CA1087774A

CA1087774A - Aqueous adhesion assistant dispersions for producing composite bodies by vulcanization

Info

Publication number: CA1087774A
Application number: CA292,170A
Authority: CA
Inventors: Henning Abendroth; Joachim Galinke; Norbert Wiemers
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1976-12-01
Filing date: 1977-12-01
Publication date: 1980-10-14
Also published as: JPS5371137A; SU795494A3; GB1592503A; FR2372857B1; FR2372857A1; US4111880A; IT1089044B; DE2654352A1

Abstract

ABSTRACT OF THE DISCLOSURE
An aqueous adhesion assistant or binder disper-sion for use in the production of composite bodies by vul-canizing a vulcanizable rubber composition on a substrate which is stable under vulcanization conditions comprising water and at least one dispersing agent and a solids content of from 20% to 50% by weight of a solids composi-tion of per a) 100 parts by weight of an organic oligomeric to polymeric film-former, b) from 5 to 100 parts by weight of an aromatic poly-C-nitroso compound, c) from 5 to 100 parts by weight of a phosphorus-containing compound selected from the group consisting of an organic phosphonic acid, a compound pro-ducing an organic phosphonic acid under vulcanization condi-tions, a phosphoric acid partial ester, and a compound producing a phosphoric acid partial ester under vulcaniza-tion conditions, and d) from 0 to 200 parts by weight of customary fillers and pigments having an improved effect on the vulcanized bond; as well as the method of bonding rubbers to solid substrates employing said aqueous dispersion.

Description

~Q8'~774 The present inventlon relates to aqueous adhesion a~sistant or binder dispersion~ for use in the produetlon of coEposlte bodies by vuleanizing a vule~nizable rubber com-position on a substrate which 18 stable under vuleanizing eondition~, and the method o~ bondin~ rubber~ to ~olld substrates.
Adhesion assistants or binders for the bonding Or rubber by vuleanization onto ~ubstrstes which aro ~table under vuleanization conditlon~, sueh as metals or also textiles, plasties or elastomers, have long been known.
m e binders sultable for unlversal bonding o~ elastomeric materials to metallie substrates at elevated tomperatures normally eontain polymerle fllm-formers, bonding aids, fil-lers and additlves as well as organie solvents. U.S.Patent 3,878,134, issued April 15, 1975 to Ozelli et al,de~erlbes one sueh compo~itlon. A preferred group are produets whlch contaln halogenated or ehlorosulronated rubbers as film formers, polyfunetlonal lsoeyanates and/or organo-silanes, as well as aromatie poly-nitroso-eompounds as bonding aids, carbon black, 8iliclc acld, basle lead phos-phite and/or zinc oxlde as filler~ and addltiveæ, and aro-matie and/or halogenated hydrocarbon~ as solvonts.
Alao known are binders whieh eontaln aqueou~
aisporsions or solution~ Or speeifle earboxgl group-containing rubbers a~ main eomponent6, ln eombination with the usual solvents, as well as the eombination o~ aqueous Polymer dispersione with resoreinol/formaldehyde resins.
While the conventional adhesion assistantæ or binders have the dlsadvantages eonneeted with the w e Or organie ~lvents with respeet to toxieity, eombustibillty, economic erficiency, etc., the binders based on aqueous dispersions or solutions known until now actually do not show these disadvantages. However, what hinders a broader use of the e systems is their lack of universality with respect to the elastomeric substrates to be bonded.

