CH618212A5 - Adhesive based on organic silicon compounds - Google Patents

Description

The invention relates to adhesives which can be produced for joining individual packs. These adhesives of elastomeric materials and in particular of vulcanizable materials are defined in claim 1, elastomeric materials with inorganic substrates. Further advantages of the adhesives according to the invention and

618212

A method for gluing elastomeric materials to substrates and for producing elastomer-substrate composites connected by an adhesive bond result from the following description.

According to the invention, it has been found that compositions which contain at least one isocyanato-organosilane, preferably in combination with at least one polyisocyanate, which is characterized by the presence of at least two free isocyanate groups, unexpectedly perform well as adhesive materials for bonding a large number of elastomers and in particular of vulcanizable elastomers with inorganic substrates. The isocyanato-functional organosilanes, which are referred to below as isocyanatosilanes and are suitable for use in the adhesive according to the invention, can be described in very general terms as compounds which include both the hydrolytic reactions typical of alkyl esters of silicas and those for isocyanates can experience typical reactions with active hydrogen-containing compounds.

In addition to producing firm adhesive bonds 20 with a large number of elastomers, the compositions according to the invention improve the environmental stability of the bonded arrangement. It has further been found that the presence of one or more aromatic nitroso compounds can improve the strength of the adhesive bond and / or increase the resistance to the environment, and that the versatility of the adhesive compositions can be further expanded. Furthermore, it was found that the presence of one or more polymeric, film-forming additives can result in further improvements, in particular with regard to the film properties. The compositions of the invention provide strong bonds, which is highly desirable in many technical applications. A particularly unexpected feature of the invention is the ability of the compositions described here to be used as single-layer adhesive systems in single packs, which provide solid rubber-to-metal bonds with improved strength against attack by environmental influences. In addition, the preferred adhesive compositions according to the invention are further distinguished by their stability at ambient temperatures during storage and handling. \

The reason for the improvement in stability has not been fully clarified.

which contain materials containing free isocyanate groups, a limited pot life due to the high reactivity of the isocyanate groups with water and other active hydrogen-containing compounds. The addition of aromatic nitroso compounds and / or of polymeric, film-forming additives introduces impurities such as water 50 and reactive oximes, which would be expected to have a detrimental effect on the stability, since such impurities tend to have both the isocyanate content as well as hydrolyzing the silicic acid portion of the isocyanatoorganosilanes and also reacting with the other 55 components, e.g. B. on the free isocyanate groups of the free polyisocyanate, which would lead to premature gelation of the adhesive compositions. It is believed that the improvement in stability could be the result of acidic buffering, which may affect the inventive masses as a result of any or all of the latent, i.e. H.

free, acidity of the polyisocyanate component, an acidic contribution from randomly present and dissociated, free silicic acid groups or an acidic contribution from the polymeric, film-forming auxiliary substance. This postulate is set forth in 65 U.S. Patent 3,830,784, which describes improvements in storage stability, i. H. The stability during the storage and handling of rubber-on-metal adhesive compositions containing free polyisocyanates relates to the same mechanism for improving the storage stability, as specified in US Pat. No. 3,830,784, could also be effective for the compositions according to the invention.

The isocyanatosilanes used according to the invention are distinguished by the presence of a free isocyanate group and at least two hydrolyzable groups according to the following general formula:

OCN - R ° - Si - (OR2).

3 ~ a whose symbols are defined in claim 1.

The exact nature of the residue Z is not critical, i. H. the rest can have any configuration and combination of groupings that are compatible with the isocyanato groups. For example, the Z radical can be a hydrocarbon radical, or it can contain bonds such as ether, ureido, ure-than and thiourethane bonds. The radical Z can of course have substituent groups such as halogen which are compatible with the isocyanato groups.

A preferred, but not exclusive feature of the invention is isocyanatosilanes which are selected from: (1) isocyanatosilanes of the general formula:

1;

OCN - R

O

-Si - (OR) y a

and (2) isocyanatosilane adducts of multifunctional organosilanes and polyisocyanates, these adducts having as a characteristic feature at least one free isocyanate group and at least one silane group of the following general formula:

0 h

1:

- RH

C-A-R-Si

(0R2) 7 2 -a where it should be noted that these free isocyanato groups or groups and these silane groups or groups are bonded to one another via the rest of the polyisocyanate reaction participant. The isocyanatosilane adducts, i.e. H. the reaction products of multifunctional organosilanes and polyisocyanates are preferably contained in the adhesive compositions according to the invention. Such adducts are generally easier to manufacture and therefore more accessible than isocyanatosilanes produced directly from the more basic silane intermediates. (It is believed that the more basic silane intermediates for the purposes of the present invention are those that have the highly reactive, functional group -Si-H or -Si-Cl.)

In the preceding formulas, the radicals R1 and R2 have the meaning given above, and R ° is a divalent hydrocarbon radical or a divalent, halogenated hydrocarbon radical with 1 to 20 and preferably 2 to 9 carbon atoms, A = -O-, -S- , ÏNH or another divalent radical containing active hydrogen, and R is a divalent, aliphatic, cycloaliphatic or aromatic radical having 1 to 20 carbon atoms and preferably an alkylene radical having 1 to 9 carbon atoms. Adducts in which A = -O- or H-Nîist R is an alkylene radical having 2 to 4 carbon atoms, R 2 is methyl, ethyl,

618 212 4

Is methoxyethylene or methylcarbonyl and a = zero meaning benzene, dichlorobenzene and the like; halogenated, aliphatic hydrocarbons such as trichlorethylene, perchlorethylene,

Isocyanatosilanes of the following formula: propylene dichloride and the like; Ketones such as methyl isobu-

tyl ketone, methyl ethyl ketone and the like; Ether etc.

finally mixtures of such solvents / diluents. / np2 \ nmittel. The extent of the dilution is not critical

OCH - R - Si - (, 0R as long as it does not preclude an adequate film thickness of the adhesive during the final application.

are commercially available products. Such compounds can be the multifunctional organosilane compounds, which in z. B. by pyrolysis of the corresponding carbamate 10- are suitable for carrying out the invention, stand out. The carbamate can be obtained by carrying out the through the presence of a single organic chain,

Reaction between a silyl organohalide, a metal - which has at least one functional group with at least eyanate and an aliphatic, monohydric alcohol in the presence of a cleavable residue, i. H. an active hydrogen atom, e.g. B. an aprotic solvent. an amino, mercapto, hydroxy or other active Another method for the preparation of such compounds 15 has a hydrogen-containing functional group which comprises carrying out the reaction between a silicon-silicon via an organic, at least one carbon atom and hydride an olefinically unsaturated isocyanate such as containing group is preferably the little-allyl isocyanate. Examples of such isocyanatosilanes are: Tristensively an active hydrogen atom-containing functional methoxysilylpropyl isocyanate, phenyl diethoxysilyl propyl isocyanate group on the silicon atom via an organic, less natylate and methyl dimethyl siloxysilyl. 20 contain at least two interconnected carbon atoms

