BE566327A - Adhesive composition, process of bonding rubber to metal using this composition and composite structures so produced - Google Patents

Description

       

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   The present invention relates to a method of bonding rubber to metal and the resulting rubber-metal composite product. It also relates to a novel adhesive composition especially suitable for bonding rubber to metal.



     A wide variety of materials have been proposed which can be used to bond rubber to metal. Adhesives for this use generally include a combination of a material which readily bonds to rubber with a material which attaches to metal by heating the joint under pressure. Unique materials have also been described which bind to rubber as well as metal.



   Although in some earlier cases the adhesion between

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 rubber and metal is high, the general degree of adhesion is moderate to poor. In addition, the resistance to heat, moisture and solvents of the bonds provided by prior adhesives is not as great as is normally desirable in industrial applications. Another limitation in the use of these adhesive compositions is that the vulcanization conditions under which the bonding is carried out must be very carefully controlled.



   The main object of the present invention is to provide a new process for bonding rubber to metal.



   Another object is to provide a method for improving the adhesive bond of rubber to metal.



   Another object is to provide a method of binding the
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 rubber of the metal thanks to which the bond produced between the rubber and the metal has an improved resistance to heat, solvents and humidity,
Another object of the invention is to provide a method of bonding rubber to metal in which the bond can be effected under a wide variety of vulcanization conditions.
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  Yet another object is to provide improved quality fltTU0tUPe8 CRQUt-chouc-metal.



   Others stumbled among which the. new realization
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 gpéoialmont compositions useful as adh6blfg will appear from the description oi-aprba.



  The prooddé of the present invention QQfittJ with a view to attaching oaQUtoheuo to Metgl by 1nt @ rpê1t1n between a Qorpn in oaoueohono and a metal body of a @ intermediate ph 'capable of cPadh4rer rubber ei aJ <né + => < . , Jduffage under pressure of.la tïMsturs oomposl1..l ;;, '.;,' LIllt; 1'lJ :: 1.: 3 intermediate consisting of a material ll 'J, t. l, LI;> dzadhàrer to the metal and a Poly-0-nitroso aromatq compound.



  The IJréS .- 'H1.e 1r1llentiQA will be better oomPiend.ra in ::' t;:; r <.t'ôi., nt to the drawing on thefU <el n. figures 1 to 6 rf: jd '".q,' f.Pl1l, scljema% iqaw <4ent and greatly enlarged sections of a5soiùbLage; ',:. I-'ü. til'15B prepared

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 according to various embodiments of the invention.



   In all the figures of this drawing, the same references designate materials of the same nature, namely:
Reference 1 denotes metal, reference 2 denotes rubber, reference 3 denotes a mixture of adherent for metal and of mono-C- or di-C-nitroso aromatic compound, reference 4 denotes an adherent for metal, reference 5 denotes a mono-C or di-C-aromatic nitroso compound, reference 6 denotes a metal of an olefin, vulcanizable and of a mono-C- or di-C-aromatic nitroso compound. the reference 7 denotes a mixture of an adherent for
 EMI3.1
 metal, a vulcanizable olefin and a mono-O- or di-C-nitroso aromatic compound which reference 8 denotes a çleaccroc-hage layer.



  It has been found that by using mono-nitroso aromatic compounds or a poly "" Q ... nit;, "'oso" compound such as a di-C-nitToso aXIomatic compound "together with A rubber-to-metal adhesive gives an improved bond over that which is obtained when the aromatic poly-Cnitroso compound is not included. This is generally true of everything.
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 Known type of rubberized adhesive The improvement is in fact so marked that the adhesive material with which the aromatic poly-O-nitroso compound is employed need not have any normal binding affinity for rubber. In this case, the nitroso-aromatic compound ensures the coupling between the rubber body and the intermediate binding phase.

   It is not clear exactly why the compound causes such an improved bond between the rubber body and the intermediate adhesive layer. It is believed, however, that during the

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 EMI4.1
 drc.sseen, 'assembl.ae under 1,' effect of heat and pressure.the nitroso-aromatic campos.é r'a; it with the olefinic chain structure with which it comes in contact ,, that is, the rubber band itself or the olefin tie wrap, and merges with the rubber body.



  As the? Te (5e, -Ia nitroso-aromatic molecule is linked in the phase of the release, a chemical bond is obtained.
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 between this phase and the rubber body. This theory
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 is reinforced by the fact that if one employs only an adherent compound our -m4jal which does not possess notable properties of adhesion to rubber in conjunction with the compound mono- or
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 EMI4.5
 poly-C-nitrosoj the rubber body can nevertheless be fixed securely:. metal body.
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  All that is needed therefore depending on the aspect
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 the broadest part of the invention is that, in addition to the poly-Cnitroso compound, it exhibits a material possessing properties of adhesion to metal. In such a case, the binding phase
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 intermediate comprises the material adhering to the metal and the compound
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 poly-C-n.troso,: a material adherent to the metal being at least in contact with the surface of the body of the metal and the poly-Cnitroso compound being less in contact with the rubber body.



  In the preferred embodiment of the invention, however, it is
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 also employs a vulcanizable olefin defined further
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 detail below because the inolusion of the aromatic poly-C-nitroso compound in such a system ensures or confers thereto
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 particularly marked adhesion between rubber
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 and metal. ? If 1 ', we refer more especially to the aromatic mono-0nitroso they-oi-sL: nt, in the bensene or rza.phta cycle. flUTb @ 4U @ 1 a nîtroso group (-! 0) is fixed directly on t #. ùto4µtr, cyclic carbon and ayatit J ... form:

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 wherein A is a benzene or naphthalene ring;

   R is selected from the group consisting of alkyl, alkoxy, alkanolamine, cycloalkyl, phenylalkyl, phenyl, phenoxy, phenylalkoxy, phenylamine, phenylnitrosoamine and halogens and n is an integer from 0 to 2, the total number of atoms of carbon in (R) n not exceeding 20.



   Suitable substituents (R) are: alkyl groups, such as methyl, ethyl, propyl, butyl, amyl, decyl, lauryl, myristyl, palmityl, and stearyl; alkoxy groups, such as methoxy ', ethoxy,
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 propoxy, butoxy, amyloxy, decyloxy, lauryloxy, myristyloxy, palmityloxy or stearyloxy; cyclo- groups
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 alkyl, such as cyclopropyl, oycl.obutyl, cyclopentyle, cyclohexyl, and cycloheptyl; phenylalkyl groups,
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 such as phenylmethyl and phenyldecy7.e; phenyl; phenoxy; phenylalkoxy groups, such as phenylmethoxy and phenyldecoxy; phenylamine; phenylnitrosoamine, and halogens such as chlorine and bromine.



   Examples of suitable mono-C-nitroso compounds are:
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 2-nitrosoparacymene, o> thophenylnitrosobenzene, 4-chloronitrosobenzene, paranitrosotoluene., 4-methoxynitrosobenzene, 2-benzylnitrosobenzene, 4-cyclohexyln.trosobenzene, leositrosabenzobenzobenzyln.trosobenzene, leesitrosabenzobenzobenzyln.trosobenzene, leesitrosabenzobenzobenzyln.trosobenzene, lezitrosabenzobenzobenzyln.trosobenzene, leesitrosabenzobenzobenzyln. -pentadécYl-5-Pentoxynïtrosobenzeneo 3-cyclohexYl-5-nitrosotoluenee 3-cyclopentyl-5-propoxynitrosobenzene, 2-benzyl-5-decylnitrosobenzene, 2-benzyl-5methoxynitrosobenzene, 2-benzyl-5methoxynitrosobenzopenzene-ispentyln-5-phentyl-phentosobenzene- , 3-phenyl-5-nitrosotoluene, 3-phenoxy-5-nitxosotoluene, 2-methyl-5-phenylethyloxynitrosobenzene, 2-nitroso-4, phenylnitrosoaminetoluene, 3-d6cYl-5-ehloronitrosobenzeneo 3,5-ehloronitrosobenzeneo 3,5-dinitrosobenzene , 2-phenyl-4-ôthoxynitrosobenzene,

   2-phenoxy-4.-butoxynltrosobenzene, 2-phenylethyloxy-5-butoxynitrosobenzene, 2-etho 7-4-phenylnitrosoaminenitrosobenzene.

