CA2053874A1 - Aqueous vulcanizing adhesive - Google Patents
Aqueous vulcanizing adhesiveInfo
- Publication number
- CA2053874A1 CA2053874A1 CA002053874A CA2053874A CA2053874A1 CA 2053874 A1 CA2053874 A1 CA 2053874A1 CA 002053874 A CA002053874 A CA 002053874A CA 2053874 A CA2053874 A CA 2053874A CA 2053874 A1 CA2053874 A1 CA 2053874A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- copolymers
- vinyl acetate
- binder dispersion
- alkyl halide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J119/00—Adhesives based on rubbers, not provided for in groups C09J107/00 - C09J117/00
- C09J119/02—Latex
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
ABSTRACT
The adhesive strength of an aqueous binder disper-sion consisting of: a halogenated copolymer which, in addition to other components, contains an alkylation-active monoalkenylaromatic alkyl halide; polyfunctional aromatic nitroso compounds; pigments; carbon black; anti-foaming agents; emulsifiers; and other additives, used for vulcanizing rubber onto substrates which are stable under the conditions of vulcanization, is improved, and the use of blocked isocyanates is avoided. This is achieved by adding, to increase the adhesive strength, homopolymers or copolymers of vinyl acetate that are also saponified to a certain extent, as well as, optionally, other customary additives.
The adhesive strength of an aqueous binder disper-sion consisting of: a halogenated copolymer which, in addition to other components, contains an alkylation-active monoalkenylaromatic alkyl halide; polyfunctional aromatic nitroso compounds; pigments; carbon black; anti-foaming agents; emulsifiers; and other additives, used for vulcanizing rubber onto substrates which are stable under the conditions of vulcanization, is improved, and the use of blocked isocyanates is avoided. This is achieved by adding, to increase the adhesive strength, homopolymers or copolymers of vinyl acetate that are also saponified to a certain extent, as well as, optionally, other customary additives.
Description
~C53~37~
AQUEOU~ VULCANIZING ADHE8IV~
This invention relates to an improved water-based binder for vulcanizing various types of rubber onto vul-canization-stable substrates.
It is becoming increasingly desirable to avoid the presence of volatile substances, such as solvents, in ad-hesives of the type in question. Accordingly, efforts have been made to formulate solventless systems. Thus, it is proposed in applicants' European patent 21 186 to synthe-size a homopolymer or copolymer of vinylidene chloride and/or of butadiene/acrylonitrile copolymers, aromatic nitroso compounds, blocked isocyanates, polyvinyl pyrroli-done and other auxiliaries. Although products such as these were useful, there was still a need to improve bond strength with respect to all types of rubbers, including apolar rubbers, such as natural rubber, and to increase the 2C~3!37~
economy of the binders.
A terpolymer latex consisting of a 2,3-dihalo-1,3-butadiene, an aromatic monoalkenyl alkyl halide and other monomers is known from DE-OS 34 25 381. This terpolymer may be processed together with polyfunctional aromatic ni-troso compounds, the solids typically used in this field and a film-forming agent to form an adhesive composition.
The film-forminq agents mentioned also include homopolymers and copolymers of vinyl acetate. Although binders on this basis for vulcanizing rubber onto metals and the like pro-duce useful results, it has now been found that major im-provements can be obtained when the copolymers of vinyl acetate or the vinyl acetate are/is subjected to partial saponification to the corresponding polyvinyl alcohols.
Water-based binders for vulcanizing rubber onto vul-canization-stable substrates are already known from Euro-pean patent 161 373. However, these known binders contain masked polyfunctional isocyanates. The use of masked iso-cyanates is undesirable because they can cause stability problems in storage. The known binders according to Euro-pean patent 161 373 may also contain polyvinyl alcohol, al-though there is no reference to the type or quantity of polyvinyl alcohol used. The function of the polyvinyl al-cohol in formulations such as these is merely to stabilize the constituents, i.e. polyvinyl alcohol is used as a stab-ilizer and not as a reactive component which contributes essentially to the composition of the binder.
Accordingly, the present invention relates to a water-based binder dispersion for vulcanizing rubber onto vulcan-ization-stable substrates consisting of - a halogenated copolymer containing an alkylating aromatic monoalkenyl alkyl halide in addition to other constituents, - polyfunctional aromatic nitroso compounds, - pigments, carbon black, foam inhibitors, emulsifiers and other auxiliaries, characterized in that partially saponified homopolymers or 2c53a74 copolymers of vinyl acetate and, if desired, other standard additives are present for increasing bond strength.
The most important constituent of the binder according to the invention is a halogen-containing polymer based on an alkylating aromatic monoalkenyl alkyl halide. Preferred halogenated copolymers of this type are terpolymers of - 60 to 97% by weight of a 2,3-dihalo-1,3-butadiene, - 2 to 33% by weight of an aromatic monoalkenyl alkyl halide corresponding to the formula:
0 I.
~ CX2=CX~
_ --C--R
and .
~25 tx2=cx Y--C--Z ~--C--R
1 _ ~ _ b b in which X is hydrogen, chlorine, bromine or iodine;
Y is hydrogen, chlorine or bromine; Z is hydrogen, chlorine or bromine and A is hydrogen, chlorine, bromine or a Cl_3 alkyl group, with the proviso that, of Y, Z or A, at least one is chlorine or bromine and, where A is an alkyl group, at least one of Y or Z is chlorine or bromine, and a = 1 or 2 and b = 0, 1 or 2, with the proviso that at least one b is at least 1;
and 0.5 to 10% by weight of at least one olefinically un-saturated monomer, the monomer being at least copol-ymerizable with the conjugated diene monomer and di~-ferent from the aromatlc alkyl halide.
With regard to the 2,3-dihalo-1,3-butadiene as con-jugated diene monomers, which are known commercial prod-ucts, the halogen substituent is selected from a groupconsisting of chlorine, bromine and iodine, chlorine pres-ently being the preferred halogen substituent.
With regard to the mixture of at least two different unsaturated monomers which are copolymerizable at least with the conjugated diene monomer, it is pointed out that these monomers are selected from a first group, which con-sists of ~-haloacrylonitrile, ~-haloacrylic acid, ~-halo-acrylic acid ester, ~-halovinyl ketone, ~-halovinyl ace-tate, vinyl halide, vinylidene halide, styrene and aromatic monoalkenyl alkyl halides, and from a second group consist-ing of monomeric compounds containing at least one olefin-ically unsaturated group, the monomers of the second group being different from the monomers of the first group.
At present, compounds corresponding to formula I are preferred. Representative aromatic monoalkenyl alkyl ha-lides include vinylbenzyl chloride, p-trichloromethyl vin-ylbenzene, p-(~-chloroethyl)-vinylbenzene, p-(~-chloro-butyl)-vinylbenzene, ~-chlorovinylbenzene chloride, 2,3-di-(~-chloroethyl)-vinylbenzene, 4-chloromethyl vinyl naph-thalene, the corresponding bromine and iodine analogs andthe like. At present, the preferred aromatic monoalkenyl alkyl halide is vinylbenzyl chloride (4-chloromethyl vinyl-benzene).
With regard to the second group of copolymerizable monomeric compounds, the ethylenically unsaturated com-pounds of the second group are those which can be polymer-ized by addition of unsaturated bonds, providing they do not crosslink, i.e. either only one unsaturated ethylene group is present in the compound or, where more than one group is present, they are conjugated as such or crosswise.
~he ethylenically unsaturated monomers which may be used in the terpolymers according to the invention are those which which contain either one or several CH2 = C groups.
The ethylenically unsaturated compounds containing one or more CH2 = C = groups include such compounds as styrene, p-chlorostyrene, 3,5-dichlorostyrene, p-methoxystyrene, ac-rylonitrile, methacrylonitrile, vinyl bromide, vinyl fluor-ide, vinyl iodide, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinylidene bromide, vinylidene chlorofluoride, methyl methacrylate, butyl methacrylate, methacrylamide, vinyl methyl ketone, vinyl pyridine, vinyl carbazole, vinyl methyl ether, isobutylene, ethylene, vinyl chloride, vinylidene chloride, alkyl acrylates, including methyl, ethyl, propyl, butyl and octyl acrylates, acrylic acid and methacrylic acid and other similar monoolefinic polymerizable compounds. Other unsaturated compounds con-taining more than one olefinic group which may be copolym-erized to form the terpolymers according to the invention are conjugated dienes, such as l,3-butadiene, isoprene and other 1,3-butadiene hydrocarbons, chloroprene and also 3-cyano-1,3-butylidene, trienes, such as myrcene, and com-pounds containing olefinic and acetylenic bonds, such as vinyl acetylene, vinyl ethynyl, diethyl carbonyl and the like.