The preferred isocyanatosilane adducts can have a slightly bound residue.

by carrying out the reaction between a multifunctional- In particular, the multifunctional organosilane-nell organosilane and a polyisocyanate are selected by adding the compounds which are suitable for the invention from fol-organosilane, preferably in the form of a dilute solution, gender group:

to the polyisocyanate, which likewise preferably contains 25 hydroxyorganosilanes of the following formula:

is thin at a temperature in the range of about 10 ° to ^

about 100 ° C while stirring the mixture with a mechanical (11 /

see stirrers or a similar device are manufactured

the. Although this is not absolutely necessary, a ge ^. 2 \

suitable catalyst such as dibutyltin dilaurate can be used 30 HO - R - Si - (OR) z_a den. The reaction occurs almost immediately, especially when

Catalysts are used and they run weakly where R is a divalent, aliphatic, cycloaliphatic exothermic. It is essential that the pre- or aromatic residue with 1 to 20 carbon atoms and the amount of polyisocyanate present during the reaction is such that the preparation preferably contains an alkylene residue with 1 to 9 and especially before an adduct with at least one free isocyanate group 35 2 to Is 4 carbon atoms;

is ensured. It should be noted that the mini R! a monovalent, aliphatic, cycloaliphatic or male amount in molar equivalents of NCO of the polyisocyanic aromatic radical with 1 to 20 carbon atoms and vor-th, which is required for the preparation of the adducts, a mol preferably an alkyl radical with 1 to 4 carbon atoms, one equivalent of NCO in excess of the amount of molar equi-cycloalkyl radical having 4 to 7 ring carbon atoms or one valent of NCO, which are required for reaction with the entire active 40 aryl radical with 6,10 or 14 core carbon atoms including hydrogen from the silane reactant such aryl radicals with one or more substituents must be. Optionally, the adduct is from the alkyl radicals having 1 to 4 carbon atoms;

Reaction mixture separated by conventional means can be a monovalent, aliphatic, cycloaliphatic or R2. However, it has proven advantageous to add the aromatic, organic radical with 1 to 8 carbon atoms of the organosilane reactant to a sufficient and preferably an alkyl radical with 1 to 4 carbon atoms in excess of the polyisocyanate reactant, and a = zero or 1 and preferably zero;

to complete reaction of the organosilane reaction aminoorganosilane compounds of the following general

participant to ensure, on the one hand, an isocyanate adduct formula:

with at least one free isocyanate group and on the other hand a sufficient amount of unreacted polyiso-H

to obtain eyanate-containing reaction mixture, so that the i required amount of isocyanate functionality, as shown in the following 5 _ ^ 2 \

is still executed in detail, is obtained. On R - JN - K - 01— (.UK) ^

in this way, the isolation of the silane isocyanate adduct from the reaction mixture and the subsequent addition of the adduct 55 in which R, R1, R2 and a have the previously indicated meaning to free polyisocyanate can be omitted, which and a considerable economic and technical advantage R5 hydrogen represents monovalent, aliphatic radical with 1 to. This way of working, i. H. the contacting of the 8 carbon atoms, a monovalent, cycloaliphatic radical organosilane reactant with excess polyiso- having 4 to 7 ring carbon atoms, the phenyl radical, an alkaryl cyanate reactant, has been found to be particularly advantageous in 60 radicals with 6 core carbon atoms and one or more, the cases in which the substituting alkyl radicals according to the invention with 1 to 4 carbon atoms of adhesive compositions are a polymeric, film-forming additive or -R6-NH-R7 in which R6 contains a divalent, aliphatic or auxiliary substance. cycloaliphatic or aromatic radical with 1 to 20 carbon

As already described, the use of both substance atoms and preferably at least two carbon atoms separating any one of the silane and the polyisocyanate in dilute form is preferred. Suitable solvents are, for. B. aromatic Koh- are present, wherein R6 is preferably an alkylene radical with 2 hydrocarbons such as benzene, toluene, xylene and the like; is up to 9 carbon atoms and R7 has the same meaning as halogenated aromatic hydrocarbons such as monochloro-R5 and is preferably hydrogen

618212

Mercaptoorganosilane compounds of the following general formula:

IIS - R - Si - (OR2),

p-a wherein R, R1, R2 and a have the meaning given above; as well as other organosilane compounds which have a single organic chain with 1 to 20 carbon atoms, this chain having at least one removable hydrogen atom and this removable hydrogen atom preferably being bonded to a functional group which is separated from the silicon atom by a chain of at least 3 interconnected carbon atoms is separated.

The preferred organosilane compounds are aminoorganosilane compounds as described here. It should be pointed out that both primary and secondary aminoorganosilane compounds and also those compounds which contain at least one primary amino group and one or more secondary amino groups in their structure can be used in the preparation of the compositions according to the invention. It is also possible to use aminoorganosilane compounds which contain one or more tertiary amino groups, provided that such compounds also contain at least one primary or secondary amino group. Aminoorganosilane compounds in which at least one primary amino group is present are preferred.

Typical representatives for multifunctional organosilanes that can be used for the invention are, for. E.g .: hydro-xypropyltrimethoxysilane, hydroxypropyltriethoxysilane, hydro-

10th

xybutyltrimethoxysilan, g-aminopropyltrimethoxysilane g-Ami-nopropyltriäthoxysilan, methylaminopropyltrimethoxysilane, g-aminopropyltripropoxysilane, g-Aminoisobutyltriäthoxysilan, g-Aminopropylmethyldiäthoxysilan, g-aminopropyl-äthyldiäthoxysilan, g-Aminopropylphenyldiäthoxysilan, d-Ami-nobutyltriäthoxysilan, d-Aminobutylmethyldiäthoxysilan, d-Aminobutyläthyldiäthoxysilan, g-aminoisobutylmethyldi-ethoxysilane, N-methyl-g-aminopropyltriethoxysilane, N-phenyl-g-aminoisobutylmethyldäthoxysilane, N-ethyl-d-ami-nobutyltriethoxysilane, Ng-aminopropyl-g-aminopropysilane aminoisobutyltriäthoxysilan, Ng-aminopropyl-d-aminobutyltriäthoxysilan, N-aminohexyl-g-aminoisobutylmethyldiäthoxysilan, methyl-aminopropyltriäthoxysilan, g-mercaptopropyltrimethoxysilane, 15 mercapto-ethoxilethyl-trilethoxysilane, 15-mercapto-ethoxilethyl-trilethoxysilane.

