GB2435262A

GB2435262A - Reinforcing rubber articles

Info

Publication number: GB2435262A
Application number: GB0603062A
Authority: GB
Inventors: Rodney Peter Knowles
Original assignee: NGF Europe Ltd
Current assignee: NGF Europe Ltd
Priority date: 2006-02-16
Filing date: 2006-02-16
Publication date: 2007-08-22
Anticipated expiration: 2026-02-16
Also published as: WO2007093770A3; JP2009526924A; KR20090015886A; BRPI0708070B1; WO2007093770A2; GB0603062D0; US20100233422A1; CA2642203A1; CN101384648A; GB2435262B; JP5323959B2; JP5180102B2; BRPI0708070A2; JP2012149375A; WO2007093770B1; EP1984432B1; CN101384648B; EP1984432B8; EP1984432A2

Abstract

A method for forming rubber articles, containing reinforcing strands, by extrusion or moulding, involves coating the reinforcing strands with a coating latex and drying the latex such that it remains uncured until the article containing the coated reinforcing strands is moulded or extruded. Improved adhesion between rubber matrix and reinforcing strands is obtained, particularly for filled rubber and EPDM rubber. Preferred coating latices and coated reinforcing cords for use with the method are also disclosed, the coating comprising a metal oxide, a maleimide crosslinking agent, a nitroso-compound, and halogenated rubber.

Description

Method. Composition and Articles The invention relates to reinforced

rubber articles comprising reinforcing strands, particularly coatings for such strands and methods for forming rubber articles comprising coated reinforcing strands.

Background

Within the moulded rubber goods industry, certain applications benefit from the inclusion of reinforcement, either in the form of individual fibres or textiles, in the rubber matrix of the moulded or extruded rubber article. The latter in particular permit good dimensional control of the moulded goods so that anisotropic behaviour can be designed into the product to enhance performance in the field. One such example is in the production of rubber seals for doors and windows where the introduction of a high elastic modulus cord into the rubber matrix along the length of the seal will effectively restrict stretching during processing and installation. The latter in turn will ensure that any joints that are present in the finished system will be stable without a tendency to open up and cause leakage. As the dimensional control is effective chiefly along the length of the seal, the other beneficial properties ....* 20 such as flexibility of the seal body is unaffected -allowing the product to fully * serve its intended purpose. I..

In order for a reinforcing cord to function well, it should have adequate ** S performance in respect of temperature resistance (to allow processing), high elastic modulus (to resist rubber stretch) and adhesion to the matrix rubber (so that the final article can behave as a true composite).

Often, the reinforcing cords or fibres are of glass -as this has good temperature stability and high elastic modulus. Conventionally, the treatment applied to the reinforcement fibres to improve adhesion to the matrix rubber is a resorcinol formaldehyde latex system (RFL). This utilises an appropriate rubber latex or blend of rubber latices for compatibility with the type of rubber to be used as the matrix for the rubber article, and a resin system based on resorcinol formaldehyde which cures the latex within or on the reinforcement prior to its incorporation into the rubber article. This type of system has been employed for many years.

The following abbreviations are used throughout the description: EPDM -rubber prepared from ethylene-propylene-diene monomer; BIIR -brominated isobutene isoprene rubber, CR -chloroprene rubber, CSM - chlorosulphonated polyethylene rubber, H N BR -hydrogenated acrylonitrile-butadiene rubber, NBR -acrylonitrile-butadiene rubber, SBR -styrene butadiene rubber. * SSS

* : * In a conventional process for RFL coated reinforcement cords, the * reinforcement strands, typically glass fibre, are individually dipped into an RFL treatment so that the liquid can fully coat the strands. A typical RFL treatment * would comprise of latices used either singly or in combination from the following types: -Vinyl pyridine -SBR terpolymer, SBR, CR, NBR and polybutadiene, together with a curing system based on a resorcinol-formaldehyde resin.

After dipping, excess RFL is removed by a mechanical means so that a constant level of pick-up is obtained. This amount commonly ranges from around 12 to 17% of the total weight of the glass plus RFL coating (on a dry basis). The dipped strands are then oven heated to evaporate the water and complete the curing of the resin -latex system.

The cured strands may be twisted at typically 40 to 100 turns per metre length and wound on to a bobbin to give a package that can conveniently be used in the manufacture of rubber articles at a later stage.