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 EMI6.1
 2-lauryloxy -.- romonitro sobenzene, 3 -. ; .cycltheé rl.n: i.trosobenzene, 3-cyalopentyl - benzylnitrosot:

   ne, 3-cyclopentyl-5 henylnitrosobenzene, 2-phencxy - cyclohexylnitrosobenzene, 2-phenylethoxy-4-cyclopentyInitrosobenzene, 2-cyclohexyl-4-phânylnitrosoaminenitrosobenzene, 2-phenylethoxy-4-cyclopentyInitrosobenzene, 2-cyclohexyl-4-phânylnitrosoaminenitrosobenzene, 2-chloropenzene-3,5-cyclohexylchlorosobenzene, 2-phenylethoxy-4-cyclohexylnitrosobenzene, dibenzyl.n.trosobenzene, 2-benzyl-4
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 phenylnitrosobenzene, 2-phenylethyl-4-phenoxynitrisobenzene,
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 2-phenylethyl-1-benzyloxynitrosobenzene, 2-benzyl-4phenylnitrosoaminenitrosobenzene, 2-benzyl-4-bromonitrosobenzene,, 2, / - dipheny:

  lxitrosobenzene, 2-phenyl-4-phenoxynitrosobenzene, 2-phenyl-4-peenylethoxynitrosobenzene, 2-phenyl -.- phenylnitrosobenzene, 2-phenyl - chloronitrosobenzene 2,4-dipheno., yry.itros , 2-phenoxy-4-benzyloxyni-
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 trosobenzene, 4-phenyl-nitrosoaminenitrosobenzene, 2-phenoxy-
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 4-phenylnitrosoaminenitrosobenzene, 2-phenoxY-4-chloronitrosobenzene,.-Diphenylethaxyn3.t.rosobenzene, 2-phnylpropoXY-4-phenynitrosoaminenitrosobenzene, 2-benzyloxy-4chloronitros.abenylethaxyn3.t.rosobenzene , 2-chloro-4-phenylnitrosoaminenitrosobenzene, 2,4-dichloronitrosobenzene, p-nitrosophenyldiethanolarùine-2-inéttiylni'trosonaphthalene, 6-cycl, ohe, yln.trasana, htal:

  nE. ,, 4-bensylnitrosonaphthalene, 2-ethoxynitrosonaphthalene, 6 "fluoronltyosonaphthalene, 4-phenylnitrosoaminenitrosonaphthaHme, 2-rthyl-5cyclopentylni t: vOf30naphthalene1, -nethylen. "'butY'1-S ... 6thoxynitrosonaphtaH: ± l' -, le (> - el; Î1ll- 7-fil.uco.'toh'al.ene 2-cyclopenty1.-ë-h & nzylnj.t. rfo-
 EMI6.6
 
 EMI6.7
 naphthalene, .2 "" oyolopentyl-4 ... b: romonl t: r'o :, ofJ.f, phtaldnü, le 4 ,,, .bs.zy'3, - ia.'lool.api $ alès the?, .. <'r ;; .- .. t> .. r, a7- = üzii.v: .cj. naphtha3.J lJ.thoxy "S '-' fluoronitro3c'nr.hJ .1. <--- J -fA Lhy 1-5-
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 EMI6.9
 butyln1t: Osota.lene, Jt-.CytjJIßltti tp'tl; u; 7tli # .a f -mtty 16> 26-dibazii''osonaphthalene, ttc7flty, y.i-.asr ,. naht.7.s, 3,7-diahlo> onitroson> àphtalùrio, f {; th: lh.'1.



  -. - -.



  . methyln1t1oo, talene, 2-cyc.opntyl-.:yfr:l-a#=wa. .. ;; na9htaléno, leJ.J, -diéthoxyn1trosoMphtal no, le 1,5, .. dichlúro-, ... j 18 .....

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 nitrosonaphthalene, and the like.



   If we refer more especially to the poly-C-nitroso aromatic compounds, they can be any aromatic hydrocarbon, such as benzenes, naphthalenes, anthracenes, biphenyls and the like, containing at least two nitroso (-N0) groups attached directly to non-adjacent ring carbon atoms.



   Preferred poly-C-nitroso compounds are di-C-nitroso and especially di-nitroso-benzenes and -naphthalenes, such as meta- or para-dinitrosobenzenes and meta- or para-dinitrosonaphthalenes and more will be described. The invention in detail hereinafter with reference to di-C-nitroso compounds, although it is understood that the corresponding aromatic compounds containing three or more nitroso groups can be employed.



   The nuclear hydrogens of the aromatic nucleus can be replaced by groups: alkyl, alkoxy, cycloalkyl, aryl, arylalkyl, arylamine, arylnitroso-amine, halogen and the like. The presence of these substituents on the aromatic nucleus has little effect on the utility of the di-C-nitroso compounds in the present invention, and as far as is presently known, there is no limitation on the character of the substituents, which can be organic or inorganic in nature. Hence, when reference is made to the poly-C-nitroso or di-C-nitroso compounds "aromatic compounds", "benzenes" or "naphthalenes", it is understood that these terms cover the substituted derivatives as well as the compounds. unsubstituted di-nitroso, unless otherwise specified.

   It is indicated in the literature that the compounds di-
Hydroxy-substituted aromatic C-nitroso rearrange with the nitroso group to form the oxime, and therefore, are not considered to be di-nitroso aromatic compounds as defined herein. Ortho-di-C-nitroso compounds do not exist and therefore are not included here. Preferred poly-C-nitroso aromatic compounds are, as has been said, meta- or para-di-nitroso-benzenes and naphthalenes.

   In this connection, the compounds covered by the

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 following generic formula:
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 wherein A is phenyl or lenaphthyl, R represents a7kyl, cy'c7olkyle, aralkyl, aryl., arylamine or alkoxy group containing 1 to 20 carbon or halogen atoms and n is 0 '. 3. Among the substituted derivatives the preferred are deieg. a1kyÀs1xb * titués.

   Examples of such substituted aroraatlqua -C-xi.txoso compounds are 2,5-dinitroso- 'paraoy * nqp 1? -OM, OF9-.13-dinitrosobenene., 2, fluorol, 4-diqibTo & Ofi> enone, µ-methoxy-1,3-dinitrosobenzene, '2-oàoloheaRl-1,4.dinitrosobenzene, 2-m, ethy .- ,, - dini aflobenZñe, -'y.pnty.-J., 3wdin.xoacbenne, .2- beny, l, 4-difiito.sbénZéne, 2-m.étho3c3rl., Âd3.n.rosaben., 2-chloo-1,4Ôdinitnosobenzéno,, 2-méGhy.5ya.heyl., 3dmitToxobm7énoµ le 2- thy.5benzyl -. ,, dirtcaabnrr, 2-isop.a., '-, initrosobnzn, ie 2-methyl-5-Cha.a. ,, lnaberczn, .e 2-yh .-' y .-. s3 - 4, .iTT. '' 00'I? 84 8, the CyCa.Gpn'ß'1-w'oXj ''. ¯l # .r3.2.j.I'Q9G7! - 4! 811. ' Jr? the ar6 "0;% 'C, .4yo83Cß', yi." "'.4U.C'C' -. f.," '4.1..1 ..' Cb'li'y the 2-bsn-prop , y.ll-ünitraobernap on 2..i> <> iin <yl; µ;

   the mrhxy -. = J), d.- ,. trosobaïiz & ïMe 2-thyl-5-isopropywd = çc: nx le 25-'diyches! y2.-14-diïiitpegebea le 2-lh.yis4k.44dre IWa ".li rLÉi 2-m '% hoxy-µ-1 opisg., , fiz J <t ..11 4tlé1'n 8bet¯., .- tC'io.o13 .., bnx. B..14. "lliyl-
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 , .. 'J "' '. 4isÔ'e" yBrJrw'j, a.'JL $' tiiiYi7, f "rl il 1 c - - ¯,] -, Yl- 4-6-dj.o3lop'.13 -diRiti-otc.t- te 2, -., ttm 'j', ...