The polyisocyanates which can be used for the invention can be any organic isocyanates which have at least two free isocyanate groups. The 20o suitable polyisocyanates include: aliphatic, cycloaliphatic and aromatic polyisocyanates, according to the terms commonly used in the art. Thus, it should be pointed out that any of the known polyisocyanates such as alkyl and alkylene polyisocyanates, cycloal-25 alkyl and cycloalkylene polyisocyanates, aryl and arylene polyisocyanates and combinations such as alkylene, cycloalkylene and alkylene arylene polyisocyanates can be used for the invention. These polyisocyanates serve both as a component for free polyisocyanate in the masses described 3o and as a starting material for the component in the form of the silane-polyisocyanate adduct.

Particularly preferred polyisocyanates are the polyalkylene poly (arylene isocyanates) with the following formula:

-m

(NGO)

m in which R8 is a divalent organic radical and preferably a divalent aliphatic radical having 1 to 8 carbon atoms and in particular such a radical obtained by removing carbonyl oxygen from an aldehyde or ketone, and preferably R8 is methylene;

m = 1 or 2 and preferably = 1;

n is a number with an average value in the range from zero to 15, preferably 0.1 to 4 and particularly preferably 0.3 to 1.8; and

X is hydrogen, halogen, an alkyl radical with 1 to 8 carbon atoms or an alkoxy radical with 1 to 8 carbon atoms, preferably hydrogen.

Suitable polyisocyanates are e.g. For example: tolylene-2,4-diisocyanate, 2,2,4-trimethylhexamethylene-l, 6-diisocyanate, hexamethylene-l, 6-diisocyanate, diphenylmethane-4,4'-diisocyanate, triphenylmethane 4,4 ', 4-triisocyanate, 3-isocyanatomethyl-3,5,5-tri-methylcyclohexcyl isocyanate, polymethylene polyphenyl isocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate,

2,6-tolylene diisocyanate, 1,5-naphthalene diisocyanate, naphthalene-45 1,4-diisocyanate, diphenylene-4,4'-diisocyanate, 3,3'-bi-tolylene-4,4'-diisocyanate, ethylene diisocyanate, propylene 1,2-diisocyanate, butylene-2,3-diisocyanate, ethylidene diisocyanate, butylidene diisocyanate, xylylene-1,4-diisocyanate, xylylene-1,3-diisocyanate, methylcyclohexyl diisocyanate, cyclopentylene-1,3-diisocyanate, so cyclohexylene -l, 4-diisocyanate, 4,4'-methylene-bis- (cyclohexyliso-cyanate), p-phenylene-2,2'-bis (ethyl isocyanate), 4,4'-diphenylene ether-2,2'-bis ( ethyl isocyanate), tris (2,2 ', 2 "-ethyl isocyanate benzene), 5-chlorophenylene-1,3-bis (propyl-3-isocyanate), 5-methoxyphenylene-1,3-bis (propyl-3- isocyanate), 5-cyano-55 phenylene-1,3-bis (propyl-3-isocyanate), 4-methylphenylene-1,3-bis (propyl-3-isocyanate), etc. Other polyisocyanates used for the invention include the dimers of aromatic diisocyanates, as described, for example, in US Patent No. 2 671082. A particularly preferred dimer is the T olylene di-isocyanate dimers with the following formula:

N

N

CR

3rd

itao

618212

The aromatic nitroso compounds suitable for the invention can be derived from any aromatic hydrocarbon, e.g. As benzene, naphthalene, anthracenes, biphenyls and the like, these having at least two nitroso groups bonded directly to non-adjacent ring carbon atoms. In particular, such nitroso compounds are described as aromatic poly-C-nitroso compounds having 1 to 3 aromatic nuclei, including fused aromatic nuclei, which have 2 to 6 nitroso groups which are bonded directly to non-adjacent nuclear carbon atoms. The preferred poly-C-nitroso materials according to the invention are the dinitrosoaromatic compounds, in particular the dinitrosobenzenes and dinitrosonaphthalenes, e.g. B. meta or para dinitrosobenzene and meta or para dinitrosonaphthalene. The ring hydrogen atoms of the aromatic nucleus can be replaced by alkyl, alkoxy, cycloalkyl, aryl, aralkyl, alkylene, arylamine, arylnitroso, amino, halogen and the like residues. The presence of such substituents in the aromatic nucleus or ring has only a minor influence on the activity of the poly-C-nitroso compounds as used according to the invention. As far as is known, there is no limitation on the character of the substituent, and such substituents can be organic or inorganic in nature.

Therefore, when the term poly-C-nitroso or di-C-nitroso is used to refer to “aromatic compounds”, “benzenes”, or “naphthalenes” in the description, it is to be understood that these terms are both substituted and unsubstituted Denote nitroso compounds unless otherwise stated.

Particularly preferred poly-C-nitroso compounds are characterized by the following formula:

(R9) p - Ar - (NO> 2

wherein Ar is phenylene or naphthalene; R9 is a monovalent organic radical in the form of alkyl, cycloalkyl, aryl, aralkyl, arylamine or alkoxy radicals having 1 to 20 carbon atoms, amino or halogen radicals and is preferably an alkyl radical having 1 to 8 carbon atoms; and p = zero, 1, 2, 3 or 4 and preferably zero

A partial list of suitable poly-C-nitroso compounds suitable for the invention includes: m-dinitrosobenzene, p-dinitrosobenzene, m-dinitrosonaphthalene, p-dinitrosonaphthalene, 2,5-dinitroso-p-cymen, 2 -Methyl-l, 4-dinitrosobenzene, 2-methyl-5-chloro-l, 4-dinitrosobenzene, 2-fluoro-1,4-dinitrosobenzene, 2-methoxy-l, 3-dinitrosobenzene, 5-chloro-l, 3 -dinitrosobenzene, 2-benzyl-l, 4-dinitrosobenzene and 2-cyclohexyl-1,4-dinitrosobenzene.

