used for the production of the aldimine will be released. Since this hydrolysis reaction is reversible and the chemical equilibrium clearly remains on the aldimine side, it is assumed that in the presence of groups reactive towards the amines only a part of the aldimino groups are totally or partially hydrolyzed. As the polyurethane polymer D suitable for the production of a solid polyurethane polymer at room temperature and having aldimino groups of the formula (I) is a polyurethane polymer D of the formula (XII) which is solid at room temperature and that presents isocyanate groups.

In formula (XII) p, q and R5 have the same meaning given in formula (I). As diols for the production of a polyurethane polymer D, polyether diols, polyester diols or polycarbonate diols and mixtures of these diols can be used in particular. As polyether diols also called polyoxyalkylene polyols, those which are polymerization products of ethylene oxide, 1,2-propylene oxide, 1,2-or 2,3-butylene oxide, tetrahydrofuran or their mixtures are particularly suitable. , possibly polymerized with the aid of an initiator molecule with two or more active hydrogen atoms such as water, ammonia or compounds with several OH or NH groups, such as, for example, 1,2-ethanediol, 1,2- and 1,3-propandiol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomers of dipropylene glycols and tripropylene glycols, the isomers butanediols, pentanediols, hexanediols, heptanediols, octandiols, nonandiols, decandiols, undecanediols, 1, 3- and 1,4-cyclohexanedimethanol, bisphenol A, hydrophobic bisphenol A, aniline, as well as mixtures of the aforementioned compounds. Polyoxyalkylene diols, which have a low degree of unsaturation (measured according to ASTM D-2849-69 and given in milliequivalent unsaturation per gram of Diol (mEq / g)), produced for example with the aid of so-called double metal cyanide complex catalysts (DMC catalysts), as well as polyoxyalkylene diols with a higher degree of unsaturation, produced for example with the aid of anionic catalysts such as NaOH, KOH, or alkali alcohols. Particularly suitable polyether diols are polyoxyalkylene diols, in particular polyoxyethylene diols. Especially suitable are polyoxyalkylene diols with a degree of unsaturation of less than 0.02 mEq / g and with a molecular weight in the range of 1000-30O00 g / mol, as well as polyoxypropylene diols with a molecular weight of 400-800 g / mol. Also particularly suitable are so-called polyoxypropylene diols terminated in ethylene oxide ("EO-encapped" - ethylene oxide-encapped). The latter are special polyoxypropylene polyoxyethylene diols, which are obtained, for example, because the pure polyoxypropylene diols, after the completion of the polypropoxylation reaction with ethylene oxide, can be further alkoxylated and thus contain primary hydroxyl groups. The term "molecular weight" or "molar weight" in the present document designates the average molecular weight Mn. The most suitable polyether diols are those with a degree of unsaturation of less than 0.02 mEq / g and a molecular weight in the range of 7000 to 30,000 especially between 10,000 and 25,000 g / mol. For example those polyethers that are sold under the trade name Acclaim® by Bayer. Suitable polyester diols are those produced, for example, from divalent alcohols, such as, for example, 1,2-ethanediol, diethylene glycol, 1,2-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentadiol, 1,6 -hexandiol, neopentyl glycol, or mixtures of these alcohols with organic dicarboxylic acids or their anhydrides or ester such as, for example, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelanic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, acid fumaric acid, phthalic acid, isophthalic acid, terephthalic acid and hexahydrophthalic acid or mixtures of the aforementioned acids, as well as polyester diols of lactones such as for example e-Caprolactone. Especially suitable polyester diols are the polyester diols of adipic acid, azelanic acid, sebacic acid or dodecanedicarboxylic acid as dicarboxylic acid and of hexanediol as neopentyl glycol as divalent alcohol. The polyester diols preferably have a molecular weight of from 1000 to 15,000 g / mol, in particular from 1500 to 8000 g / mol, preferably from 1700 to 5500 g / mol. Particularly suitable are the semi-crystalline, amorphous crystalline and amorphous polyesters in the form of polyester of adipic acid / hexanediol, polyester of azelanic acid / hexanediol, polyester of dodecanedicarboxylic acid / hexanediol. Suitable liquid polyols at room temperature are not widely solids at temperatures below room temperature, for example at temperatures between 0 ° C and 25 ° C. Suitable polycarbonate diols are the aforementioned divalent alcohols - used for the formation of polyester diols - with dialkyl carbonates, diaryl carbonates or phosgene. Preferred diols are polyester diols and polycarbonate diols. Especially preferred diols are polyester diols, especially a mixture of an amorphous polyester diol and a crystalline or semi-crystalline diol, or a mixture of a liquid polyester diol at room temperature and a crystalline or semi-crystalline diol, or a mixture of a partially polyester diol crystalline and one crystalline. In the case where a liquid polyester diol is used at room temperature, it is not widely solid at temperatures below room temperature, for example at temperatures between 0 ° C and 25 ° C. As diisocyanates, for the production of a polyurethane polymer containing isocyanate groups D, aliphatic, cycloaliphatic or aromatic diisocyanates can be