The terpolymer latex used in accordance with the in-vention may be prepared by emulsion polymerization of the halogenated conjugated diene with at least two different unsaturated comonomers in an aqueous medium in the presence of an ionic or a mixed ionic/nonionic surface-active sys-tem, ionic surface-active systems presently being prefer-red. It has been found that the terpolymer products which are most suitable for carrying out the invention contain 60 to 97% by weight, preferably 75 to 97% by weight and opti-mally 93 to 97% by weiqht halogenated conjugated diene and, in addition, 2 to 33% by weight, preferably 3 to 25% by weight and optimally 3 to 7% by weight of the monomer of the first group and 0.5 to 10% by weight and preferably 2 to 7% by weight of the monomer of the second group. Of particular value are terpolymer products which have ~een produced from 2,3-dihalo-1,3-butadiene, more particularly 2,3-dichloro-1,3-butadiene, in a quantity of 80 to 95% by weight, based on polymer, aromatic monoalkenyl alkyl ha-lides, more particularly vinylbenzyl chloride, in quanti-ties of 2 to 10% by weight and also olefinically unsatur-ated monomers, more particularly monomers containing at least one -COoH group, acrylic acid, methacrylic acid and/
or 2-hydroxyethyl methacrylate monophosphate in quantities of 2 to 10% by weight. Part of the aromatic monoalkenyl alkyl halides, for example 10 to 90 mol-%, may also be saponified to the corresponding hydroxyalkyl compounds.
The emulsion polymerization is carried out in a closed vessel in which space that is not occupied by the reaction mixture is kept free from oxygen, preferably a layer of inert gas, such as nitrogen, because the induction period for the polymerization reaction is prolonged by the pres-ence of oxygen and because it is desirable to carry out the reaction in the substantial absence of oxygen. Generally speaking, the emulsion polymerization is carried out by mixing the monomeric constituents with one another, emulsi-fying the mixture and subjecting the emulsion to moderate polymerization conditions until substantially the entire monomeric batch is polymerized. However, for various prac-tical reasons which need not be discussed here, it has beenfound that the emulsion polymerization of the tertiary mon-omeric system is carried out more effectively by a semi-continuous process which comprises adding an emulsion of a halogenated conjugated diene and the monomers of the first and second group at constant speed to a polymerization zone containing an aqueous solution or dispersion of the poly-merization initiator. The polymerization conditions are otherwise substantially the same as in batch polymerization processes and need not be discussed here. The polymeriza-tion reaction is exothermic and the reaction temperatureshould be kept below about 75C and preferably below about 60C. Virtually any catalyst or initiator which forms free ZC~5387~
radicals, including the known redox catalyst systems, such as ammonium persulfate/sodium metabisulfite, benzyl perox-ide, hydrogen peroxide, di-t-butyl peroxide, azo-bis-(iso-butyronitrile), alkali metal persulfates and alkyl metal ammonium perborates, may be used in the copolymerization reaction to ensure rapid initiation of the reaction and reproducible results. After the polymerization reaction, unreacted volatile constituents may be removed by vacuum treatment at elevated temperature or by steam distilla-tion, the particular method being a matter of choice.
The choice of the surface-active agent is of major importance to the production of a latex which ensures satisfactory adhesion. It has been found that anionic surfactants or mixtures of anionic and nonionic surfactants have to be used, the mixtures presently being preferred.
Whereas cationic surfactants as such are effective emulsi-fiers, their use in the production of the elastomeric ter-polymer latex according to the invention either individu-ally or in combination with either an anionic or a non-ionic surfactant or with both adversely affects the adhes-ive properties. The surface-active systems are used in quantities of 0.01 to 15% by weight and preferably in quantities of 1 to 10% by weight, based on the weight of the monomers used. At present, it is preferred to use a mixed anionic/nonionic surface-active system with a ratio of anionic to nonionic surfactant of 1.2 to 2.1:1 and pref-erably 1.3 to 2.0:1. Representative anionic surfactants are carboxylates, such as fatty acid soaps of lauric, stearic and oleic acid and also acyl derivatives of sarco-sine, such as methyl glycine; sulfates, such as sodiumlauryl sulfate; sulfatized natural oils and esters, such as turkey red oil and alkylaryl polyether sulfates; alkylaryl polyether sulfonates; isopropyl naphthalene sulfonates and sulfosuccinates and also sulfosuccinamates; phosphate esters, such as partial esters of complex phosphates with short-chain fatty alcohols; and orthophosphate esters of polyethoxylated fatty alcohols. Representative nonionic surfactants include ethoxylated (ethylene oxide deriva-tives), monohydric and polyhydric alcohols, ethylene oxide/
propylene oxide block copolymers; esters, such as glycerol monostearate; dehydration products of sorbitol, such as sorbitan monostearate and polyethylene oxide sorbitan mon-olaurate; and amines, such as lauric acid, isopropenyl ha-lide. At present, a 1.8:1 mixture of sodium dodecyl di-phenyl ether disulfonate as the anionic surfactant and nonylphenol polyethylene glycol as the anionic surfactant is preferred. Anionic and anionic/nonionic surface-active systems which have to be used in accordance with the inven-tion are described in detail in Em~lsions: Theory and Prac-tice, by Paul Becher, Chapter 6 (Reinhold Publishing Cor-poration, New York, 196S), and in McCutcheon's Detergents and Emulsifiers, 1972 Annual.
The terpolymer latex obtained in accordance with the invention by the emulsion copolymerization of halogenated dienes and unsaturated monomers of the first and second group generally has a pH value in the range from 2 to 3.
It is possible, but not preferred, to adjust the pH to a value in the range from about 4 to 11 and preferably 6 to 10 using acid acceptors or buffers, such as zinc oxide, dibasic lead phosphate, sodium acetate/acetic acid mixtures or the like, dibasic lead phosphate presently being the preferred acid acceptor. Stabilizers of this type are of course used in a quantity sufficient to maintain the de-sired pH value because excesses can be problematical.
The binders according to the invention contain aroma-tic nitroso compounds as another key constituent. The aro-matic nitroso compounds which are suitable for carrying outthe invention are any aromatic hydrocarbons, such as ben-zene, naphthalene, anthracene and diphenyl, which contain at least two nitroso groups attached directly to non-adja-cent ring carbon atoms. Nitroso compounds such as these are known as aromatic poly-C-nitroso compounds containing 1 to 3 aromatic nuclei, including aromatic nuclei fused to one another containing 2 to 6 nitroso groups which are at-tached directly to non-adjacent ring carbon atoms. At present, preferred poly-C-nitroso materials are aromatic nitroso compounds, more particularly dinitrosobenzenes and dinitrosonaphthalenes, such as meta- or para-dinitrosoben-zenes and meta- or para-dinitrosonaphthalenes. The ring hydrogen atoms of the aromatic nucleus may be replaced by alkyl, alkoxy, cycloalkyl, aryl, arylnitroso, halogen and similar groups. The presence of such substituents at the aromatic nucleus has little effect on the activity of the poly-C-nitroso compounds according to the invention. As far as it has hitherto been possible to tell, there are no limitations in regard to the nature of the substituent which may be organic or inorganic. Accordingly, any refer-ence to the "aromatic" poly-C-nitroso comopound, "benzene"
or "naphthalene" is understood to encompass both substi-tuted and unsubstituted nitroso compounds, etc., unless otherwise stated.
A partial non-limiting list of suitable poly-C-nitroso compound suitable for carrying out the invention includes m-dinitrosobenzene, p-dinitrosobenzene, m-dinitrosonaph-thalene, p-dinitrosonaphthalene, 2,5-dinitroso-p-cymol, 2-methyl-1,4-dinitrosobenzene,2-methyl-5-chloro-1,4-dinitro-sobenzene, 2-fluoro-1,4-dinitrosobenzene, 2-methoxy-1,3-dinitrosobenzene, 5-chloro-1,3-dinitrosobenzene, 2-benzyl-1,4-dinitrosobenzeneand2-cyclohexyl-1,4-dinitrosobenzene.
The binders according to the invention contain partly saponified homopolymers or copolymers of vinyl acetate as another characteristic constituent. Compounds such as these are referred to herein as polyvinyl alcohol. They are used in quantities of 1 to 15% by weight and preferably in quantities of 1.5 to 5% by weight, based on binder. The degree of saponification of the polyvinyl alcohols used, i.e. the percentage number of hydroxyl groups, based on the acetate groups originally present, is between 40 and 98~.
Particularly favorable results are obtained with degrees of saponification of 80 to 90%.
Suitable polyvinyl alcohols are derived on the one hand from vinyl acetate homopolymers and on the other hand from copolymers thereof. Suitable copolymers are copoly-mers of vinyl acetate with olefins, halogenated olefins, vinyl ethers, olefinically unsaturated mono- or dicarbox-ylic acids and/or - to a limited extent - esters thereof.
In addition to the saponification products of polyvinyl acetate, therefore, preference is attributed to saponifi-cation products of polyvinyl acetate-co-vinyl butyrate, saponification products of vinyl acetate/ethylene/vinyl chloride copolymers, saponification products af vinyl acetatelacrylates, of vinyl acetate/maleic acid dibutyl ester copolymers, of vinyl acetate/styrene acrylate co-polymers and of vinyl acetate/methyl acrylate copolymers.
Copolymers of vinyl acetate, ethylene and vinylidene chlor-ide having the degrees of saponification mentioned are also suitable. In the copolymers mentioned, the vinyl acetate content in mol-% of the copolymer as a whole is more than 30 mol-%, preferably more than 50 mol-% and, more prefer-ably, more than 70 mol-%.