  ..4, 'Î, 3' .. 'E'aL' '.' LiYVIW.tfr3i J. 2-tr-n.f 1 o.
 EMI8.5
 d: Ln1trosOb, 2,3-d.tyl; - r'y, ,,. r, tyl.r.::, linJob & àµW, $ 1 ,. 2-methyl-4-benzyl - 1;, - 1 3..rirt? te.,;: ', h /; l1O: n,
 EMI8.6
 
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 2-, o; p, - ethotp-5-thyl-1,4-dinitr> nr, 2-t; ç. rt pty.-3-initroa% J'-

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 dieyelohexyl-3-methyl-1,4-dinitrosobenzene, 1e.2,5-dicyclo-
 EMI9.2
 pentyl-4-benzyl-1,3-dinitrosobenzene, 2,5-dicyclopentyl-3-ethoxy-1,4-dinitrosobenzene, 2,5-dicyclohexyl-4-chloro-
 EMI9.3
 1,3-dinitrosobenzene, 2,5-dibenzyl-3-methyl-1 ,, - dinitrosobenzene, 2,5-dibenzyl-4-cyclohexyl-1,3-dinitrosobenzene, 2,5-dibenzyl-3-raethoxy -1, .- Dinitrosobenzene, 2,5-dibenzyl-4-fluoro-1,3-dinitrosobenzene, 2-methyl-3-nethoxty-6-amyloxy-1,4dinitrosobenzene, 2-cyclopentyl-4-methoxy- 5-isopropoxy-1,3-dinitrosobenzene,

   2-ethoxy-3-benzyl-5-bùtoxy-1,4-dinitrosobenzene, 2-fluoro-4-Biethoxy-6-butoxy-13-dinitrosobenzene
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 2,3-difluoro-5-heptyl-1,4-dinitrosobenzene, 2,4-dichloro-5-
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 cyclohexyl-1,3-dinitrosobenzene, 2,5-dibromo-3-benzyl-1,4-dinitro. sobenzene, 2-chloro-4-fluoro-5-butoxy-1,3-dinitrosobenzene, 2-ethyl-3 -cyclopentyl-5-benzyl-1, .- dinitrosobenzene, 2-methyl-4-butoxy-5 -cyclohexyl-1,3-dinitrosobenzene, 2-isopropoxy-3-chloro-5-cyclopentyl-1, .- dinitrosoben, zene 2-benzyl-4-ethyl-6-anyloxy-1,3-dinitrosobenzene, 2 -methyl-3-benzyl-5-bTomo-1,4-dinitrosobenzene, 2-chloro-4-methoXY-5-heptyl-1., 3-dinitro sobenzene., 2-cyclohexyl-3methoxy-5-benzyl- 1,4-dinitrosobenzene, 2-benzyl-4-fluoro-
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 6-cyclopentyl-1,3-dinitrosobenzene, 2-isopropoxy-3-chloro-6-cyclohexyl-1,4-dinitrosobenzene,

   2-benzyl-4-ethoxy-5-
 EMI9.7
 bromo-1,3-dinitrosobenzene, 1,4-dinitrosonaphthalene, 2-methoxy-1., 4-dinitrosonaphthalene., 2-methyl-7-isopropyl-1,4-dinitrosonaphthalene, 2-methyl-1, 4-dinitrosonaphthalene, 6-cyclohexyl-1,3-dinitrosonaphthalene, 4-benzyl-1,5dinitrosonaphthalene, 2-ethoxy-16-dinitrosonaphthalene, ¯le 6-fluoro-1 ,, - dinitrosonaphthalene, 2-ethyl- 5-cyclopentyl-18-dlnitrosonaphthalene, 1-methyl-7-benzyl-2.6-dinitrosonaphthalene, 5-butyl-8-ethoxy-2,7-dinitrosonaphthalene, 6 = ethyl -? - fluoro-1,1-dinitrosonaphthalene, 2-cyclopentyl- 8-benzyl-1,3-dmitrosonaphthalene, 4-cyclohexyl-7-methoxylj5-dinitrosonaphthalene, 2-cyelopentyl -.- bromo-16-dinitro-

 <Desc / Clms Page number 10>

 
 EMI10.1
 sonaphthalen le, .- benzyl8 - hi? toxy-ls'l. " at ;

   .; - l. i.> .. #,. ¯.:. = .ast¯! E, 2-benzl - chlora-l, -dinitrosompâ i i 1 ..: µ; loxyr-8fl.oro-N6 - .. n.rosonaphthalénc :, le 1-.,; I ' n, -1.- 1:>; x ".. <1:,, 7-
 EMI10.2
 dinitrosoi ..; -. lêne, the 5, $ - dicyr'.oni a.,; ¯.¯? p.i., ::. xi ;, xwso-naphthalene, 2,6-di'benzyl - l, -? inifirasorxahtelêrre, 2-ethoXY-7-amyloxy-l, 5-diiiitrosonaplitaljùie;

   5,7dichlaro-1, & din.trosonaphthalene? .- ethyl-3-methyl-5i-sopropyl-1.7-dinitrosonaplitalene, 2-cyclopentyl-5,7-dicyclohexyE = 1,8-d> itrosonaphitz: lene, l, 5-dïé thoxy-bztyTHa6-d.rj.itrosonaphtFlêne, lx., 5 - trichlaro-2jdinitrosonapbtalene, le, 5-diethyl-7-cyclohe.yl-l, l-dinitrosonaphthalene, le -ethyl.-6 -bEnzyl - rëthyl-1,3-d: ir¯trasound, phthalene, 2-, ethyl -irsQpropoxy --- ethyZ-l, 5-dinitroson.phtül.êne, 2-ethyl-àl-chloro-5 -heptyl-1,6-diniti% osonc.phtaiéne, the 2.5-dicyclopenty -. =. $ h.y1-lr7-dinitrosonaphthalene, the 2,, 6-dicyclohexYl-4benzyl-1, µ-dinitrosonaphthalene, the 1, 5 -dir.yclohc, Yyl -'- methoxy-, 6dinitposonaphthalene, 1, 5.-dir.yclopenty .-- chlazo -, '- din.trosonaphta.l.ênez îe? "- dibenzyl-5-nthyl- . ,, .- c3.n, .. rosrna, h: L.ene, the ¯ 2j'Td.i'be2.zy1,5-cyc.aentyl -., 3-dïnitrasonlhi.fx.êc:

  , ,, 1-di'benzy.w 8-methoxy-1, j-dinitroJonaphthalene, 28-dtber.yl-5-chlorc'- ..,. I1, Qeipa.tlài, e '2-ethyl- -hh <.) y -, 'itnylfy-l /
 EMI10.3
 d.n.'cao2, .ra 2-cyclohexyl-4t '': -: ---) - 'th ..: y ldin1trolonaphthalenejl 1-me thvxy. 5 -b: nzjf 1 -.? -: -jl7, '", t, s-,' ia dinitl" osone.p'taltm8, the t-iJtCl '7 "' 1, rtél,;: (: .y7lreyCS.: yh dini t: f: tnatal .ne1 le 6-eMt'lr <r) "8'-ty! - ', j: Id Ll' (11 () n" ph L léna, +8, "dC.I.OTC1-'Î" jßC: .C) itt1 f, d J .J.,. 1 11 j id 1.1 '' '' "l'J, ', l [il Hh le 2l%." "D? 5'tTJiCy'-,"' ' y. "j" '. i1..1tHçiFiyl-al..fr, .i .;':, 1 <"'' '' ') G'1.G?' LT" ^ 1'e, .éj ' 1. "11 Ll'riittn b, t;:, i; t ...,,. l 'J. he94' '-'? z2l-e2,., t'r ", .. '' A: rr; i, t:,,;.,;.

    = t yclopentrl..l, S-d1n1trosorulrht ... Ú ",.,,:, - ,,, rrc, .t3't3a, 'i' - ,? itro3.1.'3'OArFth tv rtt-, 1 - r ...., j, .¯- 1: yf 'x Î3ll't "' ,, 'Ciih.3'ljt: 1 <. i; wi v. ,, i, '{' 1Ür: J.t'o ... 1,4- d1n1t, sona1 la 2ilu- '. ",,' i ': J /" il in :.' 1 t. L t) "'(1ini-
 EMI10.4
 'i, llb, J.4. 2-cyclopintjr .-, E.Tf,:; rl ..- raitJ.1, 5-1.ïlitroso.- - -. "'-'" - ""

 <Desc / Clms Page number 11>

 
 EMI11.1
 Naphthalene, 4-benzyl-5-chloro-8-cyclohexyl-1,6-dinitrosonaphtaleene, 2-isopropoxy-6-fluôi% o-8-eyciopen i>; 1-. s7-dinitrosonaphthalene, Z-benzyl-5-butoxy-7chloro-1, md.rW trosona, phthalene.