An ob~ect of the present invcntion is to devolop a universally usable stable one-component binder ~or bond-ing a plurality of rubber types at elevated temperatures to a variety of substrates, which contain practically no volatile organic ~ol~ents or other en~ironmentally unde-sirable substances and yet furnish firm and resistant bonds.
Another ob~ect of the present invention is the obta~ning o~ an aqueous adhesion assi~tant orb~nder disper-sion for use in the production of composite bod~es by vul-canizing a vulcanizable rubber composition on a substrate which is stable under vulcanization conditi~n8 compris~n6 water and at lea~t one dispersing agent and a ~o~ds content of from 2~% to 50% by weight of a solids compo8~-t~on o~ per -a) 100 part9 by weight Or an organic oligomeric to polyme~ic film-former, b) from 5 to 100 parts by weight o~ an - aromatic poly-~-nitroso compound, c) from 5 to 100 parts by weight o~ a phosphorus-containing cQmpound selected from the group eons~st~ng of an organie phosphonie aeid, a eompound pro-dueing an organie phosphonic-ae~ under vulcanl~ation eondi-tions, a phosphorie acid partial ester, and a eompound 1087 7'74 produc~ng a phosphoric acid partial e~ter under vulcaniza-tion conditions, and d) from 0 to 200 parts by weight Or customary ~iller~ and pigments having an improving effect on the vulcanized bond.
A further obJect o~ the pre~ent invention is the improvement in the process of producing composite bodies by bonding vulcanizable rubber compositions to sol~d substrates stable under vulcanization conditions comprising coating a solid substrate stable under vulcanizing conditions with an adhesion assistant or binder, laminating a vulcanizable rubber composition thereto and vulcanizing the laminate, the improvement con~isting of employing an aqueous adheslon assistant or binder dispersion comprising water and at lea~t one disper~ing agent and a solid~ content of from

2~% to 50% by weight of a solids composit~on of per a~ 100 parts by weight o~ an organic oligomeric to polymeric f~lm-former, b) ~rom 5 to 100 parts by weight Or an 0 aromatic poly-~nitro~o compound, c) from 5 to 100 parts by weight o~ a phosphorus-containing compound selected from the group consisting of an organlc phosphon~c acid, a compound p~o-duc~ng an organic phosphonicacid under vulcanlzation condi-tions, a pho~phoric acid partial ester, and a compound producing 8 phosphoric acid partial ester under vulcanizs-tion conditions, snd d) ~rom 0 to 200 parts by wel8ht o~
customary fillers and pigment~ having an improving efiect on the vulcsn~zed bond.

These and other ob~ects of the invention wtll become more apparent as the description thereof proceeds.