Although no theoretical explanation for the effects observed in accordance with the invention can be given at the present time, the hydroxyl groups of the polyvinyl al-cohols which must be present in accordance with the inven-tion would appear to react with the other constituents dur-ing establishment of the bond under vulcanizatiqn condi-tions.
According to the invention, favorable results are ob-tained with polyvinyl alcohols having a molecular weight in the range from 14,000 to 100,000. It has been found in this regard that the molecular weight is only of minor im-portance to the result obtained. However, the expert can increase the viscosity by increasing the molecular weight and, hence, can vary the processing properties of the bind-er. However, it has been found that binders based on rela-tively high molecular weight polyvinyl alcohols show better adhesion of the uncured binder film to metals or primers which is often desirable for automated application proces-ses. Binders in which the polyvinyl alcohol has molecular weights in the ran~e from 30,000 to 75,000 have proved to be successful for this purpose, so that this molecular weight range may be regarded as preferred.
Quantitatively, the binders according to the invention preferably contain 5 to 20% by weight halogenated polymer, 2 to 20% by weight of at least one polyfunctional aromatic nitroso compound, 0.2 to 15% by weight polyvinyl alcohols and 0.2 to 6% by weight auxiliaries. The balance to 100%
~ by weight is water. The total solids content of the prepa-rations is between 10 and 50% by weight and preferably be-tween 20 and 30% by weight.
The dispersions according to the invention may also contain typical adhesion-improving fillers, more particu-larly carbon black in quantities of 0.2 to 10% by weight,zinc oxide in quantities of 0.1 to 10% by weight or, if desired, basic lead phosphite and the like. Pigments may also be incorporated. Another advantage of the binders according to the invention is that the masked isocyanate compounds, which are described as essential in preparations of the type in question, for example in the binder accord-ing to DE-PS 29 23 651 and in German patent application ~E
34 00 851, need not be used. Technically, the presence of masked isocyanates is generally critical to the stability of the binders, particularly at elevated temperatures such as can occur in warehouses in summer. To prepare the bind-ers according to the invention, a latex of the halogenated polymer based on an alkylating aromatic monoalkenyl alkyl halide is initially prepared by emulsion copolymerization.
The other constituents and, if desired, water are added to the latex. After preliminary dispersion in a suitable unit, the latex is then ground in a ball mill to a fineness of less than 2 mils.
The water-based binders according to the invention are suitable for bonding vulcanizable elastomers to a number of substrates, including for example numerous metals, such as iron, stainless steel, lead, aluminium, copper, brass, bronze, monel metals, nickel, zinc and the like. They are also suitable for treated metals, such as phosphated steel, galvanized steel, and may also be used for glass and cer-amic materials and for high-melting plastics, such as ara-mide fibers for example. Emphasis is placed on their fav-orable effect in particular in the vulcanization of polar rubbers, for example nitrile rubber, onto aramide fibers or metals.
The binders are conventionally applied to the sub-strate surfaces, for example by dip coating, spray coating, brush coating and the like. It may be advisable in some cases to carry out a pretreatment with a primer of chlorin-ated rubber, phenolic resin or the li~e. After coating, the substrate surfaces are left to dry before being fitted together. After the surfaces have been fitted together, the composite structures are conventionally heated to bring about vulcanization.
~ x am p 1 e s In the tests, the product according to the invention was investigated for its basic adhesive properties and tested for comparison with known products.
Standard test methods, such as ASTM-D 429, Method A or Method ~, were used for the tests.
The metals were pretreated in the usual way.
Vulcanization was carried out in a press under the vulcanization conditions indicated in the Tables. After vulcanization, all the composites were stored for approxi-mately 24 hours and then subjected to the individual tests.
Of the formulations listed in Table 1, Nos. 1 to 3 correspond to the water-based binders according to the invention while formulation No. 4 is a product correspond-ing to EP 161 373.
For all the tests, the water-based binder was applied over a primer (based on a phenolic resin).
~t~n~ard a~hesion an~ corrosion test This test determines the shear strength of the bond and, at the same time, evaluates the failure pattern ~C53874 formed.
In the corrosion test, the composite elements are stored for 2 h in water at 95 to 98C while a load of 2 kg/in is applied to the bond line.
The results expressed as 100 R (100 R = 100% failure in the rubber) in Table 2 show satisfactory adhesion and strength both in the adhesion test and in the corrosion test for all the rubber mixtures used.
Tensile test The test according to ASTM-D 429, Method A, determines the tensile shear strength of a rubber/metal composite.
The result of this test (see Table 3) shows that 100~
failure in the rubber is always obtained in the tensile test as well, irrespective of the rubber mixture. The dif-lS ferences between the strength values are due to mixing.
Preheating resistanc~
To test preheating resistance, the coated test plates are placed in the vulcanizing mold for the preheating time at 153C and are then directly vulcanized onto the NR mix-ture.
The failure patterns indicated in Table 4 show a dis-tinctly better preheating resistance for binder No. 3 than for binder No. 4. Even after heating for only 8 minutes, binder No. 4 i3 no longer able to establish a firm bond.
Binder No. 3 performs satisfactorily after preheating for 14 minutes.
~ydrolysis stability The automotive industry requires a resistance to Gly-santin~/water (1:1) at 135C of more than 42 hours for EPDM
composite elements used in the vicinity of radiators.
A resistance to damper liquid (Glykosafe~610, a prod-uct of BASF) of 7 days at 130C is required for engine bearings (NR composite).
Different EPDM or NR mixtures were bonded with binders Nos. 3 and 4 and subjected to the described stability tests.
Table 5 shows the distinct superiority of binder No.
2c5387 3 to binder No. 4.
Boiling w~t-r resi~tance In addition to the hydrolysis tests mentioned, the boiling water test (as already described) clearly shows to what extent a safe bond is established.
As shown in Table 6, all NR mixtures are bonded so firmly with binder No. 3 that satisfactory boiling water resistance is achieved. Binder No. 4 fails completely.
The described tests showed that only limited adhesion and very poor stability are achieved with the hitherto known binder according to European patent o 161 373.
In contrast, the binder according to the invention performs satisfactorily in all the tests. The resistance to Glysantin0 and Glykosafe~610 achieved with the binder according to the invention is particularly remarkable.
In addition, the binder according to the invention is also satisfactory in regard to spraying behavior, spray pattern, sedimentation or substrate adhesion and stripping resistance.
Binders Nos. 1 and 2 in Table 1 correspond in their adhesion and resistance behavior to binder No. 3 which has been described in detail. They are only inferior to binder No. 3 in viscosity or thixotropic behavior so that a broad account is not necessary.
The chemical names of the commercial products are given after the Tables.
Formulation of the NR mixtur-Mixture constituents _ NR SMR 5 CV 60 100 parts Stearie acid 2 parts Vulkanox~HS 1 part Zno RS 10 parts Pine tar 2 parts CK 3 25 parts VulkacitL 0.33 part Vulkacit~DM 0.58 part Sulfur 2.75 parts Vuleanization: 153C/10 mins.
Formulation of the BBR mixture Mixture eonstituents .
Buna H~ls~1500 100 parts Stearie aeid 1 part Zno RS 5 parts Corax03 50 parts ParafluxO 8 parts Vulkaeit~CZ 0.95 part Sulfur 1.6 parts Vuleanization: 153C/30 mins.
For~ul~tion of NBR ~ixtur-Mixture constituents Perbunan0 N 3807 lOO parts Hycar0 1312 lO parts Alnovol0 Ph 809 15 parts VulkanoxO MB 1 part Vulkanox0 AP 1 part Zno active 5 parts Arovel0 FEF 20 parts Regal0 R 35 parts Stearic acid 1 part Winnofil S 20 parts Vulkacit CZ 1 part Vulkacit Thiuram 3 parts Sulfur 0.2 part Vulcanization: 153C/15 mins.
Foruul~tio~ of th- IIR ~ixtur-Mixture constituents Esso-butyl0 325 lOO parts Stearic acid 1 part Zno RS 5 parts Corax 3 50 parts Vulkacit0 DM 1 part Ethyl-Tellurac 1.5 parts Sulfur 1 part Vulcanization: 160C/30 mins.
Formulation of the CR mixtUro ZC53874 Mixture constituents _ Baypren~ 110 50 parts Baypren0 210 50 parts Stearic acid 0.5 part MgO light 4 parts Vulkanox~ MB 0.5 part Vulkanox~ 4010 NA 1 part Antiozonant AFD 0.5 part Antiozonant wax 1111 part Thermax~ MT 140 parts Ingraplast~ S 10 parts Rhenosorb0 C 5 parts Zno RS 5 parts Vulkacit Thiuram~MS1 part Vulkacit~ DOTG 1 part Sulfur 0.5 part Vulcanization: 160C/20 mins.
2~53874 Formulatlon o~ EPDN mixture No. 1 Mixture constituents Keltan0 512 lOO parts Stearic acid 0.5 part Vulkanox0 HS 1.5 parts ZnO RS 5 parts Corax~ 3 9O parts Gulf security032050 parts BDMA0 1.5 parts Perkadox0 14/40 8.5 parts Vulcanization: 160C/25 mins.