  If one refers more specifically:!. El E "Î1 / ant to the material adhering to the metal it can be chosen from a wide variety of materials.
 EMI11.2
 organic compounds, namely compounds and polymers, as well as mixtures thereof which possess adhesive properties towards metal characteristic of adhesives ordinarily employed in the manufacture of metallic elements bonded by adhesives to each other and to other elements structural structures supporting loads. These materials have in the bonded assembly a bond strength of a high degree, usually at least about 3.6 kg per linear centimeter in the peel test, and a high degree of cohesion.

   The cohesion and adhesion properties of these materials in the assembly must be at least substantially equal to the cohesive strength of the rubber bonded to the metal and these cohesive and adhesion properties are developed under the conditions ordinarily employed to vulcanize the rubber. mass of the rubber body.

   Organic compounds and polymeric materials adhering to metal surfaces in the above manner are well
 EMI11.3
 known and include ta) eontiongation polymers. thermosets, such as:!: '6s.1nes-- phnQ "" ,, ± J.J¯ç1, éhrd @ epoxy resins, polyester veined ion; the regmeg tJ] if.i.zj.J; 1e @t analogs (b) the polymerQg) and cofolym "Po5 of ma.t, ierQs polarag ethylenically unsaturated, such as polyv1ny-uty; r1 1 ioyv.yimf ' ¯ral polyvinyl acetate, 1 ehlerug dQ p? LyîT1, nyl @ eh3 vinyl it6lVis67rFtk'd! 4BE8k / B vinyl @t "JQ chloride il @ v1nleJ chlorinated eepelypères of uâatB 6 / vinyl garlic @ gt du ciLLernrg vinyl, acrylic acid hydrate; 1 * # copolyn! 0C of agedrylic 4ç-i-dg and conjugated dienes ,. such as pu, t [J, (iJJ1tHS '", hJ 1 l t; ih1o; ro'" butadiene-1.12;

   2,3-diohlorobu.tadiene-1, jt 0urs ad..ts po thalogénés; dMid methgarlic polymers 3ys methacrylic diacid and dibnee cfijuaués; 1 & 5 oQpglr1neres of

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 EMI12.1
 vinyipyridine and conjugated dienes, and icurk products of
 EMI12.2
 reaction * with polyacids, and the like,! -) rubbers
 EMI12.3
 halogenated such as natural rubber hL ;? and chlorinated synthetic rubber; for example, olycn.:.v;zerm chlor9, chlorinated polybutadiene; chlorinated copolymers of buta, diene and styre-blends of chlorine rubber with hydrohalogen rubber or hypohalogen rubber, and the like;

   (d) polyisocyaaates such as P, P "-diisocyanato-diphenylmethane, 1-lhexamethylenediisocyanate., PPP" -triisocyanato-triphenylmethan <3,3'-dim.éthl-4,4'-biphenylénedüsocyana.te, 3,3'-dimethoxy¯ 4,4'-baPhênylnedüsocyanate, aniline-phosgenated resins
 EMI12.4
 aldehyde, such as those described in the United States patent
 EMI12.5
 of America No. 2,683,730 of July 13, 1954 and the like.
 EMI12.6
 



  The rubber which can be bonded to metal according to the present invention can be selected from any of the natural rubbers and olefinic synchetic rubbers comprising the
 EMI12.7
 polychloroprene, polybutadiene, neoprene, Buna-S., 1e lwk1-1V, .LE
 EMI12.8
 butyl rubber, brominated butyl rubber and the like.



  The metals to which the rubber can be attached can also be selected from ordinary structural metals such as
 EMI12.9
 that iron., lea-cier (including stainless steel), leada 1-aluminum, copper, brass, bronze. ' ! .:; i.1;,; 1 1.:<Jnel, the niceelo-9 zinj, and the like.



  In the implementation of the present invention, an intermediate phase comprising the nitroso coMpose and the material adhering to the metal between the rubber body and the surface of the metal body which 1-loniiesiie bind .



  In the intermediate $ hase the cornyos é ri r-ac 4sts, tJ.cu must at least be available at the interface euLm a ..- 'r 1'lz:> 1r # t-ot.i!:. Chouc e la hs, ss i.di and 1 s.dlzérent s.oJr.>; ì,. ,, l, daa. e :: tr, au inoin: disponbils at 1-'1 = ierface between the field of Mptal and La ph. He intervenes in this intermediate phase-irc ;; Jt o-dinjt'r.-rjt constitutes by -1: 0 application of a mixture, rigq to: of. rz3 nL.; t arom & tjLcp and adhere for metal¯, coiwih illuatro at 1 4 ", -. h

 <Desc / Clms Page number 13>

 figure 1.

   The intermediate phase can, however, also be formed by application of the components adorned. Regarding this latter embodiment, any of several processes can be followed, namely, the application of the aromatic di-C-nitroso compound to the skin. surface of rubber and metal adhesive on the metal surface, 1 -application of metal adhesive on the metal surface and then inapplication over all of the aromatic nitroso compound or inapplication of the aromatic nitroso compound on the surface rubber, then apply the metal bond over it,

   all of these processes producing the structure shown in Fig. 2. Various combinations of these means can be employed, such as inapplying a mixture of high content and aromatic nitroso compound and low in metal adherent to the rubber body and application of A mixture of nitroso compound and metal adherent high in metal adherence on top of the metal or on the metal body.

   The exact process followed is not criticized the important factor being the interposition between the rubber and the metal to
 EMI13.1
 connect with an intermediate phase COll1.pJ? Gns.x) the compound 4i-C-ni aromatic tToso and an adherent for iùétE; 1, the aromatic G9mp96 d1MCnitroso being at least available, for the rubber. in view of the adhesion 'to rubber and the follower for met'?}, being to. less available to metal for an adhesion. As indicated in connection with the preferred embodiment of the invention, a readily olefin Tulcani # ab is also employed. such as; olyr99ut.Tin., PQlych19r0btdiêns and their partially pst.h.la? products. leg copolymers .partially 1Po2t ... halogn @ s d} isgblJ "Gyl.ÚJ, -0t;

   of bute.diene, in pal "ticulie1" the copolymerref3 paTîie1î. # so <> ni jK .-: .- t <¯.rsē's dB0; r: Us in the patent 4es -Ittatm - Uni2 ¯. ' .¯received. ¯3- G,, 1). .7 m?,; Rs'19, .9 Les ¯ene j5 ,, loe6 1 ', 01) 1111 t1' '') bu: tz, Ó, in? $} Poly # 1 cyclo.pent-adlene " the tet: rch1-oX 'cy'çÜop-eIJ- tE, dj.Bn-t) the rubbers: PAl "ti,: el1'EJment .yrsha., ogene, the eatJv, tch9UÇ, S prtielletBent 1w: PÔhQ.l , genes -and the like .. From tell * 91éj'j.Jl1E easily bridge

 <Desc / Clms Page number 14>

 
 EMI14.1
 vulcanizable, that is to say that they 2> OLt: ...--- '' 'read polybutadiene.

   Preferably 1 '' '' 'zincs as vulcanizable as poly-2-tr11c1U .. ... particularly advantageous ae cp r.e; ''. 1.- pc ... lychloroprene, èpoly-2-chlorobu'Caú..L: .... ú \.:, - 1 ') ;. -.za - ::; .-ichlorobutadiene-1, 3 and poly-2,3 - ui,:, ..¯ ¯. ¯¯¯., ¯, .. r, ': I post-bromine
 EMI14.2
 such as those containing an EC 1 content; ioTn <. . There is approximately 7.5 to 42 mol, preferably 15 to 36 mol., o.



  When ca-i employs an ol.é "ine rul; ¯-a, i. ... :: ... C0H1Út element of the intermediate linking phase, it can be applied to the mixture with the compound ni troso-aro.ú121Jicnle , only eoajae represented
 EMI14.3
 in Figure 3, or mixed with the aromatic nitroso compound
 EMI14.4
 and the adherent for metal as shown in Fig. 4. As the vulcanizable olefin, when not used aar-s the intermediate binding jJhD.se a principalāw L ¯.yes 1> uL II} ' , <, z..ca - ..: r ¯ =; - raiiérFnce with the rubber, it must be \ ... J.'l: au. minus ui.:zrn .. ¯ a .1 interface
 EMI14.5
 between the rubber body and the) lF f: C. 1i = <. R,>,., F <- <j, = ire of connection.



  When we apply the three COhlpOSrl1L, ".L'iu, 1 ':'" u,.:. '' :: 11 UCJ, éir15e on the surface of the rubber or (i-, w'- 'L .... 1' l! T! R. CL naturally the compound nitroso arornatiatze are t:> 1 s.>. >;: i ..,,., ¯; f., rzis of the rubber surface and 1 <Acr ,,: ut} 1r.U ('fez' #, "ll'Í '(; z :: r available vis-à-vis the metal. jit ",,: '1 -!' J 1:" 1 ': 11 l (qil 1 a mixture of leol6frie and (': lüilCl;, ':: i.', ".1 ,,,,?, T. Iuue alone to Î1. '. Ç d.4 $ rubber or 51 <, ,,,> i;! RI 1i c ::, .. i ctin.c' .Ii F applied containing the adherent to ¯st1 R1l1 '1.'1 5 <> 1 1;. <: = Of Metcl for constitu {tl "' 1.â structure illustrated 1:,: 1 \.,:, .111 '(O.



  Since it is COflLU; ucx¯¯ .. 1 l '1 Hu J "f 1 l ,,:, t è.', Vt: r [.. desirable to constitute a 'COt =.:' .'R- . ,,:.,,, 1 bonding adhesive and body dt o., Y, ',.,,' -..-; u {i JI 'I use such a layer of a <> ci <> <.;,,, j, 1),.-s.,;, 1 us, I i.Lclu.



  The C'i'l.âi. $, L.El.i.'t The H, $ includes IbW'T.tr. ::, tt2 .1,., "- r: .3. = 'L1 . 'E.7.T1 atua43 rubber, or synthetic I,) J.;,. Ti = ....' ,; 0 ,, <bzz rubber, or an Óletin vu.lé ;; UJJ.,: I1bl 'i "l.}'} J .. JJ1'j, q ... (1 -i -t :; ' ) -li,
 EMI14.6
 and we pellt the applique0Sµ either to the 5Urfac% to cr, outc-huac, #miL par-.

 <Desc / Clms Page number 15>

 
 EMI15.1
 above the adhesive layer in the form of ::: lt .... (18 solution or a preformed sheet. Such layers.% ü 1-1 - ochage are chosen on the basis of the rubber body ec adhere well to that -this.



  The increased adhesion to the rubber body resulting from the use of the aromatic di-C-nitroso compound according to the present invention is applicable herein by improving the adhesion between the bonding phase and the tie layer as illustrated in Figures 5 and 5. 6.



  For this reason and since the primer layer is melted with the rubber body, it is considered here as part of the rubber body. Thus, when referring to a rubber body or to the surface of the rubber body, it is understood that we are referring both to the rubber body itself when no tie layer is employed as to the primer layer fused with the rubber body when a primer layer is employed.



   Reference was made above to the application of the various components of the adhesive binding phase to either of the
 EMI15.2
 surfaces to be joined or both. The particular mode of application is not critical to the broader aspects of the invention and one or more of the components can be applied in finely divided solid form and in liquid form, the latter being the most advantageous. When one or more
 EMI15.3
 of the components is applied as (IJ: 1118 liquida it can serve as a liquid vehicle or a solvent can be used for the one or more of the components,: The application of various components as a solution of at least 1? a drîl2-- is i3Pél'érab1e, In this regard, we generally prefer cn x> 1 than PB, dt18; r'E: pt Jn; rJ;

   fl1étgl "and .. '. 1 vl.'1d'. &;. f19 in t3ldl.Cài = 1¯jng ;, pe-7-ëYl., in management while the compound niiroso .1l'01fgt; 1 .. .qU (j Í'flUt tll @ sn! D1¯me suspended in this solution. (: f1ti; e 1U :::, ;;. il; J ..; t,; it8 eët inelue in the case where l 'one refers to 1 ROïRposifiQn geug forms 4' a solution. As solvent, one is [1Jp..lI} J- "!" i; cut organic liquid and mixture of these in which a you j, i = i, i;> 1. # tir # of the ingredients to be applied is soluble to the degree d6t> * min to p * ii? la, referred to if bé of the

 <Desc / Clms Page number 16>

 
 EMI16.1
 solution and the exact means of application to be employed.

   Generally, the solids content of such a solution can range from about 5 to 30%, although in most cases where the composition is to be applied by brushing, this solids content will be on the order of about 10 to 25%. Any solvent employed should also be readily volatile so that a prolonged drying period is not encountered. Preferred solvents especially for the preferred compositions given below are aromatic hydrocarbons, such as benzene, toluene, xylene and the like, and chlorinated aromatic hydrocarbons such as.
 EMI16.2
 as mdnoehloobenzàn, diohlorobenzàne and the like.

   One can include it by deviating from small amounts of aliphatic carburea dhv & rooarburgg cl% -lQroaliphatiquem, cetene, ethers and / or alcohols.



     - After applying the adhesive component (s)
 EMI16.3
 as described above and all solvent has evaporated, the rubber surface and the metal surface intended for
 EMI16.4
 be bonded, and the assembly is heated under pressure to cause the rubber to vulcanize and bond. Depending on the type of cure, the exact time and temperature of curing will vary depending on the nature of the body employed as well as that of the ingredients of the adhesive phase; In general, however, the treatment temperature remains between eron 132 and 177 C and the duration is of the order
 EMI16.5
 d-lenvirm 20 to-60 minutes.

   As with a general purpose adhesive which requires only a single application of material, it is generally preferable to use a mixture of all materials intended to be present in the intermediate phase of LG1Qn, to Bib one.



  . mixture of the aromatic nitroso compound and the metal adhesive as well as the vuleanizable olefin, when one is mixed.



  In any mixture, the aromatic nitroso compound Dora is present in quintities as low as about 1% by weight based on 7% by weight of the solids. Quantities of comDoo6 nitrogo t1qùe very much greater than this quantity jaerrie augei high that 90-95 $ p..euvsnt t1 "& used ±! # Adhere to mast 1.1 f; 5t equal-

 <Desc / Clms Page number 17>

 effectively at relatively low levels such as around 5%
 EMI17.1
 and it may be present in an amount as high as about 94. g by weight based on the weight of the solids in the mixture. When an olefin is employed, its amount can vary widely from 5% up to about 94% on the same basis.



   With particular reference to the aromatic nitroso compounds, the functional portion of this material is made up of the group or nitroso groups themselves. Therefore, in any intermediate phase of bonding of the present invention the amount of at least nitroso groups available for the aromatic compound will be employed such that the nitroso groups constitute at least about 0.4% of the solids of the intermediate phase of the present invention. bond at least adjacent to the rubber surface. The amount of aromatic mono-C-nitroso compound employed can be much greater than this value, ', and can be up to that providing about 42% by weight of nitroso groups in the solids of the intermediate linkage phase at least adjacent to the surface of the rubber.



   Particularly advantageous metal adhesives
 EMI17.2
 for use in admixture with the aromatic compound .aon.ppC-n, tro, so (and also with an olefin if one is employed) are chlorinated rubbers. Especially advantageous olefins for use in such a mixture are the polymers.
 EMI17.3
 of Ghioro-substituted butadiene such as ,, âJ.y crl: .exonrn.e, a.-d.croa'ua.? .-, 3? and the postbrominated polysiers of 2;, 3- ichlorobutane-1,3 of the pre (i. t8.



  The following examples iinit aonnss to illustrate the smus drawback: limiting the PQj.qt0 ± S they ¯,.; #:;, Ri.% - 1 <> n5 which may vary and the ingredients may vary% 1 - <. = ,}: '<3lli) laced p11r to'antre, s, fulfilling --a function BQPi7QleLcç.



  ':; ": \>" "TY1' :) kJ -r. L We apply to. The brush a yd: .s: eç¯r: s.;: .Ant in 25 pawti of 'N4 ... din : it,; sophényla: nil1s :;) 75 i rubber

 <Desc / Clms Page number 18>

 
 EMI18.1
 natural chlorine (67% 'of chlorine, viscosity 125 cops at 25 <20% solution in toluene) and 250 parts of on a strip
 EMI18.2
 of cold rolled steel degreased and sanded to 60.3!> 25 mm, and allowed to dry for about 30 ml.

   On 1: .J¯,; lique sai? Here. adhesive coated surface a 6.3 sheet of a fresh unvulcanized natural rubber sheet, consisting of 100 parts smoked foil, 30 parts tunnel black, 15 parts zinc oxide, 2, 75 parts of acid
 EMI18.3
 sbariùe, 3 parts of sulfur, 0.6 part of, tëtramethylthiurarl-e ionosulphide, 2 parts of pine tar and 0075 part of phê, nyl-'ta-za, phtylauline, we place the whole in a mold and we vulcanizes under pressure for 30 minutes at 149. The assembly is then removed from the mold and allowed to cool. The link that
 EMI18.4
 The result is such that one cannot remove the rubber from the metal without tearing the body of the owl.



  LX3MPLZ Ut. An adinesity consisting of 25 parts of mononittosobenzene, 75 parts of ce-outohouc n-aturol ch1oT6, viscosity! 125 opue ot 350 part @ deol-u .: a degreased and sandblasted steel surface; It is geo-iooe-iooe for about 30 minutes. A sheet of comp P56, of unvulnered natural rubber, 414, fralohmpnt iris sheet, consisting of 100 parts of teuilloo fui46co, is applied to the adhesive-coated surface; 0 parts of Uri black, 15 parts of zinc oxide; one part of stearic acid-ueo-2 ′ of sulfur, 1.5 parts of bonzothiazyl acid and 0.2 part of zinc diinethyldithlocerba7tiate; the ensomble is placed in a mold and vulcanized for 30 minutes at 155.

   The resulting bond is such that the rubber cannot be detached from the metal without tearing the body of the elastomer.



   EXAMPLE III-
An adhesive consisting of 50 parts of N, 4-
 EMI18.5
 .n3.odiphlara3.ne, 50 parts of an ide catalyzed phenol-formaldehyde resin, meltable and soluble, 4 parts of hexamethylene

 <Desc / Clms Page number 19>

 
 EMI19.1
 tetramine, and 125 parts of a mixture of: z-.¯w: eE.1 ':., of' nethanol and methyl ethyl ketone at a surface 'a> a ;; fi. clégraisséo and sanded and left to dry. A freshly sheeted, unvulcanized natural rubber compound plate, of the type employed in 1, is applied to the adhesive coated surface. example I, the assembly is placed in a mold and vulcanized under pressure for
 EMI19.2
 30 rnn at 155. The seat is removed from the mold and allowed to cool. Examination of the assembly shows that a strong bond has formed.



  EXEMEPLE IV. -
An adhesive consisting of 10 parts of N, 4-
 EMI19.3
 dinitrosodiphenylamine, 30 parts of post-brominated poly- "23 - diehlorobutadiene- 1,3 (about 27 mol.% bromine) 70 parts of chlorinated natural rubber, grade 125 cps and 300 parts of toluene, on a steel surface degreased and sanded and left to dry.

   A plate of unvulcanized, freshly sheeted natural rubber compound is applied to the adhesive coated surface. consistent
 EMI19.4
 in 100 parts of smoked leaves, 5 parts of walnuts. A.'9 15 part, 5 of zinc oxide, 1 part of stearyl acid, that, 2 parts of sulfur, 1 part of benzotliinx disulphide; 1, e Rt o; 2 pai? Tic of dimethyldi th1ocar'balna te of Z; 1: tl.0 j on pi, o, = e 1 a l-nf.10Ülb; L11 clhnf-l lm mold 6 is vulcanized under pressure ps: ', fa, 3. 20 iîl; Ln1J; tifl ;; fi 111211 We use a similar way an adhesive seems e- ai, t. pr'écGclOl1 h, a;!. s np Containing no compound nitroso, un j! lt-n'll1'e Ez1't. 1; - ::} i1}, ['as l JI f .., dh6 .... returned by a method êGIIl1; .le to e011G c1heJ 'itc;

   in Irt Specification dressai AST14 2 9 '' 'Fiethnde Ij. ! JMiRJ 3t (; "'; / 1j. The rubber is peeled or stained from i7.é'.¯ ê (I6' = ui, ai ;: -.i, ', 10" <51..ni ha : w: adhesion in If1.g / ar4 $ L "ç, ;; 0JY.} Ú [1.ff, @ ',.; bt.; 1,1u f1.V.:Ù :, li = me '=; ii + 1 <<;, <; ,,' j! jL-. chlorinated cabbage and Fg: Lydj.e; hl (JrClt, 1ItlrHI ': IF'; 3cs, ''; t. h! I ); 11 '<: f'; Jt:: rpt., 1ïî; until, 1 less than J, 6 Kg / cm '. ["Ôi r $:, t =. <; I> 1 .., i: {, PoII1l1 1.; q V b, t;

   I 'j>, tJ'tF>; 1 t j containing the oompos ± aitrogo. 35 t- rct, fi-ii <. iJonç 'j, i 1> lit:] e; â9 Kg /; J !! and tears MtablG11J. @ nt daj-ia '1 C. r3r., dÉ!, '' eJ5tc'i ':?'?;, ('fi .'jj = indicates -a '83, ¯I; t3? 11.l [Jün "nn <n <, 1> jn , '', 1Üd! F; Ú8'.tdh-: <<lilasseublage à 1 "adherent.G1f no ÍJ1.1: t'o :: J6.

 <Desc / Clms Page number 20>

 
 EMI20.1
 we apply an aâëlf consisting of 5 parts -de para- ¯ -nīr.ph, ery.ae * 310,, Va les é * po'1-2, jd.ch3nrobuad3'-3., post46mf (ivia7 (m 15 MOI.,. Yo Ber) 7th parts of natural rubber. Chlor6 ,;! Quality 225 cpsj, 300 parts of toluene and 10 'parts of my.isobut.ctone to a steel surface degreased and sandblasted .and left to dry.

   Apply to the adhesive-coated surface
 EMI20.2
 a freshly sheeted, unvulcanized natural rubber sheet, consisting of 100 parts smoked foil, 50 parts FT carbon black, 5 parts zinc oxide, parts stearic aid, 2 , 5 parts sulfur, 2 parts
 EMI20.3
 of ph4yl-bet ,, a-naphthylamine and 1 part of benzothiazyl disulfide. And vulcanized under pressure for 30 minutes at 135. A similar adhesive is employed in a similar manner but not
 EMI20.4
 containing no nitroso compound.

   The bad adhesion in the case of the adhesive containing the nitroso compound is such that one cannot detach the rubber from the metal without tearing the body of the
 EMI20.5
 The adhesion in the case of the adhesive not containing the nitroso compound is such that the rubber can be detached from the metal with relative ease, the separation occurring.
 EMI20.6
 prinoOaleme1St between the adhesive and the body of the elastomare.



    EXAMPLE VI.-
An adhesive consisting of 15 parts of N, 4-
 EMI20.7
 dinitrcssodiphenylantn4j 15 parts of 2 # 3-dichlorobutadiene-1 # 3 post-bromine (approx. 29 mol @% Br), 85 parts of chlorinated natural rubber, grade 125 cps and 300 parts of toluene on a degreased chrome stainless steel surface and sanded, and let dry.

   Apply a plate of
 EMI20.8
 compound of unvulcanized ORS rubber, tralchment sheeted, consisting of 100 parts of ORS elastomer (standard), 50 parts of HAF black, 3 parts of zinc oxide, 2 parts of stearic acid,
 EMI20.9
 1.8 parts of sulfur, one part of N-cyclohoxyl-2-bonsothiazoleaullènàmidea 1.25 part of phenyl-btta-naphthylaaine and 10 parts

 <Desc / Clms Page number 21>

 of pine resin and the assembly is vulcanized under pressure for 30 minutes at 142. A similar adhesive is employed in a similar manner, but not containing the nitroso compound. The adhesion in the case of the adhesive containing the nitroso compound is such that one cannot peel the rubber from the metal without tearing the body of the elastomer.

   The adhesion in the case of bonding to the adhesive without the nitroso compound is notably inferior, the detachment mainly occurring between the adhesive and the elastomer body.



  EXAMPLE VII. -
An adhesive consisting of 50 parts of 2,5-dinitroso-paracymene, 50 parts of an acid-catalyzed, meltable and soluble phenolformaldehyde resin, 4 parts of hexamethylene-tetramine and 125 parts of a mixture of parts is applied. of methanol and methyl ethyl ketone with a brush, on a cold rolled steel strip, degreased and sanded, 60.3 x 25 mm, and allowed to dry for about 30 min. A 6.3 mm plate of an unvulcanized natural rubber compound consisting of 100 parts of smoked sheets is applied to the adhesive coated surface.



  40 parts of tunnel black, 10 parts of zinc oxide, 2.5 parts of sulfur, 0.5 part of 2-mecaptobenzole, 0.5 part of benzothiazyl disulfide, 0.2 part of zinc diethyldithiocarbamate , 2 parts of pine tar and 1.5 parts of phenyl-beta-naphthylamine, The rubber-metal assembly coated with adhesive is vulcanized for 30 mm at 155 The resulting bond is such that the rubber cannot be detached metal without tearing the body of the elastomer.



    EXAMPLE VIII.-
As described in the previous example 1, an adhesive consisting of 50 parts of paradinitrosobenzene, 50 parts of polyvinylbutyral (XYHL grade) and 333 parts of methanol is employed. The natural rubber compound used in Example VII 'is used and the assembly is vulcanized under pressure for 20 minutes at 160.

 <Desc / Clms Page number 22>

 



  The resulting bond is such that the rubber cannot be detached from the metal without tearing the body of the elastomer.



  EXAMPLE IX. -
An adhesive consisting of 10 parts is applied to the steel surface and treated in the manner of the previous examples.
 EMI22.1
 of 235.parad.nitcaymne, 30 parts of poly-2.3-dichlorobutadiene-
1.3 (40 emulsion polymer, approx.90% conversion), 70 parts of chlorinated natural rubber (125 cps grade) and 300 parts of toluene. The natural rubber compound used in Example VII was employed, and the assembly was vulcanized under pressure for
20 mm to 155.



   An adhesive similar to the previous one except that it does not contain the nitroso compound is treated at the same time as the cement containing the nitroso compound.



   In both cases, the adhesion is measured by a method similar to that described in specification ASTM D42-475, M @@ hode B. In this test, the rubber is peeled or peeled from the metal at an angle of 90 and evaluated. adhesion in Kg / cm. The assembly obtained with the mixture of chlorinated rubber and polychlorobutadiene resists 3.9 kg / cm. The assembly with the adhesive containing the nitroso compound is resistant to 9.3 kg / cm and tears notably in the material. body of the elastomer, indicating a resistance of
Haison more than double that of control tape.



   EXAMPLE X. -
An adhesive consisting of 15 parts of para-para is applied to the steel surface and treated as described above.
 EMI22.2
 dinitrosobenzsne, 30 parts of poly, 3.d.corabutadine -., 3 crc.é. (envircm bzz no ..; 6 Br) 70 parts of chlorinated natural rubber (grade 12 cps and 300 parts of toluene. The elastomer used is a butyl rubber compound (GRI) consisting of 100
 EMI22.3
 basic polymeric acid, 54 parts of SRF black, 5 parts of oxide, zinc, 2 - ,, parts of sulfur 1 part of tetraethyl disulphide and 0.5 part of 2- mercaptobenzothiazo.e, The adhesive coated elastomer-metal assembly is vulcanized under

 <Desc / Clms Page number 23>

 pressure to 150.



   At the same time as the adhesive containing the nitroso compound is treated a binary mixture of chlorinated rubber and brominated polychlorobutadiene.



   The adhesion is measured as in Example IX. The "binary" mixture of chlorinated rubber and polychlorobutadiene resists 2.2 kg / cm. The adhesive containing the nitroso compound is resistant to 17.1 Kg / cm, which is an almost eight-fold improvement over the control adhesive.
 EMI23.1
 



  EXEiIPLE XI. -
An adhesive consisting of 10 parts of paradinitrosobenzene, 30 parts of poly-2,3-dichlorobutadiel, 3 post-brominated (about 27 mol% Br) is applied to the steel surface and treated as described above. , 70 parts of chlorinated natural rubber (quality 125 cps) and 300 parts of toluene. The elastomer used is a standard GRS compound consisting of 100 parts of base polymer, 50 parts of HAF black, 3 parts of Zinc oxide, 2 parts of stearic acid, 1.8 parts of sulfur, 1 part of Ncyclohexyl -2-benzothiazolesulfenamide, 1.25 part of phenyl-beta-naphthylamine and 10 parts of pine resin. The elastomer-metal assembly coated with adhesive is vulcanized for 3P min under pressure at 140.



   At the same time, a "binary" mixture of the chlorinated rubber and the brominated polychlorobutadiene is treated.



   The adhesion is measured as in Example IX. The binary mixture of chlorinated rubber and brominated polychlorobutadiene gives an adhesion of 6.8 Kg / cm, the separation occurring between the adhesive and the elastomer. The adhesive assembly containing the nitroso compound resists 14.8 Kg / cm, tearing in the body of the elastomer.



    EXAMPLE XII.-
An adhesive consisting of 20 parts of adhesive is applied to the steel surface and treated as described above.

 <Desc / Clms Page number 24>

 
 EMI24.1
 2.5 dinitrosoparacymene, 30 parts of post-brominated poly-2,3dichlorobutadiene-1,3 (about 27 mol% Br), 70 parts of chlorinated natural rubber (quality 125 cps) and 300 parts of toluene. At the same time, a binary mixture of chlorinated rubber and chlorobutadiene is treated.

   The elastomer used is a natural rubber compound consisting of 100 parts of smoked foil, 5 parts of tunnel black, 15 parts of lead oxide, 10 parts of zinc oxide ,. 2.5 parts of 2-mercaptobenzothiazole, 1.5 parts of sulfur
 EMI24.2
 2 parts of phenyl-beta-naphthylamine, 2 parts of pine tar and 2 parts of wax. The adhesive-coated elastomeric metal assembly is vulcanized, under pressure, for 30 minutes at 140 C.



  The obtained layered product can be separated with the binary mixture, the rupture occurring between the cement and the rubber. the adhesion obtained with the adhesive containing the nitroso compound is such that the rubber cannot be detached from the metal without tearing the body of the elastomer.
 EMI24.3
 



  , Examples XIII to XVII i ... usxnt, ut.7..satiori of two coating adhesive systems.



   Examples XIII to XVII, Elastomer compounds. natural rubber
 EMI24.4
 
<tb>
<tb> sheet <SEP> smoke <SEP> 100 <SEP> parts
<tb> black <SEP> from <SEP> oven <SEP> to <SEP> abrasion <SEP> high <SEP> 50 <SEP> "
<tb> (HAF)
<tb> <SEP> zinc <SEP> oxide <SEP> 15 <SEP> "
<tb> <SEP> stearic acid <SEP> 1 <SEP> "
<tb> sulfur <SEP> 2 <SEP> "
<tb> <SEP> benzothiazyl <SEP> disulfide <SEP> 1.5 <SEP> "
<tb> <SEP> zinc <SEP> dimethyldithiocarbamate <SEP> 0.2 <SEP> "
<tb> neoprene
<tb> neoprene <SEP> type <SEP> WRT <SEP> 100 <SEP> parts
<tb> black <SEP> from <SEP> oven <SEP> end <SEP> 50, <SEP> "
<tb> <SEP> zinc oxide <SEP> <SEP> 5 <SEP> "
<tb> magnesium <SEP> <SEP> <SEP> <SEP> 4.

   <SEP> "
<tb> <SEP> stearic acid <SEP> 0.5 <SEP> "
<tb>
 
 EMI24.5
 2-mercaptoimidaZoline 05 "
 EMI24.6
 
<tb>
<tb> GR-S
<tb> GR-S <SEP> (standard <SEP> 100 <SEP> parts
<tb> black <SEP> de <SEP> smoke <SEP> (from <SEP> tunnel) - <SEP> 60 <SEP> "
<tb> <SEP> zinc oxide <SEP> <SEP> 5 <SEP> "
<tb> sulfur <SEP> 0.35 <SEP> "
<tb> <SEP> tetraethylthiuram <SEP> disulfide <SEP> 3.5 <SEP> "
<tb>
 

 <Desc / Clms Page number 25>

 
 EMI25.1
 In each case the cement bends # - j '. - .¯ :: .'- ¯i;> 1) parts of poly-2.'13-dichlorobutad: .ene15 '3 ¯. ¯ (about 2 * 7
 EMI25.2
 mol. $ r 20 parts of 9 5?.? ONC '.? j3z "". ï. # I, tl:.'.:. v; ot 3'JL ¯.? 'r.i.r i: .c3. toluene.

   The primary coatings are, .p;.: Ftc: ae l4acie-r degreased and sanded, and left. to dry for about 30 minutes
 EMI25.3
 The secondary cements are then applied .j, a>? .. 5.e = to; sus the primary coating and allowed to dry. One then applies the elastomeric compound indicated on the metal rô; .riwr dadh, és¯fô and one vulcanizes elastomer india, ié., On raét.i'î- (- :.}, :: ', Ll'J, " 'a 110SJ- vulcanizes the assembly under pressure for: !!:.: 30 min at 150.

   The bonds thus formed have such a resistance that in all cases, attempts to detach the rubber from the metal lead to the rupture of the body of the elastomer,
 EMI25.4
 Example Composition of 1 "coating) rii11ai- Eiastowète N 1" 0 of mete.l. ---- ¯..employee -
 EMI25.5
 
<tb>
<tb> XIII <SEP> 100 <SEP> parts <SEP> condensate <SEP> resinous <SEP> neoprene
<tb>
 
 EMI25.6
 phenol-aldehyde solut2- -0. '1 :: m :: ketones, cataly base ,, 5 ---, solid
 EMI25.7
 
<tb>
<tb> thermosetting.
<tb>
 
 EMI25.8
 



  200 parts methylethyletone.



  XIV 100 parts polyvinYJ.f) L1, t},! '-. L, rubber
 EMI25.9
 
<tb>
<tb> quality <SEP> XYHL. <SEP> natural
<tb> 666 <SEP> parts <SEP> methanol.
<tb>



  XV <SEP> 100 <SEP> parts <SEP> neoprene <SEP> chlorinated <SEP> rubber
<tb> (chlorine <SEP> 67%, <SEP> viscosity <SEP> solution <SEP> natural
<tb>
 
 EMI25.10
 at 20; in toluene 1? fl -rsç
 EMI25.11
 
<tb>
<tb> 25 C).
<tb>



  300 <SEP> parts <SEP> toluene.
<tb>
 
 EMI25.12
 



  XVI 100 parts P9P'9P99iï - ¯¯wt:. ,, ar, fF GR-S
 EMI25.13
 
<tb>
<tb> triphenylmethane.
<tb>
 
 EMI25.14
 



  300 parts 1'1t th chloride: {Lèn "'." XVII 100 parts chloride of ¯¯¯FS-; >; y-, rôo,> to> 1> 1>. <; chlorinated (Vinyon N).



  .00 wono parties chlc; 1. <; 1:. <=>; = # =. ;. ¯
 EMI25.15
 EXEIVIPLE XVTTI. An adhesive consisting of r-i-i 'ruz5 prti3 de,' H; 11t,
 EMI25.16
 chlorinated cabbage (quality 125 CiJs)> 2 ¯ - ';! L-.'; 8 J; .. "1 1. ' t ':' S, #.; ..-. B: i ,, and 300 parts of toluene for. ' natural rubber not mxl canà; 5 "'c': ', ¯. consisting of 100 parts of leaf; #> r- / c ',.:;,;. # .1 {. ' at - - . , tunnel, 15 parts of z oxide, fl = i .; = .- ¯; ..-. ", 1 ,:.>, 3 parts sulfur, A 6 parts 1.5 1.;. <:: =,.; .- <: ..;.,.;> ± <:.:; 1:

 <Desc / Clms Page number 26>

   thiuran 2 parts of pine tar and 0.75 part of phenyl-beta-naphthylamine under the -conditions indicated in Example VII.



   The same is done for an adhesive consisting of 75 parts of chlorinated rubber (grade 125 cps), 25 parts of sulfur and 300 parts of toluene. The adhesion is measured in Kg / cm.



   The sulfur-containing mixture produces a bond resistant to
2.0 Kg / cm. The mixture containing nitrosobenzene produces a bond resistant to 15.4 kg / cm.



   EXAMPLE XIX. -
Applying an adhesive containing 50 parts of para-dinitrosobenzene, 50 parts of an oxide derivative of alkyl bisphenol esterified with fumaric acid, 1.5 parts of benzoyl peroxide, 0.5 part of cobalt naphthenate. , 140 parts
 EMI26.1
 of toluene and 10 parts of methyl ethyl oetone to a degreased and sanded steel surface and allowed to dry for about 1 hour.

   A plate of freshly sheeted, unvulcanized natural rubber compound consisting of 100 parts rocket digger, 30 parts tunnel black, 15 parts zinc oxide, 2.75 parts was applied to the adhesive coated surface. stearic acid, 3 parts sulfur, 0.6 part tetramethylthiuram monosulfide, 2 parts pine tar and 0.75
 EMI26.2
 part of phenyl-beoe-naphthylamino and vulcanized lsanemb3-ag under pressure for 30 min at 155 The bond which ends small is such that one cannot detach the elastomer from the metal without tearing the body of the elastomer, EXAMPLE XX.-
An adhesive consisting of 50 p-
 EMI26.3
 dinitrosobenzene, 35 parts of an epichlorohydrin-bi condensate, Uiéi.

   Nyl (epoxide equivalent of irvir, oy 9Q.QOp 15 parts of anhydride plltaliqqp and 10 parts of methyl, thyloetone to a degreased anodized duraluminum surface, and allowed to dry for about 1 hour. Apply to the coated surface with adhesive a plate of the freshly sheeted unvulcanized natural rubber compound of the type employed in Example XIX and vulcanized
 EMI26.4
 - '-i.! ËË & -E '; $ rut -, - h-¯..z:,.

 <Desc / Clms Page number 27>

 the assembly under pressure for 30 minutes at 155 The connection which
 EMI27.1
 result is such that one. can not detach ("t 'i.9 ::. astomer of metal without tearing the body of 1 9 elastor> ZCr.



   Although the compositions described herein are especially useful for bonding rubber to metal, some of these have other uses, due to their adhesive and film-forming properties.



   Numerous variations are possible by the choice of the aromatic mono- or di-C-nitroso compound and of the adherent for metal as well as of the reactive olefin, and of their quantities, without
 EMI27.2
 that we leave the frame of the wcßa =: ¯ i ',, v.entiol1o RE' l 'N 1¯7 -, .. i 0 l'J 80 --------- ¯.- ------
1.- Adhesive composition characterized in that it comprises a material capable of adhering to metals and a. mono- or poly-C-nitroso compound.


    

Claims (1)

2. A composition according to claim 1, characterized in that the material capable of adhering to metals is a thermosetting condensation polymer, a polymer or copolymer of ethylenically unsaturated polar materials ;. a rubber =. EMI27.3 halogenated cabbage or a polyisoc; 2.! 1a t ,; 3.- Composition Sl1iV'J.'ll: i, -,; =. J; .- idi.L;: ii, înn 1, <iar, éLété; ized in that the nitroso compound is composed of me ' ! J, - .C- ± 1J U: oso of the above formula. 4. -. Composition according to lL l: t.iJ,: mrllú & tion 1 characterized in that the nitroso compound is a dj'-c-nibroso compound of formula (IT) above, 58 "'" Composition according to the. E; '\ ler1ciir'dtion 4 characterized in that the compound, di - C-nitiasc. t = st hrl iLL4t .. nu par-a-, dini t; OSObenzene or naphthalene. 6 .... Next composition]; I ,,,, -iao # la :: tliiq <= i <des L - '' ïf't.c '!,.' Lrï.tiOll: 3 '), to! 5, characterized in this 4U " '::;' "î; ompI '\ l [l: 1 r-.:¯ ac? eiït: ur.e .: vulcanizable olefin. <Desc / Clms Page number 28> 7. - Composition according to 'claim 1, characterized in that it comprises a chlorinated rubber, a polychlorobutadiene and the nitroso compound. 8. A composition according to claim 1, characterized in that it comprises a chlorinated rubber, poly-2,3-dichlorobutadiene-1,3 brominated and the nitroso compound. " 9. A composition according to claim 1, characterized in that it comprises a polyisocyanate, a poly-2,3-dichlorobutadiene-1,3 brominated and the nitroso compound. 10. A composition according to claim 1, characterized in that 'it comprises a polyisocyanate, polychloroprene and the nitroso compound. 11. A composition according to claim 1, characterized in that it comprises a polyisocyanate and the nitroso compound. 12. A composition according to any one of claims 9 to 11, characterized in that the polyisocyanate is an aniline phosgenated-aldehyde resin. 13. A process for attaching rubber to a metal by means of the adhesive composition according to 1) any one of the preceding claims. 14.- Metal-rubber compound structure. characterized in that it comprises a rubber attached to a metal by a method according to claim 13.