The drawbacks of the adhe~ion assistants or binders of the prior art were solvsd and the ob~ect~ of the invention were achieYed by an adheslon asslstant or binder in the ~orm of an aqueou~ disper~ion which contains per a) 100 parts by weight o~ an organic oli-gomeric or polymeric film-~ormer, b) from 5 to 100 parts by weight of an aromatic poly- ~nitroso compound, c) from 5 to 100 parts by weight of an organic pho~phonic acid or of a pho~phoric acid partial ester ana possibly d) up to 200 part~ by weight Or customar~
bond-~mproving fillers.
More particularly, the present in~ention relates to an aqueous adhesion assistant or binder dispersion ~or use in the production of compo~ite bodies by vulcanizing a vulcanizable rubber compositlon on a substrate which is stable under vulcanization condition~ comprtsing water and at least one dispersing agent and a so~ias content of from 20% to ~0% by weight of a solids compos~-t1on o~ .per a) 100 parts by welght o~ an organic oligomeric to polymeric film-~ormer, b) from 5 to 100 partc by weight of an aromat~c poly-C-nitroso compound, 10877'74 c) f~om 5 to 100 parts by weight of a phospho~us-containing compound selected ~rom the group c~nsist~ng of an organic phosphonic ac~d, a compound pro-ducing an organic phosphonicacid under vulcanlzation condi-tions, a phosphoric acid partial ester, an~ a compound producing a phosphoric acid partlal ester under vulcaniza-tion conditions, and d) from 0 to 200 parts by weight o~
customary fillers and pigmcnts having an improving e~fect .
on the vulcanized bond'.
The lnvent~on also relates ~o t~e lmprovem~nt in the proces~ Or producing composite bodies by bonding vuloanizable rubber compositions to solid ~ubstrate~
stable under vulcanlzation conditlons cQmprising coat~ng a solld s~pstrate stable under vulcanizing co~d~tions with an adheslon assistant or binder, lam~na~ing a vulcanizable rubber composit~on ther~to and vu~canizinæ ~h~ laminate, ` . -the improvement con~isti~g o~ employ~ng an aqueouS adhasion ass~stant or binder dispers~on comprising water and at .
least one d~sporsin~ agent and a sol~ds con~ent o~ ~rom 20~ to 50~-by weigh~ of a sol~ds composi~ion o~ per a) 100 parts by we~ght o~ an organic oligo~r~c to polymeric ~lm-~ormor, b) ~rom 5 to 100 parts by we~gh~ o~ a~ .
aromatlc poly-C-nitroso compound~
c) ~rom 5 to 100 parts br weight o~ a phosphorus-contain~ng compound selecte~ ~rQm tha group 1087~74 consist~ng of an organic phosphonic ac~, a compound pro-ducing an org~n;c p~osp~onic ac~dunder Yulc~n~zation condi-tions, a phosphoric acid partial es~er, and 2 CO~pOUna producing a phosphoric acid partial ester under ~u~can~za-tion conditions, and d) ~ro~ 0 to 200 parts by weig~ o~
customary fillers and p iomen~s ha~ng an improving efrect ~n the ~ulcanized bond.
me fllm-forming matcrlals of org~n~c oligQmeric or polymeric nature su~table for use in the aqueous dlsper-sions of the invention are, for example, polgmer~ and co-polymer~ of polar, e~hylenically unsaturated compcunds such as polyvinyl butyralj polyvinyi ~ormal~ polyvlnyl acetatej chlorinated polyvinyl chloride, copolymers or vi~yl acetate and vingl chloridej chlorinated copolymers ~f v~nyl acetate and v~ngl chlorlde, poly(meth)acrylic acid, copQlymsrs of (meth)acrylic acid with con~ugated dienes such as 1,3-buta-diene, 2-chloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene and the like, including post-halogenated products thereo~
as.well as copolymers oi vingl pyridine and con~ugated diene~
including poly~alent reaction products thereof. Preferred film-form~ng materials are halogen-containlng rubbers or polychloroprene, chlorinated polychloroprane, chlor~nated natural rubber, chlorinated polybutadiene, chlorinated polyethylene, chlorinated ethylene/propylene copolymers, other chlorinated compounds such as a chlor~nated e~hylenR/
propylene copolymer with other d~enes as well as chlorinated copolymers of butadiene with styrene. Also enterlng into consideration are chlorosu~fonated polyethylenes, polypro-pylenes and polyethylene/propylenes, brominated 10~37'774 poly(2,3-diehloro-1,3-butadiene), eopolymers of a-ehlor-aerylonitrile with 2,3-diehloro-1,3-butadiene, eopolymers Or a-bromaerylonitrile with 2,3-diehloro-1,3-butadiene, mixtures of halogen-eontaining rubber with hydrohalogenatea rubbers. Other suitablo polymerie film-~ormers are natural rubbor, butyl rubber, ethylene/propylene eopolymer rubber, ethylene/propylene/diene terpolymor rubber, polymer~ and eopolymers Or dienes with 4 to 12 earbon atoms such as polybutadienej polybutsdiQne/styrene, polybutadlene/aerylo-nitrile. In practice, ehlorosul~onated polyethylene orpolypropylene has proved suecessful a~ ~ilm-~orming msterial.
me poly-nitroso compounds suitable ror the production Or the blnders of the invention are derived ~rom a variety of hydroearbons, in partieular aromatie ones.
Essentially they are polg-¢-nitroso eompounds, in partieular, aromatie poly-C-nitroso eompounds with 1 to 3 aromstle nuelel, ineluding eyelized aromatic nuelei having 2 to 6 nitroso groups whieh are attached direetly to non-ad~aeent ring earbon atoms. m e preferred poly-C-nltroso eompounds of the invention are aromatie hydroearbon di-C-nitroso eompounds, sueh a~ dinitroso-benzenes and dinitroso-naphthalenes, e.g. meta- or pars-dinitro~o-benzene and mets-or para-dinitroso-n~phthalene~. me ring hydrogen stom~ Or the aromatic nueleus may be substituted by alkyl, alkoxy, eyeloalkyl, aryl, aralkyl, alkaryl, arylamino, arylnitro~o, ~mino, ha~ogen, and the like. The presence o~ such sub-stituents in the aromatie nueleus or ring hss little e*~eet on the aetivlty of the poly-C-nitroso eompound~. The following are mentionod a8 being suitable ~or the purpose of the inventlon, for example: m-dinitroso ben~one, lo~m4 p-dinitroso-benzene, m-dinitro60-naphthalene, p-dinitroso-naphthalenej 2,5-d~nitroso-p-eymene, 2-methgl-1,4-dinitroso-benzene, 2-methyl-5-chloro-1,4-dinitroso-benzene, 2-fluoro-1,4-dinitro~o-benzene, 2-methoxy-1,3-dinitroso-ben~ene, 5-chloro-1,3-dinltroso-ben~ene, 2-ben~yl-1,4-dinltroeo-ben-zene and 2-cyclohexyl-1,4-dinitroso-bonzone.
Naturally, also, the nitroso group-forming com-pounds, namely oximes with oxidizlng agents, ean be used.
From 5 to 100 parts of thQ aromatie poly-C-nitroso eompounds sre employed in the aqueous dlsp~rsion per 100 parts o~ the organie film-~ormer.
The organie phosphonlc aeids and pho~phorlc aeid partial e~ter~, to be used according to the invention a~ a third es~ntial eomponent, eontain at least one phosphonic or phosphoric acid group as well as an organie radieal with on~ or more functional groups. For example, they m~y ~e e~pres~ed by the general ~ormula OH OH
I
X - (C) - P - O or re6peetively X - (C) - O - P - O
0~ 0~