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. . 0 ~ rl ~ q~
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.!C U U :~ ~3 O o ,C ~1 ~1 In o o ~ o o a~ a~ ~ x ~
.) O ~: 3 _ _ _ _ _ _ _ .,~
I ~ I~
_ ` ~ ~0 _, ~ ~ ~ ~o _ ~ O O _l 0 O ~ ,1 _ _ h X a) ~ O h E~
o~O ~ ~ ~D N ~a .C ~I) _ O X ~ ~ ~ O P~ O
1 X a~ 1~ ~ ~ u ~ _ ~ ~5 'I .q :,~, ,, ~rl O _ ~r h 10 O O t~ 'CS t~
,~ _ ~ --~ o o In h ~ O
.-1 o ~1 U ~: ~ o In _I h ~1 _ O ~ 13 h ~ ~ O ~
~1 ~~ 1 _ ~ h :~ _ X ~ ~ ' _l .,1 ~ ,1 ~. O
~ _ a t~ ~ ~ o ~
o o~ n ~ ~I X ~ o O r~ ~1 0 ~ 1 h ~ ~n ~1 I I -- ,C .~:1 rl ~ ~ I ~ O O
o~ m 0 ~ X -- E-l ~ X P~ O h r~ h ~ O
a~ ~ ~r o o ,1 o h ~1 C ~n 3 3 h C J~
,~ C~ C~ O O ~ ~ ~ _ _ _ ,~
~ m 1~ ~ N ~ V N 3 ~
E~
Table 2 _tand~r~ adheslon and aorros~on test Substrate: steel Test method: ASTM-D 429, Method B
Binder: No. 3 over primer Mixture Adhesion test Boiling water test Adhesion Failure value pattern _ NR 42 daN/in lOO R lOO R
SBR 80 daN/in lOO R lOO R
CR 35 daN/in lOO R lOO R
EPDM 55 daN/in lOO R lOO R
IIR 48 daN/in lOO R lOO R
NBR 45 daN/in lOO R lOO R
Rey to raw materials Vulkacit0L (zinc-N-dimethyl dithiocar-bamate) Vulkacit0DM (dibenzothiazyl disulfide) Vulkacit~CZ (benzothiazyl-2-cyclohexyl sul-finamide) Vulkacit0 Thiuram MS (tetramethyl thiuram monosul-fide) Vulkacit0 Thiuram (tetramethyl disulfide) Vulkacit0DOTG (di-o-tolyl guanidine) Ethyl-Tellural0 (tellurium diethyl dithiocar-bamate) Vulkanox0HS (2,2,4-trimethyl-1,2-dihydro-quinoline, polymeric) Vulkanox0MB (2-mercaptobenzimidazole~
2C538~4 Vulkanox04010 NA (N-isopropyl-N'-phenyl-p-phenyl-enediamine) Vulkanox0AP (co~densation product of aldol/
naphthylamine) Antiozonant wax III (mixture of various hydrocar-bons) Antiozonant AFD (unsaturated ether) Corax03 (carbon black ASTM N 330) CK03 (carbon black ASTM S 300) Arovel0FEF (carbon black ASTM N 550) Regal0R (carbon black ASTM N 774) Thermax0MT (carbon black ASTM N 99O) Gulf security0320 (paraff. mineral oil) Pine tar (pinewood tar) Paraflux0 (saturated polymerized petroleum hydrocarbons) Ingraplast0S (naphthenic mineral oil) Winnofil0S (calcium carbonate coated with calcium stearate) Rhenosorb0C (calcium oxide) BDMA0 (butyl glycol dimethacrylate) Perkadox014/40 (1,3-bis-(t-butylperoxyisopro-pyl)-benzene) 2C538~4 Table 3 Ton~ile test Substrate: steel Test method: ASTM-D 429, Method A
Binder: No. 3 over primer MixtureAdhesion valueFailure pattern _ NR 6.2 MPa 100 R
SBR10.2 MPa 100 R
CR 5.8 MPa 100 R
EPDM4.9 MPa 100 R
IIR8.9 MPa 100 R
NBR6.4 MPa 100 R
Table 4 Preheating re~istan¢e Substrate:steel Test method: ASTM-D 429, Method B
Binder: either No. 3 or No. 4 over primer Binder layer thickness: approx. 18 - 20 Mixture: NR
Vulcanization: 153C
Preheating time Binder No. 3 Binder No. 4+) 8 mins.100 R 90 R
10 mins.100 R 40 R
12 mins.100 R 10 R
14 mins.100 R 0 R
16 mins.80 R 0 R
+) Comparison Example according to EP 161 373 Table 5 2CS3874 ~ydrolys~ J~a,bi~
Substrate: steel Test method: ASTM-D 4 2 9, method B
Binder: No. 3 or No. 4 over primer Glysant~n~/water ~1:11, 3 days/135C
Mixture Binder No. 3Binder No. 4+) EPDM No. 1 100 R 10 R
EPDM No. 2 100 R 0 R
EPDM No. 3 100 R 0 R
Gly~osafe~C10. 7 ~a~s/130C
Mixture Binder No. 3Binder No. 4 NR No. 1 100 R 90 R
NR No. 2 100 R 90 R
NR No. 3 100 R 20 R
NR No. 4 100 R 30 R
) Comparison Example according to EP 161 373 Table 6 ZC53874 90il~g water resistanc~
Substrate: steel Test method: ASTM-D 429, method B
Binder: No. 3 or No. 4 over primer ..
Mixture Binder No. 3 Binder No. 4+) NR No. 1 100 R 0 R
NR No. 2 lOo R o R
NR No. 3 100 R 0 R
NR No. 4 100 R 0 R
) Comparison Example according to EP 161 373
AQUEOU~ VULCANIZING ADHE8IV~
This invention relates to an improved water-based binder for vulcanizing various types of rubber onto vul-canization-stable substrates.
It is becoming increasingly desirable to avoid the presence of volatile substances, such as solvents, in ad-hesives of the type in question. Accordingly, efforts have been made to formulate solventless systems. Thus, it is proposed in applicants' European patent 21 186 to synthe-size a homopolymer or copolymer of vinylidene chloride and/or of butadiene/acrylonitrile copolymers, aromatic nitroso compounds, blocked isocyanates, polyvinyl pyrroli-done and other auxiliaries. Although products such as these were useful, there was still a need to improve bond strength with respect to all types of rubbers, including apolar rubbers, such as natural rubber, and to increase the 2C~3!37~
economy of the binders.
A terpolymer latex consisting of a 2,3-dihalo-1,3-butadiene, an aromatic monoalkenyl alkyl halide and other monomers is known from DE-OS 34 25 381. This terpolymer may be processed together with polyfunctional aromatic ni-troso compounds, the solids typically used in this field and a film-forming agent to form an adhesive composition.
The film-forminq agents mentioned also include homopolymers and copolymers of vinyl acetate. Although binders on this basis for vulcanizing rubber onto metals and the like pro-duce useful results, it has now been found that major im-provements can be obtained when the copolymers of vinyl acetate or the vinyl acetate are/is subjected to partial saponification to the corresponding polyvinyl alcohols.
Water-based binders for vulcanizing rubber onto vul-canization-stable substrates are already known from Euro-pean patent 161 373. However, these known binders contain masked polyfunctional isocyanates. The use of masked iso-cyanates is undesirable because they can cause stability problems in storage. The known binders according to Euro-pean patent 161 373 may also contain polyvinyl alcohol, al-though there is no reference to the type or quantity of polyvinyl alcohol used. The function of the polyvinyl al-cohol in formulations such as these is merely to stabilize the constituents, i.e. polyvinyl alcohol is used as a stab-ilizer and not as a reactive component which contributes essentially to the composition of the binder.
Accordingly, the present invention relates to a water-based binder dispersion for vulcanizing rubber onto vulcan-ization-stable substrates consisting of - a halogenated copolymer containing an alkylating aromatic monoalkenyl alkyl halide in addition to other constituents, - polyfunctional aromatic nitroso compounds, - pigments, carbon black, foam inhibitors, emulsifiers and other auxiliaries, characterized in that partially saponified homopolymers or 2c53a74 copolymers of vinyl acetate and, if desired, other standard additives are present for increasing bond strength.
The most important constituent of the binder according to the invention is a halogen-containing polymer based on an alkylating aromatic monoalkenyl alkyl halide. Preferred halogenated copolymers of this type are terpolymers of - 60 to 97% by weight of a 2,3-dihalo-1,3-butadiene, - 2 to 33% by weight of an aromatic monoalkenyl alkyl halide corresponding to the formula:
0 I.
~ CX2=CX~
_ --C--R
and .
~25 tx2=cx Y--C--Z ~--C--R
1 _ ~ _ b b in which X is hydrogen, chlorine, bromine or iodine;
Y is hydrogen, chlorine or bromine; Z is hydrogen, chlorine or bromine and A is hydrogen, chlorine, bromine or a Cl_3 alkyl group, with the proviso that, of Y, Z or A, at least one is chlorine or bromine and, where A is an alkyl group, at least one of Y or Z is chlorine or bromine, and a = 1 or 2 and b = 0, 1 or 2, with the proviso that at least one b is at least 1;
and 0.5 to 10% by weight of at least one olefinically un-saturated monomer, the monomer being at least copol-ymerizable with the conjugated diene monomer and di~-ferent from the aromatlc alkyl halide.