used, for example the following: 1,6-hexamethylene diisocyanate (HDI), 2-methylpentamethylene-1,5-diisocyanate, 2, 2,4- and 2,4,4-trimethyl-1,6-hexamethylene diisocyanate (TMDI), 1,2-dodecamethylene diisocyanate, lysine diisocyanate and lysine ester, cyclohexan-1, 3- and -1,4-diisocyanate and mixtures of those isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (= isophorone diisocyanate or IPDI), perhydro-2,4'- and -4,4'-diphenylmethane diisocyanate ( HMDI or H? 2MDI), 1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI), 1,3- and 1,4-bis- (isocyanato-methyl) -cyclohexane, m- and p- diisocyanate xylylene (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 , 2,4- and 2,6-toluylene diisocyanate and mixtures of these isomers (TDI), 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate and mixtures of these isomers (MDl), 1,3- and 1,4-phenylene diisocyanate, 2,3,5,6-tetramethyl-1,4-diisocyanatobenzene, naphthalene-1,5-diisocyanate ( NDI), 3,3'-dimethyl-4,4'-diisocyanatodiphenyl (TODI), oligomers and polymers of said isocyanates; as well as mixtures of the aforementioned isocyanates. Preferably they are MDl, TDI, HDI, H12MDI and IPDI. The production of the polyurethane polymer D takes place in a known manner directly from diisocyanates and diols, or by means of stepped adduction processes, such as those known for the chain elongation reactions. It is essential that the polyurethane polymer D present in isocyanate groups and that at room temperature is solid. In a preferred embodiment, the polyurethane polymer D is produced by a reaction of at least one diisocyanate and at least one diol, the isocyanate groups being opposite the hydroxyl groups in a stoichiometric excess.

Advantageously the ratio between the isocyanate and hydroxyl groups, briefly called "NCO / OH ratio", is 1.3 to 2.5, especially 1.5 to 2.2 The polyurethane polymer D has a molecular weight of preferably 1000 g / mol, especially one between 1200 and 50,000 g / mol, preferably one between 2000 and 30,000 g / mol. In addition the polyurethane polymer D presents (p + q) isocyanate groups, being (p + q) equal to 2. It is clear to the technician that the diols used for the production of the polyurethane polymer in general have a general technical quality and therefore represent mixtures of oligomers of different head lengths, monomer composition and OH functionality. The technical diols thus obtained, especially the polyether diols, thanks to their manufacturing process as well as a majority fraction of diols, also contain monools in such a way that their average OH functionality is not equal to 2 but is somewhat less than 2. On the other hand, by the use of trifunctional initiators, monomers or crosslinkers in addition to the diols and monools may also contain other fractions of thiols, such that the average OH functionality may also be somewhat greater than 2. The reaction between the aldimine of the formula (XI) and the compound D to give the polyurethane polymer containing aldimino groups of the formula (I) is carried out under known conditions, such as are typically used for the reactions between the reactive groups participating in the reaction, for example at 20 to 100 ° C. Preferably, it is carried out at a temperature at which the polyurethane polymer D is liquid. The reaction is carried out using a solvent or preferred without solvent. Optionally, additives such as, for example, catalysts, initiators or stabilizers can be used. The reaction for the aminoaldimine is preferably carried out without catalyst, while for the aldimines of hydroxy, mercapto and urea using a catalyst, such as those used for the urethanization reaction between isocyanates and alcohols, for example an organotin compound, an bismuth complex, a tertiary amine compound or a combination of those catalysts. If the reaction is carried out between the aldimine of the formula (XI) and the polyurethane polymer D to form the polyurethane polymer of the formula (I), stoichiomcally, this is a molar equivalent of active hydrogen of the aldimine (XI ) in a molar equivalent of isocyanate groups of the polyurethane polymer D, whereby the reactive groups are completely reacted, a dialdimine is obtained as the addition product of the formula (I). However, it is preferred to carry out the addition reaction between the aldimine of the formula (XI) and the polyurethane polymer D in a sub-stoichiomc manner, that is less than one molar equivalent of active hydrogen of the aldimine (XI) by one molar equivalent of isocyanate groups of the polyurethane polymer D. These are the isocyanate groups only partially reacting which leads to at least one polyurethane polymer of the formula (I) containing aldimino groups, which likewise contains isocyanate groups, ie q = 1 . The polyurethane polymers containing the aldimino group of the formula (I) are those of the formulas (la), (Ib) and (le), wherein R1, R2, R3 R4 and R5 have the meanings already mentioned and R8 represents a monovalent hydrocarbon radical with 1 to 20 carbon atoms, optionally having a group of carboxylic acid ester, nitrile, nitro, phosphonic acid ester, sulphone or sulfonic acid ester. The polyurethane polymers of the formula (I) containing the aldimino group are the same as the aldimines of the formula (XI) are odorless. Under the right conditions, especially excluding moisture, they are stable to storage. In the case of moisture entry the aldimino groups can be formally hydrolyzed to amino groups through intermediate stages, where the aldehyde A used for the production of the aldimine of the formula (XI) will be released.