While this approach is suitable for some products, in some fields it is becoming necessary to decrease the cost of finished components. A favoured route to this end is to reduce the level of (relatively) expensive synthetic rubber polymer within the rubber matrix and replace this with various fillers, such as carbon black, calcium carbonate and plasticizing oil. Whilst this may lower the overall cost of the rubber compound as a mixture of materials, it ..

may also increase the difficulty in obtaining adequate adhesion between the * reinforcing strands and the filled rubber matrix. With currently available S..

reinforcements, this means that a satisfactory finished product may be difficult : * to obtain when a highly filled rubber matrix is employed. This is particularly the * case for products where the matrix rubber comprises EPDM rubber.

With the conventional RFL system a partial solution to this problem has been found by application of a specific adhesive layer on to the outside of the reinforcing cord. While this may be acceptable for certain applications, it can lead to the need for additional process steps and process equipment, as well as additional coating material for the reinforcement cords.

Hence there is a need to provide a reinforcing cord with improved adhesion in particular to highly filled rubber compounds -for example EPDM (rubber prepared from ethylene propylene diene monomer), so that a satisfactory level for processing and finished performance is obtained. There is also a need for a process for providing such cords which can employ conventional processing equipment without the need for excessive modifications. For instance, it would be advantageous if the coating used for forming or binding a reinforcing cord together from individual strands also provided improved adhesion to rubber matrices such as those comprising EPDM rubber, particularly filled rubber matrices.

Summary of the invention

In a first aspect, the invention provides a method for forming by extrusion or *.S.

* 20 moulding a rubber article comprising reinforcing strands of a strengthening * : material in a rubber matrix comprising EPDM rubber, the method comprising S..

the sequential steps of: : :*; i) coating the strands with a coating latex curable at the temperature of * S. extrusion, curing or moulding, such that the coating latex remains substantially uncured after coating, ii) drying the coating latex to form a coating film such that the coating film remains substantially uncured after drying, iii) forming the rubber article comprising the reinforcing strands in a rubber matrix comprising EPDM rubber by extrusion or moulding and curing at a temperature and for a time whereby the coating film on the strands is substantially cured within the rubber matrix.

A second aspect of the invention provides a coating latex, for coating filamentary strengthening material for extruded or moulded rubber articles, comprising a metal oxide, a maleimide crosslinking agent, a nitroso-compound, and halogenated rubber dispersed in water.

Preferably, the coating latex is used for coating filamentary strengthening material for extruded or moulded rubber articles having a rubber matrix comprising EPDM rubber. The latex is preferred also for use when the rubber matrix is filled or highly filled as described herein. Use for a filled rubber matrix comprising EPDM rubber is particularly preferred.

The coating latex of the second aspect of the invention is a preferred latex for S...

* 20 use in the method of the first aspect of the invention. * .

S S S * **

A third aspect of the invention provides a cord for reinforcing rubber articles, :: : * the cord comprising strands of strengthening material coated with a coating * film formed by drying a coating latex according to the second aspect of the invention.

Preferably, the cord is used for strengthening extruded or moulded rubber articles having a rubber matrix comprising EPDM rubber. The cord is preferred also for use when the rubber matrix is filled or highly filled as described herein. Use in a filled rubber matrix comprising EPDM rubber is particularly preferred.

A fourth aspect of the invention provides a rubber article comprising a rubber matrix and a cord according to the third aspect of the invention.

Preferably, the rubber article has a rubber matrix comprising EPDM rubber.

The rubber article preferably has a rubber matrix which is filled or highly filled as described herein. Rubber articles having a filled rubber matrix comprising EPDM rubber are particularly preferred.

Without wishing to be bound by theory, it is believed that the delaying of the curing or crosslinking of the coating until the coated reinforcement is inside the rubber matrix leads to the possibility of crosslinking between the coating and the rubber matrix, enhancing the adhesion between the cord and the S...

* ** 20 rubber matrix, particularly when the rubber matrix comprises EPDM rubber. S* * * I S * ** *..

Detailed description: a S * * I *0 *

*.: In the method of the present invention, resorcinol formaldehyde resin, used in the conventional method for coating reinforcement cords, is replaced by a mixture of curatives and the processing conditions for drying of the dipped strand are chosen so that curing or crosslinking of the latex does not occur at the drying stage and is delayed until the reinforcement cord is inside the rubber matrix comprising EPDM rubber, such that crosslinking of the coating takes place at least partly contemporaneously with the curing of the rubber matrix.

The strands making up the reinforcing cord may be suitably formed into a cord prior to their incorporation into the rubber article. Preferably the strands are formed into a cord after coating the strands with the coating latex.