With regard to the 2,3-dihalo-1,3-butadiene as con-jugated diene monomers, which are known commercial prod-ucts, the halogen substituent is selected from a groupconsisting of chlorine, bromine and iodine, chlorine pres-ently being the preferred halogen substituent.
With regard to the mixture of at least two different unsaturated monomers which are copolymerizable at least with the conjugated diene monomer, it is pointed out that these monomers are selected from a first group, which con-sists of ~-haloacrylonitrile, ~-haloacrylic acid, ~-halo-acrylic acid ester, ~-halovinyl ketone, ~-halovinyl ace-tate, vinyl halide, vinylidene halide, styrene and aromatic monoalkenyl alkyl halides, and from a second group consist-ing of monomeric compounds containing at least one olefin-ically unsaturated group, the monomers of the second group being different from the monomers of the first group.
At present, compounds corresponding to formula I are preferred. Representative aromatic monoalkenyl alkyl ha-lides include vinylbenzyl chloride, p-trichloromethyl vin-ylbenzene, p-(~-chloroethyl)-vinylbenzene, p-(~-chloro-butyl)-vinylbenzene, ~-chlorovinylbenzene chloride, 2,3-di-(~-chloroethyl)-vinylbenzene, 4-chloromethyl vinyl naph-thalene, the corresponding bromine and iodine analogs andthe like. At present, the preferred aromatic monoalkenyl alkyl halide is vinylbenzyl chloride (4-chloromethyl vinyl-benzene).
With regard to the second group of copolymerizable monomeric compounds, the ethylenically unsaturated com-pounds of the second group are those which can be polymer-ized by addition of unsaturated bonds, providing they do not crosslink, i.e. either only one unsaturated ethylene group is present in the compound or, where more than one group is present, they are conjugated as such or crosswise.
~he ethylenically unsaturated monomers which may be used in the terpolymers according to the invention are those which which contain either one or several CH2 = C groups.
The ethylenically unsaturated compounds containing one or more CH2 = C = groups include such compounds as styrene, p-chlorostyrene, 3,5-dichlorostyrene, p-methoxystyrene, ac-rylonitrile, methacrylonitrile, vinyl bromide, vinyl fluor-ide, vinyl iodide, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinylidene bromide, vinylidene chlorofluoride, methyl methacrylate, butyl methacrylate, methacrylamide, vinyl methyl ketone, vinyl pyridine, vinyl carbazole, vinyl methyl ether, isobutylene, ethylene, vinyl chloride, vinylidene chloride, alkyl acrylates, including methyl, ethyl, propyl, butyl and octyl acrylates, acrylic acid and methacrylic acid and other similar monoolefinic polymerizable compounds. Other unsaturated compounds con-taining more than one olefinic group which may be copolym-erized to form the terpolymers according to the invention are conjugated dienes, such as l,3-butadiene, isoprene and other 1,3-butadiene hydrocarbons, chloroprene and also 3-cyano-1,3-butylidene, trienes, such as myrcene, and com-pounds containing olefinic and acetylenic bonds, such as vinyl acetylene, vinyl ethynyl, diethyl carbonyl and the like.
The terpolymer latex used in accordance with the in-vention may be prepared by emulsion polymerization of the halogenated conjugated diene with at least two different unsaturated comonomers in an aqueous medium in the presence of an ionic or a mixed ionic/nonionic surface-active sys-tem, ionic surface-active systems presently being prefer-red. It has been found that the terpolymer products which are most suitable for carrying out the invention contain 60 to 97% by weight, preferably 75 to 97% by weight and opti-mally 93 to 97% by weiqht halogenated conjugated diene and, in addition, 2 to 33% by weight, preferably 3 to 25% by weight and optimally 3 to 7% by weight of the monomer of the first group and 0.5 to 10% by weight and preferably 2 to 7% by weight of the monomer of the second group. Of particular value are terpolymer products which have ~een produced from 2,3-dihalo-1,3-butadiene, more particularly 2,3-dichloro-1,3-butadiene, in a quantity of 80 to 95% by weight, based on polymer, aromatic monoalkenyl alkyl ha-lides, more particularly vinylbenzyl chloride, in quanti-ties of 2 to 10% by weight and also olefinically unsatur-ated monomers, more particularly monomers containing at least one -COoH group, acrylic acid, methacrylic acid and/
or 2-hydroxyethyl methacrylate monophosphate in quantities of 2 to 10% by weight. Part of the aromatic monoalkenyl alkyl halides, for example 10 to 90 mol-%, may also be saponified to the corresponding hydroxyalkyl compounds.
The emulsion polymerization is carried out in a closed vessel in which space that is not occupied by the reaction mixture is kept free from oxygen, preferably a layer of inert gas, such as nitrogen, because the induction period for the polymerization reaction is prolonged by the pres-ence of oxygen and because it is desirable to carry out the reaction in the substantial absence of oxygen. Generally speaking, the emulsion polymerization is carried out by mixing the monomeric constituents with one another, emulsi-fying the mixture and subjecting the emulsion to moderate polymerization conditions until substantially the entire monomeric batch is polymerized. However, for various prac-tical reasons which need not be discussed here, it has beenfound that the emulsion polymerization of the tertiary mon-omeric system is carried out more effectively by a semi-continuous process which comprises adding an emulsion of a halogenated conjugated diene and the monomers of the first and second group at constant speed to a polymerization zone containing an aqueous solution or dispersion of the poly-merization initiator. The polymerization conditions are otherwise substantially the same as in batch polymerization processes and need not be discussed here. The polymeriza-tion reaction is exothermic and the reaction temperatureshould be kept below about 75C and preferably below about 60C. Virtually any catalyst or initiator which forms free ZC~5387~
radicals, including the known redox catalyst systems, such as ammonium persulfate/sodium metabisulfite, benzyl perox-ide, hydrogen peroxide, di-t-butyl peroxide, azo-bis-(iso-butyronitrile), alkali metal persulfates and alkyl metal ammonium perborates, may be used in the copolymerization reaction to ensure rapid initiation of the reaction and reproducible results. After the polymerization reaction, unreacted volatile constituents may be removed by vacuum treatment at elevated temperature or by steam distilla-tion, the particular method being a matter of choice.
The choice of the surface-active agent is of major importance to the production of a latex which ensures satisfactory adhesion. It has been found that anionic surfactants or mixtures of anionic and nonionic surfactants have to be used, the mixtures presently being preferred.
Whereas cationic surfactants as such are effective emulsi-fiers, their use in the production of the elastomeric ter-polymer latex according to the invention either individu-ally or in combination with either an anionic or a non-ionic surfactant or with both adversely affects the adhes-ive properties. The surface-active systems are used in quantities of 0.01 to 15% by weight and preferably in quantities of 1 to 10% by weight, based on the weight of the monomers used. At present, it is preferred to use a mixed anionic/nonionic surface-active system with a ratio of anionic to nonionic surfactant of 1.2 to 2.1:1 and pref-erably 1.3 to 2.0:1. Representative anionic surfactants are carboxylates, such as fatty acid soaps of lauric, stearic and oleic acid and also acyl derivatives of sarco-sine, such as methyl glycine; sulfates, such as sodiumlauryl sulfate; sulfatized natural oils and esters, such as turkey red oil and alkylaryl polyether sulfates; alkylaryl polyether sulfonates; isopropyl naphthalene sulfonates and sulfosuccinates and also sulfosuccinamates; phosphate esters, such as partial esters of complex phosphates with short-chain fatty alcohols; and orthophosphate esters of polyethoxylated fatty alcohols. Representative nonionic surfactants include ethoxylated (ethylene oxide deriva-tives), monohydric and polyhydric alcohols, ethylene oxide/
propylene oxide block copolymers; esters, such as glycerol monostearate; dehydration products of sorbitol, such as sorbitan monostearate and polyethylene oxide sorbitan mon-olaurate; and amines, such as lauric acid, isopropenyl ha-lide. At present, a 1.8:1 mixture of sodium dodecyl di-phenyl ether disulfonate as the anionic surfactant and nonylphenol polyethylene glycol as the anionic surfactant is preferred. Anionic and anionic/nonionic surface-active systems which have to be used in accordance with the inven-tion are described in detail in Em~lsions: Theory and Prac-tice, by Paul Becher, Chapter 6 (Reinhold Publishing Cor-poration, New York, 196S), and in McCutcheon's Detergents and Emulsifiers, 1972 Annual.
The terpolymer latex obtained in accordance with the invention by the emulsion copolymerization of halogenated dienes and unsaturated monomers of the first and second group generally has a pH value in the range from 2 to 3.
It is possible, but not preferred, to adjust the pH to a value in the range from about 4 to 11 and preferably 6 to 10 using acid acceptors or buffers, such as zinc oxide, dibasic lead phosphate, sodium acetate/acetic acid mixtures or the like, dibasic lead phosphate presently being the preferred acid acceptor. Stabilizers of this type are of course used in a quantity sufficient to maintain the de-sired pH value because excesses can be problematical.