In the absence of isocyanate groups, this is in the case of polyurethanes of the formula (I) with q = 0, it is assumed that only a part of the aldimino groups are hydrolyzed partially or totally, since this hydrolysis reaction It is reversible and the chemical equilibrium clearly remains on the side of the aldimine. In the case of polyurethane polymers of the formula (I) with q = 1, on the other hand, the free amino groups react with the isocyanate groups, which leads to the crosslinking of the polyurethane polymer. The reaction of the isocyanate groups with the aldimino hydrolyzable groups is not necessary to take place through amino groups. Obviously, reactions with intermediate stages of the hydrolyzing reaction are also possible. For example it is possible that a hydrolysable aldimino group in the form of a semiaminal reacts directly with an isocyanate group. With the concepts "crosslinking" or "crosslinking reaction" throughout the document is designated the process caused by the chemical reaction of isocyanate groups for the formation of high molecular weight polyurethane synthetic materials, even if this is formed mainly chains. The compositions described may optionally contain a polyurethane polymer P containing isocyanate groups. Preferably it is a polyurethane polymer D, as already described for the production of a polyurethane polymer of the formula (I) containing aldimino groups, this is a polyurethane polymer containing solid isocyanate groups at room temperature. The aldimino groups present in the composition are typically in an over-stoichiometric, stoichiometric or sub-stoichiometric ratio relative to the isocyanate groups contained in the composition.

Advantageously, the ratio between the aldimino groups and the isocyanate groups 0.3 to 1.1, especially 0.5 to 1.05. In the case that the polyurethane polymer having aldimino groups of the formula (I) does not contain isocyanate groups, that is in the formula I) represents zero, or in the case of the polyurethane polymer of the formula (I) which contains aldimino groups containing two or more aldimino groups, this is for example represents a bond of the formula (le), thus the composition necessarily contains a polyurethane polymer P containing isocyanate groups. In this way an adequate proportion of aldimino groups to isocyanate groups is obtained as shown above. In case the polyurethane polymer of the formula (I) containing aldimino groups only contains an aldimino group and an isocyanate group, this is for example represents a compound of the formula (la) or (Ib), thus it is optional presence of a polyurethane polymer P, since in this case also a composition without polyurethane polymer P has a suitable proportion of aldimino groups to isocyanate groups. The composition described has a surprisingly low content of monomeric diisocyanates. This is especially advantageous for use as a hot melt adhesive, since the monomeric diisocyanates during their application produce gases and as toxic substances represent a damage to the health of the worker. The content of monomeric diisocyanates is especially very low when the composition as a polyurethane polymer mainly contains a polyurethane polymer of the formula (I), which is produced by means of the sub-stoichiometric reaction of a polyurethane polymer D with an aldimine of the formula (XI), in particular with less than half molar equivalent of active hydrogen of the aldimine (XI) per one molar equivalent of isocyanate groups of the polyurethane polymer D. In a preferred production process of the composition described all the components of the composition containing monomeric diisocyanates, during the reaction of the aldimines of the formula (XI), are present in the reaction mixture with the polyurethane polymers D containing isocyanate groups. The compositions prepared in this manner have the minimum content of monomeric diisocyanates. Preferably the composition described has a content of monomeric diisocyanates of <; 0.3% by weight, especially from < _0.2% by weight and especially < 0.1% by weight. The described composition also contains other components such as those usually used according to the state of the art, in particular: non-reactive thermoplastic polymers, such as homo- or copolymers of unsaturated monomers, in particular of the group including ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate and higher esters thereof and (meta) acrylate, being especially suitable the copolymers of ethylene vinyl acetate (EVA), poly-s-olefins (APAO), polypropylene (PP) and polyethylene (PE); - catalysts for the reaction of the aldimino groups and / or the isocyanate groups, especially acids or hydrolyzable compounds to form acids, such as for example organic carboxylic acids such as benzoic acid, salicylic acid or 2-nitro benzoic acid, anhydrides of organic carboxylic acids such as phthalic anhydride or hexahydrophthalic acid anhydride, silyl ester of organic carboxylic acids, organic sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid or 4-dodecylbenzenesulfonic acid or other organic or inorganic acids; metal compounds, for example tin compounds, for example dibutyltin diacetate, dibutyltin dilaurate, dibutyltin distearate, dibutyltin diacetylacetonate, dioctyltin dilaurate, dimethyltin dichloride, dibutyltin oxide, tin carboxylate (II), stannoxanes such as lauryl-tantanoxane, bismuth compounds such as bismuth octoate (III), bismuth neodecanoate (III) or bismuth oxinate (III); tertiary amines such as 