The coating of the strands of the cord may be carried out by conventional methods such as dipping or spraying. Dipping is a preferred process for application of the coating latex. The water content of the latex is adjusted in order to give a suitable viscosity for the chosen coating process. Typically the water content of the latex is from 20 to 90% by weight, but may be even higher if required for a specific coating process.

After application of the coating latex, the coating layer is dried in order to form * S.. 20 a coating film. It is important that the drying process does not lead to * substantial curing or crosslinking of the coating film. The details of the drying *SS process will thus depend upon the coating latex chosen and the amount and : :*; thickness of coating layer on the reinforcing strands, but typically will involve * heating the coated reinforcing strands cord to a temperature in the range 90 to 130 C until most of the water has been lost from the coating latex: i.e. the coating latex will have a moisture content of 3% by weight or less, preferably I % by weight or less (as measured by equilibrium weight loss at 200 C).

Typical drying times in the method of the invention are less than 30 minutes, preferably less than 10 minutes, more preferably less than 5 minutes.

The coating film should be substantially uncured after drying. The degree of cure for rubbers is conventionally measured by means of monitoring the elastic modulus for samples in a commercially availably curemeter such as a moving die rheometer. By substantially uncured it is meant that the material of the coating film has an elastic modulus of less than 20% of its fully cured elastic modulus, preferably less than 10%. The elastic modulus and degree of cure of the coating on the cord can be measured indirectly by solvent swelling methods.

The rubber article is formed by extrusion or by moulding of a rubber matrix around the coated reinforcing strands of the invention. Conventional extrusion followed by in-line oven curing, or secondary moulding techniques may be used, at a temperature and for a time such that the rubber of the rubber matrix and the coating film are substantially cured within the rubber matrix of the S...

rubber article. By this it is meant that the materials attain at least 80% * : preferably at least 90% of their fully cured elastic modulus. Typically, a moulding or extrusion temperature in excess of 140 C, preferably 150 C will

-

be used for a suitable time. Curing after extrusion or moulding may be carried out by a suitable method such as heating in a conventional or microwave oven, hot air treatment, hot salt solution bath or fluidised bed. Typical curing requires heating at 200 C for 1 minute.

The coating latex for the first aspect of the invention may be any suitable latex which can be dried to a film without substantial curing or crosslinking taking place. A preferred coating latex is the coating latex of the second aspect of the invention, and comprises a halogenated rubber, metal oxide, maleimide crosslinking agent and nitroso-compound dispersed in water. It has been found that such a latex can be readily dried without risk of excessive curing. It has also been found that this latex forms a film which provides excellent adhesion to rubber matrices, particularly filled or highly filled rubber matrices as described herein, more particularly rubber matrices comprising EPDM rubber, especially filled rubber matrices comprising or consisting of EPDM rubber.

Suitable halogenated rubbers for use in the coating latex of the second aspect of the invention include brominated and chlorinated rubbers. Preferred halogenated rubbers include chloroprene rubber, chlorosulphonated polyethylene rubber, and mixtures thereof. Particularly preferred for high S...

adhesive strength is chlorosulphonated polyethylene rubber. For low cost reliable adhesion with filled rubber matrices, chloroprene rubber may be utilised. The halogenated rubber is suitably present at a level such that the non-aqueous part of the latex comprise from 10 to 80% by weight of S. * * *: halogenated rubber, preferably from 20 to 50%. Preferably, the non-aqueous part of the latex comprises at least 1 % by weight, more preferably at least 3% by weight of chlorosulphonated polyethylene rubber as at least part of the halogenated rubber. By non-aqueous part of the latex is meant any ingredient of the latex which is not water, irrespective of whether it is soluble in water.

Other synthetic rubbers may also be present in latex form as part of the coating latex of the second aspect of the invention. For instance SBR latex may be present at up to 80% by weight of the non-aqueous part of the latex.

The metal oxide for use in the coating latex of the second aspect of the invention may be any known metal oxide such as the oxides of zinc, cadmium, magnesium, lead, zirconium. Zinc oxide is preferred for its particular compatibility with the coating latex of the invention. The metal oxide is present suitably from I to 25%, preferably from 3 to 17%, more preferably from 4 to 11 % by weight of the non-aqueous part of the latex.

Water, preferably deionized water, is used in the coating latex of the second aspect of the invention to provide an aqueous latex. This is suitably present as from 20 to 90% by weight of the coating latex.