Practically all of the polymeric materials which have hitherto been used as film formers or film-forming additives in adhesive formulations are suitable for the invention. For example: thermosetting condensation polymers such as thermosetting phenolic resins, thermosetting epoxy resins, thermosetting polyester resins, thermosetting triazine resins and the like, polymers and copolymers of polar, ethylene-like unsaturated materials such as polyvinyl butyral, polyvinylformal and vinylvinylchloride, copolymerized vinyl acetate, chlorinated Vinyl acetate and vinyl chloride, polymers of acrylic acid, copolymers of acrylic acid and conjugated dienes such as 1,3-butadiene, 2-chloro-l, 3-butadiene, 2,3-dichloro-l, 3-butadiene and the like including post-halogenated products thereof, polymers of methacrylic acid, copolymers of methacrylic acid and conjugated dienes, copolymers of vinyl pyridine and conjugated dienes including polyvalent reaction products thereof, cellulose-like materials such as cellulose acetate and butyrate and the like. Particularly preferred, film-forming materials are halogen-containing rubbers including, but without limitation, chlorinated natural rubber, polychloroprene, chlorinated polychloroprene, chlorinated polybutadiene, chlorinated polyethylene, chlorinated ethylene-propylene copolymers, chlorinated ethylene / propylene-non-conjugated diene terpolymers, chlorinated Butadiene and styrene, chlorosulfonated polyethylene, brominated poly (2,3-dichloro-1,3-butadiene), copolymers of alpha-chloroacrylonitrile and 2,3-dichloro-1,3-butadiene, copolymers of alpha-bromoacrylonitrile and 2,3 -Dichlor-l, 3-butadiene, mixtures of such halogen-containing rubbers with hydrohalogenated rubbers of hypohalogenized rubbers. Mixtures of two or more such halogen-containing rubbers and the like. Other suitable polymeric, film-forming additives include cellulose-like esters such as cellulose acetate butyrate, natural rubber, butyl rubber, ethylene / propylene copolymer (EPM) rubber, ethylene / propylene / diene terpolymer (EPDM) rubber, polymers and copolymers of dienes with 4 to 4 bis Carbon atoms such as polybutadiene, which also includes copolymers of such dienes and one or more different monomers copolymerizable therewith, e.g. B. SBR rubber and butadiene / acrylonitrile rubber. As already described, halogenated, polymeric materials and especially chlorinated and brominated rubbers are the preferred film-forming materials for the invention.

The adhesives according to the invention are produced in a conventional manner and according to methods known per se, so that they do not have to be explained in detail. As a general rule, the silane isocyanate adduct and free polyisocyanate are mixed before adding other ingredients such as the aromatic nitroso compound, film-forming polymeric material, filler, and the like. In those cases where the adduct has been isolated, the adduct is added directly to the free polyisocyanate, both materials preferably being diluted, under conditions such that a homogeneous mixture is safely obtained. In such a case, the free polyisocyanate may be the same as that used in the preparation of the adduct, but it may also be different, or it may comprise a mixture of two or more polyisocyanates, one of which may be the same polyisocyanate as that for Formation of the adduct was used. In a second and more preferred case, the adduct is prepared from the reaction of the silane and an excess of polyisocyanate to obtain a reaction mixture comprising the adduct and free polyisocyanate. In this case, if the amount of free polyisocyanate is insufficient to produce the appropriate ratio of free polyisocyanate adduct, additional free polyisocyanate can be added to the reaction mixture. Such added free polyisocyanate can of course be the same as or different from the polyisocyanate used in making the adduct, and it can comprise a mixture of two or more polyisocyanates, one of which may optionally be the same polyisocyanate as that used to make it of the adduct was used. As a general rule, the amount of polyisocyanate used in the preparation of the adduct is preferably such that no additional polyisocyanate has to be added to the reaction mixture. The mixture prepared in this way is itself suitable for use as a primer and adhesive composition, or as a base composition in which the aromatic nitroso compounds, the film-forming, polymeric

6

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

7 618212

materials, the filler materials such as carbon black and the like. It was found that the adhesives according to the invention

Chen, extenders, pigments, diluents, etc. additives can be used especially for gluing a large variety of ela-sets, the usual procedures for stomeric materials and in particular of vulcanizable, adhesive compositions are used. elastomeric materials with themselves or with other sub-

5 strats are suitable for the production of the adhesives according to the invention. Elastomers that can be glued is the isocyanatosilane in an amount in the range of 2.5 to z. For example: natural rubber, polychloroprene rubber, styrene-100 and preferably from about 2.5 to 50 and particularly preferably butadiene rubber, nitrile rubber, rubber made from ethylene / prefers from about 5 to about 40 parts by weight, the polyisopropylene copolymer ( EPM), rubber made of ethylene / propyl cyanate is present in an amount of 100 x parts by weight and x len / diene terpolymer (EPDM), butyl rubber, polyurethane is equal to the amount, in parts by weight, of isocyanatosilane component rubber and In addition, the isocyanatosilane and the free ren per se, which can be effectively bonded, include tex polyisocyanate, a minimal amount of total free isotiles or fabrics such as fiberglass, polyamides, polyesters , eyanat, including the amount supplied by both the isocyanatosilane and aramids, for example Kevlar (trade name of EI du Pont de and the free polyisocyanate), which Nemours & Company [Inc.], Wilmington , Delaware, USA) and 1 mole equivalent of isocyanate per mole of isocyanatosilane is the same, as well as metals and their alloys such as steel. Preferably, the total free isocyanic steel, lead, aluminum, copper, brass, bronze, nat content is in the range of 1 to about 20, and preferably 1 Monel, nickel, zinc and the like including up to about 12 and particularly preferably from 2 to about 8 mole-treated metals such as phosphated steel, galvanized equivalent per mole of isocyanatosilane. It should be noted that steel and the like, glass, ceramic materials and the like, that the invention has great flexibility in manufacture.

development of adhesive masses, which u. a. include: Isocyanatosilane per se; Isocyanatosilane and aromatic nitroso The adhesives are bonded to the substrate surfaces; Isocyanatosilane, aromatic nitroso compound in a conventional manner such as by immersion, spraying, brushing and polymeric, film-forming additive; Isocyanatosilan and most and the like applied. Preferably the free polyisocyanate; Isocyanatosilane, free polyisocyanate and 25 substrate surfaces allowed to dry after coating, aromatic nitroso compound; Isocyanatosilane free before they are brought together. After the surface polyisocyanate, aromatic nitroso compound and polymer are combined, the composite structural film-forming additive, with isocyanatosilane and free doors being heated in a conventional manner, are particularly preferred to cure or polyisocyanate-containing compositions. Vulcanization of the adhesive masses and the simultaneous vulcanization in the aromatic nitroso compounds, polymeric, film-filming of the non-vulcanized elastomeric formulation lead to additive and inert filler-containing masses.

is the aromatic nitroso compound in an amount

Range from 5 to 200, preferably from about 50 to about 150. The invention is illustrated by the following examples

Parts by weight; the polymeric, film-forming additives are explained, all parts in parts based on weight, generally in an amount of from about 10 to about 200.35 hen, unless stated otherwise.

preferably from about 75 to about 150 parts by weight; and In several examples, the substrate to which the inert filler is generally glued in an amount in the elastomeric material was not a primer

Range from about 10 to about 200, preferably from about 25 unless otherwise specified. The composite up to about 175 parts by weight, these amounts being okay under conventional conditions with respect to each case based on 100 parts of combined time and temperature for the specific elastomer out of vulcanized weight of isocyanatosilane and free polyisocyanate - nized. The perfect binding was in accordance with the ASTM standard. dard D-429, method B was investigated by modifying the peeling angle to 45 °.

As described above, the adhesives according to the invention can, in addition to the isocyanatosilane, the free poly 45 The bonded structures were subjected to various isocyanates, the aromatic nitroso compound, the polyme tests, including peeling, film-forming additives and inert filler material at room temperature (ZT) , a boiling water test, conventional additives such as pigments, extenders, and the salt spray test. With the ZT deduction text, the chewing

Contain solvents, diluents, and the like, protective body from the metal at an angle of 45 ° with the amount of such additives subtracted within the usual range of use of a Scott tensile tester and wise applied range. the required force in kg / 2.54 cm was recorded. When examined in boiling water, the glued

Because of ease of use, as is the case with the samples, after being scratched on the bond line and common in the art, the ingredients are mixed and dispersed in a liquid by bending the rubber back from the metal pre-carrier, which, after the mass 55 were soaked in boiling water for two hours - can be easily evaporated. Immersed. In the salt spray test, the samples were tested after playing with suitable supports, aromatic and halogen scoring and pre-stressing a spray jet of the aromatic hydrocarbons such as benzene, toluene, salt solution (5% sodium chloride) for 48 hours at 37.8 ° C xylene, Chlorobenzene, dichlorobenzene and the like; halogen- (100 ° F) exposed. The samples thus treated were tested for their kidney aliphatic hydrocarbons such as trichlorethylene, relative adhesive strength by peeling off the rubber body of perchlorethylene, propylene dichloride and the like; Examined ketones from the metal.

such as methyl ethyl ketone, methyl isobutyl ketone and the like;

Ether, petroleum varieties etc. including mixtures sol- With the values given in the examples becomes a carrier. The amount of carrier is not critical and break in values of the percentage error in the rubber body.

Usually it is such that a total solids content 65 is expressed as e.g. B. 95 R means that 95% of the error or obtained from about 5 to about 100, i.e. H. 100% solid breakage occurred in the rubber body, the remaining fault system, and preferably ranging from about 5 to about 30% by weight of 1 or breakage between the adhesive composition and the metal. or the like occurred.

618212

8th

example 1

A series of adhesive compositions which contained isocyanate-propyltriethoxysilane were produced using the following approaches:

0

—NH-C-N- (CH0) -. Si (OCH -) «<- y J

p '3

adhesive

A-l

A-2

A-3

A-4

chlorosulfonated polyethylene

35

35

35

35

Dinitrosobenzene

30th

30th

30th

30th

Soot

40

40

40

40

Isocyanatosilane

-

15

15

15

Polymethylene polyphenylene isocyanate

-

-

15

30th

Xylene

214

214

214

214

GH-, j>

10th

A main approach or

A premix of adhesive A-1 was prepared in a conventional manner. Adhesive formulations A-2, A-3 and A-4 were prepared in a conventional manner by mixing the corresponding components into equal parts of the main batch

The adhesive compositions thus formulated were then applied to non-primed, sand-blown, degreased sections of cold-rolled steel and left to dry. The steel sections coated in this way were brought into contact with a sulfur-vulcanizable natural rubber mixture. Each of the arrangements was vulcanized at 153 ° C (307 ° F) for 15 minutes.

Following the vulcanization cycle, the bonded assemblies were examined for their resistance to environmental conditions after the boiling water test (À H2O). The results are summarized in Table I below:

Table I

had included.

The molar equivalent ratio of total free isocyanate to isocyanatosilane adduct in the reaction mixture was about 2.8: 1.

Example 3

Following the procedure of Example 2, 193 g of methylaminopropyltrimethoxysilane in 772 g of benzene was added to a continuously conducted mixture of 359 g of polyethylene polyphenylene isocyanate (2.7 NCO functionality) and 1436 g of trichlorethylene, to give a viscous, liquid reaction mixture obtained, the free polymethylene polyphenylene isocyanate and polymethylene polyphenylene isocyanate / methylaminopropyltrimethoxysilane adduct with a free isocyanate functionality of about 1.7 and a single silane grouping with the structure

0

I!

-NH-C-ÎJ- (CH2) ^ Si (OGE,) 5 OH.

included.

The molar equivalent ratio of total, free isocyanate: isocyanatosilane adduct in the reaction mixture was about 2.2: 1.

adhesive

A HîO test break

A-l

0 R (broke in 1.25 h)

A-2

26 R

A-3

59 R

A4

64 R

These values show that adhesive formulations which contain isocyanatosilane compositions have a significantly improved resistance to degradation by attack from environmental conditions.

Example 2

A reaction vessel equipped with a stirrer and kept at room temperature under a nitrogenate atmosphere was filled with 133 g of polymethylene polyphenylene isocyanate with an average isocyanate functionality of 2.7.532 g of trichlorethylene and 0.1 ml of dibutyltin dilaurate. The mixture was stirred at room temperature to a uniform consistency. 60 g of hydroxypropyltrimethoxysilane and 240 g of trichlorethylene were then added to this mixture with continuous stirring. This addition was accompanied by an immediate, slightly exothermic reaction of less than 50 ° C. After the addition of the silane trichlorethylene was completed, the reaction mixture was stirred for an additional 5 minutes and allowed to cool to room temperature. The reaction mixture was a viscous liquid, which was free polymethylene polyphenylene isocyanate and polymethylene polyphenylene isocyanate / hydroxypropyltrimethoxysilane adduct, which had a free isocyanate functionality of about 1.7 and a single silane group with the following structure

Example 4

Following the procedure of Example 2, 179 g of g-aminopropyltrimethoxysilane in 1611 g of benzene was added to a continuously stirred mixture of 1000 g of polymer 40-methylene polyphenylene isocyanate (2.7 NCO functionality) and 100 g of trichlorethylene to give an amber-colored, viscous reaction liquid obtained which free polymethylene polyphenyl isocyanate and polymethylene polyphenylene isocyanate / 45 g-aminopropyltrimethoxysilane-isocyanatosilane adduct with a free isocyanate functionality of 1.7 and a single silane grouping with the structure

50

0

11

-NH-C-NH- (CH2) 5S i (OGII ^)

contained.

55 The molar equivalent ratio of total, free isocyanate to isocyanatosilane adduct in the reaction mixture was approximately 8.1: 1.

Example 5

60 Following the procedure of Example 2, 179 g of g-aminopropyltriethoxysilane in 1611 g of benzene was added to a continuously stirred mixture containing 400 g of polyethylenepolyphenylene isocyanate to give an amber, viscous reaction mixture, the free polyethylenepolyphenylene isocyanate and polymethylene polyphenylene -socyanate / g-aminopropyltriethoxysilane-isocyanatosilane adduct with a free isocyanate functionality of 1.7 and a single silane grouping with the structure

9

618212

-NH-C-NH (CH2) 3Si (OC2H5) 3

contained. *

The molar equivalent ratio of total free isocyanate to isocyanatosilane adduct in the reaction mixture was about 2.7: 1.

Example 6

The reaction product of Example 2, which contained isocyanatosilane adduct, free polymethylene polyphenylene isocyanate and trichlorethylene, was coated on a fiberglass cloth by immersion without further treatment and allowed to dry for five hours. The fiberglass fabric coated in this way was then glued with a polychloroprene rubber formulation of the following mixture:

Parts by weight

Polychloroprene rubber

100

Soot

60

Plasticizers

10th

Diurethane from tolylene diisocyanate

and nitrosophenol

6

Polymethylene polyphenylene isocyanate

3rd

Calcium oxide

4th

ZT peel test

attempt

Coatings kg

(lbs)

fracture

1

1

31.8

(70)

70 R

2nd

2nd

36.3

(80)

100 R

These values show that compositions which contain at least one isocyanatosilane with free isocyanate functionality and at least one polyisocyanate are powerful adhesives for bonding vulcanizable elastomeric materials to a substrate, in this case a fiberglass substrate.

Example 7

10 The reaction product of Example 4, which contained isocyanatosilane adduct with free isocyanate functionality, polymethylene polyphenylene isocyanate, trichlorethylene and benzene, was used without further treatment to bond non-primed, sandblown, degreased, cold-rolled,

15 steel and fiberglass fabric with a polyurethane-vulcanizable nitrile elastomer approach using the following mixture:

The composite was vulcanized at 160 ° C (320 ° F) for 20 minutes. The adhesion of the vulcanized composite was determined after the peel test at room temperature with the following results:

25th

Parts by weight

Butadiene acrylonitrile rubber

100

Soot

65

Plasticizers

20th

Diurethane of tolylene diisocyanate and

6

p-nitrosophenol

Polymethylene polyphenylene isocyanate

6

Zinc dimethyldithiocarbamate

2nd

30th

The bonded assemblies were vulcanized at 153 ° C (307 ° F) for 20 minutes. The adhesion of the vulcanized assemblies was tested after the peel test at room temperature. 35 examined the following results:

ZT peel test

Substrate adhesive coating kg (lbs) breakage

1

stole

Control®

1

PBHb

0R

2nd

stole

Example 4

1

54.4

(120) SB0

100 R

3rd

stole

Example 4

1

53.5

(118) SB

100 R

4th

stole

Example 4

2nd

49.9

(110) SB

100 R

5

stole

Example 4

2nd

56.7

(125) SB

100 R

6

Fiberglass

Control®

1

15.4

(34)

50 R

7

Fiberglass

control

1

15.9

(35)

50 R

8th

Fiberglass

Example 4

1

34.5

(76) SB

100 R

9

Fiberglass

Example 4

1

34.5

(76) SB

100 R

10th

Fiberglass

Example 4

1

38.6

(85) SB

100 R

11

Fiberglass

Example 4

1

34.0

(75) SB

100 R

a = polymethylene polyphenylene isocyanate, 10% in Trichlorätl len b = peeled by hand, practically no sticking c = break in the elastomer

These values show the performance of compositions which contain at least one isocyanatosilane with free isocyanate functionality and at least one free polyisocyanate, as adhesive materials for connecting vulcanizable elastomers to substrates such as metals and glass fibers.

Example 8

Following the procedure of Example 2, 179 g of g-aminopropyltrimethoxysilane in 716 g of benzene was added to a continuously stirred mixture of 750 g of polymethylene poly

lyphenylene isocyanate and 750 g of trichlorethylene were added to give 55 a viscous, liquid reaction mixture containing isocyanatosilane adduct with free isocyanate functionality and free polymethylene polyphenylene isocyanate, the equivalent ratio of total free isocyanate to adduct being about 6.6: 1.

60

Without further treatment, the reaction mixture thus prepared was used to bond a polyurethane elastomer which contained 12.5 parts of 4,4'-methylene-bis- (2-chloroaniline) as vulcanizing agent to 100 parts by weight of elastomer, with no primer provided, sandblown, degreased, cold-rolled steel. For comparison purposes, the polyurethane elastomer approach was bonded to metal substrates using the following control adhesive:

618212

10th

Polymethylene polyphenylene isocyanate, 25% in trichlorethylene

Following the vulcanization cycle, the bonded units were examined after the peel test at room temperature and at 100 ° C (212 ° F), and they were also examined for environmental resistance after the salt spray test. The results are summarized in Tables II to IV below.

Adhesive: (A) reaction mixture from Example 8.

(B) Polymethylene polyphenylene isocyanate, 25% in trichlorethylene.

Table!!

Salt spray exposure, breakage of adhesive after 72 h after 168 h

13

14

15

16

A A B B

50 R 50 R OR OR

ZT peel test

attempt

Adhesive kg

(Isb)

fracture

1

A

112

(248) SB

100 R

2nd

A

122

(270) SB

100 R

3rd

B

94

(208) SB

50 R

4th

B

94

(208) SB

50 R

Table III

212 ° F peel test

attempt

Adhesive kg

(Ibs)

fracture

5

A

76

(168) SB

100 R

6

A

68

(150) SB

100 R

7

B

63

(139) SB

100 R

8th

B

84

(186) SB

100 R

Table IV

attempt

adhesive

Salt spray exposure, break after 72 h after 168 h

9

A

90 R

10th

A

90 R

11

B

75 R

12

B

75 R

These values show that the mixtures according to the invention provide adhesive compositions which not only provide strong rubber-to-metal bonds, but also significantly improve the resistance to environmental influences.

Example 9

Following the procedure of Example 2, 15,179 g of g-aminopropyltrimethoxysilane in 716 g of trichlorethylene were added to a continuously stirred mixture of 750 g of poly-methylene polyphenylene isocyanate and 750 g of trichlorethylene. The reaction mixture was diluted with 200 g trichlorethylene, stirred for a further 5 min and cooled to room temperature 20. The reaction mixture thus prepared, which contained isocyanatosilane adduct with free isocyanate functionality and free polymethylene polyphenylene isocyanate and had an equivalent ratio of total, free isocyanate: adduct of about 6.6: 1, was divided into several equal parts without further treatment.

Several of the same parts were used to produce adhesive compositions, the following components (parts by weight) being added in a conventional manner:

30th

adhesive

B

D

Reaction mixture from Example 9 100

Dinitrosobenzene 35 trichlorethylene 300

Xylene

100

100

100

10th

20th

30th

325

350

425

17th

34

51

The adhesives were used to bond non-primed, sand-blown, degreased, cold-rolled steel with sulfur-vulcanizable natural rubber compounds and butyl rubber compounds . The 45 results are summarized in Table V below.

Table V

ZT peel test

AH2O-

Elastomer

Adhesive kg

(lbs)

fracture

fracture

Natural rubber

A

PBH

0R

Not un

tries

Natural rubber

B

21.8

(48)

100 R

20 R

25 R

Natural rubber

C.

24.1

(53)

100 R

55 R

30 R

Natural rubber

D

23.2

(51)

100 R

70 R

70 R

soft natural rubber

A

PBH

0R

soft natural rubber

B

14.5

(32) SB

100 R

15.9

(35) SB

90 R

soft natural rubber

C.

13.6

(30) SB

100 R

12.3

(27) SB

100 R

soft natural rubber

D

15.0

(33) SB

100 R

14.1

(31)

100 R

Butyl rubber

A

PBH

0R

*

11

618212

ZT waiver test

AH: 0-

Elastomer

Adhesive kg

(lbs)

fracture

fracture

Butyl rubber

B

48.1

(106)

100 R

43.1

(95)

100 R

40.0

(88)

100 R

Butyl rubber

C.

(105)

100 R

43.1

(95)

90 R

Butyl rubber

D

40.9

(90) SB

90 R

43.6

(96)

80 R

42.7

(94)

90 R

Example 10

Several of the same proportions of the reaction mixture from Example 9 were used to prepare adhesive compositions, to which the following components (parts by weight) were conventionally added:

hold (TSC) of about 20 wt .-% according to the following information, the amounts in parts by weight are given:

adhesive

B-l

B-2

B-3

Reaction mixture from example

Q

100

100

100

Dinitrosobenzene

30th

30th

30th

Chlorinated

35

-

-

Ethylene / propylene / non-conjugated

gated diene terpolymer

Chlorosulfonated polyethylene

-

35

-

Chloroacrylonitrile / dichlorobuta-

-

-

35

diene copolymer

Trichlorethylene

180

495

437

Xylene

256

151

101

20th

These adhesives were used to bond non-primed, sandblasted, degreased, cold-rolled steel with a sulfur-vulcanizable natural rubber formulation. Following the vulcanization cycle, the bonded units were subjected to the peel test at room temperature and the boiling water test with the following results:

C-l

Parts by weight C-2 C-3

C-4

Reaction mixture of

100

100

100

100

Example 11

Dinitrqsobenzol

30th

30th

30th

30th

Chlorinated

35

-

-

-

Ethylene / propylene / noncon-

jugated

Diene polymer

Chlorosulfonated

-

35

-

-

Polyethylene

Chloroacrylonitrile / dichlorobu-

-

-

35

-

tadiene copolymer

Trichlorethylene

400

400

400

400

Xylene

260

260

472

120

35

Each adhesive was kept at room temperature for an extended period of time and viscosity measurements (Brookfield viscometer, spindle No. 2 at 30 rpm) were carried out with the following results:

ZT peel test

AH2O-

Adhesive kg

(lbs)

fracture

fracture

B-l

24.1

(53)

100 R

100 R

100 R

B-2

24.5

(54)

100 R

100 R

100 R

B-3

20.9

(46)

100 R

100 R

100 R

Viscosity (cP)

adhesive

C-l

C-2

C-3

G4

time

At the start

38

282

290

60

1 week

75

286

292

160

2 weeks

78

320

236

76

3 weeks

75

303

192

75

6 weeks

85

360

370

80

Example 11

Following the procedure of Example 2, 179 g of g-aminopropyltrimethoxysilane in 716 g of trichlorethylene were added to a continuously stirred mixture of 750 g of poly-methylene polyphenylene isocyanate and 3000 g of trichlorethylene, thereby obtaining a reaction mixture containing free polymethylene polyphenylene isocyanate and polymethylene / polyphenylene isocyanate Aminopropyltrimethoxysilane with a free isocyanate functionality of 1.7 and a single silane grouping included. The equivalent ratio of total free isocyanate to adduct in the reaction mixture was approximately 6.6: 1.

The reaction mixture was divided into several parts and adhesive compositions with a total solids content of

These values show the excellent storage stability at ambient temperature of the adhesive compositions described here.

55

Example 12

Following the procedure of Example 2, 179 g of g-aminopropyltrimethoxysilane in 385 g of xylene and 358 g of trichlorethylene were added to a continuously stirred mixture of 60 g of 750 g of polymethylene polyphenylene isocyanate, 1500 g of xylene and 1500 g of trichlorethylene to give a viscous reaction mixture, the isocyanatosilane adduct with free isocyanate functionality and free polymethylene polyphenylene isocyanate and had an equivalent ratio 65 of total, free isocyanate: adduct of about 6.6: 1.

The reaction mixture prepared in this way was used without further treatment to produce adhesive compositions with a

618212

12

Total solids content of about 15% by weight used as follows, the amounts being given in parts by weight:

adhesive

D-1 D-2 D-3 D-4 D-5

Reaction mixture of Example 12 Dinitrosobenzol chlorosulfonated polyethylene

Chloracrylonitrile / dichlorobutadiene copolymer

100 100 100 100 100

30 30 30 30 30 35 -

35 -

adhesive

D-l

D-2

D-3

D-4

D-5

Chlorinated

-

-

-

35

-

Ethylene / propylene / -

non-conjugated

Diene terpolymer

Cellulose acetate butyrate

Xylene

330

220

220

168

35 337

Trichlorethylene

400

715

715

777

598

Samples of each adhesive batch were kept at room temperature and 54.4 ° C (130 ° F) for extended periods of time and viscosity measurements were made periodically with the following results:

time

Adhesive, viscosity (cP) D-l D-2

ZT 54.4 ° C ZT

54.4 ° C

D-3 ZT

54.4 ° G

D-4 ZT

54.4 ° C

D-5 ZT

54.4 ° C

At the start

35

35

70

70

115

115

90

90

1 week

-

46

-

179

-

178

-

180

2 weeks

-

62

-

160

-

112

-

44

3 weeks

-

92

-

190

- ■

80

-

30th

4 weeks

20th

190

68

230

130

165

40

30th

5 weeks

25th

350

75

172

135

70

55

25th

6 weeks

-

408

-

138

-

2300

-

45

7 weeks

-

850

-

170

-

paste

-

25th

8 weeks

-

paste

-

> 1000

-

355

-

25th

9 weeks

-

paste

-

1975

-

550

-

30th

140 140 paste paste

Example 13

A number of adhesive batches were made by conventionally combining the following components (parts by weight):