wherein (C) is a bivalent organie radieal, pos~bly ~ub-~tituted by halogen, hydroxyl groups, amino group6, al~yl or aryl radieals and which may optlonally eontain hetero-group6, such as O O
Il 1~
-- O --, -- S --, -- C -- O --, --NH--, --NH-- C O -- !

and the like groups X ie hydrogen or a ~unctional group, for example, ~mino, hydroxyl, epo~y, vinyl, mercapto, halo-gen and the like.

1~ ~774 ~ ore particularly, the organic pho~phonic acids or phosphoric acid partial esters have the rormula selected rrOm the group consi~ting Or X - Y or X - O - Y
where Y is OH snd X iB
_ p -- O
OH

an organic group selected from the group consisting Or lower alkenyl, cyclohexonyl, hydroxy-lower alkenyl, halo-lower alkenyl, carboxy-lower al~enyl, epoxy-lower alk~
epo~y-lower alkoxy- `
10 /lowor alkyl, epoxy-cyclohexyl, amino-lowor alkyl, hydroxy-lower alkyl, mercapto-lower alkyl, halo-lower alkyl, di-phosphonomethyl-amino-lower alkyl, phenyl-hydroxy-pho~-phonomethyl, amlnophenyl-hydroxy-phosphonomethyl, halophenyl-hydroxy-pho~phonomethyl, phenyl-amino-phosphonomethyl, halo-phenyl-amlno-phoaphonomethyl, hydroxy-phosphonomethyl, lower alkyl-hydro~y-pho~phonomethyl, halo-lower alkyl-hydroxy-phosphonomethyl, and amlno-lower alkyl-hydroxy-phosphonomethyl. me acid groups may also be pro~ent in a latent form and be relea~ed only under the bonding condi-tlons ~rom preliminary ~taee~ such as ester~. Suitableorganic phosphonic or phosphoric acid partial estcrs are, ~or e~ample, v~nyl pho~phon~c acid, cyclohexene-(3)-phoa-phonlc acid, ~-hydrDxy-butene-~2)phosphonic acld, l-hydroxy-l-phenylmethane~ dlphosphonic acid, l-hydro~y-l-methyl-l,l-diphosphonic acid, l-am~no-l-phenyl-l,l-dipho~phonlc acid, 3-a~lno-1-hydro~y-propane-1,1-diphosphonic acid, amino-tris-(methylene pho~phonic acid), ~-aminopropyl pho~phonic acid, ~-mercaptopropyl pho~phon~c acld, ~-chloropropyl pho~phoni~ acid, 1,2-epo~yethane phosphonic 10~7774 acid, 3,4-epoxy-cyclohexane phosphonic acid, ~-glycidoxy-propyl phosphonic acid, phosphoric acld mono-2-aminoethyl ester, phosphoric acid mono-l-carboxyvinyl ester, phosphoric acid mono-2-hydroxyethyl ester.
For the purpose Or the invention, also oligomeric or polymeric phosphonic aclds as~ for instance, polyvinyl phoaphonic acid, are suitable.
Naturally, mixture~ of the mentioned compounds may also be used. ~t is also possible to use reaction product~ of the organlc phosphonlc acid~ or phosphoric acid partial esters having functional group~ with strengthening and/or bond-improving resins or pre-resins known in them-selves. Exampleæ of ~uch re~ins or pre-resins are phenol/
formaldehyde~ alkylphenol/formaldehyde or resorcinol/
formaldehyde resin~, resole~, novolacs, condensation prod-ucts from epichlorhydrin and poly-phenols, such as diphengl-ol propane, novolacs, as well as styrene-m~lelc acld an-hydrlde copolymers, etc. From 5 to 100 parts Or the organlc phosphonic acids or phosphorlc acid partial ester~
havlng functlonal group~ ~eemployed ln the aquoou~ dlsper-sion per 100 partæ of the organic film-former.
Lastly the disporslons of the inYention may contain the usual bond-improving f~llers. For this there enter into con~ideration carbon black, silicic acid, zinc oxide, basic lead pho~phite and the like. Al~o, lf doslred, pigmcnt~ may bo incorporated From 0 to 200 parts o~ the flllers and plgments are employed ln the aqueous dispersiQn per 100 part~ Or the organic fllm-former.
m e sultable dlepersion aids are primarily surface-active compound~, in particular, non-ionic ~urfac~-actlve compound~. Suitable are, for example, t~o othylene ~Qsm~