S * **S SI..

A maleimide crosslinking agent is present in the coating latex of the second * S * aspect of the invention. The maleimide crosslinking agent may be a S..

bismaleimide or a polymaleimide or mixtures thereof. Suitable bismaleimides and polymaleimides are such as disclosed in US 4,323,662 at column 5 line 14 to column 6 line 42. A suitable commercial maleimide crosslinking agent is BMI-M-20 polymaleimide supplied by Mitsui Toatsu Fine Chemicals Inc. The maleimide crosslinking agent is suitably present as from 2 to 30% by weight of the non-aqueous part of the coating latex, preferably from 5 to 20%, more preferably from 6 to 15%.

The coating latex of second aspect of the invention also suitably comprises a nitroso-compounci. The nitroso-compound of the present invention can be any aromatic hydrocarbon, such as benzenes, naphthalenes, anthracenes, biphenyls, and the like, containing at least two nitroso groups attached directly to non-adjacent ring carbon atoms. More particularly, such nitroso compounds are described as aromatic compounds having from I to 3 aromatic groups, including fused aromatic groups, having from 2 to 6 nitroso groups attached directly to non-adjacent carbon atoms of the aromatic groups. Preferred nitroso compounds are the dinitroso aromatic compounds, especially the dinitrosobenzenes and dinitrosonaphthalenes, such as the meta-or para-dinitrosobenzenes and the meta-or para-dinitrosonaphthalenes. The nuclear hydrogen atoms of the aromatic nucleus can be replaced by alkyl, alkoxy, cycloalkyl, aryl, aralkyl, alkaryl, arylamine, arylnitroso, amino, halogen, and like groups. The presence of such substituents on the aromatic nuclei has little I.. effect on the activity of the nitroso compounds in the present invention. As far *IS.

as is presently known, there is no limitation as to the character of the substituent, and such substituents can be organic or inorganic in nature. Thus, S..

where reference is made herein to nitroso-compound, it will be understood to include both substituted and unsubstituted nitroso compounds, unless * S. otherwise specified.

Particularly preferred nitroso compounds are characterized by the formula: (R)m -Ar -(NO)2 wherein Ar is selected from the group consisting of phenylene and naphthalene; R is a monovalent organic radical selected from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, alkaryl, arylamine, and alkoxy radicals having from I to 20 carbon atoms, amino, or halogen, and is preferably an alkyl group having from 1 to 8 carbon atoms, and m is zero, 1, 2, 3, or 4, and preferably is zero.

Nitroso-compounds which are suitable for the coating latex of the second aspect of the invention include m-dinitrosobenzene, p-dinitrosobenzene, m- d initrosonaphthalene, p-d initrosonaphthalene, 2,5-d initroso-p-cymeme, 2- methyl-I,4d initrosobenzene, 2-methyl-5-chloro-I,4-d initrosobenzene, 2-fluoro- I,4dinitrosobenzene, 2-methoxy-I -3-dinitroso-benzene, 5-chloro-1,3- d initrosobenzene, 2-benzyl-I,4-dinitrosobenzene, 2-cyclohexyl-1,4-dinitrosobenzene and combinations thereof. Particularly preferred nitroso compounds include p-dinitrosobenzene and m-dinitrosobenzene, especially p-dinitrosobenzene. The non-aqueous part of the coating latex of the second aspect of the invention suitably comprises from 3 to 50% by weight of nitroso-compound, preferably from 6 to 35%, more preferably from 9 to 17%. S...

* : The coating latex of the second aspect of the invention may also include other S..

ingredients which do not interfere with the action of the invention, for instance : : up to 3% by weight of surfactant and/or dispersing agent. Carbon black may * also be present in the coating latex, suitably from 0.5 to 10% by weight of the non-aqueous part of the coating latex, preferably form I to 4 % by weight.

It should be emphasised that the latex described above is a working example of a suitable coating latex which can be dried onto the reinforcing strands to form a coating without substantial curing. Other suitable latices may also be used in the method of the first aspect invention.

The strands of strengthening material are of any suitable fibre or strand-like material, preferably selected from the group consisting of glass, polyester, aramid, carbon fibres and mixtures thereof. Particularly preferred for good adhesive bonding to the rubber matrix are glass fibres.

The strands of strengthening material suitably have a weight per unit length (tex value) from 50 to 1000 g/km, preferably from 100 to 500 g/km.