The binders according to the invention contain aroma-tic nitroso compounds as another key constituent. The aro-matic nitroso compounds which are suitable for carrying outthe invention are any aromatic hydrocarbons, such as ben-zene, naphthalene, anthracene and diphenyl, which contain at least two nitroso groups attached directly to non-adja-cent ring carbon atoms. Nitroso compounds such as these are known as aromatic poly-C-nitroso compounds containing 1 to 3 aromatic nuclei, including aromatic nuclei fused to one another containing 2 to 6 nitroso groups which are at-tached directly to non-adjacent ring carbon atoms. At present, preferred poly-C-nitroso materials are aromatic nitroso compounds, more particularly dinitrosobenzenes and dinitrosonaphthalenes, such as meta- or para-dinitrosoben-zenes and meta- or para-dinitrosonaphthalenes. The ring hydrogen atoms of the aromatic nucleus may be replaced by alkyl, alkoxy, cycloalkyl, aryl, arylnitroso, halogen and similar groups. The presence of such substituents at the aromatic nucleus has little effect on the activity of the poly-C-nitroso compounds according to the invention. As far as it has hitherto been possible to tell, there are no limitations in regard to the nature of the substituent which may be organic or inorganic. Accordingly, any refer-ence to the "aromatic" poly-C-nitroso comopound, "benzene"
or "naphthalene" is understood to encompass both substi-tuted and unsubstituted nitroso compounds, etc., unless otherwise stated.
A partial non-limiting list of suitable poly-C-nitroso compound suitable for carrying out the invention includes m-dinitrosobenzene, p-dinitrosobenzene, m-dinitrosonaph-thalene, p-dinitrosonaphthalene, 2,5-dinitroso-p-cymol, 2-methyl-1,4-dinitrosobenzene,2-methyl-5-chloro-1,4-dinitro-sobenzene, 2-fluoro-1,4-dinitrosobenzene, 2-methoxy-1,3-dinitrosobenzene, 5-chloro-1,3-dinitrosobenzene, 2-benzyl-1,4-dinitrosobenzeneand2-cyclohexyl-1,4-dinitrosobenzene.
The binders according to the invention contain partly saponified homopolymers or copolymers of vinyl acetate as another characteristic constituent. Compounds such as these are referred to herein as polyvinyl alcohol. They are used in quantities of 1 to 15% by weight and preferably in quantities of 1.5 to 5% by weight, based on binder. The degree of saponification of the polyvinyl alcohols used, i.e. the percentage number of hydroxyl groups, based on the acetate groups originally present, is between 40 and 98~.
Particularly favorable results are obtained with degrees of saponification of 80 to 90%.
Suitable polyvinyl alcohols are derived on the one hand from vinyl acetate homopolymers and on the other hand from copolymers thereof. Suitable copolymers are copoly-mers of vinyl acetate with olefins, halogenated olefins, vinyl ethers, olefinically unsaturated mono- or dicarbox-ylic acids and/or - to a limited extent - esters thereof.
In addition to the saponification products of polyvinyl acetate, therefore, preference is attributed to saponifi-cation products of polyvinyl acetate-co-vinyl butyrate, saponification products of vinyl acetate/ethylene/vinyl chloride copolymers, saponification products af vinyl acetatelacrylates, of vinyl acetate/maleic acid dibutyl ester copolymers, of vinyl acetate/styrene acrylate co-polymers and of vinyl acetate/methyl acrylate copolymers.
Copolymers of vinyl acetate, ethylene and vinylidene chlor-ide having the degrees of saponification mentioned are also suitable. In the copolymers mentioned, the vinyl acetate content in mol-% of the copolymer as a whole is more than 30 mol-%, preferably more than 50 mol-% and, more prefer-ably, more than 70 mol-%.
Although no theoretical explanation for the effects observed in accordance with the invention can be given at the present time, the hydroxyl groups of the polyvinyl al-cohols which must be present in accordance with the inven-tion would appear to react with the other constituents dur-ing establishment of the bond under vulcanizatiqn condi-tions.
According to the invention, favorable results are ob-tained with polyvinyl alcohols having a molecular weight in the range from 14,000 to 100,000. It has been found in this regard that the molecular weight is only of minor im-portance to the result obtained. However, the expert can increase the viscosity by increasing the molecular weight and, hence, can vary the processing properties of the bind-er. However, it has been found that binders based on rela-tively high molecular weight polyvinyl alcohols show better adhesion of the uncured binder film to metals or primers which is often desirable for automated application proces-ses. Binders in which the polyvinyl alcohol has molecular weights in the ran~e from 30,000 to 75,000 have proved to be successful for this purpose, so that this molecular weight range may be regarded as preferred.
Quantitatively, the binders according to the invention preferably contain 5 to 20% by weight halogenated polymer, 2 to 20% by weight of at least one polyfunctional aromatic nitroso compound, 0.2 to 15% by weight polyvinyl alcohols and 0.2 to 6% by weight auxiliaries. The balance to 100%
~ by weight is water. The total solids content of the prepa-rations is between 10 and 50% by weight and preferably be-tween 20 and 30% by weight.
The dispersions according to the invention may also contain typical adhesion-improving fillers, more particu-larly carbon black in quantities of 0.2 to 10% by weight,zinc oxide in quantities of 0.1 to 10% by weight or, if desired, basic lead phosphite and the like. Pigments may also be incorporated. Another advantage of the binders according to the invention is that the masked isocyanate compounds, which are described as essential in preparations of the type in question, for example in the binder accord-ing to DE-PS 29 23 651 and in German patent application ~E
34 00 851, need not be used. Technically, the presence of masked isocyanates is generally critical to the stability of the binders, particularly at elevated temperatures such as can occur in warehouses in summer. To prepare the bind-ers according to the invention, a latex of the halogenated polymer based on an alkylating aromatic monoalkenyl alkyl halide is initially prepared by emulsion copolymerization.
The other constituents and, if desired, water are added to the latex. After preliminary dispersion in a suitable unit, the latex is then ground in a ball mill to a fineness of less than 2 mils.
The water-based binders according to the invention are suitable for bonding vulcanizable elastomers to a number of substrates, including for example numerous metals, such as iron, stainless steel, lead, aluminium, copper, brass, bronze, monel metals, nickel, zinc and the like. They are also suitable for treated metals, such as phosphated steel, galvanized steel, and may also be used for glass and cer-amic materials and for high-melting plastics, such as ara-mide fibers for example. Emphasis is placed on their fav-orable effect in particular in the vulcanization of polar rubbers, for example nitrile rubber, onto aramide fibers or metals.
The binders are conventionally applied to the sub-strate surfaces, for example by dip coating, spray coating, brush coating and the like. It may be advisable in some cases to carry out a pretreatment with a primer of chlorin-ated rubber, phenolic resin or the li~e. After coating, the substrate surfaces are left to dry before being fitted together. After the surfaces have been fitted together, the composite structures are conventionally heated to bring about vulcanization.
~ x am p 1 e s In the tests, the product according to the invention was investigated for its basic adhesive properties and tested for comparison with known products.
Standard test methods, such as ASTM-D 429, Method A or Method ~, were used for the tests.
The metals were pretreated in the usual way.
Vulcanization was carried out in a press under the vulcanization conditions indicated in the Tables. After vulcanization, all the composites were stored for approxi-mately 24 hours and then subjected to the individual tests.
Of the formulations listed in Table 1, Nos. 1 to 3 correspond to the water-based binders according to the invention while formulation No. 4 is a product correspond-ing to EP 161 373.
For all the tests, the water-based binder was applied over a primer (based on a phenolic resin).
~t~n~ard a~hesion an~ corrosion test This test determines the shear strength of the bond and, at the same time, evaluates the failure pattern ~C53874 formed.
In the corrosion test, the composite elements are stored for 2 h in water at 95 to 98C while a load of 2 kg/in is applied to the bond line.
The results expressed as 100 R (100 R = 100% failure in the rubber) in Table 2 show satisfactory adhesion and strength both in the adhesion test and in the corrosion test for all the rubber mixtures used.
Tensile test The test according to ASTM-D 429, Method A, determines the tensile shear strength of a rubber/metal composite.
The result of this test (see Table 3) shows that 100~
failure in the rubber is always obtained in the tensile test as well, irrespective of the rubber mixture. The dif-lS ferences between the strength values are due to mixing.
Preheating resistanc~
To test preheating resistance, the coated test plates are placed in the vulcanizing mold for the preheating time at 153C and are then directly vulcanized onto the NR mix-ture.
The failure patterns indicated in Table 4 show a dis-tinctly better preheating resistance for binder No. 3 than for binder No. 4. Even after heating for only 8 minutes, binder No. 4 i3 no longer able to establish a firm bond.
Binder No. 3 performs satisfactorily after preheating for 14 minutes.
~ydrolysis stability The automotive industry requires a resistance to Gly-santin~/water (1:1) at 135C of more than 42 hours for EPDM
composite elements used in the vicinity of radiators.
A resistance to damper liquid (Glykosafe~610, a prod-uct of BASF) of 7 days at 130C is required for engine bearings (NR composite).
Different EPDM or NR mixtures were bonded with binders Nos. 3 and 4 and subjected to the described stability tests.
Table 5 shows the distinct superiority of binder No.
2c5387 3 to binder No. 4.
Boiling w~t-r resi~tance In addition to the hydrolysis tests mentioned, the boiling water test (as already described) clearly shows to what extent a safe bond is established.