oxide adducts to alkylphenols, such as nonylphenol or higher fatty alcohols or higher fatty alcohol partial esters with phosphoric acid. Ordinarily from 0.5% to 2 5% by weight,based on the amount of water, aro employed. In addition to the nonionic surface-active compounds, the dls-persions Or the invention may also contain stabilizers for the dispersion such as thQ water-soluble colloids, 8uch a~
methyl cellulose, methyl hydro~ypropyl cellulose, hydroxy ethyl cellulose, polyvinyl alcohol. Ordinarilg from O to

3~ by woight, preferably from 0.5% to 3% by weight, based on tho amount of wator, of the dispersion stabilizers are employed.
It has been foun~ that the aqueous adhesion assistant or binder dispersion~ of the invention are suit-able for bonding a plurality of vulcanizable, elasto~eric materiala to them~elves or to other substances. These include vulcanizable mixtures based on natural rubber, polychloroprene rubber, styrene~butadiene rubber, nitrile rubber, rubber rrom ethylene/propylene copolymers (EPM), rubber from ethylene/propylene/dlene terpolymers (EPD~), butyl rubbe~, polyurethane rubber, etc. The substrates stable under vulcani~ation conditions are thoæe materials which do not alter their shape under conditions of vulcani-zation, that ~8, heating to temperatures of up to about 200C undcr preseures o~ up to 3000 gm/cm2. Preferably, the solid eubstrates are high temperature-resistant ~a~rics made from fiberglas6, pol~amides or polye~ters and, in particular, metal~ such aa ~ron, stainlees steel, lead, alum~num, copper, brassj bron~e, monel mRtals, nickel, zinc and the like, including treated metals such as phoaphatized eteel~ electroplated ~teel and, lastly, glaee and cer~mic materials.

~7~7r74 ~ he aqueous adhesion assistant or b$nder dis-per~ion~ are applied on the ~ubstrate surraces in the eon-ventional manner such as by immersion, spraying, brushlng and the li~o. A M er the coating, the ~ubstr~te ~ur~ace~
are allowed to dry before they are lPm~nated After the sur~ace~ have been ~oined togethcr with the ~ulcantzable rubber ~ur~aces, the laminate structures sre heated ln the convcntion~l manner, to cause vulcan~ation.
The aqueous adhesion ass$stant or binder d$spers~ons o~ the invention should have a ~lids contont ~uch that they are ~till ea~y to ~pread or to ~pray. me ~olids content ~8 between about 20~ and 50~ by woight.
Org~nic solvent~ can be w ed concQmitantly in minor quan-tity, but their proportion should not excoed 5~ by weight o~ the liquid pha~e.
The following example~ are illustrative o~ the practice of the invention without being limitative in any re~pect.
EXA~P~ES
In the following ex~mples, the rubber mixtures designated below by A, B, C, D, E, an~ F wero vulcanized on substrate~. The compo~ition of the mixture and the vulcan~zatlon conditions are ~tated below All part~ are part6 by weight unlo~ otherwi~e ~pecl~led.
Mixture A(NR) Parts Natural rubber (smokcd ~heet) 100 Zlnc oxlde 10 Stearic acid Phenyl-~-naphthylamine ~ine tar 2 Carbon blflck CK3 25 '7774 ~ixture A(NR) Part6 Zn dimethyl dithioearbamate0.33 Dibenzothlazyl di~ulfide 0.58 Sulfur 2.75 Vuleanization eondltlons: 10 mlnute~ at 153C