Reinforcing cords according to the invention suitably comprise from 65 to 95% by weight of reinforcing fibre, preferably from 75 to 93%, more preferably from to 90%, with the remainder of the reinforcing cord comprising the non-aqueous part of the coating latex in dried form. * a..

The various aspects of the invention may be used with unfilled or lightly filled * rubber matrices comprising EPDM rubber, but show particular advantages over conventional RFL coating methods for rubber matrices comprising a filler :: * in addition to the EDPM rubber and the curing system for the rubber matrix, such as where the rubber matrix is highly filled and comprises at least lOOphr filler, preferably at least 200phr filler, more preferably at least 300 phr filler. By phr is meant parts by weight of filler in the rubber matrix compared to 100 parts by weight of rubber in the rubber matrix.

Typical fillers are not primarily involved in chemical curing of the matrix and are added at least to reduce the raw material cost for the article. Fillers include but are not limited to carbon black, calcium carbonate in fine particulate form (such as with a weight median particle diameter of 500 pm or less) and paraffinic oils and waxes. The use of carbon black can have the benefit of enhancing curing.

Although the method of the first aspect of the invention is applicable with a rubber matrix comprising EPDM rubber, it is highly preferred if the rubber matrix comprises EPDM rubber as at least 20% by weight of the rubber in the rubber matrix, more preferably at least 50%, even more preferably at least 80%. It is most preferable that the rubber of the rubber matrix consists essentially of EDPM rubber, meaning that at least 90%, preferably at least 95%, more preferably at least 99%, most preferably all of the rubber of the rubber matrix is EPDM rubber. Other rubbers such as ethylene/propylene rubber, hydrogenated acrylonitrile-butadjene, butadiene rubber and mixtures ss thereof may also be present in the rubber matrix. The weight of rubber means * the weight of polymeric rubber prior to curing and does not include the weight * of any cure system. *s I * I * I

The coating latex of the first aspect of the invention and the reinforcing cords of the third aspect of the invention may be used with matrix rubbers such as EPDM, ethylene/propylene rubber, hydrogenated acrylonitrile-butadiene, butadiene rubber and mixtures thereof. However it is preferred to use these aspects of the invention with a rubber matrix comprising EPDM rubber as at least 20% by weight of the rubber in the rubber matrix, more preferably at least 50%, even more preferably at least 80%. It is most preferable that the rubber of the rubber matrix consists essentially of EDPM rubber, meaning that at least 90%, preferably at least 95%, more preferably at least 99%, most preferably all of the rubber of the rubber matrix is EPDM rubber. These preferred EPDM rubber contents are also applicable to the articles of the fourth aspect of the invention.

The invention will now be described further by reference to the following non-

limiting examples. a * , .11 I. I$ * * S * IS * S *s S * S I * I S. S

S S S a SI

Example I

Dipping systems were formulated using the following ingredients: -

Table I

Exi Ex2 Ex3 Ex4 Ex5 Ex6 Ex7 Ex8 Ex9 Maleimide crossljnker1 4.30 8.61 8.61 8.61 12.9 21.6 13.0 21.5 43.0 p-dinitroso-benzene 6.49 13.0 13. 0 13.0 19.5 32.5 19.6 32.5 64.9 ZnO 3.39 6.78 6.78 6.78 10.2 17.0 10.2 17.0 33.9 Surfactant2 0.19 0.38 0.38 0.38 0.57 0.95 0.57 0.95 1.89 Disp. Agent3 0.32 0.63 0.63 0.63 0.95 1.59 0.95 1.58 3.17 Carbon black4 1.58 3.17 3.17 3.17 4.75 7.94 4.77 7.92 15.8 Mill water: 19.9 39.8 39.8 39.8 59.7 99.7 59.9 99 199 CSM latex5 6.3 12.7 12.7 12.7 19.0 31.7 309.1 238.6 63.3 CR latex6 59 29 59 147 88 147 --- SBR latex7 290 290 249 124 166 ----Dilutionwater 109 95 108 144 119 141 82 81 75 (1) BMI-M-20 (Mitsui Toatsu Fine Chemicals, mc) (2) Polywet Z1766 (Uniroyal mc) (3) Marasperse CBOS-4 (American Can Company) (4) Sterling NS (Cabot Corp) (5) Hypalon 450 (Sumitomo Corp) (comprising 40% by weight water) : 10 (6) Lipren T (PolymerLatex Ltd) (comprising 40% by weight of water) (7)lntex 084 (Polymeri Europa UK Ltd) (comprising 41% by weight of water) $ All water used was delonised S. *

S

The dipping formulations indicated above were prepared as follows: The first 7 ingredients for each example were milled in a ceramic bead mill for approximately 30 minutes. The mixtures were then transferred to a paddle type stirred vessel and the latices added under gentle agitation. The final dilution water was then added under the same conditions and stirring continued for a further 30 minutes.