2,2'-dimorpholino diethyl ether and other morpholino ether derivatives, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] undec-7-ene; combinations of the aforementioned catalysts, in particular mixtures of acids and metal compounds, or of metal compounds and tertiary amines; - reactive diluents or crosslinkers, for example oligomers or polymers of diisokanates such as MDl, PMDI, TDI, HDI, 1, 12-dodecamethylene diisocyanate, cyclohexan-1, 3- or 1,4-diisocyanate, IPDI, perhydro-2,4'- Y -4,4'-diphenylmethane diisocyanate (H12MDI), 1,3- and 1,4-tetramethylxylylenediisocyanate, especially isocyanurates, carbodiimides, uretonimines, biurets, allophanates and iminooxadiazinedione diisocyanates, adducts of diisocyanates with short chain polyols, and adipic acid dihydrazide and other dihydrazides, as well as blocked hardeners in the form of polyaldimines, polyketimines, oxazolidines or polyoxazolidines; - fillers, plasticizers, adhesives, especially compounds containing silanes, UV absorption agents, UV and thermal stabilizers, antioxidants, protection agents against the fuel oil, optical brighteners, pigments, dyes and drying agents, as well as other substances that are commonly used in compositions containing isocyanate. In a preferred embodiment the described composition is free of soot. In another preferred embodiment the composition described is completely free of fillers. Such a composition is especially suitable for the adhesion of substrates, at least one of the substrates to be transparent or translucent adhering. Suitably the sum of the polyurethane polymers of the formula (I) containing aldimino groups and the polyurethane polymer P containing isocyanate groups is 40 to 100% by weight, especially 75 to 100% by weight, preferably 80 to 100% by weight, in relation to the total composition. The described composition is produced and preserved in the absence of moisture, for example in packaging to climate-proof systems, such as for example a barrel, a bag or a cartridge, exhibits good storage stability. With the concept "storage stable" and "storage stability" with respect to a promoter for synthetic materials is meant in this document the state in which the viscosity of the promoter for synthetic material in the period of time considered does not increase or, at the most, increases so much that the promoter for synthetic material can continue to be used as intended. For the way in which a reactive hot melt adhesive works it is important that the adhesive can melt, that is that the application temperature has a sufficiently low viscosity, to be applied, and because upon cooling it exhibits a sufficient adhesive strength fast, just before the crosslinking reaction ends with the humidity of the air (initial resistance). It has been shown that the compositions described for the usual application temperatures for hot melt adhesives in the range of 85CC to 200 ° C, typically 120 ° C to 160 ° C, have a very manageable viscosity and that upon cooling they present rapidly good adhesion During the application of the composition described in contact with moisture, especially in the form of moisture in the air. Parallel to the physical hardening as a result of the solidification on cooling also begins the chemical cross-linking with moisture, in which mainly the starch groups present hydrolyze by moisture medium and in the manner already described react quickly with existing isocyanate groups. The excess isocyanate groups also crosslink with moisture in a known manner. The moisture required for chemical crosslinking may come from the air (air humidity), but the composition may also be contacted with a component containing water. For example, by means of brush or spraying, or to the composition during the application, a water-containing component can be added, for example in the form of a paste containing water, which is mixed, for example, by means of a static mixer. The compositions described when crosslinking with moisture have a strongly reduced tendency to form bubbles, since during the crosslinking by the presence of aldimino groups, depending on the stoichiometry, little or no carbon dioxide is formed. In a preferred embodiment, the described composition is used as a hot melt adhesive of polyurethane, abbreviated as PUR-RHM. During use as PUR-RHM the composition is used to adhere a substrate S1 and a substrate S2. An adhesion encompasses the steps of i) heating a composition as described above, at a temperature between 85 ° C and 200 ° C, especially between 120 ° C and 160 ° C; ii) applying the hot composition on a substrate S1; iii) contacting the applied composition with a second substrate S2 during the open time; wherein the second substrate S2 consists of the same or different material as the substrate S1. Stage iii) typically follows a step iv) of the chemical crosslinking of the composition with moisture. The technician understands that the crosslinking reaction, depending on the factors in the composition used, the substrates, the temperature, the environmental humidity and the adhesion geometry, may already begin during adhesion. The main part of the crosslinking, however, usually takes place after adhesion. The substrates S1 and / or S2 can, if necessary, receive a pre-treatment prior to the application, these previous treatments especially include cleaning and physical activation processes, for example sanding, sandblasting, brushing, corona treatment, plasma treatment, flamed, etched with acid or the like or