~l~ture B (SBR) Part~
Styrene-butadlen~ rubber 100 Zlne oxide 5 Stearic aeid FEF earbon blaek (Corax 3) 50 Saturated polymerie petroleum hydroearbons (liquld) 8 N-eyelohexyl-2-benzthio-phthalimide 0.2 Benzthiazyl-2-eyclohexyl-sulfen~mide 0.95 Sulfur 1.6 Vulcanization eonditions: 30 mlnutes at 153C

Mixture C (CR) Parts Polyehloroprene rubber 100 ~agnesium oxide 4 Phenyl-~-naphthylamine 2 ~T earbon blaek (Sterl~ng) 80 Vaseline ~(~.P.~33-35C) Naphthenie oil 5 Tetramethylthiuram monosul~id~ 0.5 Di-o-tolylguanidlne o.5 2-~ercaptobenzl mi dazoline 0.5 Sulfur Vuleanization eondltions: 30 minut~s at 153C

1087'774 ixture D (EPn~ Parts Ethylene/propylene/diene terpolymer rubber 100 Zinc oxide 5 Stoarlc acld Phenyl-~-naphthylamine Carbon b~ack CK3 75 Zinc N-ethylphonyldithiocarbamate Zn salt of 2-mercaptobenzo-thiazole 0.8 Dipentamethylenothiuram tetra~ulfide Sulrur 2 Vulcanlzation condition~: 30 minutes at 153C

Mixture E (lIR) Part~
Butyl rubber 100 Stearic acid Zinc oxide 5 Carbon black Cora~ 3 50 Dibenzothiazyl disulfide Tellurium diethyldithiocarbamate 1.5 Sulrur Vulcanization condition~: 30 m~nutes at 160C

Mixture F (NBR) Part~
Nitrile rubber (31% acrylonitrile) 100 Stesric acid Zinc oxide 5 Dibutyl phthalate 10 Sterling carbon black . 65 Terpene re~in 10 Tetramethylthiuram di~ul~ide 0.31 Sulfur Vulcanization conditions: 30 minute~ at 150C

10~7774 Production Or the Aqueous Adhesion Assistant or Binder Dispersion of the Invention 100 parts by weight of a 30~ aqueous dl~persion of chlorosulfonated polyethylene (35~ Cl and 1% S), which contained per 100 parts, a~ emulsifier, 1.5 part~ by weight o~ the addit~on product Or 20 mols Or ethylene oxide onto 1 mol of nonylphenol, 1.5 part6 by w~ight of polyvingl alcohol (6aponification degree 8a%) and 0.3 part~ by weight of hydroxypropylmethgl cellulose (methgla-tion degree 1,9, propoxylation degree approx. 0.1), were mixed with 30 parts by welght of a 50% aquoou6 diæpersion of dinitro60benzene/zinc oxide (4:1). A~ter dis~olving or di~persing 6 part~ by weight o~ the organic pho~phonic acld having functional groups or of the phosphoric acid partial ester h~ving functional groups, the binder is ready for use.
m e binders were applied twice with a 60~t brush on degreased, sandblasted steel pla*es (25 x 60 mm), wait-ing with the ~econd application about 1 hour a~tor the ~irst application. Then the sample plate was le~t ln air at roo~ temperature forl5 hours. Followlng this, the cited rubber mixture~ were vulcanized on an area of 2~ x 25 mm according to the condltions customary for the respecti~e rubber type as given above.
The composite ob~ect~ obta~ned wor~ to~ted according to AST~-D 429 B, but by modifying the peeling anglo to 45. The bond values determined (~p/2.~c~) a~
well as the tear patterns in ~
R - Separation in the rubber RC ~ Separation between rubber and blnder ~ = Separation betuben metal and blnder are listed for various aqueous adhesion assistant or binder dispersion~ in the iollowlng table~.
In Tab~e 1, the phosphonlc acids used are indi-cated in the first column, then follow as a runction of the rubber mi~ture th~ valuos mea~ured ~or tho ps~ling strcngth as well a~ the tear pattcrn in %. In ~dditlon, a comparlson test without phosphonic acid is includod Table 1 .
Binder Rubber typQ
NR S~R CR EPDM IIR N~R
~ee~i~g strehgth ~n kp/2.5cm and tear pattern Vinyl phos-31 65 50 40 65 40 phonic acldlOOR lOOR lOOR 90R/lORC lOOR lOOR
. .
~-aminopropyl 33 47 52 43 51 43 phosphonic acld lOOR 50RC/R lOOR lOOR lOOR lOOR
! --- ---- - . _ Comparl~on test 2~ 32 0 0 30 30 wlthout phos- 50R/50 90RC/lOR 50~/50R.lOORC lOORC 30M/~OR~
phonic acld RC 40RC