As shown in Table 6, all NR mixtures are bonded so firmly with binder No. 3 that satisfactory boiling water resistance is achieved. Binder No. 4 fails completely.
The described tests showed that only limited adhesion and very poor stability are achieved with the hitherto known binder according to European patent o 161 373.
In contrast, the binder according to the invention performs satisfactorily in all the tests. The resistance to Glysantin0 and Glykosafe~610 achieved with the binder according to the invention is particularly remarkable.
In addition, the binder according to the invention is also satisfactory in regard to spraying behavior, spray pattern, sedimentation or substrate adhesion and stripping resistance.
Binders Nos. 1 and 2 in Table 1 correspond in their adhesion and resistance behavior to binder No. 3 which has been described in detail. They are only inferior to binder No. 3 in viscosity or thixotropic behavior so that a broad account is not necessary.
The chemical names of the commercial products are given after the Tables.
Formulation of the NR mixtur-Mixture constituents _ NR SMR 5 CV 60 100 parts Stearie acid 2 parts Vulkanox~HS 1 part Zno RS 10 parts Pine tar 2 parts CK 3 25 parts VulkacitL 0.33 part Vulkacit~DM 0.58 part Sulfur 2.75 parts Vuleanization: 153C/10 mins.
Formulation of the BBR mixture Mixture eonstituents .
Buna H~ls~1500 100 parts Stearie aeid 1 part Zno RS 5 parts Corax03 50 parts ParafluxO 8 parts Vulkaeit~CZ 0.95 part Sulfur 1.6 parts Vuleanization: 153C/30 mins.
For~ul~tion of NBR ~ixtur-Mixture constituents Perbunan0 N 3807 lOO parts Hycar0 1312 lO parts Alnovol0 Ph 809 15 parts VulkanoxO MB 1 part Vulkanox0 AP 1 part Zno active 5 parts Arovel0 FEF 20 parts Regal0 R 35 parts Stearic acid 1 part Winnofil S 20 parts Vulkacit CZ 1 part Vulkacit Thiuram 3 parts Sulfur 0.2 part Vulcanization: 153C/15 mins.
Foruul~tio~ of th- IIR ~ixtur-Mixture constituents Esso-butyl0 325 lOO parts Stearic acid 1 part Zno RS 5 parts Corax 3 50 parts Vulkacit0 DM 1 part Ethyl-Tellurac 1.5 parts Sulfur 1 part Vulcanization: 160C/30 mins.
Formulation of the CR mixtUro ZC53874 Mixture constituents _ Baypren~ 110 50 parts Baypren0 210 50 parts Stearic acid 0.5 part MgO light 4 parts Vulkanox~ MB 0.5 part Vulkanox~ 4010 NA 1 part Antiozonant AFD 0.5 part Antiozonant wax 1111 part Thermax~ MT 140 parts Ingraplast~ S 10 parts Rhenosorb0 C 5 parts Zno RS 5 parts Vulkacit Thiuram~MS1 part Vulkacit~ DOTG 1 part Sulfur 0.5 part Vulcanization: 160C/20 mins.
2~53874 Formulatlon o~ EPDN mixture No. 1 Mixture constituents Keltan0 512 lOO parts Stearic acid 0.5 part Vulkanox0 HS 1.5 parts ZnO RS 5 parts Corax~ 3 9O parts Gulf security032050 parts BDMA0 1.5 parts Perkadox0 14/40 8.5 parts Vulcanization: 160C/25 mins.
_ .
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I o ~ ,~ o ~ u ~
~ m _I h _ N
~ C) o\ o\ o\ o\,o\ o\d~ R
~D ~ ~ ~ X ~:0 ~1 . . . . . . . ~
r~ I o ~ ~ o~1 ~ ~ O
) _ h -- ~q a) . a~ ~
.. ~ h ~ O ~ ~
~ ~ ~ o _ ~
_ _ 0 I ~ ~ O
. . 0 ~ rl ~ q~
O O --1 0 Ul 0 ~ O o S .C 0 h ~
.!C U U :~ ~3 O o ,C ~1 ~1 In o o ~ o o a~ a~ ~ x ~
.) O ~: 3 _ _ _ _ _ _ _ .,~
I ~ I~
_ ` ~ ~0 _, ~ ~ ~ ~o _ ~ O O _l 0 O ~ ,1 _ _ h X a) ~ O h E~
o~O ~ ~ ~D N ~a .C ~I) _ O X ~ ~ ~ O P~ O
1 X a~ 1~ ~ ~ u ~ _ ~ ~5 'I .q :,~, ,, ~rl O _ ~r h 10 O O t~ 'CS t~
,~ _ ~ --~ o o In h ~ O
.-1 o ~1 U ~: ~ o In _I h ~1 _ O ~ 13 h ~ ~ O ~
~1 ~~ 1 _ ~ h :~ _ X ~ ~ ' _l .,1 ~ ,1 ~. O
~ _ a t~ ~ ~ o ~
o o~ n ~ ~I X ~ o O r~ ~1 0 ~ 1 h ~ ~n ~1 I I -- ,C .~:1 rl ~ ~ I ~ O O
o~ m 0 ~ X -- E-l ~ X P~ O h r~ h ~ O
a~ ~ ~r o o ,1 o h ~1 C ~n 3 3 h C J~
,~ C~ C~ O O ~ ~ ~ _ _ _ ,~
~ m 1~ ~ N ~ V N 3 ~
E~
Table 2 _tand~r~ adheslon and aorros~on test Substrate: steel Test method: ASTM-D 429, Method B
Binder: No. 3 over primer Mixture Adhesion test Boiling water test Adhesion Failure value pattern _ NR 42 daN/in lOO R lOO R
SBR 80 daN/in lOO R lOO R
CR 35 daN/in lOO R lOO R
EPDM 55 daN/in lOO R lOO R
IIR 48 daN/in lOO R lOO R
NBR 45 daN/in lOO R lOO R
Rey to raw materials Vulkacit0L (zinc-N-dimethyl dithiocar-bamate) Vulkacit0DM (dibenzothiazyl disulfide) Vulkacit~CZ (benzothiazyl-2-cyclohexyl sul-finamide) Vulkacit0 Thiuram MS (tetramethyl thiuram monosul-fide) Vulkacit0 Thiuram (tetramethyl disulfide) Vulkacit0DOTG (di-o-tolyl guanidine) Ethyl-Tellural0 (tellurium diethyl dithiocar-bamate) Vulkanox0HS (2,2,4-trimethyl-1,2-dihydro-quinoline, polymeric) Vulkanox0MB (2-mercaptobenzimidazole~
2C538~4 Vulkanox04010 NA (N-isopropyl-N'-phenyl-p-phenyl-enediamine) Vulkanox0AP (co~densation product of aldol/
naphthylamine) Antiozonant wax III (mixture of various hydrocar-bons) Antiozonant AFD (unsaturated ether) Corax03 (carbon black ASTM N 330) CK03 (carbon black ASTM S 300) Arovel0FEF (carbon black ASTM N 550) Regal0R (carbon black ASTM N 774) Thermax0MT (carbon black ASTM N 99O) Gulf security0320 (paraff. mineral oil) Pine tar (pinewood tar) Paraflux0 (saturated polymerized petroleum hydrocarbons) Ingraplast0S (naphthenic mineral oil) Winnofil0S (calcium carbonate coated with calcium stearate) Rhenosorb0C (calcium oxide) BDMA0 (butyl glycol dimethacrylate) Perkadox014/40 (1,3-bis-(t-butylperoxyisopro-pyl)-benzene) 2C538~4 Table 3 Ton~ile test Substrate: steel Test method: ASTM-D 429, Method A
Binder: No. 3 over primer MixtureAdhesion valueFailure pattern _ NR 6.2 MPa 100 R
SBR10.2 MPa 100 R
CR 5.8 MPa 100 R
EPDM4.9 MPa 100 R
IIR8.9 MPa 100 R
NBR6.4 MPa 100 R
Table 4 Preheating re~istan¢e Substrate:steel Test method: ASTM-D 429, Method B
Binder: either No. 3 or No. 4 over primer Binder layer thickness: approx. 18 - 20 Mixture: NR
Vulcanization: 153C
Preheating time Binder No. 3 Binder No. 4+) 8 mins.100 R 90 R
10 mins.100 R 40 R
12 mins.100 R 10 R
14 mins.100 R 0 R
16 mins.80 R 0 R
+) Comparison Example according to EP 161 373 Table 5 2CS3874 ~ydrolys~ J~a,bi~
Substrate: steel Test method: ASTM-D 4 2 9, method B
Binder: No. 3 or No. 4 over primer Glysant~n~/water ~1:11, 3 days/135C
Mixture Binder No. 3Binder No. 4+) EPDM No. 1 100 R 10 R
EPDM No. 2 100 R 0 R
EPDM No. 3 100 R 0 R
Gly~osafe~C10. 7 ~a~s/130C
Mixture Binder No. 3Binder No. 4 NR No. 1 100 R 90 R
NR No. 2 100 R 90 R
NR No. 3 100 R 20 R
NR No. 4 100 R 30 R
) Comparison Example according to EP 161 373 Table 6 ZC53874 90il~g water resistanc~
Substrate: steel Test method: ASTM-D 429, method B
Binder: No. 3 or No. 4 over primer ..
