CA1088696A

CA1088696A - Isocyanto-functional organo silanes and adhesives therefrom

Info

Publication number: CA1088696A
Application number: CA233,912A
Authority: CA
Inventors: Nicholas J. Gervase
Original assignee: Lord Corp
Current assignee: Lord Corp
Priority date: 1974-09-17
Filing date: 1975-08-21
Publication date: 1980-10-28
Also published as: DE2540080C2; SE7510043L; TR18921A; IT1046974B; FR2285391A1; CH618212A5; DE2540080A1; JPS51125130A; AT351652B; DK415675A; DK152136B; SU1429937A3; GB1526953A; NL185525C; SE425745B; NL7510952A; BE833508A; NL185525B; CA1095926A; BR7505906A

Abstract

Compositions comprising at least one isocyanate-functional organo-silane, preferably in combination with at least one polyisocyanate, and, optimally, at least one aromatic nitroso compound have been found to be un-expectedly effective as storage-stable, single-package, one-coat adhesive systems for bonding a variety of elastomeric materials to themselves and other solid substrates, such as metal, fabric, ceramic, and the like substrates.

The isocyanatosilanes, employed in the present invention are characterized by the presence of at least one free isocyanate moiety and at least two hydrolyzable groups according to the general formula wherein R1 is a monovalent aliphatic, cycloaliphatic or aromatic radical having from 1 to 20 carbon atoms, and is preferably selected from the group consisting of alkyl radicals having from 1 to 4 carbon atoms, cycloalkyl radicals having from 4 to 7 ring carbon atoms, aryl radicals havlng 6, 10, or 14 nuclear carbon atoms, and such aryl radicals containing one or more substituent alkyl groups having from 1 to 4 carbon atoms;
R2 is a monovalent aliphatic, cycloaliphatic or aromatic organic radical containing from 1 to 8 carbon atoms and is preferably selected from the group consisting of alkyl radicals having from 1 to 4 carbon atoms, where R3 is an alkylene group having from 1 to 4 carbon atoms and R4 is an alkyl group having from 1 to 4 carbon atoms;
a is zero or 1, and preferably is zero; and Z is a divalent organic radical attached to the silicon atom via a carbon-silicon bond.

Description

1~188696 ~

This invention relates to adhesive compositions. More particularly, the invention relates to adhesive compositions suitable for bonding elastomeric materials, especially vulcanizable elastomeric materials, at elevated temperatures to inorganic substrates and to other substrates including themselves.
It is well-known to employ adhesive compositions for bond-ing elastomeric materials to substrates, including elastomeric, fabric, metal, and other solid substrates. In the as yet unconsummated search for the ideal all-purpose adhesive, there have been developed a variety of adhesive compositions which have been utilized with varying degrees of success in bonZing elastomeric materials to themselves or to other substrates to form laminates and composite articles. As a gen~ral rule, the known adhesives which have been effective as single-coat rubber-to-metal bonding agents are limited with respect to the type of elastomer to be bonded. That is to say, an adhesive which is capable of providing an acceptable bond with butadiene/
styrene elastomers may be unsatisfactory with ethylene/
propylene/nonconjugated diene terpolymer (EPDM) elastomer or polyisobutylene/isoprene q~

~i ( ( 1 1~8~69~;

elastomer. This lack OI ve~atilily which is characteristic of the general class of one-coat adhesive systems can be partially alleviated by the use oI
two-coat adhesive systems which utilize a primer coat applied over the metal substrate and a cover coat (which adheres well to the elastomer) inter-spersed between the elasto~ner and the primer. In addition to the problem of versatility, both the one-coat and two-coat adhesive systems suffer from one or more other disadvantages, includinga general inability to afford optiml~m adhesion, particularly at elevated service temper~tures; poor storage stability at room and/or elevated temperatures; poor resistance to prebake;
and the resistance of the adh3sive bond to environmental conditions such as solvents, moisture and the like, is too often poorer than is normally desired in many commercial applications. Thus, there rern~inC a need for more effective adhesive formulations, particularly one-coat adhesive formulations which can be employed in bonding elastomeric materials to various substrates including themselves, which are shelf-stable for extended periods prior to use, which car be employed with a variety of elastomeric m~terials, and which are resistant to degradation from environmental factors It is an object of this invention to provide adhesive compositions for bonding a variety of elastorners at elevated temperatures to various sub-strates, particularly metal substrates .
i, It is another ohject of this invention to provide adhesive compositions which afford strong elasto~er-substr~te adhesive bonds and which adhesive bonds exhibit high environmental resistance.
These and other objecis, aspects, and advantages of the invention, including a method for bonding elastomeric materials to substrates, and adhesively-joined elastorr er-substrate composites, will be readily apparent 'rom a consideration of the specification and the appended claims.

, ~088696 In accordance with t~ present invention, it has been discovered t~t compositions comprising at least one isocyanato organosilane, pref-erably in combination with at least one polyisocyanate characterized by the presence of at least two free isocyanate groups, are unexl?ectedly effec~ive as adhesive materials for bonding a variety of elastomers, particularly vulc~ni~ble elastomers, to inorganic substrates. The isocyanato ~lnctional organosilanes, whichwillbe referredto hereafter as isocy~n~to~ilanes,whic}
are suitable for use in the present invention, can be broadly described as those compounds capable of undergoing both the hydrolytic reactions typica~
of alkyl esters of silicic acid and the reactions with active hydrogen~ontair~in compounds typical of isocy~n~te.s.
In addition to affording strong adhesive bonds with a variety of elastomers, the compositions of the invention improve the environment~l resistance of the bonded asseml31y. It has also been discovered that the in-corporation of one or more aromatic nitroso compounds can-improve the stren~th of the adhesive bond and/or improve the environmental resistance, and can further extend the versatility of the adhesive compositiorLs. It has further been discovered th~t the inclusion o~ one or more polymeric film-forming adjuncts can provide further improvements, particularly in relation to film properties. The compositions of the invention provide strong bonds which is highly desired in man~ commercial applications. A particularly une~ected feature of the invention is the capability of the herein described cornpositions to function as single-package, one-coat adhesive systems whic~
afford strong rubber-to-metal adhesive bonds having an improved resistance to environmental attack. In addition, tho preferred adhesive compositions of the invention are further characterized by their stability at ambient '.

~88696 . .

temper~tures during storage and h3ndling.
The reason for the i-mprovement in stability is not fully und~rstood.
Generally, adhesive compositions comprising free iso~yanate-containing materials have a limited pot life, due to the high reactivity of the iso-cyanate group with water and other active hydrogen-cont~ining compounds.
The inclusion of aromatic nitroso compounds and/or polymeric film-formin adjuncts introduces impurities such as water and reactive oximes which ould be expected to h~ve a deleterious effect on stability, since such impurities tend to hydrolyze both the isocyanate and the silicic ester portions of the isocyanato or~anosilane and also react with the other com-ponents, e. g., through the free isocyanate groups of the free polyisocyan~t~
thereby leading to premature gelation of the adhesive compositions. It lS
hypothesized that the improv~ment in stability could be due to the acidic buffering which is inherent in the compositions of this invention due to any or all of the latent, i.e., free, acidity of the polyisocyanate component, an acidic contribution from random and dissociated free silicic acid groups, o]
an acidic contribution from the polymeric film-forming adjunct. This postu lation is disclosed in U. S. ~'atent No. 3,830,784, which is directed to improvements in shelf stability, i. e., storage and handling stability of rubber-to-metal bonding compositions cont~ining free polyisocyanates. The same means of improving shelL stability taught under U. S. 3,830,784 may in fact be operative for the compositions of the present invention.
The isocyan~osilanes employed in the present invention are characterized by the presence of at least one free isocyanate moiety and at least two hydrolyzable grou~s according to t~ eneral formula . . .

, ~8t3~
`

OCN - Z - Si - (OR ) 3 -a wherein R1 is ~ monovalent aliphatic, cycloaliph~tic or aromatic radical having from 1 to 20 carbon atoms, and is preferably selected from the group consisting of alkyl radicals having from 1 to 4 carbon atoms, cycloalkyl radicals having from 4 to 7 ring carbon atoms, aryl radicals having 6, 10, or 14 nuclear carbon atoms, and such aryl radicals cont~inin one or more substituent alkyl groups having from 1 to 4 carbon atoms;
R is a monovalent aliphatic, cycloaliphatic or aromatic orgaxlic radical cont~ining from 1 to 8 carbon atoms and is preferably selected fror the group consisting of alkyl radicals having from 1 to 4 carbon atoms, -R3 - O - R4, and - C - R4, where R3 is an alkylene group having from to 4 carbon atoms and R4 is an alkyl group having from 1 to 4 carbon atom a is zero or 1, and preferably is zero; and Z is a divalent organic radical attached to the silicon atom via a carbon-silicon bond. The exact nature of the Z radical is not critical, i. e the radical can have any confi~uration and combination of groupings that ar cornp~tible with the isocyan2to groups. ~or example, the Z radical can be a hydrocarbon radical, or it can contain lin~ages such as ether, ureido, urethane, and thiourethane linhages. The Z radical can, of course, contai substituent groups such as h~logen which are compatible with the iso-cyanato g-roups.
Isocyanatosilanes which are preferably, but not exclusively so, em-ployed in the practice o f the invention are selected from the group consisti , ' , .

~,~886~6 of (1) isocyanatosiLanes having the general formula Ra OCN-R-Si-(O:R2)3_a or (2) isocyanatosilane adduc~s of multifunctional ogranosilanes and poly-isocyanates, said adducts h~ving as characteristic features at least one free isocya-~ate group and at least one silane grouping having the formula Ra - NH - C - A - R - Si - (OR2)3_a it being understood that said free isocyanate group(s) and said silane grouping(s) are joined to each other through the residue of the polyisocyanate reactanl. The isocyanatosilane adducts, i.e., the reaction products of multifunc~ional organosilanes and polyisocyanates, are presently preferxed for forming adhesive compositio~Ls according to the invention. Such adducts are generally easier to prepare and are consequently more readily available than are isocyanatosilanes prepared directly from the more basic silane imermediates. (The ~ore basic silane intermediates are for present p~rpos2s, assumed to be those with the highly reactive - Si - H or - Si - Cl functionality. ) In the foregoing formulae, R1, R2 and a are as previously defined;
R is selected l~rom t~e group consisting of divalent hydrocarbon and ~logen~ied hydxocarbon radicals having from 1 to 20, preferably 2 to 9, carbon atoms;

., :~.

8~696 .~ . .
~ is selected from the group consisting of - O -, - S -, ~N--, and other groups containing an active hydrogen: and is a divalent aliphatic, cycloaliphatic, or aromatic radical h3ving from 1 to 20 carbon atom~, and is preferably an alkylene radical having fror 1 to 9 carbon atoms. Especiaaly preferred are adducts in which A is - O -or E-N ; R is an alkylene group having from 2 to ~ carbon atoms, R2 is methyl, ethyl, rnethoxyethylene or methyl carbonyl, and a is zero IsocyanatosiLanes corresponding to the formula .
Ra O~N - R - Si - (oR2 )3-a are known articles of commerce. Such compounds can be prepared, for example, by the pyrolysis of the corresponding carbamate. The carbamate can be prepared by effecting reaction between a silylorganohalide, a metal cyanate and an alip~tic monohydric alcohol in the presence of an aprotic soLvent. Another method for preparing such compounds comprises effecting reaction between a silicon hydride and an olefinicalay un.~tll~ted isocyanat~
such as allyl isocyanate. Such isocyanatosilanes include, without limitation, trimethoxysilylpropylisocyanate, phenyldiethoxysilylpropylisocyanate, and methyldi methoxys ilylbutylisocyanate .
The presently preferred isocyar~tosil~ne adducts can be readily prepared by effecting reaction between a multifunctional organosilane and a polyisocyanate by adding the organosilane, preferably as a dilute solution, to the polyisocyanate, aLso prelerably diluted, at a terrperature in the rang~
from about 10 to about 100 C, whiLe agitating the mixture by a mechanical stirrer or similar device. ~Thile not essential, a suitable catalyst, such as _ 7 _ 8869~;

dibutyltin dilaurate, can be ernployed. The reaction is essentially inst~t~n~c particularly when catalysts are employed, and is accompanied by a mild exotherm. It is essential th~Lt the amount of polyisoc:yanate present during the reaction be such as to ensure obtaining an adduct h~ving at least one free isocyanate group. Thus it will be appreciated that the miniml]rn amount, in molar equivalents of NCO, of polyisocyanate required to form the addùcts of the invention is one molar equivalent of NCO in excess of the amount, in molar equivalents of NCO, required to react with a~l the active hydrogen of the silane reactant. If desired, the adduct can be separated from the reactio mix~llre by conventional means. However, it has been found advantageo~Ls to add the organosilarle reactant to a sufficient excess of the polyisocyanate reactant to ensure complete reaction of the organosilane reactant to afford, on the one hand,an isocyanate adduct having at least one free isocyanate group and7 on the oth~r hand, a reaction mi~tl]re cont~ining sufficient un-reacted polyisocyanate to provide the requisite amount of isocyanate function~lity, as will be set forth in greater detail, infra. In this manner, th isolation of the silane-isocyanate adduct from the reaction mixture and the subsequent addition of the adduct to free polyisocyanate can be dispensed with, thereby a~fording a significant economic advantage. This method, i. e., contacting the organosilane reactant with excess polyisocyan~te reactant, has been found to be particularly advantageous in those instances wherein the adhesive compositions of tlle imTention contain a polymeric film-former adjunct.
~ s noted, at present it is preferred to employ both the silane and the polyisocyanate in dilute form. Suitable solvents include aromatic hydrocarba , such as benzene, tol uene, xylene, and the like; ~alo~enated aromatic hydro-carbon suchas monochlorobenzene, dichlorobenzene, and the like;

,~ -- 8 --. -. .

8869~;

halogenated alipha~ic nydrocarbons, such as trichloroethylene, perchloro-ethylene, propylen^ dichloride, and the llke; ketones, such as methyl isobutyl ketone, methyl ethyl ketone, and the like, ethers, and the like;
` including mixtures of such solvents/diluents. The degree of dilution is not critical. As long as it does not prohibit an adequate film thickness of the adhesive in the end application.
The multifunctional organosilarle compounds which are suitable for use in the practice of the invention are characterized by the presence of a single organic chain cont~ining at least one functional group having at least one extractable, i. e., active, hydrogen atom, such as an amino, mercapto, hydroxy, or other active hydrogen-cont~ining functional group being con-nected to silicon through an organic group cont~ining at Least one carbon ato Preferably, the functional group containing at least one active hydrogen ator is connected to the siLicon ato-m by an organic group cont~ ining at least two interconnected ca:,^bon atoms.
More particularly, the multifunctional organosilane compounds which are suitable for use in the practice of the invention are selected from the group cons;sting of hydroxyorgano silanes having the formula HO - R - Si - (OR2 )3_a wherein R is a divalent aliphatic, cycloalipl,latic or aromatic radical h3ving -from 1 to 20 carbon atoms, and is prefe-rably an alkylene ~adical havi from 1 to 9, most preferably 2 to 4, carbon a~oms;
R1 is a monovale~ aliphatic, cycloaliphatic or aromatic radical h~ving from 1 to 20 carbon acoms) and is prefe~ably selected from the grou~

consisting oE alkyl radicals h~vin~ from 1 to 4 carbon atoms, cycloalkyl _ 9 _ :.

~ ~8869~

radicals having :Erom 4 l:o 7 ring carbon atoms, and aryl radicals having 6, . 10, or 14 nuclear carbon atoms, and including such aryl radicals Cont~3 ini ng one or more substituent alkyl groups h~ving from 1 to 4 carbon atoms;
R2 is a monovalent aliphatic, cycloaliphatic or aromatic organic radical collt~inin~ from 1 to 8 carbon atoms, and is preferably seLected from the group co-nsisting of alkyl radicals having ~rom 1 to 4 carbon atoms, o R~ - O - R4, and - C - R4, where R3 is an alkylene group having fror~ 1 to 4 carbon atom~ and R4 is an alkyl group having from 1 to 4 carbon atorns;
and a is zero or 1, preferably zero;
J aminoorganosilane compounds having the characteristic formula H I a R5 - N - R - Si - (oR2 )3-a wherein R, R1, R2 and a are as previously defined: and R5 is selected from the group consisting of hydrogen, monovalent aliph~tic radicals having from 1 to 8 carbon atorn~, monovalent cycloaliphati( radicals having from 4 to 7 ring carbon atoms, phenyl, alkaryl radicals havi]
6 nuclear carbon atoms and containing one or more substituent alkyl groups ! having from 1 to 4 carbon atoms, and - R6 -NE - R7, wherein R6 is selecte from th~ group consisting of divalent aliphatic, cycloaliphatic and aromatic radicals h~ving from 1 to 20 carbons, there being preferably at least two . carbon atoms separating any pair of nitrogen atoms, with R6 being preferabl an alkylene group of 2 to 9 carbon atoms: and E~7 being the same as R5 and ! preferably is hydrogen;

mercapto oryanosiLane compolmds h3ving the ~h~ract~ri~tic iormula Ra HS - R - Si - (0~2 )3_a wherein R, R~ 2 and a are as previously defined;
and other organosilane compounds having a single organic chain bavi~
from 1 to 20 carbon atoms, said chain having at least one extractable hydrogen atom, said extractable hydrogen atom preferably being ~tt~,ch~A to a functional group separated from the silicon atom by a chain of at least 3 interconnected carbon atoms.
The preferred org~nosilane compounds for use in the practice of the invention are aminoorganosilane compounds as herein de~cribed N wi~l be appreciated that both primary and secondary aminoorganosilane compoun and also such compounds cont~ining in their structure at least one primary amino grouping and one or more secondary amino groupings can be employe in forming the compositions of this invention.- It is also possible l~o employ aminoorganosilane compounds containing one or more tertiary amino groupings providing such compounds contain also at least one primary or secondary amino grouping. At present, aminoorganosilane compounds characterized by the presence of at least one primary amino groupi-ng are preferred.
Representative mulhfunctional organosilanes which aré suitable for use in the practice of the invention include without limitation hydroxypropyl trimethoxysilane, hydroxypropyltriethoxysilane, hydroxyl~utyltrimethoxy--j silane, g-aminopropyltrimethoxysilane, g-aminopropyltriethoxysilane, c ~8869~

methyl ~m inopropyltrimethoxysilane, g-arninopropyLtripropoxysilane, g-aminoisobutyltriethoxysilane, g-arninopropyknethyldiethoxysilane, ~-amino-propylethyldiethoxysilane, g-ammopropylphenyldiethoxysilane, d-arrlino-butyltriethoxysilane, d-aminobutylmethyldiethoxysilane, d-aminobut~l-ethyldiethoxysilane, g-arr~inoisobutylmethyldiethoxysilarle, N-methyl-t~-a-rninopropyltriethoxysilane, N-phenyl-g-aminoisobutylmethyldiethoxysilane, N-ethyl-d-aminobutyltriethoxysilane, N-g-aminopropyl-g-aminopropyl-triethoxysiLane, N-~-arnino~thyl-g-aminoisobutyltriethoxysilane, N-g-ami-nopropyl-d-aminobutyltriethoxysilane, N-aminohexyl-q-aminoisobutyl-methyldiethoxysilane, methyl~ m i nopropylt~ethoxysilane, g -mercapto -propyltrimethoxysilane, mercaptoethyltriethoxysilane, g-aminopropyl-methoxydiethoxysilane, and the like.
The polyisocy~n~tes which can be employed in the practice of the present invention can be any organic isocyanate having at least two free isocyanate groups. Included within the purview of suitable polyisocy~n?~t~
are aliph~tic, cycloaliphatic, and aromatic polyisoc~Tanates, as these terms are generally interpreted in the art. Thus it will be appreciated th~t any of the known polyisocganates such as alkyl and alkylene polyisocyanates, cycloalky~ and cycloalkylene polyisocy~n~tes, aryl and arylene poly-isocyan~tes, and combinations such as alkylene, cycloalkylene and alkylene arylene polyisocyanates, can be emplo~Ted in the practice of the present i-nvention. These polyisocyanates can serve both as the free polyisoc~nate compone~t of the he-rein described compositions and as a starting material for the silane-poly~socyanate adduct component.
Particularly preferred polyisocyanates are the polyalkylene poly-(aryleneisocyan~tes) having the forrnula , , 1~88~9~

(X)5-m -- (X)4-m --- (X)5-m R8 ~ R8 [~

(NCO)m (NCO)m _n (NCO)Xn wherein R8 is a divalent organic radical, preferably a divalent aliphatic radical having Irom 1 to 8 car~on atoms, especia~ly such radicals obtained by removing the caroonyl oxygen from an aldehyde or ketone, and preferably is methylen~
m is 1 or 2, and is preferably 1;
n is a digit having an average value in the range frorn zero to 15, preferably 0.1 to 4, and most preferably 0. 3 to 1. 8; and X is selected from the group consisting of hydrogen, halogen, alkyl radicals having from 1 to 8 carbon atoms, and alkoxy r~ic~l~ having from 1 to 8 carbon atoms, and pre ~ erably is hydrogen.
Suitable polyisocyana.tes include without limitation tolylene-2, 4-diisocya~ate, 2, 2, 4-tri methylh~ R.rnethylene^1, 6-diisocyanate; hexamethyle]
1, 6 -diisocyanate, diphenylrnethane-4, 4' -diisocyanate, triphenylmethane-4, 4', 4-triisocyanate, 3-isocyana~omethyl-3, 5, 5-trimethylcyclohexylisocyanat polymethylene polyphenylisocyanate, m-phenylenediisocyan~te, p -phenylen~
diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthalenediisocyanate, naphth.alene-1,4-diisocyanate, diphenylene_4,4'diisocyan~te, 3,3'-bi-tolyl~

:i 4, 4' -diisocyanate, ethylene diisocyanate; propylene-1, 2-diisocyanate, , butylene-2,3-diisocya~ate, e~hylidenediisocyanate, butylidenediisocyanate, xylylene-1, 4-diisocyanate, xylylene-1, 3-diisocyan~te, methylcyclohexyl-: diisocyan~te, cyclopentylene-1,3-diisocyanate, cyclohexylene-1,4-diisocya . .

.i - 13 -~ .i ~88696 4,4'-met~lylene-bis(cyclohex~rlisocyanate~, p-phenylene-2,2'-bis(ettnyl-isocyanate), 4, 4'-diphenylene ether-2, 2' -bis(ethylisocyanate), tris(2, 2', 2"-cthylisocyanate benzene), 5 -chloro -phenylene-1 , 3 -bis(propyl -3 -isocya-n~te), 5-methoxy-phenylene-1,3-bis(propyl-3-isocyanate), 5-cyanophenylene-1, 3 -bis (propyl -3 -isocyanate), 4 -methyl -phenylene-1, 3 -bis (propyl -3 -isocyanate and the like. Other poLyisocy~-n~tes which can be employed in the practice of the invention include the arom~tic diisocyanate dimers, such as those described in U. S. Patent No. 2,671,082. A particularly preferred dimer is the tolylene diisocyanate dimer having the formu~a H3C ~¦ \` C / ~ C~3 OCN O ~CO

The arom~tic nitroso compounds which are suitable for use in the practice of the present invention can be any arornati.c hydrocarbon, such as benzenes, naphthalenes, anthracenes, biphenyls, and the like, cont~ i ni n~ at least two nitroso groups attached directly to non-adjacent rin~ carbon atoms More particularly, such nitroso compounds are described as poly-C-nitroso arom~tic compounds having from 1 to 3 aromatic nuclei, including fused aromatic nuclei, havi-ng from 2 to 6 nitroso groups attached directly to non-adjacent nuclear ca-rbon atoms. The presently preferred po~y-C-nitroso materials are the di-nitroso aromatic compounds, especially t~le dinitroso-benzenes and dinitrosonaphthalenes, such as the meta- or paradinitroso_ benzenes and the meta- or paradinitrosonaphthalenes. The nuclear hydroger ~ ~38~36~ -i atoms o f the aromatic nucLeus can be replaced by alkyl, alkoxy, cycloalkyl, aryl, aralkyl, all~aryl, arylamine, arylnitroso, amino, halogPn, andthelil~e ~roups. The presence of such substituents on the arornatic nucleus has little efect on the activity of ~he poly-C-nitroso compounds in the present invention. As far as is presently known, there is no limitation as to the character of the substituent, and such substituents can be organic or in-organic in nature. Thus, wh^re refe~ence is rnade herein to poly-C-nitroso or di-C-nitroso "aromatic compound, " benzenes, " or "naphtkalenes, " it will be understood to include both substituted and unsubstituted nitroso com-pounds, unless otherwise sp~cified.
Particularly preferred poly-C-nitroso compounds are characterized by the formula (R9 )p - Ar - ( NO )2 ~

wherein Ar is selected from the group consisting of phenylene and naphthalene;
R9 is a monovalent organic radical selected from the group consistir , of alkyl, cycloal~yL, aryl, aralkyl, alkaryl, arylamine and alkoxy radicals i,, }~ving from 1 to 20 carbon atorns, arnino, or halogen, and is pref~rably an lkyl grotip h~ving ~rom 1 to 8 carbon atoms; and p is ~ero, 1, 2, 3, or 4 and is preferably zero.
A partiaL non-limitiny listing of suit~ble poly-C-mtroso compounds which are suitable for use in the practice of the invention include m-dinitroc benzene, p-dinitrosobenzene, m-dinltrosonaphthalene, p-dinitrosonaphthale

2, 5 -dinitroso -p-cymen~, 2 -rnethyl-1, 4-dinitrosobenzene, 2-methyl-5 -chloro-1, 4-dinitrosobenzene, 2-fluoro-l, 4-din;trosobenzene, 2-~nethoxy-1,

3-dinitrosobenzene, 5-chloro-1, 3-dinitrosobenzene, 2-benzyl-1, ~L-dinitros~
benzerle, and 2-cyclohe~yl-1,4~dinitrosobenzerle.

.

~1~8~369~
Substantially any of the polymeric materials wh~ch have been here-tofore employed as film formers or film-forming adjunc~s in adhesiv-e formul~tions are suitable for u~;e in the practice o-f the present invention Such film-:Eorming polymeric materials include, without limitation, thermo-setting condensation polymers, such as thermosetting phenolic resins.
thermosetting epoxy resins, thermosetting polyester resins, thermosetting triazine resins, and the like; polymers and copolymers of polar ethylenicall~
unsaturated materials, such as poly(vinyl butyral); poly(vinyl formal); poly-(vinyl acetate); chlorinated poly(vinyl chloride); copolymers of vinyl acetate and vinyl chloride; chlorinated copolymers of vinyl acetate and vinyl chlorid~
polymers of acrylic acid; copolyrmers of acrylic acid and conjug~ted dienes, such as 1, 3-butadiene; 2, chloro-1, 3-butadiene; 2, 3-dichloro-1, 3-butadiene, and the like, and including after-halogenated products thereof; polymers of methacrylic acid; copolymers of methacrylic acid and con3ugated dienes;
copolymers of vinyl pyridine and conjugated dienes, and including polyvalent reaction products thereof; cellulosic materials such as cellulose acetate butyrate; and the like Particularly preferred film forming materials are haloen-containing rubbe~s, including without limitation, chlorinated natu~a rubber; polychloroprene; chlorinated polychloroprene; chlorinated poly-butadiene; chlorinated polyethylene; chlorinated ethylene/propylene co-polymers; chlorinated ethylene/propylene/non-conjugated diene terpolymers i chlorinated copolymers of butadiene and styrene; chlorosulfonated poly-ethylene; brominated poly(2, 3 -dichloro -1, 3-butadiene); copolymers of alpha ` chloroacrylonitrile and 2,3-dichloro-1,3-butadiene; copolymers of alpha-bromoacrylo-nitrile and 2, 3 -dichloro -1, 3-butadiene;mixtures of such haloge;
containing rubbers with hydro~lo~enated rubbers of hypohalogenated rubbe~

.

. .

69~

mi~ res oE two or more such halogen-containing rubbers and the lil~e.
Other suitable polyrneric film--forming ~adjuncts include cellulosic esters such as cellulose acetale butyrate; natural rubber, butyl rubber,ethylene/
propylene copolyrner (EPM) rubber, ethylene/propylene/diene terpolymer (EPD~) rubber, polymers and copolymers of dienes h~ving from 4 to 12 carbon ato-ms, such as polybutadiene, and including also copolymers of such dienes a~d one or more different monomers copolymerizable therewi~h, such as SBR and butadiene/acrylonitrile rubber. As indicated, halogenated polymeric materials, and particularly chlorinated and bromin?ted rubbers, are preferred film-forming materials in the practice of the invention.
The adhesive compositions o this invention are prepared by conventi means, and such well-k-nown techniques will not be discussed here in detail.
As a ~eneral rule, the silane-isocyanate adduct and free pol~isocyænate will be mixed prior to incorporating any other ingredients, such as aror~atic nitroso compound, film-forming polymeric material, filler, and the like. In those instances wherein the adduct has been isolated, the adduct will be add~
directly to the free polyisocyanate, with both materials preferably being diluted, under conditions such as to ensure a homo~eneous mixture. rn this inst~nce, the free polyisocyanate can be the same as th~t used in preparing the adduct, it can be differe-n~, or it can comprise a mixture of two or more polyisocyanates, one of whlch can be, if desired, the same polyisocyanate as was used in forming the adduct. In a second and more preferred instance the adduct is formed from the reacLion of the silan~ and an e~cess of poly-isocyanate to afford a re~ction mi~ure comprising adduct and free poly-isocyanate. In this case, if the amo-~m of free polyisocyan~te is insufficient to provide the proper free polyisocyanate: adduct relationship, additional ( ( ~38696 free pol~ ocyan~te can De added to t~le reaction mi~ture. Such added free polyisocyanate c~n, of course, be th~ same or different Erom ~he poly-isocyanate employed in forminy the adduct, and can include a mixtl~re of t~F~o or more polyisocyanates, one of which can be, if desired, the same polyisocyanate as was emPlo~ed in forming the adduct As a general rule, it is preferred that the amount of polyisocyanate employed in forming the adduct be such that no additional polyiso~yanate need be added to the reaction mixtllre The th~s-prepared ~mi2tllre is itself suitable for use as a primer and adhesive composition; or as a base composition into which the aromatic nitroso compounds, film-forming polymeric materials, filler materials suchascarbonblackandtl~elike, extenders, pigments, diluents, etc., can be incorporated, employing conventional techriques for formulating adhesive compositions.
In forming the adhesive compositions of the present inverition, the isocyanatosilane will be present in an amount in the range from about 2. 5 to 100, preferably about 2. 5 to about 50, and most preferably about 5 to about 40, parts by weight; with the polyisocyanate being present in the amount of 100-x parts by weight, wherein x is equal to the amount, in parts by weight, of isocyanatosilane component. In addition, the isocyanatosil~ne and free polyisocyanate must provide a minimum amount of tota~ free isocyanate, including that provided b-l both the isocyanatosilane and free polyisoc~n~te, equal to one molar equivalent of isocyanate per mol of isocyanatosilan~
Preferably, the total free isocyanate content will be in a range fro~n 1 to about 20, preferably 1 to about 12, and most preferably 2 to about 8, molar equivalerlts p~r mol oE isocyanatosilane. It will be appreciated th~t the in-vention affords a great dea: of Ele~ibility in preparing adhesive compositions-' .

~- ( ~Q88696 inclucling, inter alia, isocyanatosiL~ne p~r se; isocyan~tosilane and aromatic nitro;.o compound; isocyanato~ilane, arom~tic nitroso compound and poly-meric film-~ormillg adjunct; isocyan~tosilane and free polyisocyanate;
isocyanatosilane, free polyisocyanate, and aromatic nitroso compound;
isoc~anatosilane, free polyisocyanate, aromatic nitroso compound, and polymeric film-forming adjunct; with the compositions comprising isocyanat~
silane and free polyisocyanate being particularly prelerred. In those com-positions cont~ ini n~ aromatic nitroso compounds, polymeric film-forming adjuncts, a~d inert filler, the aromatic nitroso compound will generally be present in an amount in the range from about 5 to about 200, preferably fro~r about 50 to about 150, parts by weight; the polymeric film-forming ad~uncts will generally be present in an amount in the range from about 10 to about 200, preferabl y from about 75 to about 150 p~rts by weight; and the inert filler will generally be present in an amount in the range from about 10 to about 200, preferably about 2~ to abou~ 175, parts by weighti said amounts in each instance being on a basis of 100 parts by combined weight of isoc~yan;
silane and free polyisocyarlate.
As noted previously, in addition to isocyanatosilane, free poly-isocyanate, aromatic nitroso compound, polymeric film-forming adjuncts, and inert filler material, the adhesive compositions of the invention can include conventional additives such as pigments, extenders j solvent, diluenl and the like with the amount of sucln additives being within the range con-ventionally employed.
For ease Or application, as is conventional in this art, the componer will be mixed and clispersed in a liquid ca rrier which, once the composition has been applied, can be readily evaporated. EY~mples of suitable carriers ..

6~

i are aromatic and halogen~ted aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, and the like; halogenated alipl~tic hydrocarbons su-h as trichloroeth~Tlene, perchloroethylene, propyle ~! dichloride, and the like; ketones such as -methyl ethyl ketone, methyl isobutyl ketone, and the like; ethers, naphtlnas, etc., including rnixtures of such carriers. The amount of carrier is not critical and will ordinarily be such as to provide a total solids content ranging from about 5 to about 100, i. e., 100 percent solids system, and preferably from about 5 to about 30, percent by weight.
The adhesive compositions of the present invention have been Eound to be particularly suitable for bonding a wide variety of elastomeric materials, especially vulcanizable elastomeric materials, to themselves or to other substrates, pa:,^ticularly inorganic substrates. Elastomers which can be bonded include without limitation natural rubber, polychloroprene rubber, styrene-butadiene rubber, nitrile rubber, ethylene/propylene copolymer , rubber (EP~); ethylene/propylene/diene terpolymer rubber (EPDM); butyl rubber, polyurethane rubber, and the like. Substrates other than the elastomers per se which can be effectively bonded include fabrics such as fiberglass, polyamides, polyesters, aramids, e.g., Kevlar, atrademarkof E 1. du Pont de Nemours 8.T Co,npany, (Inc. ), Wilmington, Delaware, and the like; and metals and their alloys such as steel, stainless steel, lead, (~ ~e~
B all~minl~m, copper, brass, bro-nze, Monel metals, nic~el, zinc, and the like includin~ treated me~ls such as phosph~tized steel, c~3~kTanized steel, and the like; cjlass; ce-r~mics; and the like.
The adhesivt? compositions are applied to substrate surfaces in a con ventional m nner such as by dipping, spraying, brusning, and the like.

~, - 2~) -.: .

- ~ c 1l~8~3696 Prefer.lbly, the substra~e surîaces are allowed to dry aiter coaiing before being brought togetller. ~fter the s-lrE~ces h~ve b~en joined, the composite structures are heated in a conventional manner to ef~ect curing of the adhesive compositions and simultaneous vulc~ni7~tion of the uncured elastomer stock.
The following examples are provided for purposes of illustrating the invention, it being understood that the invention is not limited to the examples nor to the specific details therein enumerated. In the examples, amounts are parts by weight unless otherwise specified.
In the several e~mples, the substrate to which the elastomeric material was bonded w~s not primed, unless otherwise noted. The composite assembly was cured at conventional conditions of time and temperature for the specific elastomer. The adhesive bond was tested according to ASTM
standard D-429, Method B, modified to 45 angle of pull.
The bonded structures are subjected to various tests, including room temperatures (RT) pu117 the boiling water test, and the salt spray test In the RT pull test, the rubber body is peeled from the metal at a 45 angle using a Scott tensile tester and the for~e required in pounds per inch is recorded. In the boiling ~rater test, bonded samples, after having beerl score~
; at the bond line and prestressed by bending the rubber body back from the metal, are immersed in boiling water for two hours; and in the salt spray test, the samples, afier scoring and prestressing, are exposed to a spray of salt solution (50/7c sodium chloride) for 48 hours at 100 F. The samples so treated a-re tested for relative bond strength by pulling the rubber body from the metal.
i,' . , In tlle data given in the E~amples, f~ilure is expr2ssed in terms oE
. . .

., i, - 21 -.

. 1~88696 percent of failure in the rubber body, e. g., 95 R means that 95 percent o~
the -failure occurred in the rubber body, with the rern~ining failure being between the adhesive composition and the metal, or the like.

EXA~PLE I

A series of adhesive compositions containing isocyanatopropyl-trietho~silane were prepared according to the schedules:

Adhesive ; A 1i A-2 A-3 A-4 Chlorosulfonated polyethylene 35 35 -35 35 Dinitrosobenzene 30 30 30 30 Carbon black 40 40 40 40 Isocyanatosilane - 15 15 15 Polymethylene polyphenyleneisocyanate - - 15 30 X;ylene 214 214 214 21a~

In forming the co~npositions, a masterbatch of adhesive A-l was prepared in a conventional manner. Adhesive formulations A-2, A-3 and A-4 were prepared by blending the respective components into aliquot portions of the masterbatch in a conventional manner.
The thus-formulated ad~sive compositions were then coated onto non-pri~ed, grit-blasted, degreased, cold-rolted steel coupons and allowed to dry. The thus-coated steel coupons were placed into contact with a sulfur-vulc~ ni ~le natural rubber composition. Each of the assemblies was cured at 307 F for 15 minutes.

FoLlowing the vulcanization cycle, the bonded asserrlblies were tested for environmental resistance according to the bolling water ( ~ H20) test. The results are reported in the following table:
.~ .

~ .

~Q~696 H20 Test Adhesive Failure A-1 O E~ (Failed in 1~ hrs. ) The foregoing da a dernonstrate that adhesive formulations cont~ining isocyanatosilane compositions have significantly improved resistance to degradation from ~tt~ck by environmental conditions.

E~MPLE ll A reac~ion vessel, equipped with an agitation me~s and maintained at room temperature under a nitrogen atmosphere, was ~harged with 133 g polymethylene polyphenyleneisocyanate having an average lsocyanate func-tionality of 2. 7, 532 ~ trichloroethylene and 0. 1 rn1 dibutyltin dilaurate.
The mixture was stirred at room temperature to a uniform consistency. To this mixture there was added, ~Tith continuous stirring, 60 g hydroxypropyl-trimethoxysilane in 240 g trichloroethylene. This addition was accompanied by an immediate mild e~otherm oE less than 50 C. When the addition of ' silarle-trichloroethylene 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 fluid comprising free polymethylene poly-phenyleneisocyanate and polymethylene polyphenyleneisocyanate/hydroxy-propyltri-methoxysilane adduct having a free isocyanate funct;or~lity of about ;' .

(~
1~869fi 1. 7 and a single silane grouping having the structure o Il - NH - C - O - (CH2)3 Si (O CH3)3 The molar equivalent ral:io of total free isocyanate to isocy~n~tosi~ane adduct in the reaction mi~h~re was about 2.8:1.

EXAMPLE III

.
Following the procedure of E~mple Il, to a continuously stirred tnixt~lre of 359 g polymethylene polyphenyleneisocyanate (2. 7 NCO func-tionality) and 1436 g trichloroethylene there was added 193 g methylamino-propyltrimetho~ysilane in 772 g benzene to afford a viscous fluid reaction mi~ilre comprising free polymethylene polyphenyleneisocyanate and poly-methylene polyphenyleneisocyanate/methylaminopropyltrimethoxysilane addu having a free isocyanate functionality ol about 1. 7 and a sing~e silane groupir having the structure Il - NH - C - N - (CH2)3 Si (O CH3)3 Ti~e molar equivalent ratio of total free isocyanate: isocyar~tosilane adduct in the reaction m; ~, re was about 2 . 2:1.

EXA~rLPLE IV

Following the procedure o:f Example 11, to a continuously stirred mixture o:E 1000 g polyme~hylene polyphenyleneisocyan~te (2. 7 NCO func-tionality) and 100 g trichloroethylene there was add~d 179 g amino-propyl-' trimetho~ysilane in 1611 g benæene to afford an amber viscous reaction fluic -- 2 ~ -"

~ 3869~

comprising free polymethylene polyphenyleneisocyanate and polymethylene polyphenyleneisocyanate/~-aminopropyltrimethoxysilane isocyanatosilane adduct having a free isocyan~te function~lity of 1. 7 and a single silan~
grouping having the structure - NH - C - NH - (CH2)3 Si (OC 3 3 The molar equivalent ratio of total free isocyanate to isocyanatosilane adduct in the reaction mixtt]re was about 8. I:1.

EXAMPLE V

Following the procedure of Exsmple rl, 179 g g-aminopropyltriethoxy silane in 1611 g ben~ene was added to a continuously stirred mixture containi 400 g polymethylene polyphenyleneisocyanate to afford an amber viscous reaction mi~l]re comprising free polymethylene polyphenyleneisocyanate and polymethylene polyphenyleneisocyanate/g-aminopropyltriethox~silane isocyanatosilane adduct having a free isocyanate functionality of 1. 7 and a single silane grouping having the structure O
11 .
NII - C - NH - (C~2)3 Si (OC?,H5)3 -The molar equivalent ratio of totaL free isocyanate to isocyanatosilane adducin the reaction mi~lre was about 2. 7:1.

E.XAMPLE VI

The reaction product of E~mple Il, comprising isocyanatosilane adduct, free polymethylene potyphenyleneisocyanate and trichloroetnylene, without f~rther trea~ment, was dip-coated onto a fiberglass Eabric and allow ; - 2~

( ( as~6s~ - .

to dry Eor ~ hours. The thus-coated fiberglass i~bric was then bonded to a polychloroprene rubber stock of the composition:

Parts by Wei~ht Polychloroprene rubber 100 Carbon black 60 Plasticizer 10 Diurethane of tolylene diisocyanate and nitrosophenol 6 Polymethylene poLyphenyleneisocyanate 3 Calcium o~ide 4 The assembly was cured at 320 F for 20 minlltes The adhesion of the cured assembLy was evaluated In accordance with the room temperature pull test, with the following results:

RT Pull R~n Coats Lbs. Failure rrhe fore~oing data demonstra.tes that compositions containing at leas one isocyanatosilane ~ving free isocyanate functionality and at least one polyisocyanate are effective adhesives for bonding vulc~ni7~ble eLastomeric materials to a substrate~ in this instance, ~ fiberglass substrate.

EX~ PLE VII

The reaction product of EY.ample IV, cornprising isoc~anatosilane i.
I adduct having free isocyanate functionality, polymethylene polyphenylene-i isocyanate, trichloroetlQ~lene and benæene, without further treatment, was .. . .

,~.
- 2~ -_ lQ88696 used to bond non-primed,grit-blasted,degreased,cold-rolled steel and fiber-glas~ bric to a diurethane-vulcaniæable n:itrile elastomer stock having the . composition:

Parts by Weiç~ht Butadiene-acrylonitrile rubber 100 Carbon black 65 Plasticizer 20 Diurethane of tolylene diisocyanate & ~-nitrosophenol 6 Polymethylene polyphenyleneisocyan~te 6 Zinc dimethyldithiocarba~te . 2 The bonded assemblies were cured at 307 F for 20 minllt~ The adhesion of ihe cured asser~blies were evaluated in accordance with the room temperature pull test, with the following results: .

- RT Pull - Run Substrate ~dhesive Co~ts - Lbs.. - Failure .
Steel Oontrola 1 PBH~ 0 R
2 Steel Example IV 1 120 SBC 100 R
' 3 Steel Exarnple IV 1 118 SB 100 R
Steel ~xamp~e IV 2 110 SB 100 R
Steel hxample IV 2 12~ SB 100 R
6 Fi.berglass Controla 1 34 50 R
7 }.iberglass Comrol 1 35 50 R
8 Iiberglass Example IV 1 76 SE~ 100 R
9 Fiberglass EY~ampLe rV 1 7~ SB 100 R
Fiberglass Example IV 1 85 SB 100 R
11 Fiberglass Exa~nple IV 1 75 SB 100 R

a = Polymethylene polyphenyleneisocyan~te @ 10~ in trichloroeth~TlenP
b_ Pulled by hand, no sl~bst~ntial adhesion.
!, C - StocL; break.

'I'he foregoing data demonstrates the effectiveness of compositions . containillg at least one isoc~anatosilane having free isocyanate function~lity .~ .

~8~36~`~

and at least one :Eree polyisoc~anace as adhesive rnaterials ~for bonding vulc~r~i7.~l~1e elastome~s to substrates such as metals and fibers.

E~AMPIJE VIII

.
Following the procedure o~ Example II, 1'79 g ~-aminopropyl-trimethoxysilane in 716 g benzene was added to a continuously stirred mi~ctllr of 750 g polymethylene polyphenyleneisoc~anate and 750 g trichloroethylene to a:~ford a viscous fluid reaction mi~llre comprising isocy~n~to~ilane adduct having free isocyanate functionality and free polymethylene polyphenylene-isocyanate, and having a total free isocyanate: adduct equivalent ratio of about 6.6:1.
The thus-prepared reaction mi~l]re, without furthertre~tment, was used to bond a polyurethane elastomer cont~ ining 12. 5 PHR (parts by weight per 100 parts by weight of elastomer) 4, 4' -methylene-bis -(2-chloroaniline) vulr~ni7.in~agenttonon-primed, grit-blasted, degreased, cold-rolledsteel For cornparison purposes, the polyurethane elastomer stock was bonded to the metal substrates using the following control adhesive: -Polymethylene polyphenyleneisocyanate @ 25C,~ in trichloroet'nylene.

Following the vul-~ni7~tion cycle, the bonded assemblies were testec according to the room temperature pull test by pulling at room temperature and at 212 F. and tested for environmental resistance according to the salt spray test. The results are reported in the following tab~es:

Adhesive: (A) Reaction mi~llre of ~.~mple VIII.

- (B) Polyrnethylene polyph.enyleneisocyanate @ 25~c in trichloroethylene.

..

c~ ( ~ 69S

TAB r,E
.

RT :E~ull Run Adhesive Lbs. Failure

4 B 208 SB 50 R

TABLE Il 212 F. Pull Run Ad~esive Lbs. Failure 6 ~ 150 S~3100 R

- .

TABLE IrI

Salt SprayExposure, Failure Run Adhesive After 72 hrs.- After 168 hrs.

! 13 A --- 50 R
, ~4 ,,~ __ 50 R
j 15 B --- OR
1~ E3 --- O R

Tr~ foreg~ing data demonstrate that compositions of the present invention provide adhesive compositions whic~ afford not only strong rubber i to-metal bonds but also substar-tially improve environmental xesistance.
.~
' E XAMP LE IX
, Follouling the pxc ceclure of F.xample II, 1'79 g ~-aminopropyltrimetho silane in '~1~ g trichloroethylene was added to ~ continuously stirred mixtur~

., .

8~696 of rl50 g polymethylene polyphenyleneisocyanate and 750 g trichloroethylene.
The reaction mixture was diluted~ with 200 g trichloroethylene, stirred for an additional 5 minutes and cooled to room temperature. The thus-prepared reaction mi~lre comprising isocyanatosilane adduct having free isocyanate functionality and Eree polymethylene polyphenyleneisocyanate and having a total free isocyan~te: adduct equivalent ratio of about 6 6:1, without further treatment, was divided into several aliquot portions.
Several of the aliquot portions w~re employed to prepare adhesive compositions by combining in a conventional manner the following ingr~ ents (parts by weight):

Adhesive A B C D
- Reaction mixture of Example IX 100 10~ 100 100 Dinitrosobenzene - 10 20 30 Trichloroethylene 300 325 350 ~25 Xylene - 1~ 34 51 The adhesives were employed to bond non-primed, grit-blasted, degreased, cold-rolled steel to sulfur-~ulc~ni~hle natural and butyl rubber stocks. Following the vulcanization cycle, the bonded assemblies were teste~
according to the room temperature pull test and for environmental resistanc~
according to the boiling water test ( A 1~2O) The results are reported in the followin~ table:

; , !

~l -- 30 --, ., c ~ 108~9~i ` RT Pul.l ~ EI20 ~' Elastomer Adhesive Lbs.11'3il.ure Failure N~;ural rul~ber A PT31I 0 R Not tested . ~atural rul:)ber . B 48 100 R 20 R
, 25 R
,! Natural rubber C 53 100 R 55 R
;. 30 R
Natural rubber D 51 100 R 70 R

Soft natural rubber A PBH 0 R
Soft n~u~al rubber B 32 SB100 R

Soft natural rubber C 30 SB100 R

Soft natural rubber D 33 SB100 R

Butyl rubber A PBH 0 R
Butyl rubber B 106 100 R

Butyl rubber C 105 100 R

Butyl rubber D 90 SB 90 R
9~ 80 R

E XAMPLE X

_, !
Several of the aliquot ~ortions of the reaction mi~ re of Example IX
were employed to prepare ad~esive compositions by combining in a conventior ma~mer the following ingredients (parts by weight):

Adhesive B-1 B-2 B-3 l~eaction mi xtllre~ E7~mple l~ 100 100 100 Dinitrosobenzene 30 30 30 Chlorin~ted ethylene/propylene/
non-conjugated terpolyrner 35 _ _ Chlorosulfonated pol~ethylene - 35 Chloro~crylonitrile/dic'nlorobutadiene copolymer - - 35 Trichloroethylene 180 495 437 ~lene 256 151 101 ., .

;:

(~

.i The adhesiv*s were ernployed to bond to non-prirr ed, grit-bla~ted, degreased, cold-rolled steel sulur-vutc~ni7~ e natural rubber stock.
Following the vul,^~nir~,~tion cycle, the bonded assemblies were subjected to room temperature pull and boiling water tests with the following results:

RT Pull ~ H2O
Adhesive Lbs. F~ilur,s ~ailure B-2 54 100 ~ 100 R

B-3 46 100 ~ ' 100 R

EXaMPLE Xl:

FolLowing the procedure OI E~mple II, to a continuous~y stirred mixhlre of 750 g polymethylene polyphenylenelsocyanate and 3000 g trichlo~
~, ethylene there was added 179 g g-aminopropyltrimethoxysilane in 716 g trichloroethylene ~o afford a reaction rni~llre comp~ising free polymethylen i ' i polyphenyleneisocyanate and polymethylene polyphenyleneisocyanate/g-aminopro~yltrimethoxysilane having a free isocyanate functionality of 1,7 d a single silane gouuping. The equivalent ratio of total free isocyanate tc '` adduct in the react,ion mixture was about 6. 6~
The reac~ion mixture was separated into several'portions and adhes composi~ions having a total solids content (TSC~ of abou~ 20 weight perc~nt were prepared as follows, the amounts being parts by weight:

, . .
.. .
.

:

'`~ ' . la~s6s~

. Parts by Weight C-1_ C-2 C-3 C-4 . Reac~ion mixture, Example ~r 100 100 100 100 Dinitrosobenzene 30 30- 30 30 . Chlorinated ethylene/propylene/
non-conjugated diene terpolymer 35 Chlorosulfonated polyethyLene - 35 - - -. Chloroacrylonitrile/dichlorobutadiene copolymer - - 35 ` TrichLoroethylene 400 400 400 400 Xylene 260 260 9;72 120 Each adhesive was rnaintained at room temperature for an ~tP-n~e~
period andviscosity measure~ents (Brookfield ~iscometer, No. 2 spindle at 30 RP~) were made with the following results:

Adhesive C-1 C-2 C-3 C-4 .
Tirne Viscosity, CPS

Initial 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 The foregoing data de~onstrates the excellent ambient temperature storage stability of the herein described adhesive compositions.
. .
,I EXA~lPIJE ~I

Followlng the procedure of Example Il, 179 g g-aminopropyltrimethoxy silane in 385 g x~lene and 353 g trichloroethylene ~Jas added to a continuously stirred mi~{ture of 750 g poly~nethylene polyphenyleneisocyanate, 1500 g xylent and 1500 ~ trichloroethylene to aEford a viscous reaction mixture comprising isocyanatosilane adduct having Eree isocyanate functionality and free poly-methylene polyphenyleneisocyanate, and having a total free isocyanate:

, (~
1~8~696 .

;, adduct eq~ivalent r~tio of a~o~lt G. ~
. i The thus-prepared reaction mi~t~lre, without further treatment was . ern-pLoyed to prepare adhesive com~ositions .having a total solids content of about 15 weight per~ent as follows, amounts being in parts by weight:
,, .
Adhesive D-1 D-2D-3D-4 D-5 Reaction mixtllre~ ~x~.mple XII 100 100 100 100 100 Dinitrosob~r~ene 30 30 30 30 30 Chlorosul~onated polyeth~lene - 35 - - -Cllloroacrylonitrile/dichlorobutadiene copolymer . -; - 35 - -Chlorinated ethylene/propylene/non-conjugated diene terpoly.mer - - -- 35 Cellulose acetate butyrate - - - - - 35 Xylene 330 220 220 168 337 Trichloroethylene 400 715 715 777 598 Sa-mples of each adhesive ~ormulation were maintained at room tem-perature and 130 F for an extended period and viscosity measurements periodically taken ~.~Jith the following results:
Adhesive -- Viscosity, cps Tim e: ~T 130F RT 130F ~T 130F RT 130F RT 130 ~F
niti~l 35 35 70 70 115 115 90 90 140 140 1 week - 46 - 179 - 178 - 180 Paste Paste 2 weeks - ~2 - 1~0 - 112 - 44 3 w_eks - 92 - 193 - 80 - 30 4 ~vee~s 20 190 68 230 130 lS~ 40 30 ~5 weeks 25 350 75 172 135 70 55 25 !6 weeks - 408 - 138 - 2300 - 45 7 wee'~s - 850 - 1'70 - Paste - 25 8 weeks - Pas~e - ~1000 - 355 - 25 9 weeks - Paste - 1975 - 550 - 30 EY~MPI.E XIII

A series of adhesive formulations were prepared by combining in a . convention~l manr~er the following ingredien~s (parts by weight):

- 3~ -.

?

lh~ J-~. r~
ChloIo~ulforlat~ 1 polyethylene 35 3~ 3.~
Dinitrosobenzene 30 30 30 Polymethylene polyphenyleneisocyan~te 4;0 - 42 g-Aminopropyltriethoxysilane - 10 Isocyanatosilane (polyrnethylene poly-phenyleneisocyanate/g-Amino -propyltriethoxysilane adduct ) - - 8 Trichloroethylene/xylene ~ ~O~c 600 600 600 The adhesives were employed to bond sulfur-vulc~niY~hle natural rubber to non-primed, grit-blasted, degreased, cold-rolled steel. Following the vulcaniz~tion cycle, the bonded assemblie~; were subjected to room temper~ture pull and boiling water tests with the following results:

RT Pull ~ H2O
Adh~sive Lbs.Failure Failure E-1 40 45 R 0 R (within 10 sec. ) E-2 50 0 R 0 R (within 10 sec. ) E-3 43100 R 100 R (after 2 hrs . ) 100 R (after 6 hrs. ) The foregoing data is a comparison of adhesive compositions prepare in accordance with this invention versus adhesive co-mpositions containing th starting material~ employed to form isocyanatosil~ne compositions. The data~lle self-explanalory.

.
EY~P L,E ~IV
, Isocyanatosilane adducts were prepared according to the procedure of E~xample II from ~-aminopropyltriethoxysilane and tolylene diisocyanate, , methylene~bis(phenyl isocyanate) and methylene-bis(cyclohexylisocyarL~te), respectivTely. Th~ reaction mixtures in each instance ~r~ere employed withou further treatment to Corm adhes;~e compositions containing chloros~llfon3ted _ 35 -886~ ( polyethyle-ne, dinitrosobenzene and carbon black. r~he thus prepared adh_siv~
compositions were e:Efec, ive for bondin~ sulLur-vulcanizable natural rubber stocl;s to steel substraces, and also ~ormed bonded rubber-to-metal assembl that were resistant to e~vironmental conditions.

. .

,,, ~ .
_ 3 ~ -

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. An adhesive composition consisting essentially of i) from about 2.5 to less than 100 parts by weight of at least one isocyanatosilane having the formula wherein R1 is a monovalent aliphatic, cycloaliphatic or aromatic radical having from 1 to 20 carbon atoms; R is a monovalent aliphatic, cycloaliphatic or aromatic radical having from 1 to 8 carbon atoms; a is zero or 1; and Z is a divalent organic radical attached to the silicon atom via a carbon-silicon bond;
ii) 100-x parts by weight of at least one free polyisocyanate, wherein x is the amount, in parts by weight, of said isocyanato-silane;
iii) an effective amount of at least one aromatic nitroso com-pound;
iv) from 0 to about 200 parts by weight per 100 parts of com-bined weight of said isocyanatosilane and said free polyisocyanate of at least one film-forming adjunct; and v) from 0 to about 200 parts by weight per 100 parts of combined weight of said isocyanatosilane and said free polyisocyanate of at least one inert filler material.

2. An adhesive composition consisting essentially of i) from about 2.5 to less than 100 parts by weight of at least one isocyanatosilane selected from the group consisting of a) isocyanatosilanes having the general formula or b) isocyanatosilane adducts of multifunctional organo-silanes and polyisocyanates, said adducts being characterized by the presence of a single reactive isocyanate moiety; and at least one silane grouping having the formula wherein R0 is selected from the group consisting of divalent hydrocarbon and halogenated hydrocarbon radicals having from 1 to 20 carbon atoms; R1 is a monovalent aliphatic, cyclo-aliphatic or aromatic radical having from 1 to 20 carbon atoms;
R2 is a monovalent aliphatic, cycloaliphatic or aromatic radical having from 1 to 8 carbon atoms; A is selected from the group consisting of - O -, - S -, ? N -, and other groups contain-ing an active hydrogen; R is a divalent aliphatic, cycloaliphatic, or aromatic radical having from 1 to 20 carbon atoms; and a is zero or 1;
ii) 100-x parts by weight of at least one free poly-isocyanate, wherein x is the amount, in parts by weight, of said isocyanatosilane;
iii) an effective amount of at least one aromatic nitroso compound;
iv) from 0 to about 200 parts by weight, per 100 parts of combined weight of said isocyanatosilane and said free polyiso-cyanate, of at least one film-forming adjunt; and v) from 0 to about 200 parts by weight, per 100 parts by combined weight of said isocyanatosilane and said free polyiso-cyanate, of at least one inert filler material.

3, An adhesive system consisting essentially of i) from 2.5 to less than 100 parts by weight of at least one isocyanatosilane having the general formula wherein R0 is selected from the group consisting of divalent hydrocarbon and halogenated hydrocarbon radicals containing from 1 to 20 carbon atoms;
R1 is a monovalent aliphatic, cycloaliphatic or aromatic radical having from 1 to 20 carbon atoms;
R2 is a monovalent aliphatic, cycloaliphatic or aromatic radical having from 1 to 8 carbon atoms; and a is zero or 1;
ii) 100-x parts by weight of at least one free poly-isocyanate, wherein x is the amount, in parts by weight, of said isocyanatosilane;
iii) an effective amount of at least one aromatic nitroso compound, said amount being sufficient to obtain an effective adhesive bond;
iv) from 0 to about 200 parts by weight, per 100 parts of combined weight of said isocyanatosilane and said free poly-isocyanate, of at least one polymeric film-forming adjunct; and v) from 0 to about 200 parts by weight, per 100 parts of combined weight of said isocyanatosilane and said free poly-isocyanate of at least one inert filler material.

4. A composition according to claim 3 wherein the amount of said aromatic nitroso compound is in the range from about 5 to about 200 parts by weight, per 100 parts by combined weight of said isocyanatosilane and said free polyisocyanate.

5. A composition according to claim 4 wherein the amount of said film-forming adjunct is in the range from about 10 to about 200 parts by weight.

6. A composition according to claim 4 wherein the amount of said inert filler is in the range from about 10 to about 200 parts by weight.

7. A composition according to claim 6 wherein the amount of said film-forming adjunct is in the range from about 10 to about 200 parts by weight.

8. A composition according to claim 3 wherein x is in the range from about 2.5 to about 50 parts by weight.

9. A composition according to claim 8 wherein the amount of said aromatic nitroso compound is in the range from about 5 to about 200 parts by weight, per 100 parts by combined weight of said isocyanatesilane and said free polyisocyanate.

10. A composition according to claim 9 wherein the amount of said film-forming adjunct is in the range from about 10 to about 200 parts by weight.

11. A composition according to claim 9 wherein the amount of said inert filler is in the range from about 10 to about 200 parts by weight.

12. A composition according to claim 9 wherein the amount of said film-forming adjunct is in the range from about 10 to about 200 parts by weight and the amount of said inert filler is in the range from about 10 to about 200 parts by weight.

13. A composition according to claim 8 wherein said isocyanatosilane has the formula wherein R0 has from 2 to 9 carbon atoms; R1 is selected from the group consisting of alkyl radicals having from 1 to 4 carbon atoms, cycloalkyl radicals having from 4 to 7 ring carbon atoms and aryl radicals having 6, 10 or 14 nuclear carbon atoms; and R2 is selected from the group consisting of alkyl radicals having from 1 to 4 carbon atoms, -R3 - O - R4, and , where R3 is an alkylene group having from 1 to 4 carbon atoms and R4 is an alkyl group having from 1 to 4 carbon atoms; the amount of said aromatic nitroso compound is in the range from about 5 to about 200 parts by weight, per 100 parts of combined weight of said isocyanatosilane and said free polyisocyanate; the amount of said film-forming adjunct is in the range from about 10 to about 200 parts by weight and the amount of said inert filler is in the range from about 10 to about 200 parts by weight.

14. A composition according to claim 13 wherein said isocyanatosilane is isocyanatopropyltriethoxysilane.

15. An adhesive composition consisting essentially of i) from about 2.5 to less than 100 parts by weight of at least one isocyanatosilane selected from the group consisting of isocyanatosilane adducts of multifunctional organosilanes and polyisocyanates, said adducts being characterized by the presence of a single reactive isocyanate moiety and at least one silane grouping having the formula wherein R0 is selected from the group consisting of divalent hydrocarbon and halogenated hydrocarbon radicals having from 1 to 20 carbon atoms; R1 is a monovalent aliphatic, cycloaliphatic or aromatic radical having from 1 to 20 carbon atoms; R2 is a monovalent aliphatic, cycloaliphatic or aromatic radical having from 1 to 8 carbon atoms; A is selected from the group consisting of - O -, - S -, ? N -, and other groups containing an active hydrogen; R is a divalent aliphatic, cyclo-aliphatic, or aromatic radical having from 1 to 20 carbon atoms;
and a is zero or 1;
ii) 100-x parts by weight of at least one free polyiso-cyanate, wherein x is the amount in parts by weight, of said isocyanatosilane adduct;
iii) an effective amount of at least one aromatic nitroso compound;
iv) from 0 to about 200 parts by weight, per 100 parts of combined weight of said isocyanatosilane adduct and said free polyisocyanate, of at least one polymeric film-forming adjunct;
and v) from 0 to about 200 parts by weight, per 100 parts of combined weight of said isocyanatosilane adduct and said free polyisocyalante, of at least one inert filler material.

16. A composition according to claim 15 wherein x is in the range from about 2.5 to about 50 parts by weight.

17. A composition according to claim 16 wherein said polyisocyanate employed in forming said adduct has the formula where R8 is a divalent organic radical having from 1 to 8 carbon atoms; X is selected from the group consisting of hydrogen, halo-gen, alkyl radicals having from 1 to 8 carbon atoms, and alkoxy radicals having from 1 to 8 carbon atoms; m is 1 or 2; and n is a digit having an average value in the range from zero to 15.

18. A composition according to claim 17 wherein the amount of said aromatic nitroso compound is in the range from about 5 to about 200 parts by weight.

19. An adhesive composition according to claim 15 consisting essentially of i) from about 2.5 to less than 100 parts by weight of at least one isocyanatosilane adduct of multifunctional organosilanes and polyisocyanates, said adducts having as characteristic features a single free isocyanate group, at least one silane grouping, and the structure the free isocyanate group and silane grouping of said adduct being joined to each other through the residue of said poly-isocyanate reactant; wherein A is selected from the group consisting of - O -, - S -, - N ? , and other groups containing an active hydrogen;

R is a divalent aliphatic, cycloaliphatic or aromatic radical having from 1 to 20 carbon atoms;
R1 is a monovalent aliphatic, cycloaliphatic or aromatic radical having from 1 to 20 carbon atoms;
R is a monovalent aliphatic, cycloaliphatic or aromatic radical having from 1 to 8 carbon atoms; and a is zero or 1;
ii) 100-x parts by weight of at least one free polyiso-cyanate, wherein x is the amount, in parts by weight, of said isocyanatosilane adduct;
iii) an effective amount of at least one aromatic nitroso compound;
iv) from 0 to about 200 parts by weight, per 100 parts of combined weight of said isocyanatosilane adduct and said free polyisocyanate, of at least one polymeric film-forming adjunct;
and v) from 0 to about 200 parts by weight, per 100 parts of combined weight of said isocyanatosilane adduct and said free polyisocyanate, of at least one inert filler material.

20. A composition according to claim 19 wherein the amount of said aromatic nitroso compound is in the range from about 5 to about 200 parts by weight.

21. A composition according to claim 20 wherein x is in the range from about 2.5 to about 50 parts by weight.

22. A composition according to claim 19 wherein the amount of said film-forming adjunct is in the range from about 10 to about 200 parts by weight.

23. A composition according to claim 22 wherein the amount of said aromatic nitroso compound is in the range from about 5 to about 200 parts by weight.

24. A composition according to claim 19 wherein the amount of said inert filler is in the range from about 10 to about 200 parts by weight.

25. A composition according to claim 24 wherein the amount of said aromatic nitroso compound is in the range from about 5 to about 200 parts by weight.

26. A composition according to claim 19 wherein the amount of said aromatic nitroso compound is in the range from about 5 to about 200 parts by weight; the amount of said film-forming adjunct is in the range from about 10 to about 200 parts by weight; and the amount of said inert filler is in the range from about 10 to about 200 parts by weight.

27. A composition according to claim 19 wherein said polyisocyanate employed in forming said adduct has the formula whereih R8 is a divalent organic radical having from 1 to 8 carbon atoms; X is selected from the group consisting of hydrogen, halogen, alkyl radicals having from 1 to 8 carbon atoms, and alkoxy radicals having from 1 to 8 carbon atoms; m is 1 or 2;
and n is a digit having an average value in the range from zero to 15.

28. A composition according to claim 27 wherein the amount of aromatic nitroso compound is in the range from about 5 to about 200 parts by weight.

29. A composition according to claim 27 wherein the amount of said film-forming adjunct is in the range from about 10 to about 200 parts by weight.

30. A composition according to claim 27 wherein the amount of said aromatic nitroso compound is in the range from about 5 to about 200 parts by weight and the amount of said film-forming adjunct is in the range from about 10 to about 200 parts by weight.

31. A composition according to claim 27 wherein the amount of said inert filler is in the range from about 10 to about 200 parts by weight.

32. A composition according to claim 27 wherein the amount of said aromatic nitroso compound is in the range from about 5 to about 200 parts by weight and the amount of said inert filler is in the range from about 10 to about 200 parts by weight.

33. A composition according to claim 27 wherein the amount of said aromatic nitroso compound is in the range from about 5 to about 200 parts by weight, the amount of said film-forming adjunct is in the range from about 10 to about 200 parts by weight and said inert filler is in the range from about 10 to about 200 parts by weight.

34. A composition according to claim l9 wherein said free polyisocyanate has the formula wherein R8 is a divalent organic radical having from 1 to 8 carbon atoms; X is selected from the group consisting of hydrogen, halogen, alkyl radicals having from 1 to 8 carbon atoms, and alkoxy radicals having from 1 to 8 carbon atoms; m is 1 or 2;
and n is a digit having an average value in the range from zero to 15.

35. A composition according to claim 34 wherein the amount of aromatic nitroso compound is in the range from about 5 to about 200 parts by weight.

36. A composition according to claim 34 wherein the amount of said film-forming adjunct is in the range from about 10 to about 200 parts by weight.

37. A composition according to claim 34 wherein the amount of said aromatic nitroso compound is in the range from about 5 to about 200 parts by weight and the amount of said film-forming adjunct is in the range from about 10 to about 200 parts by weight.

38. A composition according to claim 34 wherein the amount of said inert filler is in the range from about 10 to about 200 parts by weight.

39. A composition according to claim 34 wherein the amount of said aromatic nitroso compound is in the range from ab?
5 to about 200 parts by weight and the amount of said inert fill?
is in the range from about 10 to about 200 parts by weight.

40. A composition according to claim 34 wherein the amount of said aromatic nitroso compound is in the range from about 5 to about 200 parts by weight; the amount of said film-forming adjunct is in the range from about 10 to about 200 parts by weight, and the amount of said inert filler is in the range from about 10 to about 200 parts by weight.

41. A composition according to claim 19 wherein each of said free polyisocyanate and said polyisocyanate employed in forming said adduct have the formula wherein R8 is a divalent organic radical having from 1 to 8 carbon atoms; X is selected from the group consisting of hydrogen, halogen, alkyl radicals having from 1 to 8 carbon atoms, and alkoxy radicals having from 1 to 8 carbon atoms; m is 1 or 2; and n is a digit having an average value in the range from zero to 15.

42. A composition according to claim 41 wherein the amount of said aromatic nitroso compound is in the range from about 5 to about 200 parts by weight.

43. A composition according to claim 41 wherein the amount of said film-forming adjunct is in the range from about 10 to about 200 parts by weight.

44. A composition according to claim 41 wherein the amount of said aromatic nitroso compound is in the range from about 5 to about 200 parts by weight and the amount of said film-forming adjunct is in the range from about 10 to about 200 parts by weight.

45. A composition according to claim 41 wherein the amount of said inert filler is in the range from about 10 to about 200 parts by weight.

46. A composition according to claim 41 wherein the amount of said aromatic nitroso compound is in the range from about 5 to about 200 parts by weight and the amount of said inert filler is in the range from about 10 to about 200 parts by weight.

47. A composition according to claim 41 wherein the amount of said aromatic nitroso compound is in the range from about 5 to about 200 parts by weight; the amount of said film-forming adjunct is in the range from about 10 to about 200 parts by weight; and the amount of said inert filler is in the range from about 10 to about 200 parts by weight.

48. A composition according to claim 19 wherein the amount of said isocyanatosilane adduct is in the range from about 2.5 to about 50 parts by weight.

49. A composition according to claim 48 wherein each of (iv) and (v) are zero.

50. A composition according to claim 48 wherein the amount of said aromatic nitroso compound is in the range from about 5 to about 200 parts by weight.

51. A composition according to claim 48 wherein the amount of said film-forming adjunct is in the range from about 10 to about 200 parts by weight.

52. A composition according to claim 48 wherein the amount of said aromatic nitroso compound is in the range from about 5 to about 200 parts by weight and the amount of said film-forming adjunct is in the range from about 10 to about 200 parts by weight.

53. A composition according to claim 48 wherein the amount of said inert filler is in the range from about 10 to about 200 parts by weight.

54. A composition according to claim 48 wherein the amount of said aromatic nitroso compound is in the range from about 5 to about 200 parts by weight and the amount of said inert filler is in the range from about 10 to about 200 parts by weight

55. A composition according to claim 48 wherein the amount of said aromatic nitroso compound is in the range from about 5 to about 200 parts by weight; the amount of said film-forming adjunct is in the range from about 10 to about 200 parts by weight; and the amount of said inert filler is in the range from about 10 to about 200 parts by weight.

56. A composition according to claim 19 wherein the amount of said isocyanatosilane adduct is in the range from about 2.5 to about 50 parts by weight and said polyisocyanate employed in forming said adduct has the formula wherein R8 is a divalent organic radical having from 1 to 8 carbon atoms; X is selected from the group consisting of hydrogen, halogen, alkyl radicals having from 1 to 8 carbon atoms, and alkoxy radicals having from 1 to 8 carbon atoms;
m is 1 or 2; and n is a digit having an average value in the range from zero to 15.

57. A composition according to claim 56 wherein said aromatic nitroso compound is present in the range from about 5 to about 200 parts by weight.

58. A composition according to claim 56 wherein the amount of said film-forming adjunct is in the range from about 10 to about 200 parts by weight.

59. A composition according to claim 56 wherein the amount of said aromatic nitroso compound is in the range from about 5 to about 200 parts by weight and the amount of said film-forming adjunct is in the range from about 10 to about 200 parts by weight.

60. A composition according to claim 56 wherein the amount of said inert filler is in the range from about 10 to about 200 parts by weight.

61. A composition according to claim 56 wherein the amount of said aromatic nitroso compound is in the range from about 5 to about 200 parts by weight and the amount of said inert filler is in the range from about 10 to about 200 parts by weight.

62. A composition according to claim 56 wherein the amount of said aromatic nitroso compound is in the range from about 5 to about 200 parts by weight; the amount of said film-forming adjunct is in the range from about 10 to about 200 parts by weight; and the amount of said inert filler is in the range from about 10 to about 200 parts by weight.

63. A composition according to claim 19 wherein the amount of said isocyanatosilane adduct is in the range from about 2.5 to about 50 parts by weight and said free polyisocyanate has the formula wherein R8 is a divalent organic radical having from 1 to 8 carbon atoms; X is selected from the group consisting of hydrogen, halogen, alkyl radicals having from 1 to 8 carbon atoms, and alkoxy radicals having from 1 to 8 carbon atoms; m is 1 or 2; and n is a digit having an average value in the range from zero to 15.

64. A composition according to claim 63 wherein each of (iv) and (v) are zero.

65. A composition according to claim 63 wherein the amount of said aromatic nitroso compound is in the range from about 5 to about 200 parts by weight.

66. A composition according to claim 63 wherein the amount of said film-forming adjunct is in the range from about 10 to about 200 parts by weight.

67. A composition according to claim 63 wherein the amount of said aromatic nitroso compound is in the range from about 5 to about 200 parts by weight and the amount of said film-forming adjunct is in the range from about 10 to about 200 parts by weight.

68. A composition according to claim 63 wherein the amount of said inert filler is in the range from about 10 to about 200 parts by weight.

69. A composition according to claim 63 wherein the amount of said aromatic nitroso compound is in the range from about 5 to about 200 parts by weight and the amount of said inert filler is in the range from about 10 to about 200 parts by weight.

70. A composition according to claim 63 wherein the amount of said aromatic nitroso compound is in the range from about 5 to about 200 parts by weight; the amount of said film-forming adjunct is in the range from about 10 to about 200 parts by weight; and the amount of said inert filler is in the range from about 10 to about 200 parts by weight.

71. A composition according to claim 19 wherein the amount of said isocyanatosilane adduct is in the range from about 2.5 to about 50 parts by weight and each of said free poly-isocyanate and said polyisocyanate employed in forming said adduct have the formula wherein R8 is a divalent organic radical having from 1 to 8 carbon atoms; X is selected from the group consisting of hydrogen, halogen, alkyl radicals having from 1 to 8 carbon atoms, and alkoxy radicals having from 1 to 8 carbon atoms;
m is 1 or 2; and n is a digit having an average value in the range from zero to 15.

72. A composition according to claim 71 wherein each of (iv) and (v) are zero.

73. A composition according to claim 71 wherein the amount of said aromatic nitroso compound is in the range from about 5 to about 200 parts by weight.

74. A composition according to claim 71 wherein the amount of said film-forming adjunct is in the range from about 10 to about 200 parts by weight.

75. A composition according to claim 71 wherein the amount of said aromatic nitroso compound is in the range from about 5 to about 200 parts by weight and the amount of said film-forming adjunct is in the range from about 10 to about 200 parts by weight.

76. A composition according to claim 71 wherein the amount of said inert filler is in the range from about 10 to about 200 parts by weight.

77. A composition according to claim 71 wherein the amount of said aromatic nitroso compound is in the range from about 5 to about 200 parts by weight and the amount of said inert filler is in the range from about 10 to about 200 parts by weight.

78. A composition according to claim 71 wherein the amount of said aromatic nitroso compound is in the range from about 5 to about 200 parts by weight; the amount of said film-forming adjunct is in the range from about 10 to about 200 parts by weight; and the amount of said inert filler is in the range from about 10 to about 200 parts by weight.

79. A composition according to claim 71 wherein R8 is methylene; X is hydrogen; m is l; n has an average value in the range from about 0.1 to about 4; the amount of said aromatic nitroso compound is in the range from about 5 to about 200; the amount of said film-forming adjunct is in the range from about 10 to about 200 parts by weight; and the amount of said inert filler is in the range from about 10 to about 200 parts by weight.

80. A composition according to claim 71 wherein R8 is methylene; X is hydrogen; m is l; n has an average value in the range from about 0.1 to about 4; A is -NH-; R is propylene; R2 is methyl; a is zero; the amount of said aromatic nitroso compound is in the range from about 5 to about 200; the amount of said film-forming adjunct is in the range from about 10 to about 200 parts by weight; and the amount of said inert filler is in the range from about 10 to about 200 parts by weight.

81. A composition according to claim 71 wherein R8 is methylene; X is hydrogen; m is l; n has an average value in the range from about 0.1 to about 4; A is -NH-; R is propylene; R2 is ethyl; a is zero; the amount of said aromatic nitroso compound is in the range from about 5 to about 200; the amount of said film-forming adjunct is in the range from about 10 to about 200 parts by weight; and the amount of said inert filler is in the range from about 10 to about 200 parts by weight.