In the ~ollowing Table 2, the ~alues for addi-tional phosphonic acid are glven as described above.
Table 2 Binder Rubber type - NR SBR EPDM
Peeling strength in kp/2.5cm and tesr pattern . . .. , l-Hydroxyethane 30 69 40 dipho~phonic acld lOOR lOOR 9QR~lQRC
l-Phenyl-l-hydroxy 36 74 38 methane-l,l- lOOR lOOR 90R/lQRC
dipho~phonlc acid l-Phonyl-l-amino 31 51 33 methsne-l,l-dlp lOOR lOOR 5QR/5QRC
phosphonlc acld To check the shelf life, the binder mixture containing vinyl phosphonic acid was stored for 6 weeks at 25C. Then, after stirring thoroughly, sample sheets were bonded with various rubber mixtures by vulcanization as described above. The results obtained are reported in the following Table 3.

Table 3 _bber mixture NR SBR CR EPDM IIR NPeeling strength in kp/2.5cm and tear pattern in ~
Without storage 31 65 50 40 65 40 lOOR lOOR lOOR 90R/lORC lOOR lOOR

6 weeks/25 29 61 42 40 60 46 lOOR lOOR lOOR 80R/20RC lOOR lOOR
_ .

The preceding specific embodiments are illus-trative of the practice of the invention. It is to be under-stood, however, that other expedients known to those skilled in the art or disclosed herein, may be employed without departing from the spirit of the invention or the scope of the appended claims.

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1, An aqueous adhesion assistant or binder disper-sion for use in the production of composite bodies by vul-canizing a vulcanizable rubber composition on a substrate which is stable under vulcanization conditions comprising water and at least one dispersing agent and a solids content of from 20% to 50% by weight of a solids composi-tion of per a) 100 parts by weight of an organic oligomeric to polymeric film-former, b) from 5 to 100 parts by weight of an aromatic poly-C-nitroso compound, c) from 5 to 100 parts by weight of a phosphorus-containing compound selected from the group consisting of an organic phosphonic acid, a compound pro-ducing an organic phosphonic acid under vulcanization condi-tions, a phosphoric acid partial ester, and a compound producing a phosphoric acid partial ester under vulcaniza-tion conditions, and d) from 0 to 200 parts by weight of customary fillers and pigments having an improving effect on the vulcanized bond.

2. The aqueous dispersion of claim 1 wherein said organic oligomeric to polymeric film-former is a halogenated rubbery polymer or copolymer of polar, ethylenically-unsaturated compounds.

3. The aqueous dispersion of claim 1 wherein said organic oligomeric to polymeric film-former is a chlorosulfonated rubbery polymer or copolymer of polar, ethylenically-unsaturated compounds.

4. The aqueous dispersion of claim 1 wherein said organic oligomeric to polymeric film-former is a chlorosulfonated polyethylene.

5. The aqueous dispersion of claim 1 wherein said aromatic poly-C-nitroso compound is a di-C-nitroso aromatic hydrocarbon.