Mixture Binder No. 3 Binder No. 4+) NR No. 1 100 R 0 R
NR No. 2 lOo R o R
NR No. 3 100 R 0 R
NR No. 4 100 R 0 R
) Comparison Example according to EP 161 373
Claims (10)
1. A water-based binder dispersion free from masked isocyanates for vulcanizing rubber onto vulcanization-stable substrates consisting of a halogenated copolymer based on an alkylating aromatic monoalkenyl alkyl halide, polyfunctional aromatic nitroso compounds, pigments, carbon black, foam inhibitors, emulsifiers and other auxiliaries and (for increasing bond strength) partly saponified homopoly-mers or copolymers of vinyl acetate.
2. A binder dispersion as claimed in claim 1, charac-terized in that, based on the dispersion as a whole, it contains - 5 to 20% by weight of the halogenated copolymer, - 2 to 20% by weight of the polyfunctional aromatic nitroso compound, - 1 to 15% by weight of the partly saponified homopoly-mers or copolymers of vinyl acetate, - 0.2 to 15% by weight pigments, carbon black, foam inhibitors, emulsifiers and/or other auxiliaries and - balance to 100% by weight water.
3. A binder dispersion as claimed in claim 1 or 2, characterized in that copolymers of vinyl acetate with olefins, halogenated olefins, vinyl ethers, olefinically unsaturated carboxylic acids and/or dicarboxylic acids and/or esters thereof are used as the copolymers of vinyl acetate.
4. A binder dispersion as claimed in any of claims 1 to 3, characterized in that 40 to 98% and preferably 80 to 90%
of the acetate groups originally present in the homopoly-mers or copolymers of vinyl acetate are saponified to the corresponding polyvinyl alcohols.
of the acetate groups originally present in the homopoly-mers or copolymers of vinyl acetate are saponified to the corresponding polyvinyl alcohols.
5. A binder dispersion as claimed in any of claims 1 to 4, characterized in that the partly saponified homopolymers or copolymers of vinyl acetate have molecular weights in the range from 14,000 to 100,000 and preferably in the range from 30,000 to 75,000.
6. A binder dispersion as claimed in any of claims 1 to 5, characterized in that the halogenated polymers based on an alkylating aromatic monoalkenyl alkyl halide consist of - 60 to 97% by weight of at least one 2,3-dihalo-1,3-butadiene;
- 2 to 33% by weight of at least one aromatic mono-alkenyl alkyl halide corresponding to the formula I.
or II.
in which X is hydrogen, chlorine, bromine or iodine;
Y is hydrogen, chlorine or bromine; Z is hydrogen, chlorine or bromine and A is hydrogen, chlorine, bromine or a C1-3 alkyl group, with the proviso that, of Y, Z and A, at least one is chlorine or bromine and, where A is an alkyl group, at least one of Y and Z is chlorine or bromine, and a = 1 or 2 and b = 0, 1 or 2, with the proviso that at least one b is at least 1; and - 0.5 to 10% by weight of at least one olefinically unsaturated monomer which is at least copolymerizable with the conjugated diene monomer and different from the aromatic alkyl halide.
- 2 to 33% by weight of at least one aromatic mono-alkenyl alkyl halide corresponding to the formula I.
or II.
in which X is hydrogen, chlorine, bromine or iodine;
Y is hydrogen, chlorine or bromine; Z is hydrogen, chlorine or bromine and A is hydrogen, chlorine, bromine or a C1-3 alkyl group, with the proviso that, of Y, Z and A, at least one is chlorine or bromine and, where A is an alkyl group, at least one of Y and Z is chlorine or bromine, and a = 1 or 2 and b = 0, 1 or 2, with the proviso that at least one b is at least 1; and - 0.5 to 10% by weight of at least one olefinically unsaturated monomer which is at least copolymerizable with the conjugated diene monomer and different from the aromatic alkyl halide.
7. A binder dispersion as claimed in any of claims 1 to 6, characterized in that the halogenated polymers based on an alkylating aromatic monoalkenyl alkyl halide contain monomers bearing carboxylic acid groups as further con-stituents.
8. A binder dispersion as claimed in any of claims 1 to 7, characterized in that the halogenated polymers based on an alkylating aromatic monoalkenyl alkyl halide consist of 80 to 95% by weight dichlorobutadiene, more particularly 2,3-dichloro-1,3-butadiene, 2 to 10% by weight acrylic and/or methacrylic acid and 2 to 10% by weight vinyl benzyl chloride.
9. A binder dispersion as claimed in any of claims 1 to 8, characterized in that the halogenated polymers based on an alkylating aromatic monoalkenyl alkyl halide are partly saponified to the corresponding hydroxyalkyl compound.
10. Binders as claimed in claims 1 to 9, characterized in that dinitrosobenzenes, more particularly 1,3- and 1,4-di-nitrosobenzene, are used as the polyfunctional aromatic nitroso compounds.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3913691A DE3913691C1 (en) | 1989-04-26 | 1989-04-26 | |
| DEP3913691.4 | 1989-04-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2053874A1 true CA2053874A1 (en) | 1990-10-27 |
Family
ID=6379467
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002053874A Abandoned CA2053874A1 (en) | 1989-04-26 | 1990-04-17 | Aqueous vulcanizing adhesive |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0470105B1 (en) |
| JP (1) | JP3179476B2 (en) |
| KR (1) | KR920701375A (en) |
| AT (1) | ATE109191T1 (en) |
| AU (1) | AU635927B2 (en) |
| CA (1) | CA2053874A1 (en) |
| DE (2) | DE3913691C1 (en) |
| DK (1) | DK0470105T3 (en) |
| ES (1) | ES2057557T3 (en) |
| MX (1) | MX174476B (en) |
| RU (1) | RU2021313C1 (en) |
| TR (1) | TR24514A (en) |
| WO (1) | WO1990012847A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6902760B2 (en) | 2000-12-14 | 2005-06-07 | Henkel Kommanditgesellschaft Auf Aktien | Aqueous one-coat rubber-metal bonding agents |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4217437C3 (en) * | 1992-05-26 | 2003-10-30 | Nuovakautschuk Gmbh | Process for repairing vehicle tires damaged by puncture injuries, for example, and associated repair set |
| RU2543181C2 (en) * | 2013-05-14 | 2015-02-27 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Волгоградский государственный технический университет" (ВолгГТУ) | Adhesive composition |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4483962A (en) * | 1983-07-22 | 1984-11-20 | Lord Corporation | Aqueous adhesive systems |
| DE3400851A1 (en) * | 1984-01-12 | 1985-07-25 | Henkel KGaA, 4000 Düsseldorf | AQUEOUS VOLCANIZATION ADHESIVE |
-
1989
- 1989-04-26 DE DE3913691A patent/DE3913691C1/de not_active Expired - Fee Related
-
1990
- 1990-04-11 TR TR90/0341A patent/TR24514A/en unknown
- 1990-04-17 EP EP90906190A patent/EP0470105B1/en not_active Expired - Lifetime
- 1990-04-17 CA CA002053874A patent/CA2053874A1/en not_active Abandoned
- 1990-04-17 AU AU54315/90A patent/AU635927B2/en not_active Ceased
- 1990-04-17 WO PCT/EP1990/000618 patent/WO1990012847A1/en active IP Right Grant
- 1990-04-17 ES ES90906190T patent/ES2057557T3/en not_active Expired - Lifetime
- 1990-04-17 DE DE59006637T patent/DE59006637D1/en not_active Expired - Lifetime
- 1990-04-17 JP JP50596890A patent/JP3179476B2/en not_active Expired - Lifetime
- 1990-04-17 DK DK90906190.5T patent/DK0470105T3/en active
- 1990-04-17 AT AT90906190T patent/ATE109191T1/en active
- 1990-04-17 KR KR1019910701455A patent/KR920701375A/en not_active Application Discontinuation
- 1990-04-25 MX MX020453A patent/MX174476B/en unknown
-
1991
- 1991-10-25 RU SU915010131A patent/RU2021313C1/en active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6902760B2 (en) | 2000-12-14 | 2005-06-07 | Henkel Kommanditgesellschaft Auf Aktien | Aqueous one-coat rubber-metal bonding agents |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0470105B1 (en) | 1994-07-27 |
| EP0470105A1 (en) | 1992-02-12 |
| KR920701375A (en) | 1992-08-11 |
| JPH04504868A (en) | 1992-08-27 |
| RU2021313C1 (en) | 1994-10-15 |
| JP3179476B2 (en) | 2001-06-25 |
| MX174476B (en) | 1994-05-18 |
| AU635927B2 (en) | 1993-04-08 |
| TR24514A (en) | 1991-11-01 |
| AU5431590A (en) | 1990-11-16 |
| WO1990012847A1 (en) | 1990-11-01 |
| DE3913691C1 (en) | 1990-09-06 |
| DK0470105T3 (en) | 1994-11-21 |
| DE59006637D1 (en) | 1994-09-01 |
| ATE109191T1 (en) | 1994-08-15 |
| ES2057557T3 (en) | 1994-10-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |