DE2610848C3 - Laminate and process for its manufacture - Google Patents

Description

The vulcanization or adhesion of rubber to metals has hitherto been achieved using various methods. These include, for example, brass, bronze and zinc plating; the use of halogenated natural or synthetic rubbers with or without special additives that promote adhesion, such as di-C-niiroso compounds or cobalt naphthenai; Isocyanates or isocyanate / rubber mixtures; and synthetic phenol / formaldehyde type resins. Each process has certain distinct disadvantages.
When a metal, such as steel, with e.g. B, brass plated

and then with a compounded vulcanizable If rubber is brought into contact and the whole thing is heated under pressure, it becomes strong Bond between the brass and the rubber presumably due to covalent copper / sulfur /

ίο rubber bonds formed this bond possesses good water and solvent resistance. The disadvantage of this approach is in the procedure justified The brass plating process is expensive and difficult to monitor. Any variations in the brass composition and theirs Crystal structure can lead to very poor adhesion to the rubber. By using brass imposes serious restrictions on the rubber specialist, since the rubber insert material! must be applied carefully in order to achieve optimal adhesion to the brass. At the Bronze plating and zinc plating have similar problems and limitations.

Chlorinated and broinated natural and synthetic Rubbers, especially if the approaches contain additives that promote crosslinking and adhesion, for example di-C-nitrosated aromatics, provide good adhesive bonds between different metals and natural and synthetic rubbers. As a result

Due to their slightly polar nature, they can adhere to metals without covalent bonds with the metal surface. This lack of chemical bonds with the metal surface is obviously a disadvantage as the Adhesion strength of such systems rapidly with increasing

J5 temperature decreases.

It has been known for many years that polyfunctional Isocyanates, such as ρ, ρ ', ρ' '- triisocyanate triphenylmethane itself and as an additive to rubber solutions, are high Provide adhesive strength between rubber and metals.

The mechanism of adhesion is not fully understood; it is believed that the isocyanates are chemical react with both the rubber and the metal surface. In the first case, deliver active Hydrogen atoms, ζ. B. hydroxyl or carboxyl group

4Ί pen caused by oxidation during rubber processing reaction sites for the formation of urethane and other bonds. When tying to the Metal surface is believed to be the most common have some hydroxyl groups with the isocyanates groups can react. In either case is the solvent resistance and the rate of degradation the adhesive strength with increasing temperature in the case of rubber bonded to metal parts with isocyanate better than you would expect if the adhesion was on

-, -, metal would only be based on physical forces. The disadvantages of systems based on Isocyanates belong because of their highly reactive isocyanate groups and poor heat aging properties these bonds have a high humidity

high sensitivity and a very short pot life.

Phenol / formaldehyde type synthetic resins generally combined with a rubber polymer latex can also be used to bond rubber to metal. This kind of

h-i adhesive can chemically react with an unsaturated one Rubber bond by adding either sulfur and accelerators from the rubber to the adhesive layer wander, followed by co-vulcanization.

or by possibly using the methylol groups of the Resols react with the rubber itself. However is the adhesion to the metal surface of a physical nature (i.e., van der Waa | s forces); the adhesive strength on the Metal is generally poor, especially at elevated temperatures.

In US-PS 29 78 377 it is mentioned that mixed polymers of butadiene and a vinyl pyridine, such as 2-methyl-5-vinylpyridine, have been used to bond rubber to metal and that in the Use with a natural rubber or a GRS composition (13-butadiene / StyroI) an excellent bond is obtained. The strength such bonds at elevated temperatures are not described and no values are given specified. In each case it was found that there were many Natural rubbers and GRS compositions are released when they bond to metals with copolymers Vinyl pyridines and butadiene have very poor adhesive strength even at normal room temperature deliver.

The prior art, for example, the US-PS 2885381 teaches that both carbon black and silica can effectively reinforce conjugated diene / heterocyclic nitrogen base polymers. Even if this Patent does not concern the adhesion to metals, but only a mass composition, i.e. rubbery conjugated diene / heterocyclic nitrogen base copolymers fortified with mineral pigments one can reasonably expect the reinforcing effect occurs in the same way when either silicon dioxide or carbon black is used Filler can be used in conjugated diene / heterocyclic nitrogen base copolymer adhesives.

It is also proposed and included in application serial no. 5 87,982 (dated June 18, 1975) been to improve the bond of rubber to ferrous metal substrates by that one Incorporated silica in rubber bonded with an interpolymer of a conjugated diene and a heterocyclic nitrogen base is bound. The procedure gives the The rubber artisan has greater freedom in rubber compounding as the preferred carbon filler can be used in place of silica in the rubber composition and in greater amounts can while still maintaining the improved adhesion.

The use of certain transition metal salts or soaps, such as cobalt naphthenate, copper naphthenate so or cobalt resinate, as additives to compounded rubbers to improve the adhesion to brass is known. However, when compounded rubbers are bonded to brass, bronze or zinc plated surfaces, is a major factor for the formation of such a bond the reaction of the sulfur present in the rubber with both the rubber as well as the plated metal, presumably with the formation of covalent rubber / sulfur / metal bonds. This fact eo relates to a completely different binding mechanism from the present invention in which none Brass or zinc plating is used. Therefore, there is some conclusion that the adhesive strength is through the addition of such transition metal compounds to the rubbers to be joined can be improved would not be possible.

The object of the present invention is to kompoun

dated vulcanizable rubbers to ferrous metals, especially iron and steel, without the Use of intermediate layers of brass, bronze or zinc to bind and thereby inter alia the Eliminate costly quality monitoring problems associated with the use of such metal coatings.

It is also an object of the present invention to bond rubber to ferrous metals, particularly steel bead wires and strands for use in tires, belts and hoses reinforced with steel, using as adhesives rubbery copolymers and interpolymers of conjugated dienes and heterocyclic nitrogen bases without the previously used intermediate layers of brass, bronze or Zinc used on the wire or strand surfaces

It is also an object of the invention to provide a bond between steel wires or strands and the surrounding rubber that is to a large extent maintains its adhesive strength at the elevated temperatures often associated with the use of, among other things, the the tires and belts listed above.

It has now been found that when high purity, finely divided silicon dioxide to form rubbery interpolymers of conjugated dienes and heterocyclic ones Nitrogen bases and especially interpolymers of conjugated dienes and vinyl pyridines are added and these compositions are used to bond compounded natural and synthetic rubbers to ferrous substrates, such as B. iron or steel, the adhesive strength is greatly improved, especially at elevated temperatures It has also been found that when the rubber feedstock contains a cobalt compound is mixed, the adhesion is promoted in a surprising manner. As can be seen from a consideration of the Surprisingly, other conventional reinforcing fillers, such as carbon black, do not have any such influence on adhesive strength when added to these interpolymers. Furthermore is Silicon dioxide is effective in both aqueous and organic solvent-based adhesive systems, while carbon black is completely ineffective regardless of the dispersion medium.

As the prior art shows that both carbon black and silica are used to reinforce conjugated diene / heterocyclic nitrogen base interpolymers are effective, the present must Invention may be based on some other phenomena which are not at present fully understood.

The invention relates to a laminate in which rubber is bonded to an iron-containing metal substrate with an adhesive layer, the laminate being characterized in that the adhesive is an interpolymer with about 40 to 99% by weight of a conjugated diene, about 1 to 20% Is weight percent of a heterocyclic nitrogen base and 0 to about 40 weight percent of at least one additional mischpolymeri sbaren monomer, and the adhesive contains about 5 to 180 parts of a high purity silica filler per 100 parts of the interpolymer on an anhydrous weight basis. Preferably the interpolymer contains from 5 to 15 percent by weight of the heterocyclic nitrogen base.

The composition of the copolymers can be varied widely within these limits, without affecting the excellent thermal bond strengths achieved by the present invention

will. In practice, as a result of the cost of au B, vinyl pyridines copolymers with a relative small content of copolymerizable heterocyclic Nitrogen base preferred; levels as low as 1% have been found to be effective.

These interpolymers can be made by any method known in the art is e.g. B. by heat, solution, suspension, mass and emulsion polymerisation, the mixed polymerisation can be radical or anionic, act irregular, block or stereospecific polymerization. The preferred method is that Emulsion polymerization.

The conjugated dienes which can be used according to the invention are preferably those with a total of 4 to 8 carbon atoms per molecule, especially those with 4 to 6 carbon atoms each Molecule. These compounds include hydrocarbons such as 1,3-butadiene, isoprene, piperylene, methylpentadiene, 23-dimethyl-1,3-butadiene, 23-diethyI-13-but & diene. Halogenated hydrocarbons such as haloprene, e.g. B. chloroprene and methylchloroprene, u :: d lower alkoxy-substituted Hydrocarbons such as methoxy and ethoxy derivatives of the conjugated ones listed above Serve such as 2-methoxybutadiene and 3-ethoxy-1,3-buladiene.

In the case of polymerizable heterocyclic nitrogen bases, which can be used according to the invention are those of the pyridine, quinoline and Isoquinoline series which are copolymerizable with a conjugated diene and which are only one

CH ₂ = C - substituents
and preferably the

CH ₂ = C-R group

where R is either a hydrogen atom or a methyl group. That means that the substituent either a vinyl or an alpha methyl vinyl group (Isopropenyl group). Of these compounds, the pyridine derivatives are preferred. The most diverse substituted derivatives can also be used, but the total number of carbon atoms should be used the groups substituting the nucleus, e.g. B. the alkyl groups, not be greater than 15, as the The rate of polymerization decreases somewhat as the size of the alkyl groups increases. Connections where the Alkyl substituents are methyl and / or ethyl groups are commercially available and are according to the invention preferred.

These preferred heterocyclic nitrogen bases have the following formulas:

R R

ίο where R is a residue from the hydrogen atoms, · Alkyl radicals, vinyl radicals, alpha-methylvinyl radicals, alkoxy radicals, Halogen atoms, hydroxy groups, cyano groups, aryloxy groups and aryl residues and combinations of these residues, such as haloalkyl residues, alkylaryl residues, hydroxyalkyl residues, Alkoxyalkyl radicals, cyanoalkyl radicals, haloaryl radicals, Alkoxyaryl radicals, cyanoaryl radicals and hydroxyaryl radicals, formed group is selected and only one of these residues

and preferably a vinyl or alpha-methyl vinyl radical and the total number of carbon atoms in the groups substituting the nucleus is not greater than 15.

It turned out to be the preferred compounds are those in which the groups R, apart from the vinyl or alpha-methylvinyl groups, Are hydrogen atoms or alkyl groups of 1 to 4 carbon atoms. Examples of such especially preferred compounds are

2-vinylpyridine, 2-vinyl-5-ethylpyridine,
2-methyl-5-vinylpyridine, 4-vinylpyridine,
23.4-trimethyl-5-vinyIpyridine,
3,4j5,6-tetramethyl-2-vinylpyridine,
3-ethyl-5-vinyipyridine,

2,6-diethyl-4-vinylpyridine,
2-isopropyl-4-nonyI-5-vinylpyridine,
2-methyl-5-undecyl-3-vinylpyridine,
2-DecyI-5- (alpha-methylvinyI) -pyridine,
2-vinyl-3-methyl-5-ethylpyridine,
2-methoxy-4-chloro-6-vinylpyridine,
3-vinyl-5-ethoxypyridine,
2-vinyl-4,5-dibromopyridine,
2-vinyl-4-chloro-5-bromopyridine,
2- (alpha-methylvinyl) -4-hydroxy-6-cyanopyridine,

2-vinyl-4-phenoxy-5-methylpyridine,
2-cyano-5- (alpha-methylvinyI) -pyridine,
S-vinyl-S-phenylpyridine,

so 2- (para-methylphenyl) -3-vinyl-4-methylpyridine.
3-vinyl-5- (hydroxyphenyl) pyridine,
1 ^^^ 1

S-vinyl-ej-di-n-propylquinoline,

2-methyl-4-nonyl-6-vinylquinoline,

4- (alpha-methylvinyl) -8-dodecylchir.olin,

3-vinylisoquinoline, 1,6-dimethyl 3-vinylisoquinoline

quinoline,

2-vinyl-4-benzylquinoline,

3-vinyl-5-chloroethylquinoline,

S-vinyl-S.e-dichloroisoquinoline,

2-vinyl-6-ethoxy-7-methylquinoline and

S-vinyl-e-hydroxymethylisoquinoline.
Interpolymers can be prepared from a mixture of two of the conjugated dienes listed above and a heterocyclic nitrogen base or from a conjugated diene and two different heterocyclic nitrogen bases. However, it is more common. InterDolvmere from a single Konineier-

ten diene, a single heterocyclic nitrogen base and to prepare at least one other polymerizable monomer. About these monomers preferably include organic compounds that contain at least one polymerizable ethylenic group from the

ι ι

-C = C -type

contain. These compounds are known in the art and include, for example, alkenes. Alkadienes and Sn roles, such as ethylene. Propylene. 1 -butylene. 2-butylene.

Isobutylene. I-odes. 1.4-pentadiene.

l.b-llevaclien. 1.7-octaclinn. Vinyl toluene.

Viny KyIoI. Ethyl vinyl benzene. Vinyl cumene.

ι. ^ - CycloocU'.dien. Cvc! Ohc \ cn. Cvclooctcn.

Bcnzyhty rol. Chlorostyrene. Bromostyrene.

Fltiorstyrene, trifluoromethylstyrene. (odstyrene, Cyanostyrene. Nitrostyrene.

N.N-dimethylaniinostyrene.

J-phenyl-3-biiten-1 oil. p-methylstyrene.

Vinyl na ph thalin. Acetoxy styrene.

Methyl! -4-vinyl benzoate. Phenoxystyrene and p-vinylphenyl ethyl ether:

Acrylic and substituted acrylic monomers.

like methyl acrylate. Ethyl acrylate.

Methyl methacrylate. Methacrylic anhydride.

Acrylic anhydride. Cyclohexyl methacrylate.

Benzyl methacrylate, Latin isopropyl methacrylate.

Octylniethacry lat. Acrylonitrile.

Methacrylonitrile. Methyl alpha chloroacrylate.

Ethyl-alpha-ethoxyacrylai.

Methyl alpha acetamidocrylate.

Butyl acrylate. Ethyl alpha cyanoacrylate.

2-ethylhexyl acrylate. Phenyl acrylate.

Phenylinethacryl.it. alpha-Chloracry Iniin I.

Ethyl methacrylate. Buty imethacrylate.

Methylate acrylate. Methacrylamide.

N.N-Di me thy! Acrylamide. N.N-Dibenzy! Acrylamide.

N-Butylacrylamide and Meihacrylyltormamid:

/. B. such as vinyl ester. Vinyl halides.

Viny lather and vinyl ketones.

like vinyl acetate. Vinyl chloroacetate.

Vinyl butyrate. Isopropenyl acetate.

\ inylfonniat. Vinyl acrylate. Vinyl methacrylate.

Vinyl methoxy acetate. Vinyl benzoate.

Vinyl iodide. Vinyl chloride. Vinyl bromide.

Vinyl fluoride. Vinylidene chloride.

Vinylidencyanide. Viny lid bromide.

1 -Chlor-1 -fluoroethylene. Vinylidene fluoride.

Vinyl methyl ether. Vinyl ethyl ether.

Vinyl propyl ether. Vinyl butyl ether.

VinyI-2-e'.hylhexyl ether. Vinyl phenyl ether.

Vinyl 2-methoxyethyl ether.

Vinyl 2-butoxyethyl ether.

ß.'i-Dihydro-l ^ -pyran.

2-butoxy-2'-vinyl oxide diethyl ether.

Vinyl 2-ethyl mercapto ethyl ether.

Vinyl methyl ketone, vinyl ethyl ketone.

Vinylpheny! Ketone. Vinyl ethyl sulfide.

Vinyl ethyl sulfone. N-vinyloxazolidinone.

N-methyl-N-vinylacetamide.

N-Viny! Pyrrolidone. Vinyiimidazoi.

Divinyl sulfide. Divinyl sulfoxide.

Divinyl sulfone. Sodium viny Isulfonai.

Methylvinvi? :! fonat and N-Vinyipyrroi:

Dimethyl fumarate. Vinyl isocyanate. Tetrafluoroethylene. Chlorine rifluorä thy len. Nitroethylene. Viny Ifuran. Vinyl carbazole and vinyl acetylene.

According to one embodiment of the invention, they are particularly preferred

Styrene. 3-phenyl-3-butene-1 oil. p-chlorostyrene,

p-methoxystyrene, alpha-methylstyrene.
in vinyl naphthalene. Methyl acrylate. Ethyl acrylate.

Methyl met ha cry Ia i. Ethyl methacrylate.
Butyl methacrylate, lat. Methyl methacrylate.
Acrylonitrile. Methacrylonitrile. Methacrylamide.
Methyl isopropyl ketone. Methyl vinyl ketone.
Methyl vinyl ether. Vinyl acetate. Vinyl chloride.
Vinyl chloride. Vinyl furan. Vinyl carbazole
and vinyl acetylene.

Πίρ Fimlctjitn ftp «. /in.:il/lirhpn iVtrtnitniprpn k ^ inn

consist only in the cost at low or does not affect the bond strength and other properties of the adhesive, or it can to modify a specific property of the adhesive. An example of this is the incorporation of monomers such as nitriles. Esters or amides that increase the polarity of the adhesive would inn it with rubbers of higher polarity to make tolerable. Such modifications can easily be made by those skilled in the art are within the scope of the present invention.

To high-purity, finely divided silicon dioxides, which for Useful in practicing the invention include all finely divided silicas having a SiO ^ content of 95 "/ ο or more, iiif an anhydrous weight basis.

These finely divided silicon dioxides can be used as a dry powder to form a solution of the interpolymer in a suitable solvent, e.g. B. THF or toluene, may be added if an adhesive is on A solvent base is desired, or slurried in water and made to an aqueous base Mixed polymer latex can be added.

Aqueous silica sols can also be used, and they are often used in the practice of the invention because of their easy dispersibility and stability in the conjugated diene / vinyl pyridine copolymer latices preferred.

The silica particle size (regardless of whether the silica is added as a powder or as a stable sol dispersed in water) generally ranges from 3 to 60 µm. although silica with smaller or larger particles ". . ■■ sizes can also be used.

The effective range of silica added to increase adhesive strength is 5 to 180 parts of silica per 100 parts of interpolymer resin solids, and the preferred range is 20 to 100 parts per 100 parts of interpolymer resin solids.

When adding to the rubber compound to be bonded, compounds of cobalt with organic carboxylic acids are generally preferred, e.g. B. Linoleates. Stearates. Oleates. Acetates. Resinates and Naphthenates. however, inorganic acid salts can also be used, e.g. B. hydrochloric acid and nitric acid. The addition is carried out using conventional processing methods on a mill or in a mixer.

The amounts of the cobalt compounds used in the rubber are chosen so that about 0.025 to about OK parts by weight and preferably

0.05 to 0.5 part by weight cobalt compound (calculated as metal) per 100 parts of the respective rubber polymer.

In addition to silicon dioxide, other additives can also be incorporated into the interpolymer adhesives before they are applied to the interpolymer adhesives before they are applied to the metal surface. There can be one or more other fillers, plasticizers. Hardeners and antioxidants can be added to modify certain characteristics of the interpolymer adhesives, such as tack, hardness, oxidation resistance and cure rate. It goes without saying that such modifications are within the scope of the invention, provided that silicon dioxide and conjugated diene / heterocyclic nitrogen base-in-polymer are also included.

/ .. A ~ " 1-

, ι..ινΐ-i

are. Examples of suitable vulcanizing agents are sulfur. Sulfur releasing agents such as thiuram disulfide, thiuram polysulfide or an alkylphenol sulfide or a peroxide such as dicumylproxide or dibenzoyl peroxide. When peroxide compounds are used as the vulcanizing agent, the accelerator and accelerator activator are often not required. Vulcanization accelerators that can be used include dithiocarbamates, thiuram sulfides, and mercaptobenzothiazoles. Examples of specific compounds that are useful vulcanization accelerators are zinc diethyldithiociirbam.it. NN-dimethyl-S-iert-butylsulfenyldithiocarbamate. Teinimelhylthiuramdisulfid. 2.2 -Dibenzthiazyldisiilfide. lliityraldchydaniline. Mercaptobenzothiazole. N-Oxydiethylcn-2-benzthioazolesulfenamide and N-Cyclohexyl-2-benzthiaz () isulphoniamide. On materials that are used in compounding and act as re-accelerators. uchö ^rf ? ⁿ Mptnllnvirlp

Any interpolymers listed above include natural and synthetic Rubbers and their mixtures to a fairly high degree, in unsaturation, i.e. H. with a minimum of about 70 Mol - "/ ο pohmerized conjugated diene. Examples preferred synthetic rubbers are polybutadiene; Polyisoprene: mixed polymers of butadiene with styrene or acrylonitrile; and polychloroprene.

According to a preferred embodiment, the laminate according to the invention contains a mixed polymer from butadiene and 2-vinylpyridine. a terpolymer Sr / oil. Butadiene and 2-vinyl pyridine, a terpolymer from 2-vinylpyridine. Isoprene and styrene, a terpolymer from 4-vinylpyridine. Butadiene and styrene or a terpolymer of 2-methyl-5-vinylpyridine. Butadiene and styrene as interpolymers.

These rubbers are expediently filled with one or more fillers. Plasticizers, Hardening agents and antioxidants compounded. The total amount of filler used is generally in the range of 25 to 150 parts by weight per 100 parts by weight of rubber. to Fillers include the various silicas. Clays. Calcium carbonate. Calcium silicate, titanium dioxide and soot. In the manufacture of the compounded feedstock used in the manufacture of tires are used, preferably at least a portion of the filler consists of carbon black. The plasticizers are generally used in amounts ranging from 1.0 to 100 parts by weight of plasticizer per 100 parts by weight Rubber ends. The amount of plasticizer that is actually used depends on the one desired softening effect. Examples of suitable plasticizers include aromatic extract oils. Petroleum plasticizers including asphaltenes, saturated and unsaturated hydrocarbons and nitrogen bases, coal tar products. Coumarone / indene resins and esters such as dibutyl phihalate and tricresyl phosphate. Mixtures of these plasticizers can of course be used. The hardeners used in the hardening system contain a vulcanizing agent and generally one or more vulcanizing accelerators together with one or more accelerator activators. The amount of these materials that are in the system are generally used in the following ranges: 0.5 to 5.0 parts by weight of vulcanizing mineral. 0.5 to 3.0 parts by weight accelerator. 0.5 to 20.0 parts by weight accelerator activator, all of which 3, based on 100 parts by weight of rubber, such as zinc oxide. Magnesium oxide and black lead, which in Compound with acidic materials can be used, for example fatty acids such as stearic acid. Oleic acid and myristic acid c. Rosin acids can also be used as the acidic material. That Antioxidant is generally in the compounding formulation in an amount in the range of for example 0.5 to 10 parts by weight per 100 parts by weight Rubber before. Examples of suitable antioxidants include phenyl - ^ - naphthylamine. Di-tert-butyl hydroquinone. 2,2,4-Trimethyl-6-phenyl-1,2-dihydroquinoline, a physical mixture of one complex diarylamine / ketone reaction product and N.N'-diphenyl-p-phenylenediamine. It goes without saying that the invention is not limited to any particular compounding approach. since the invention is in a broad scope on the use of silica-containing conjugated diene / heterocyclic Nitrogen base interpolymer adhesives for bonding a wide variety of compounded rubber compositions is applicable to iron and steel surfaces.

The adhesives according to the invention show advantageous adhesion to iron-containing surfaces (steel and iron), which have been degreased and freed from weakly adhering oxide coatings by acid etching.

The adhesive is applied to the ferrous surface by any conventional method, for example by diving. Brushing or spraying, and then briefly at room temperature or using dried by heat to remove solvents and / or water. The compounded Rubber feed is then brought into contact with the adhesive surface and the whole is vulcanized under heat and pressure to complete the binding process.

The invention also relates to a method for producing laminates from rubber and iron-containing metal substrates, in which an adhesive is applied to the metal substrate and the rubber is brought into contact therewith and bonded under heat and pressure, which is characterized. that as adhesive an interpolymer with about 40 to 99 wt .-% of a conjugated diene, about 1 ⁰ Zo of a heterocyclic nitrogen base and 0 to about 40 wt .-% to 20 wt uses at least one additional copolymerizable monomers, wherein the adhesive contains about 5 to 180 parts of a high purity silica filler per 100 parts of the interpolymer.

According to preferred embodiments of the invention Method is used as described above as preferred or particularly preferred, types of rubber, conjugated dienes, heterocyclic rubbers mentioned for the laminate according to the invention Nitrogen bases, additional monomers, mixed and terpolymers, whereby one is used for the laminate can take over the stated quantities.

The invention is explained in more detail below by means of examples.

Example I.

Rs steel wire rods (el = 0.96 mm) were degreased with a solvent and cleaned by immersing them briefly in hot, concentrated hydrochloric acid, rinsing them with water and then immersing them in an adhesive composition consisting of a mixture of (I) a butadiene / 2-vinylpyridine mixed polymer latex (composition 90:10, 12% resin solidsc) and (2) an aqueous dispersion of silicon dioxide (20% solids; type Λ, particle size 3 to 4 μm) consisted. The coated wires were dried at 170 ° C. for 60 seconds and thereafter vulcanized in an H-test mold at 135 ° C. for 60 minutes under a pressure of 60 kg / cm with the following compounded rubber composition. The ratio of silica to interpolymer on a dry weight basis in the adhesive was 30/100.

Composition A 100 Natural rubber No. I. 50 (smoked flat material; 8th RuBA 1 zinc oxide 3 Stearic acid I. Pine tar I. sulfur 1 Phenyl-j3-naphthylamine 2-mercaptobenzothiazole

Temperature tested (test rate = 200 mm / min). The adhesive strength was 30 kg / 2 cm.

The Η-test used in this and the following examples is carried out in such a way that that the coated wire is vulcanized in the center of two blocks of rubber, one each Have a width and a length of 2 cm and a thickness of 1 cm. The two blocks are through one Distance separated by 2.5 cm and the wire is 2 cm deep

ίο embedded in each block, being the total wire length 6.5 cm. The blocks «ground at a speed of 2 cm / min parallel to the wire axis auscinancler withdrawn. until the wire is torn from a block.

15th

, 5

The samples were aged 24 hours after vulcanization and then heated on and off the surface Comparative example 1

Example I was repeated except that the silica in the adhesive was omitted became. The adhesive strength at 120 "C was 5 kg / 2 cm.

Example 2

Steel bead wires (el = 0.96 mm) were degreased with a solvent and cleaned as in Example I,

₂ r _t then dipped in an adhesive composition of a mixture of (I) a butadiene / 2-vinylpyridine copolymer latex (12% resin solids) and (2) an aqueous dispersion of silicon dioxide (20% solids; type A). The ratio of silicon

jo oxids to the interpolymer was on a dry weight basis in adhesive 48/100.

The same series of tests was repeated for comparison, using adhesives without silicon dioxide was used.

The coated wires were seconds dried .inter a pressure of 60 kg / cm ² with the compounded rubber composition A at 170 ⁰ C and then 30 dried in an H-shape test at 135 ⁰ C for 60 min.

The results of the Η test for the composition of the mixed polymers are in accordance with the following standard remove.

Tabel

comparison

comparison

Butadiene (wt%) 100 2-vinylpyridine (wt%) 0 H test results (kg / 2 cm) at 120 C with SiO ₂ 9 without SiOi 10

99 95 90 85 80 70 1 5 10 15th 20th 30th 14th 30th 37 38 12th 6th 8th 8th 6th 8th 8th 5

Comparative example 2

To further explain the peculiarity of the silicon dioxide / butadiene / vinyl pyridine mixed polymer combination, tests were carried out to apply rubber composition A to steel using a natural rubber latex and a styrene / butadiene 65

Latex with and without added silica to bind (30 parts SiO _2/100 parts of latex solids).
SBR latex: composition ratio styrene / butaciien 25/75, i2% solids:
Natural rubber latex: 12% solids.

The results can be found in the following table.

Table 2

Latex composition

SBR SBR + SiO ₂ natural natural

Type A rubber rubber

+ SiO ₂ type A

H test results
kg / 2 cm at 120 ° C

<5

Example 3

Steel bead wires (d = 0.96 mm) were degreased with a solvent and cleaned as in Example 1 and then converted into an adhesive composition of a mixture of (1) a butadiene / 2-vinylpyridine mixed polymer latex (composition 90:10, 12%

Table J-

<5

<5

<5

and (?) finrr wä «prigpti dispersion of silicon dioxide (20% solids; type A) immersed. The coated wires were at 170 ⁰ C 6Or, dried and then in a H-shape test at 135 ° C for 60 minutes of Example I. vulcanized under a pressure of 60 kg / cm ² with the compounded rubber composition A. The adhesive strength was determined, the silicon dioxide content in the adhesive

Comparison I.

Parts SiO _2/100 parts of copolymer:
H test results (kg / 2 cm) at 120 ° C

0 5 30th 60 80 120 5 10 30th 33 38 38

Example 4

Example 3 (4) was repeated with the exception that butadiene / 2-M ethy 1-5-vinylpyridine copolymer latex (Composition 90:10. 12% resin solids) instead of butadiene / 2-vinylpyridine copolymer latex >; was used.

Table 4

Comparison example

Parts SiO _2/100 parts

H test results (kg / 2 cm)
at 120 C

80

29

Example 5

Steel bead wires (d = 0.96 mm) were removed with a solvent and cleaned as in Example 1 and then converted into a adhesive composition made from a mixture of (1) a butadicn / 2-vinylpyridine mixed polymer latex (composition 90:10, 12% resin solids) and (2) immersed in an aqueous dispersion of silica (20% solids: Type A). The coated wires were ^{dried at 170 ° C.} for 60 seconds and then vulcanized in an H test mold at 155 ° C. under a pressure of 60 kg / cnv with the following compounded synthetic rubber compositions.

Table 5

Butadiene rubber

Styrene / butadiene rubber

Polyisoprene rubber

RuS B

Soot C

SiO ₂ type B

zinc oxide

Stearic acid

Pine tar

Phenyl-jS-naphthylamine

Cobalt naphthenate

n-Oxydiäthylenbenzthiazyl-2-sulfenamid

Dibenzothiazyl disulfide

Cyclohexylbenzthiazylsulfenamide

sulfur

Vulcanization (min at 155 C) 100

70

10

4th
1

0.5
0.5
3.5
30th

100

28
42

1.3

100 70

5 2

0.8

1.5 20

continuation

H test results (Jcg / 2 cm) at 120 ^c C H test results, comparison (without silicon dioxide in the adhesive)

52
29

35
7th

Carbon black A, B and C are common types of filler with different origins. Carbon black A is highly abrasion resistant Furnace carbon. Soot B is soot from the middle process channel.

Example 6

Steel bead wires (d = 036 mm) were degreased with a solvent and cleaned as in Example 1, then converted into an adhesive composition of a mixture of (1) a butadiene / 2-vinylpyridine mixed polymer latex (composition 90: 10.12% resin solids) and (2) an aqueous dispersion of silicon dioxide (20% solids; type A, particle size 3 to 4 μιπ) immersed. The coated wires were dried at 170 ⁰ C 60s, then in eiiter H-Tesiform at 135 ⁰ C for 60 min vulcanized under a pressure of 60 kg / cm ² with the following compounded rubber composition. The ratio of silica to interpolymer on a dry weight basis in the adhesive was 30/100.

Composition B 100 Natural rubber No. 1 50 (smoked flat material) 8th Soot A 1 zinc oxide 3 Stearic acid 5 Pine tar 1 sulfur Phenyl-0-naphthylamine Table 6

10

is

25th

30th

35

Cobalt naphthenate 2.5

2-mercaptobenzthiazoI 1.5

The samples were aged 24 hours after vulcanization, after which half of the samples were at Tested room temperature and heated the other half to 120 ° C and tested at that temperature (Test rate = 200 mm / min).

The adhesive strengths were 48 kg / 2 cm at 120 ° C and 67 kg / 2 cm at room temperature.

Example 7

Steel bead wires (d = 0.96 mm) were degreased with a solvent and cleaned as in Example 1, then converted into an adhesive composition of a mixture of (1) a butadiene / 2-vinylpyridine mixed polymer latex (12% resin solids) and (2) An aqueous dispersion of silica (20% solids; Type A) dipped. The ratio of silica to interpolymer on a dry weight basis in the adhesive was 48/100. The coated wires were seconds vulcanized at 170 ⁰ C and then 30 dried in an H-shape test at 135 ° C for 60 minutes under a pressure of 60 kg / cm ^2. The results of the Η test of the various compositions of the copolymers are given in the table below. The same series of tests were repeated with a compounded rubber whose composition was the same except for. that no cobalt naphthenate had been added.

comparison

comparison

Butadiene (wt%)

2-vinylpyridine (wt%)

H test results (kg / 2 cm)
at 120 C

the same (without cobalt naphthenate)

100 99 95 90 85 80 70 0 1 5 10 15th 20th 30th 18th 27 39 47 48 43 13th

14th

30 37

12th

Example 8

Example 7 (3) was repeated with the exception that butadiene ^ -Methyl-S-vinylpyridine copolymer latex (Composition 90:10. 12% resin solids) instead of butadiene / 2-vinylpyridine mixed polymer latex was used.

Table 7 example

Rutadiene (ow%) 90

2-methyl-5-vinylpyridine (wt%) 10

H test result (kg / 2 cm) at 120 C 44

H test result without cobalt naphthenate 29

Example 9

Steel bead wires (d = 0.96 mm) were degreased with a solvent and cleaned as in Example I and then immersed in one of the following adhesive compositions.

Comparison: Buiadien / 2-vinyl |> yridine mixed polymer

(Composition 90: 10. 3 wt .-% resin solids in tetrahydrofuran):

Comparison: A butadiene / 2-vinylpyridine mixed polymer was used (Composition 90:10) ground in tetrahydrofuran (THF) and carbon black B in a ball mill in tetrahydrofuran. The final composition comprised 3 wt% polymer and 0.9 wt% carbon black B. in TH P. "

It was a butadiene / 2-vinylpyridine mixed polyno-

030 231/249

res (composition 90:10) in tetrahydrofuran and silicon dioxide (type A) ground in a ball mill in THF. The final composition was 3 wt% polymer and 0.9 wt% SiO ₂ in THF.
In each trial the coated wires were

Table 8

at 170 ⁰ C for 60 seconds and then dried in an H-shape test at 135 ° C for 60 minutes then dried under a pressure of 60 kg / cm ² with the compounded rubber composition B, it comprises the following results were obtained.

attempt

comparison

comparison

attempt

Interpolymer carbon black B

Silica type A - H test result (kg / 2 cm) at 120 ° C

100 100 30th - - 30th 21 40

Example 10

Steel bead wires (d = 036 mm) were degreased with a solvent and cleaned as in Example 1 and then converted into an adhesive composition of a mixture of (1) a butadiene / 2-vinylpyridine mixed polymer latex (composition 90:10, 12% resin solids) and (2) immersed in an aqueous dispersion of silica (20% solids, Type A)

Table 9

The coated wires were seconds vulcanized at 170 ⁰ C and then 60 dried in an H-shape test at 135 ° C for 60 minutes under a pressure of 60 kg / cm ² with the compounded rubber composition B

The adhesive strengths were determined, the Silica content in the adhesive was varied. The following results were obtained.

attempt

Comparison 1

10 11

Parts SiO ₂ /

100 parts of mixed polymer 0

H test result

(kg / 2 cm) at 120 C IO

5 12 24 30 36 42 48 60 80 100 120 150 26 28 43 45 48 50 54 47 49 54 46 40

Example 11

40

Example 6 was repeated with rubber composition B, the filler being as follows was replaced. In each case, the ratio of filler to polymer at the constant value became 30/100 held.

1) Watery SiO ₂ sol. Type F, pH 9.5-10.0, particle size 10-20 μm

2) Aqueous SiO ₂ sol. Type G. pH 3.0-4.0. Particle size 10-20 μπι ίο

3) SiO ₂ type B, particle size 22 μm.

4) SiO ₂ type C, particle size 4 μm.

5) SiO ₂ type D, particle size 3 μm.

6) SiO ₂ type E, particle size 16 μm. SiO ₂ content> 99.8%.

Comparison I)

Carbon black B: as milled with a ball mill

aqueous dispersion added.
Comparison 2)

Bentonite, particle size 53 μm.

Table 10

attempt

Comparison I Comparison 2

H test results
(kg / 2 cm) at 120 ° C

27

27

35

43

47

Example 12

FIs were beaded wires (d = 0.96 mm) degreased with a solvent and cleaned as in Example I, then in an adhesive sealant made of a mixture of (1) a butadiene / 2-vinylpyridine latex (composition 85: 15, 12 % Resin solids) and (2) an aqueous dispersion of silica (20% solids; Type A) dipped. The coated wires were C 60 cured at 170 "C for 60 seconds dried and then in a H-test form at 135 ⁰ minutes at a pressure of 60 kg / cm 'with the following compounded Katiischukzusammensetzungen. The ratio of the silica to the mixed polymer was on a dry weight basis in adhesive 30/100.

Tables

try

Compare J

Natural rubber No. 1
(smoked flat material)

Soot A

zinc oxide

Stearic acid

Pine tar

sulfur

Phenyh / S-naphthylamine

2-mercaptobenzothiazole

KobaJtnaphthenat

H test results (kg / 2 cm)

at 120 C

100

100

100

100

100

100

50 50 50 50 50 50 50 50 8th 8th 8th 8th 8th 8th 8th 8th 1 1 1 1 1 1 1 1 3 3 3 3 3 3 3 3 5 5 5 5 5 5 5 5 1 1 1 1 1 1 1 1 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 0.25 0.5 1.0 2.0 2.5 3.0 5.0 33 37 40 43 45 48 45 44

Example 13

Example 12 (5) was repeated with the exception that instead of 2.5 parts of cobalt naphthenate 2.5 parts of cobalt stearate were added.

The adhesive strength at 120 ° C. was 49 kg / 2 cm.

Example 14

Steel bead wires (d - 0.96 mm) were degreased with a solvent and then etched for 20 s at 55 ° C. in 36% hydrochloric acid, rinsed in water and incorporated into an adhesive composition of a mixture of (1) a styrene / butadiene -2-vinylpyridine terpolymer latex (composition I: 84: 15.12% resin solids) and (2) an aqueous dispersion of silicon dioxide (20% solids; type A, particle size 3 to 4μιη). The coated wires were seconds vulcanized at 120 ⁰ C and then 45 dried in an H-shape test at 135 ° C45 minutes under a pressure of 60 kg / cm ² with the following compounded rubber composition. The ratio of dfcs silica to terpolymer on a dry weight basis in the adhesive was 50/100.

25th

2-mercaptobenzothiazole

Pine tar

Phenyl-ji-naphthylamine

1.5
3

Rubber composition C 100 Natural rubber No. 1 50 (smoked flat material) 8th Soot A 1 zinc oxide 5 Stearic acid sulfur

The samples were aged for 24 h after vulcanization and then heated to 120 ⁰ C and tested at that temperature (test rate = 200 mm / min). The adhesive strength was 67 kg / 2 cm.

Comparative example 3

Example 14 was repeated except that no silica was contained in the adhesive. The adhesive strength at 120 ^° C. was 0.

Example 15

Steel bead wires were cleaned and etched as in Example 14 and then added to erne adhesive

Composition of a mixture of (1) a styrene / butadiene / 2-vinylpyridine terpolymer latex (different Composition, 12% resin solids) and (2) an aqueous dispersion of silica (20% solids; Type A) immersed. The ratio of the

Silica to terpolymer was 50/100 on a dry weight basis in the adhesive. The coated wires were dried at 120 ° C for 45 s and then in an H-Tectform at 135 ° C for 45 min under a pressure of 60 kg / cm ² with the compounded

Rubber Composition C vulcanized with 2.5 parts of cobalt naphthenate.

The results of the Η test with different compositions of the terpolymers are in the reproduced in the following table.

Table 12

comparison 1 1 2 I. 3 1 4th 1 5 1 6th 1 7th 1 S. 5 9 10 11th 12th Styrene (wt%) I. 98 94 84 79 74 69 54 80 15th 35 45 15th Butadiene (wt%) 99 I. 5 15th 20th 25th 30th 45 15th 70 50 40 60 2-vinylpyridine (wt%) - 15th 15th 15th 25th Il test results 46 64 70 65 61 54 39 71 (kg / 2 cm) at 120 ° C 11th 56 51 51 49

21 22

Example 16

Example 1 was repeated with the following terpolymer composition changes. Table 13

12 3 4

Butadiene

Isoprene

Styrene

Methyl methacrylate

Acrylonitrile

2-vinyl pyridine

4-vinyl pyridine

- 80 80 74

- 80 - -

5 5 - 16

- - - 5 15 - 15 -

- - 15 -

2-methyl-5-vinylpyridine - - - - io H test results 36 24 38 33 36

(kg / 2 cm) xiei 120 C

Comparative example 4

To further explain the peculiarity of the combination of silicon dioxide with the terpolymers, containing butadiene and vinyl pyridine have been attempted to bond the rubber composition of Example 14 on steel using a natural rubber latex and a styrene / butadiene Lalex

Table 14

with and without added silica made (50 parts SiO ₂ / l00Teile latex solids).

SBR latex: styrene / butadiene composition ratio = 25 / 75.12% solids;
Natural rubber latex: 12% solids.

30th

The following results were obtained.

Latex composition

SBR

SBR + SiO ₂

Natural rubber

Natural rubber + SiO ₂

H test results (kg / 2 cm) at 120 C <5

<5

<5

<5

Example 17

Steel bead wires were cleaned and etched as in Example 14 and then converted into an adhesive composition of a mixture of (1) a styrene / butadiene / 2-vinylpyridine terpolymer (composition 1: 84: 15.2% resin solids) and (2) a 20 % aqueous dispersion of silicon dioxide (type A) dipped. The coated wires were dried at 120 ° C. for 45 seconds and then in an H-test mold at 135 ° C. for 45 minutes under a pressure of 60 kg / cm ² with the compounded Rubber Composition C vulcanized. The bond strength was determined as a function of the silicon dioxide content in the adhesive.

Table 15

comparison

IO II

Parts SiO _2/0 5

100 parts of terpolymer

H test results (kg / 2 cm) 0 28

at 120 C

Example 18

Steel bead wires were cleaned and etched as in Example 14 and then into one of the following Dipped adhesive compositions.

Comparison 1:

Styrene / butiidiene / 2-vinylpyridine terpolymer (Zu-20 30 40 50 70 90 120 150 180
57 58 61 73 72 62 61 56 49

composition 15:70:15, 5% by weight resin strength

substances in tetrahydrofuran).
Comparison 2:

It became a styrene / butadiene / 2-vinylpyridine terpolymer ^ Composition 15:70:15) ir tetrahydrofuran and carbon black B ground in tetrahydrofuran in a ball mill. The final composition comprised 3.33 wt% polymer and 1.67 wt% o / o carbon black in THF.

Attempt:

It became a styrene / butadine / 2-vinylpyridine terpolymer (Composition 15:70:15) in tetrahydrofuran and silicon dioxide (type Λ) in one Ball mill ground in tetrahydrofuran. the

Table 16

The final composition was 3.33 wt% polymer and 1.67 wt% silica in THF.
In each test, the coated bead wires were dried at 120.degree. C. for 45 seconds and then vulcanized in an H test mold at 135.degree. C. for 45 minutes under a pressure of 60 kg / cm - as in Example 14.

attempt

Comparison 1 Comparison 2 attempt ι no 100 100 50 - - - 50 18th 23 48

Terpolymers
Soot B
SiO _:

II test results (kg / 2 cm)
hpi no

Example 19

FIs were made of steel bead wires as in Example 14 cleaned and etched and then put into an adhesive composition from a mixture of (1) a steel / butadiene / 2-vinyl-din-polymer latex (composition 5:80:15. 12% resin solids) and (2) one of the following fillers (20% aqueous Dispersions).

The coated wires were dried at 120 ° C. for 45 seconds and then in an H-test form as usual with the compounded rubber composition 2 (dried at i C. The results show that only in the Fillers with a high silica content effectively repel the bond strengths of these adhesives have been improved. The ratio of filler to Terpolymers was 50,100 on a dry weight basis.

^r> (1) SiO; Type B. Particle size 22 µm:

(2) SiO.-So 'type G. pH about 3.0 to 4.0. Particle size 10 to 2t) by:

Comparison No. 1 bentonite. Particle size 53 µm:
in comparison No. 2 carbon black B. (ground in a ball mill in water).

Table 17

attempt

filler

H-tester level ¹ ;
at 120 Γ

(ke / 2 cm)

1 SiO _:. Type B 37

2 SiO-SoI. 41 type G

Comparison 1 bentonite 13

Comparison 2 carbon black B 19

Example 20

Steel bead wires were used as in Example 14 cleaned and etched into an adhesive composition thereafter from a mixture of (1) a styrene / butadiene / 2-vinylpyridine terpolymer latex (composition 1: 84: 15. 12% resin solids) and (2) an aqueous dispersion of silica (20 ° ό Solids: Type A) immersed. The silica to terpolymer ratio was on a dry weight basis in adhesive 50/100. The coated wires were dried at 120 C for 45 seconds and thereafter in an H test form with the following compounded synthetic rubber compositions vulcanized to give the following results.

Table 18

Polybutadiene

Polyisoprene

Styrene / butadiene rubber (25/75)

Soot C

Soot B

Silicon dioxide

100

70

100

50

100
35

35

Continued / uni!

zinc oxide

Stearic acid Pine tar

sulfur

2.2'-dithiobisbenzihiazole

N-Cyclohexyl-2-benzthiazole-sulfenamide

N-oxydiethylene-2-ben / thiazolesulfenamide

PhenyN / f-naphthylamine

Vulcanization conditions, time (min) / temp.

II test results (kg / 2 cm) at 120 ° C

II test results (kg / 2 cm) at 120 ° C
(with SiO,)

Example 21

Steel wires (d = 0.96 mm) were degreased with a solvent. Etched for 20 seconds in concentrated hydrochloric acid at 55 C, rinsed in water and then in an adhesive composition of a mixture of (1) a .styrene / butadiene / 2-vinylpyridine terpolymer latex (composition 1:84:15. 12% W:> rz solids) and (2) an aqueous dispersion of silica (20% solids; Type A, particle size 3 to 4 µm). The coated wires were dried at 120 ° C for 45 seconds and then vulcanized in an II test mold at 135 ° C for 45 minutes under a pressure of 60 kg / cm with the following compounded rubber composition. The ratio of silica to terpolymer was on a dry weight basis in adhesive 50/100.

Composition D

Natural rubber No. 1

5 10 5 2 - 2 - 4th - 1.5 3.5 1.5 - 0.5 - 0.5 - I. - 1.3 - 1 - 40/155 C 20/145 t 50/145 C 3 5 4th

53

Soot Λ

zinc oxide

Stearic acid

Pine tar

sulfur

Phen \ l-, i-naphthylamine

Cobalt naphihenai

2-mcrcaptobenzothiazole

The samples were 24 h
aged and tested to a temperature of 120 ° C. (test rate = 200 mm / min). The adhesive strength was 70 kg / 2 cm.

50 8 1

3 5 1

2.5 1.5

heated after vulcanization and at this

Example 22

Example 21 was repeated except that ■ "· the following latices instead of the styrene / butadiene / 2- '; ynylpyridine latex were used.

Table 19

1 5 2 5 3 5 4th 5 Styrene (wt%) - - - - - 16 Methyl methacrylate (wt%) 80 - - - - Acrylonitrile (Gcw .- 'Ά) - - 80 5 - Butadiene (wt%) 15th 80 - 80 74 Isoprene (wt%) - 15th - - - 2-vinylpyridine (wt%) - - 15th 15th - 4-vinyl pyridine (wt%) 50 - - - - 2-methyl-5-vinylpyridine 44 45 - 10 H test results (kg / 2 cm) 65 46

at 120 C

Example 23

Steel bead wires were cleaned and etched as in Example 21 and then into one of the following Dipped glue compositions.

Comparison 1:

Styrene / butadiene / 2-vinylpyridine terpolymeres (composition 15:70:15. 5% by weight resin solids in tetrahydrofuran);
Comparison 2:

It became a styrene / butadiene / 2-vinyipyridine terpolymer (Composition 15:70:15) ground in tetrahydrofuran and carbon black B in a ball mill in tetrahydrofuran. The final composition

tongue showed 3.33% by weight
% By weight of carbon black in THF.

Polymer and 1.67 settlement like. " 3.33% by weight of polymer and
Wt% silica in THF.

Attempt:

It became a styrene / butadiene / 2-vinylpyridine terpolymer (Composition 15:70:15) in tetrahydrofuran and silica (type A) ground in THF in a ball mill. The end-together table 20th

In any case, the plated bead wires at 170 ° C were cured for 60 seconds and then dried in an H-shape test at 135 ⁰ C for 45 minutes under a pressure of 60 kg / cm ² with the compounded rubber composition D. The following results were obtained.

attempt comparison 12th C. comparison 18th attempt SO Tcrpolymeres 100 100 100 39 Soot B - 50 - Silicon dioxide - - H test results (kg / 2 cm) at 120

Example 24

Steel bead wires (d = 0.96 mm) were cleaned and etched as in Example 21 and then converted into an adhesive composition of a mixture of (I) a styrene / butadiene / 2-vinylpyridine terpolymer latex (composition I: 84:15 , 12% resin solids) and (2) an aqueous dispersion of silica

Table 21

(20% solids: Type A) immersed. The coated wires were seconds vulcanized at 12O ⁰ C and then 45 dried in an H-shape test at 135 ° C for 45 minutes under a pressure of 60 kg / cm 'with the compounded rubber composition D. The adhesive strength was determined, the silicon dioxide content in the adhesive being varied.

No. of attempt

comparison

10 11

Parts SiO, / 100 parts terpolymer 0 5 10 20 30 40 50 70 90 120 150 ~ 80

H-test results (kg / 2 cm) 35 54 58 59 65 69 74 69 58 62 58 46

at 120 C

BeisDie I 25

Steel bead wires (d = 0.96 mm) were cleaned and etched as in Example 21 and then converted into an adhesive composition of a mixture of (1) a styrofoam / butadiene / 2-vinylpyridine terpolymer latex (composition 5: 80: 15.12% Resin solids) and (2) an aqueous dispersion of the following fillers (20% solids). In each case the ratio of filler to polymer was kept at the constant value of 50/100. The coated wires were vulcanized at 120 s ⁰ C for 45 seconds and then dried in an H-shape test using the same compounded rubber under conditions as in Example 21st The results show that only the fillers with a high silica content could effectively improve the adhesive strengths of these adhesive terpolymers.

1. SiO \>, type B. Particle size 22 .um;

2. S1O2-SOI, type G, pH about 3.0 to 4.0, particle size about ^

Table 22

attempt

Comparison 1: bentonite, particle size 53 μm;
Comparison 2: Carbon black B (in a ball mill in water

ground);
Comparison 3: no filler.

filler

H test results (kg / 2 cm) at 120 ° C

Comparison 1

Comparison 2

Comparison 3

SiO ₂ , type B 50

SiO ₂ -SoI, type G 65

Bentonite 26

Carbon black B 33

nothing 30

Example 26

To further explain the peculiarity of the combination of silicon dioxide with terpolymers with containing butadiene and vinyl pyridine have been attempts to bond the rubber composition of Example 21 on steel using a natural rubber latex and a styrene / butadiene latex carried out with and without added silica (50 parts SiO 100 parts latex solids). The overdone Wires were dried at 170 ° C. for 1 minute and vulcanized in an H test mold as usual.

SBR latex: styrene / butadiene composition ratio = 25 / 75.12% solids;
Natural rubber latex ·. 12% solids.

26 10 29 Table 23 848 Adhesive H test result SBR latex (kg / 2 cm) SBR latex + SiO ₂ , type A at 120 C Natural rubber latex 5 Natural rubber latex + SiO ₂ , 13th Type a 12th Vinyl pyridine terpolymer laiex 10 (15:70:15) Vinyl pyridine terpolymer latex 28 + SiO ,, type A 50

30th

Example 27

In order to explain the maturity of these adhesives, also to be able to bind synthetic rubbers, was Example 21 repeated with the following modifications to the rubber to be bonded.

Table 24 I. 2 3 Rubber composition 100 _ _ Polybutadiene - 100 - Polyisoprene - - 100 SBR (styrene / butadiene 25/75) 70 - 35 Soot C - 50 - Soot B - - 35 Silicon dioxide (type B) 5 10 5 zinc oxide 2 - 2 Stearic acid - 4th - Pine tar 1.5 3, j i, 5 r · ·. et
OUII WCICl - 0.5 - 2,2'-dithiobisbenzothiazole - 0.5 - N-Cyclohexyl-2-benzothiazole sulfenamide 1 - 1.3 N-Oxydiethylen-2-Benzthiazolsulfen-
amide 1 - Phenyl-jS-naphthylamine 5 2.6 2.6 Cobalt naphthenate 40/155 ° 20/145 ° 50/145 ° Vulcanization conditions
Time (min) / temp. 27 10 12th H test results (kg / 2 cm) at 120 ° C
(without SiO ₂ ) 49 65 64 H test results (kg / 2 cm) at 120 ° C
(with SiO ₂ )

Example 28

It was iederholt with the exceptions "', that 2.5 parts of cobalt stearate was added in place of 2.5 parts of cobalt naphthenate Example 27 (5). The> Jtfestigkeit at 120 ⁰ C was 56 kg / cm 2.

Claims (5)

Claims; 1. Laminate, made of rubber with an adhesive layer on a ferrous metal substrate is bound, characterized in that the adhesive is an interpolymer with about 40 to 99% by weight of a conjugated diene; about 1 to 20% by weight of a heterocyclic diene Nitrogen base and 0 to about 40 weight percent of at least one additional copolymerizable monomer and the adhesive represents about 5 to 180 parts of a high purity silica filler each Contains 100 parts of the polymer on an anhydrous weight basis 2. Laminate according to claim 1, characterized by a mixed polymer of butadiene and 2-vinylpyridine, a terpolymer made from styrene, butadiene and 2-vinylpyridine, a terpolymer made from 2-vinyl pyridine, isoprene and styrene, a terpolymer from 4-vinylpyridine, butadiene and styrene or a terpolymer of 2-methyl-5-vinylpyridine, butadiene and styrene as an interpolymer. 3. Laminate according to claim 1 or 2, characterized by a rubber with a content of about 0.025 to about 1.0 part by weight of a cobalt compound (calculated as cobalt metal) per 100 parts Rubber. 4. Process for the production of laminates from rubber and ferrous metal substrates according to any one of the preceding claims, wherein an adhesive is applied to the metal substrate applies and brings the rubber into contact with it and connects under heat and pressure, thereby characterized in that the adhesive used is an interpolymer with about 40 to 99% by weight of one conjugated diene, about 1 to 20% by weight of a heterocyclic nitrogen base, and 0 to about 40 % By weight of at least one additional copolymerizable monomer used, the Adhesive Approx. 5 to 180 parts of a high purity silicon dioxide filler per 100 parts of the interpolymer contains. 5. The method according to claim 4, characterized in that that one is a copolymer of butadiene and 2-vinylpyridine, a terpolymer of styrene and Butadiene and 2-vinylpyridine, a terpolymer of 2-vinylpyridine, isoprene and styrene, a terpolymer from 4-vinylpyridine, butadiene and styrene or a Terpolymer of 2-methyl-5-vinylpyridine, butadiene and styrene used as interpolymers. 5. The method according to claim 4 or 5, characterized in that a rubber with a content of about 0.02 ¹ J to about 1.0 part by weight of a cobalt compound (calculated as cobalt metal) is used per 100 parts of rubber.