6. The aqueous dispersion of claim 1 wherein said aromatic poly-C-nitroso compound is dinitrosobenzene.

7. The aqueous dispersion of claim 1 wherein said phosphorus-containing compound is a compound selected from the group consisting of (1) organic phosphonic acids or phosphoric acid partial esters having the formula selected from the group consisting of X - Y or X - O - Y
where Y is and X is an organic group selected from the group consisting of lower alkenyl, cyclohexenyl, hydroxy-lower alkenyl, halo-lower alkenyl, carboxy-lower alkenyl, epoxy-lower alkyl, epoxy-lower alkoxy-/lower alkyl, epoxy-cyclohexyl, amino-lower alkyl, hydroxy-lower alkyl, mercapto-lower alkyl, halo-lower alkyl, di-phosphonomethyl-amino-lower alkyl, phenyl-hydroxy-phos-phonomethyl, aminophenyl-hydroxy-phosphonomethyl, halophenyl-hydroxy-phosphonomethyl, phenyl-amino-phosphonomethyl, halo-phenyl-amino-phosphonomethyl, hydroxy-phosphonomethyl, lower alkyl-hydroxy-phosphonomethyl, halo-lower alkyl-hydroxy-phosphonomethyl, and amino-lower alkyl-hydroxy-phosphonomethyl. and (2) polyvinyl phosphonic acid.

8. The aqueous dispersion of claim 1 wherein said component d) is present in an amount of from 25 to 100 parts per 100 parts of said film-former and is selected from the group consisting of carbon black, silicic acid, zinc oxide, basic lead phosphite and mixtures thereof.

9. In the process of producing composite bodies by bonding vulcanizable rubber compositions to solid substrates stable under vulcanization conditions comprising coating a solid substrate stable under vulcanizing conditions with an adhesion assistant or binder, laminating a vulcanizable rubber composition thereto and vulcanizing the laminate, the improvement consisting of employing an aqueous adhesion assistant or binder dispersion comprising water and at least one dispersing agent and a solids content of from 20% to 50% by weight of a solids composition of per a) 100 parts by weight of an organic oligomeric to polymeric film-former, b) from 5 to 100 parts by weight of an aromatic poly-C-nitroso compound, c) from 5 to 100 parts by weight of a phosphorus-containing compound selected from the group consisting of an organic phosphonic acid, a compound pro-ducing an organic phosphonic acid under vulcanization condi-tions, a phosphoric acid partial ester, and a compound producing a phosphoric acid partial ester under vulcaniza-tion conditions, and d) from 0 to 200 parts by weight of customary fillers and pigments having an improving effect on the vulcanized bond.

10. The process of claim 9 wherein said organic oligomeric to polymeric film-former is a halo-genated rubbery polymer or copolymer of polar, ethyleni-cally-unsaturated compounds.

11. The process of claim 9 wherein said organic oligomeric to polymeric film-former is a chlorosulfonated rubbery polymer or copolymer of polar, ethylenically-un-saturated compounds.

12. The process of claim 9 wherein said organic oligomeric to polymeric film-former is a chlorosulfonated polyethylene.

13. The process of claim 9 wherein said aromatic poly-C-nitroso compound is a di-C-nitroso aromatic hydro-carbon.

14. The process of claim 9 wherein said aromatic poly-C-nitroso compound is dinitrosobenzene.

15. The process of claim 9 wherein said phosphorus-containing compound is a compound selected from the group consisting of (1) organic phosphonic acids or phosphoric acid partial esters having the formula selected from the group consisting of X - Y or X - O - Y
where Y is and X is an organic group selected from the group consisting of lower alkenyl, cyclohexenyl, hydroxy-lower alkenyl, halo-lower alkenyl, carboxy-lower alkenyl, epoxy-lower alkyl, epoxy-lower alkoxy-lower alkyl, epoxy-cyclohexyl, amino-lower alkyl, hydroxy-lower alkyl, mercapto-lower alkyl, halo-lower alkyl, di-phosphonomethyl-amino-lower alkyl, phenyl-hydroxy-phosphonomethyl, aminophenyl-hydroxy,phosphonomethyl, halo-phenyl-hydroxy-phosphonomethyl, phenyl-amino-phosphonomethyl, halo-phenyl-amino-phosphonomethyl, hydroxy-phosphonomethyl, lower alkyl-hydroxy-phosphonomethyl, halo-lower alkyl-hydroxy-phosphonomethyl, and amino-lower alkyl-hydroxy-phosphonomethyl, and (2) polyvinyl phosphonic acid.

16. The process of claim 9 wherein said com-ponent d) is present in an amount of from 25 to 100 parts per 100 parts of said film-former and is selected from the group consisting of carbon black, silicic acid, zinc oxide, basic lead phosphite and mixtures thereof.