treatments with detergents or solvent is the application of an adhesion promoter, an adhesion promoter solution or a primer. The substrates S1 and S2 can represent a plurality of materials. Especially suitable are synthetic materials, organic materials such as leather, fabrics, paper, wood, resin-bonded wood products, textile resin composite materials, glass, porcelain, ceramics as well as metals and metal alloys, especially lacquered or coated metals with dust and metal alloys. Polyvinyl chloride (PVC), copolymers of acrylonitrile-butadiene-styrene (ABS), SMC (Compounds for the molding of laminates), polycarbonate (PC), polyamide (PA), polyester, polyoxymethylene (POM) are particularly suitable as synthetic materials. , polyolefin (PO), especially polyethylene (PE), polypropylene (PP), ethylene / propylene copolymers (EPM), and ethylene / propylene-diene terpolymers (EPDM); preferably with PP or PE treated on the surface with plasma, corona or flames. Suitable materials for the substrates S1 and S2 are transparent materials, especially transparent synthetic films, another preferred transparent material is glass, especially in the form of a plate. The thickness of the adhesive layer (thickness of the adhesive) typically amounts to 10 microns or more. In particular, the thickness of the adhesive amounts to between 10 microns and 20 millimeters, especially between 80 microns and 500 microns. In the case of thick layers due to the slow diffusion of water, crosslinking is, however, very slow. The composition described is used in particular in a production process on an industrial scale. In particular, the composition described as PUR-RHM for adhesions in which adhesion points are not visible is suitable. Thus they are on the one hand suitable especially for the adhesion of glass, especially in the construction of vehicles and windows. On the other hand they are especially suitable for adhering transparent packaging. The articles result from the adhesion procedure. These items are in particular articles of the stretch of means of transport, furniture and textiles. Examples of such articles are land or water vehicles, such as automobiles, trucks, buses, trains or boats, internal gear of automobiles such as awning, sunscreen, dashboard, door parts, trunk and the like; wood fiber materials for shower and tub; decorative films for furniture, membrane films with textiles such as cotton, polyester films in the field of coatings or textiles with automotive foams. On the other hand that type of articles, especially the articles for the branch of packaging. Especially the article of that type is a transparent package. The compositions described include: a) at least one polyurethane polymer of the formula (I) containing solid aldimine groups at room temperature of the formula (I), and b) optionally at least one polyurethane polymer P containing isocyanate groups, during use as reactive hot melt adhesive compositions have a number of advantages over the prior art. Thus they present a strongly reduced content of monomeric diisocyanates and during their use the load for workers with harmful vapors of diisocyanate is strongly reduced. With the compositions described, hot-melt adhesive compositions based on commercially available easy-to-obtain diisocyanates, such as 4,4'-MDl or IPDI with an extremely low content of monomeric diisocyanates, can be obtained. The low content of monomeric diisocyanates is obtained by means of the reaction of polyurethane polymers D with aldimines of the formula (XI), wherein the active hydrogen contained in the aldimines reacts preferably with the monomeric diisocyanates present in the polyurethane polymer. D. In addition, the compositions described during use as a hot melt adhesive have a high crosslinking speed. Also when they contain slow reaction aliphatic isocyanate groups such as IPDI or H12MDI. PUR-RHM based on purely aliphatic diisocyanates according to the state of the art generally have such a low crosslinking rate that they are not useful for most applications. In addition, the compositions described show a strongly reduced tendency to bubble formation, since during the crosslinking of the isocyanate groups with hydrolyzable aldimino groups no carbon dioxide is formed, contrary to the crosslinking of the isocyanate groups with moisture. In addition to these advantages, the compositions described during their use as hot melt adhesives show similarly good properties as the systems according to the state of the art, in fact a fast adhesion resistance, a good heat resistance and a high rigidity final with a good stretch capacity can be adapted to the requirements of the application as an adhesive. In another aspect the invention relates to a process for reducing the content of monomeric diisocyanates in polyurethane polymers containing isocyanate groups or in compositions containing polyurethane polymers containing isocyanate groups, the polyurethane polymers containing isocyanate groups being reacted with when minus one aldimine of the formula (XI). EXAMPLES a) Description of Test Methods The total content of aldimino groups and free amino groups in the compounds produced ("amino content") was determined by titration (with HCIO4 0.1 N in glacial acetic acid, against crystal violet) and NH2 / g is indicated in mmol (also when not only primary amino groups). The monomeric diisocyanate content was determined by means of HPLC (detection through an array of photodiodes) and indicated in% by weight in relation to the total composition. The viscosity was measured at the indicated temperature with a Brookfield viscometer with a spindle 27 and 10 revolutions per minute. The open time is determined as follows: the composition is applied at a temperature of 150 ° C with a thickness of 500 μm on a paper coated with silicone. This test body is then placed on a hot base at room temperature. As soon as they can be separated from the adhesive paper strips that are placed on the adhesive exerting a slight pressure, the open time has elapsed. Consequently the adhesive hardened and solidified. The tensile strength and the breaking strain are determined in accordance with DIN 53504, in test bodies with a layer thickness of 500 μm and measures of 120 mm x 20 mm. The films for producing test bodies were applied at an adhesive temperature of 140 ° C and then stored for 2 weeks at 23 ° C and a relative humidity of 50%. b) Production of aldimines of the formula (XI) Aldimin 1 In a round flask under a nitrogen atmosphere are introduced . 13 g (0.106 mol) of 2, 2-dimethyl-3-lauroyloxy-propanal. Under vigorous stirring through a dropping funnel over the course of 5 minutes, 15.00 g (0.096 mol) N-cyclohexyl-1,3-propanediamine are added, whereby the temperature of the reaction mixture increases to 36 ° C. The volatile components are then removed under vacuum (10 mbar, 80 ° C). 43.2 g of a colorless, transparent and odorless liquid, very fluid at room temperature, having an amine content of 4.39 mmol NH 2 / g are obtained. Aldimine 2 28.06 g (0.099 mol) of 2,2-dimethyl-3-lauroyloxy-propane are introduced into a round flask under a nitrogen atmosphere. Under vigorous stirring through a dropping funnel over the course of 3 minutes, 10.00 g (0.095 mol) 2- (2-aminoethoxy) -ethanol (Diglycolamine® Agent; Huntsman) are added, whereupon the temperature of the reaction mixture increases to 40 ° C. The volatile components are then removed under vacuum (10 mbar, 80 ° C). 36.3 g of a colorless, transparent and odorless liquid, very fluid at room temperature, having an amine content of 2.58 mmol NH 2 / g are obtained. Aldimine 3 In a round flask under a nitrogen atmosphere, 69.31 g (0.244 mol) of 2,2-dimethyl-3-lauroyloxy-propane are introduced. Under vigorous stirring through a dropping funnel over the course of 5 minutes, 14.72 g (0.112 mol) dipropylenetriamine are added, whereby the temperature of the reaction mixture increases to 36 ° C. The volatile components are then removed under vacuum (10 mbar, 80 ° C). 79.7 g of a colorless, transparent and odorless liquid, very fluid at room temperature, having an amine content of 4.17 mmol NH 2 / g are obtained. c) Production of polyurethane polymers D Polyurethane polymer D1 800 g of Dynacoll® 7250 (liquid polyester diol, OH index 21 mg KOH / g, Degussa), 200 g Dynacoll® 7360 (crystalline polyester diol, OH index 30 mg KOH / g, melting point 55 ° C, Degussa) and 102 g 4,4'-diphenylmethane diisocyanate (4,4'-MDI; Desmodur® 44 MC L, Bayer) were reacted according to a known procedure at 100 ° C. C to produce an NCO-terminated polyurethane polymer. The reaction product had a content determined by titration of isocyanate groups of 1.5% by weight and was solid at room temperature. Polyurethane polymer D2 The same diol mixture as in the case of the polyurethane polymer D1 was reacted with 102 g 2,4'-diphenylmethane diisocyanate (2,4'-MDI; Lupranat® MCI, BASF) according to a known procedure at 100 ° C to produce an NCO-terminated polyurethane polymer. The reaction product had a content determined by titration of isocyanate groups of 1.5% by weight and was solid at room temperature. Polyurethane polymer D3 The same diol mixture as in the case of the polyurethane polymer D1 was reacted with 107 g 4,4'-methylenedicyclohexyl diisocyanate (H12MDI; Desmodur® W, Bayer) according to a procedure known at 100 °. C to produce an NCO-terminated polyurethane polymer. The reaction product had a content determined by titration of isocyanate groups of 1.5% by weight and was solid at room temperature. Polyurethane polymer D4 The same diol mixture as in the case of the polyurethane polymer D1 was reacted with 90.4 g isophorone diisocyanate (IPDI, Vestanat® IPDI, Degussa) according to a known procedure at 100 ° C to produce a polymer of polyurethane finished in NCO. The reaction product had a content determined by titration of isocyanate groups of 1.5% by weight and was solid at room temperature. d) Production of hot melt adhesive compositions Example 1 95 parts by weight of polyurethane polymer D1 and 7.7 parts by weight of aldimine 1 were mixed homogeneously at a temperature of 130 ° C and for 1 hour at 130 ° C. The polyurethane polymer formed containing aldimine and isocyanate groups is preserved at room temperature under the exclusion of moisture. Example 2 95.0 parts by weight of the polyurethane polymer D1 and 6.5 parts by weight of aldimine 2 were mixed homogeneously at a temperature of 130 ° C and for 1 hour at 130 ° C. The formed polyurethane polymer having aldimine and isocyanate groups was stored at room temperature under the exclusion of moisture. Example 3 95.0 parts by weight of the polyurethane polymer D1 and 8.1 parts by weight of aldimine 3 were mixed homogeneously at a temperature of 130 ° C and for 1 hour at 130 ° C. The formed polyurethane polymer having aldimine and isocyanate groups was stored at room temperature under the exclusion of moisture. Example 4 (comparative) 100.0 parts by weight of the polyurethane polymer D1.

Table 1: Properties of examples 1 to 4. Example 5 Example 5 was carried out in the same way as example 1, where polyurethane polymer D2 was used instead of polyurethane polymer D1. Example 6 Example 6 was carried out in the same way as Example 2, where polyurethane polymer D2 was used instead of polyurethane polymer D1. Example 7 Example 7 was carried out in the same way as example 3, where polyurethane polymer D2 was used instead of polyurethane polymer D1. Example 8 (comparative) 100 parts by weight of polyurethane polymer D2.

Table 2: Properties of examples 5 to 8. Example 9 Example 9 was carried out in the same way as example 1, where polyurethane polymer D3 was used instead of polyurethane polymer D1. Example 10 Example 10 was carried out in the same way as example 2, where polyurethane polymer D3 was used instead of polyurethane polymer D1. Example 11 Example 11 was carried out in the same way as example 3, where polyurethane polymer D3 was used instead of polyurethane polymer D1. Example 12 (comparative) 100 parts by weight of polyurethane polymer D3.

Table 3: Properties of examples 9 to 12. Example 13 Example 13 was carried out in the same way as example 1, where polyurethane polymer D4 was used instead of polyurethane polymer D1. Example 14 Example 14 was carried out in the same way as example 2, where the polyurethane polymer D4 was used instead of the polyurethane polymer D1. Example 15 Example 15 was carried out in the same way as example 3, where polyurethane polymer D4 was used instead of polyurethane polymer D1. Example 16 (comparative) 100 parts by weight of polyurethane polymer D4.

Table 4: Properties of examples 13 to 16. From the examples presented it is clear that the compositions according to the invention have clearly lower contents of monomeric diisocyanates than the corresponding ones according to the state of the art without aldimino groups, thus guaranteeing their Applicability as reactive hot melt adhesive.

Claims (13)

1. CLAIMS 1. Composition consisting of a) at least one polyurethane polymer of the formula (I) containing aldimino groups, solid at room temperature in the formula (I), p represents an integer between 1 or 2; q is an integer between 0 and 1, with the proviso that the sum of p and q is 2; R1 is either a monovalent hydrocarbon radical with 6 to 30 carbon atoms, which optionally has at least one heteroatom, especially in the ether-oxygen form, or is a substituent of the formula (II) wherein R6 is a bivalent hydrocarbon radical of 2 to 20 carbon atoms which optionally has a heteroatom, especially in the form of ether-oxygen and R7 is a monovalent hydrocarbon radical of 1 to 20 carbon atoms; R2 and R3 represent, independently of each other, a monovalent hydrocarbon radical of 1 to 12 carbon atoms, or jointly form a single substituent representing a bivalent hydrocarbon radical of 4 to 20 carbon atoms, which is a part of a carbocyclic ring of 5 to 8 carbon atoms, preferably 6 carbon atoms, and wherein R 4 represents a bivalent hydrocarbon radical with 2 to 12 carbon atoms which optionally contains at least one heteroatom, especially in the form of ether-oxygen, especially in the form of of ether-oxygen or tertiary-nitrogen amine; R5 represents a polyurethane polymer D having solid isocyanate groups at room temperature after separation of (p + q) isocyanate groups; and X is O, S or N-R8 wherein R8 represents either a monovalent hydrocarbon radical of 1 to 20 carbon atoms, which optionally has at least one ester group of carboxylic acid, nitrile, nitro, phosphonic acid ester , sulfone or sulfonic acid ester, or is a substituent of formula (III), b) at least one polyurethane polymer P containing isocyanate groups, in the case that q in formula (I) means zero, or in cases of X in formula (I) represents N-R8 with R8 being a substituent of the formula (III).
2. 2. Composition according to claim 1, characterized in that p = 1 and q = 1.
3. Composition according to claim 1 or 2, characterized in that the polyurethane polymer D having solid isocyanate groups at room temperature is produced from at least one diisocyanate and at least one diol.
4. Composition according to one of the preceding claims, characterized in that the polyurethane polymer P is produced from at least one diisocyanate and at least one diol.
5. Composition according to claim 3 or 4, characterized in that the diol is a polyester diol.
6. 6. Composition according to claim 3 6 4, characterized in that the diol is either a mixture of an amorphous polyester diol and a crystalline or semi-crystalline diol, or a mixture of a liquid polyester diol at room temperature and a crystalline one. or semi-crystalline, or a mixture of a partially crystalline and a crystalline polyester diol, wherein the liquid polyester diol at room temperature is solid at temperatures between 0 ° C and 25 ° C.
7. Composition according to one of claims 3 to 6, characterized in that the diisocyanate is MDl, TDI, HDI, H12MDI and IPDI.
8. Composition according to one of the preceding claims, characterized in that X = O or N-R8.
9. Composition according to one of the preceding claims, characterized in that R2 = R3 = methyl and R1 is a hydrocarbon radical with 11 to 30 carbon atoms.
10. Composition according to one of the preceding claims, characterized in that the sum of the polyurethane polymers of the formula (I) containing aldimino groups and the polyurethane polymer P containing isocyanate groups is 40 to 100% by weight, special 75 to 100% by weight, preferably 80 to 100% by weight, in relation to the total composition.
11. Composition according to one of the preceding claims, characterized in that the compound of the formula (I) is produced by means of the reaction of an aldimine of the formula (XI) with a polyurethane polymer D having an isocyanate group of the formula (XII)
12. 12. Composition according to claim 11, characterized in that the aldimia of the formula (XI) is used in a smaller proportion than one molar equivalent of active hydrogen of the aldimine by a molar equivalent of isocyanate groups of the polyurethane polymer D. 13. Composition according to one of the preceding claims, characterized in that it has a content of monomeric diisocyanates of < 0.3% by weight, especially from < 0.2% by weight and especially < 0.1% by weight. - 14. Hardened composition contained by means of the reaction of moisture with a composition according to one of claims 1 to
13. 13. 15. Use of a composition according to one of claims 1 to 13 as a hot melt adhesive. 16. Use according to claim 15, characterized in that the use is made inside vehicles and constructions. 17. Use according to claim 15 or 16 as an adhesive for industrial production or for repair in civil engineering or in the internal construction of vehicles or constructions. 18. Method of adhesion of substrates S1 and S2 including the steps of: i) heating a composition as described in claims 1 to 13, at a temperature between 85 ° C and 200 ° C, especially between 120 ° C and 160 ° C; ii) applying the hot composition on a substrate S1; ii) contacting the applied composition with a second substrate S2 during the open time; wherein the second substrate S2 consists of the same or different material as the substrate S1. 19. Process according to claim 18, characterized in that step iii) follows a step iv) of the chemical crosslinking of the composition with moisture. Method according to claim 18 or 19, characterized in that at least one of the substrates S1 or S2 is a synthetic material, an organic material such as leather, fabrics, paper, wood, resin-bonded wood products, composite material textile resin, glass, porcelain, ceramics as well as metals and metal alloys, especially metals lacquered or coated with powder and metal alloys. 21. Method according to one of claims 18 to 20, characterized in that the composition is applied with a thickness greater than 10 microns, especially between 10 microns and 20 millimeters, preferably between 80 microns and 500 microns. 22. Adhered article which is produced by means of an adhesion procedure according to one of claims 18 to 21. 23. Adhered article according to claim 22, characterized in that the article is a means of transport, especially a vehicle. terrestrial or aquatic, preferably a car, a truck, a bus, a train or a ship, or a component thereof. 24. Process for reducing the content of monomeric diisocyanates in polyurethane polymers containing isocyanate groups or in compositions containing polyurethane polymers containing isocyanate groups, the polyurethane polymers containing isocyanate groups being reacted with at least one aldimine of the formula ( XI) wherein R1 is either a monovalent hydrocarbon radical with 6 to 30 carbon atoms, which optionally has at least one heteroatom, especially in the ether-oxygen form, or is a substituent of the formula (II) wherein R6 is a bivalent hydrocarbon radical of 2 to 20 carbon atoms which optionally has a heteroatom, especially in the form of ether-oxygen and R7 is a monovalent hydrocarbon radical of 1 to 20 carbon atoms; R2 and R3 represent, independently of each other, a monovalent hydrocarbon radical of 1 to 12 carbon atoms, or jointly form a bivalent hydrocarbon radical of 4 to 20 carbon atoms, which is a part of a carbocyclic ring of 5 to 8 carbon atoms. carbon, preferably 6 carbon atoms, and wherein R 4 represents a bivalent hydrocarbon radical with 2 to 12 carbon atoms which optionally contains at least one heteroatom, especially in the form of ether-oxygen, or tertiary-nitrogen amine; R5 represents a polyurethane polymer D having solid isocyanate groups at room temperature after separation of (p + q) isocyanate groups; and X is O, S or N-R8 wherein R8 represents either a monovalent hydrocarbon radical of 1 to 20 carbon atoms, which optionally has at least one ester group of carboxylic acid, nitrile, nitro, phosphonic acid ester , sulfone or sulfonic acid ester, or is a substituent of formula (III), HOT FUSION ADHESIVES OF REAGENT POLYURETHANES WITH REDUCED CONTENT OF ISOCYANATE MONOMERS The invention relates to hot-melt adhesives that harden with moisture, which contain at least one polyruetane polymer of the formula I having solid aldimino groups at room temperature, as well as at least one polyurethane polymer P having at least one an isocyanate group, if q in formula (I) is zero, or if X in formula (I) is N-R8 with R8 being a substituent of formula (III). The compositions are characterized by a clearly reduced content of isocyanate monomers and are therefore considered particularly advantageous from the point of view of occupational hygiene.