Adhesive E-l

E-2

E-3

Isocyanatosilane (polymethylene

-

8th

polyphenylene isocyanate / g-ami-

nopropyltriethoxysilane adduct)

Trichlorethylene / xylene at 50% 600

600

600

adhesive

E-l

E-2

E-3

40

The adhesives were used to bond sulfur-volcanic

Chlorosulfonated polyethylene

35

35

35

nizeable natural rubber with non-primed,

Dinitrosobenzene

30th

30th

30th

sandblown, degreased, cold-rolled steel

Polymethylene polyphenylene iso-

40

-

42

Following the vulcanization cycle, the glued cyanate

ten units the peel test at room temperature and the g-aminopropyltriethoxysilane

-

10th

-

45

Boiling water test with the following results:

ZT peel test

AH2O

Adhesive kg

(lbs)

fracture

fracture

E-l

18.2

(40)

45 R

0 R (within 10 sec)

E-2

22.7

(50)

0R

0 R (within 10 sec)

E-3

19.5

(43)

100 R

100 R (after 2 h)

100 R (after 6 h)

The previous values are a comparison of isocyanate, methylene bis (phenyl isocyanate) and methylene

Adhesive compositions prepared according to the invention bis (cyclohexyl isocyanate). The reaction mixtures with adhesive compositions which used the starting materials used in each case for the production of isocyanatosilane compositions without further treatment, from adhesive compositions which hold chlorosulfonated. These values speak for themselves. 60 polyethylene, dinotrosobenzene and soot contained. The adhesive compositions prepared in this way were efficient in bonding sulfur-vulcanizable natural rubber approaches Example 14 to steel substrates, and they formed bonded rubber-on

There were metal isocyanatosilane adducts, which were resistant to the environmental conditions of Example 2 from g-aminopropyltriethoxysilane and tolylene di es.

Claims (5)

618212 1 ^ 3-a 10 an ideal all-purpose adhesive, a large number of adhesive compositions have already been developed, which, with different wherein R1 is a monovalent, aliphatic, cycloaliphatic or successful in connecting or gluing elastomeric aromatic residue with 1 to 20 carbon atoms, R2 is a rialien is itself or with other substrates under Bil-monovalent, aliphatic, cycloaliphatic or aromatization of laminates and composite articles is a residue with 1 to 8 carbon atoms, a = zero or 1 is 15 have been. As a general rule, the well-known Adhesive and Z is a divalent, organic residue that binds to the substances that have proven to be efficient as “single coating binders”. Silicon atom via a carbon-silicon compound for rubber-on-metal, in which is, and in view of the type of elastomers to be bonded b) at least one aromatic nitroso compound is limited in one. This means that there is an adhesive for the amount of 5 to 200 parts by weight. 20 Position of an acceptable bond with butadiene-styrene- 1. Adhesives based on organic silicon compounds at elevated temperatures are suitable and as «single-layer genes, characterized in that adhesive systems» can be used. Substrates can a) as an organic silicon compound, 2.5 to 100 parts by weight in addition to the elastomeric materials themselves, metals, textiles or at least one isocyanatosilane of the following formula: 5 lines, ceramic materials and other similar substrates. . -, It is known per se, adhesive compounds for connecting (R) elastomeric materials with substrates including elasto- I amers, textiles, metals and other solid substrates to nr _ '. _. 2. use. When the search for 2. 45 formulations, and especially for single-layer adhesive formulations Nn-L A K-bi- IUK; 3-a mulations which, when connecting or gluing elastomeric materials to different substrates, the free isocyanate group and the silane grouping finally being able to be used themselves, and which for adducts to one another over the rest of the isocyanate reaction part, are long periods of storage before use, are bound in which R1, R2 and a have the meanings given in claim 1 50 which are used with a large number of elastomeric materials and R can be a divalent, ali- and which are resistant to degradation by means of conversion, cycloaliphatic or aromatic radical 1 to exercise factors are stable. 20 carbon atoms, R ° is a divalent hydrocarbon. The object of the invention is therefore adhesives for the rest of the compounds or a divalent, halogenated hydrocarbon / or the bonding of a multiplicity of elastomers with increased residues having 1 to 20 carbon atoms and A -O-, -S-, -NH- 55 th temperatures with different substrates and in particular-or another divalent group with an active water with metal substrates or substrates. Furthermore, the adhesives according to the invention are a strong adhesive binder. 2. Adhesive according to claim 1, characterized in that it is stomeric in the case of elastomers in the form of ethylene / that it also contains a film-forming additive in an amount of propylene / non-conjugated diene terpolymer (EPDM) or from 10 to about 200 parts by weight . unsatisfactory for polyisobutylene / isoprene elastomers 2nd PATENT CLAIMS or with other substrates including yourself 3. Adhesive according to claim 1 or 2, characterized thereby. This lack of versatility, which means that it also contains an inert filler in an amount of 10 25, a feature of the general class of single layer adhesive to about 200 parts by weight. systems, can be done in part by using two- 4. Adhesive according to one of claims 1 to 3, characterized in that layer-adhesive systems are avoided, which are characterized in that they use isocyanatosilane from the following group of primer coating or base coating, which is applied to the metal substrate, and a cover coating. i) Isocyanatosilanes of the following general formula 30 layering (which adheres well to the elastomer) and which is applied between the elastomer and the primer layer / R1 v. In addition to the problem of versatility However, I have both single-layer and two-layer o 2 and adhesive systems including one or more disadvantages OCN-R -Si- (OR) 2_a 35 the general inability to produce an optimal Liability, especially at elevated working temperatures, ii) Isocyanatosilane adducts of multifunctional organo- poor storage stability at room temperature or silanes and polyisocyanates, these adducts as characteristics- at elevated temperatures, poor resistance, at least one free isocyanate group and against early hardening. Furthermore, the at least one silane grouping with the following structure on resistance of the adhesive bond to environmental evidence: conditions such as solvents, moisture and the like are often significantly worse than is normally desired in numerous technical applications. Therefore Il I a there is a need for more efficient adhesive 5. Adhesive according to one of claims 1-4, characterized in that manure between the elastomer and the substrate, characterized in that it contains the isocyanatopro as isocyanatosilane, this adhesive bond containing pyltriethoxysilane to environmental influences. 60 is very stable Surprisingly, adhesives have now been found which contain at least one isocyanate-functional organosilane, preferably in combination with at least one polyisocyanate and at least one aromatic nitroso-65 bond, which are unexpectedly effective and stable on storage and in