In order to measure the adhesive properties of the treatment, a number of the cords were aligned on jig in a parallel direction and moulded against rubber compound to form test pieces. The type of measurement made is commonly referred to as a peel test' where the cords and the rubber part of the moulding are pulled apart under tension. The degree of force required to cause separation is a measure of the adhesion between the two components.

Pre-plied glass cords comprising 5 x 140 tex (glkm) strands were wound on a purpose made jig in a parallel arrangement and treated with the above mixtures so as to give a uniform coverage of the glass cord surface.

Following the coating treatment, they were then dried for 30 minutes at 60 C.

A commercial highly filled test rubber compound based on a curable EPDM with a filler level of 325 phr was attached to the dried cord surface and the cords removed from the jig. Further drying for 15 minutes at 60 C was then applied to remove any residual moisture. The completed arrangement of *: 20 cords with rubber compound was then press moulded for 8 minutes at 180 C to effect cure of the rubber and bonding to the cords. a. a * * * *

*..: After allowing time for the moulded samples to cool to room temperature, they were tested for peel adhesion level between treated cords and cured rubber.

The results in terms of force (measured in Newtons) per 25mm of sample width that were obtained are given in the following table: -

Table 2

Test I Test 2 Exi 48.4 46.5 Ex2 46.2 39.9 Ex3 67 60 Ex4 163.2 177.4 Ex5 110 129 Ex6 140 184.3 Ex7 100.3 112.2 Ex8 118.8 167 Ex9 30.9 31.2 As a comparison value, glass cords produced with conventional RFL that is commonly used with normally filled EPDM rubber for this type of application 0.ee,, gave a peel adhesion value of 17 N/25mm when used with the filled rubber as U...

S''. used in the examples of table 2. S. *

. .: 10 S...

From the result table above it is clear that the mixtures covered by the invention result in much improved adhesion to the commercial, highly filled * S EPDM rubber.

Example 2

Dipping systems were formulated using the following materials: -

Table 3

ExlO Exil Ex12 Poly BMI 6.7 6.3 10.1 p-dinitrosobenzene 10.1 9.5 15 ZnO 5.3 5.0 8.0 Surfactant 0.29 0.28 0.45 Disp. agent 0.49 0.47 0.75 Carbon black 2.5 2.3 3.7 Mill water: 31 29 47 CSM1latex 9.8 9.3 15 CR2latex 63 86 52 PB3latex 74 50 60 (1) Hypalon 450 (Sumitomo Corp) (comprising 40% by weight water) (2) Lipren T (PolymerLatex Ltd) (comprising 40% by weight of water) (3) Genflo 8028 (Omnova Solutions Inc.) (comprising 50% by weight of water) *S*S * S * SS *:*. The above dips were prepared in a similar manner to those in example 1. In this case however there was no dilution water required to allow the processing *. of the strands on a commercial dipping unit. S. S S * S S.

Glass strands of 330 tex (g/km) were individually dipped into each of the solutions and then passed through small orifices to reduce the pick up to from 16 to 20% by weight of coating expressed as weight of dried coating with respect to weight of untreated strands (corresponding to 13.8 to 16.7% by weight of dried coating with respect to the weight of final dried coated strands). The strands were dried in an oven to simply remove the water but not to allow any curing or crosslinking reactions to occur.

Three strands were plied together on a conventional ring type machand given a twist level of 60 turns per metre. This operation was carried out in order to produce cord samples that were of a suitable size for testing for peel adhesion to the rubber test compound.

Cords from each trial run were wound on a jig in a parallel alignment and placed in a press mould with the test rubber compound (highly filled EPDM as for example I detailed above).

Cunng of the test samples was carried out by heating at 149 C for 30 minutes.

I * S

*: . : After allowing time for the moulded samples to cool to room temperature, they * 20 were tested for peel adhesion level between treated cords and cured rubber.

S.:. The results in terms of force (measured in Newtons) per 25mm of sample width that were obtained are given in the following table: -

S S S S 55

Table 4

Trial no. Average peel adhesion (N/25mm) ExlO 52 Exil 46,58 Ex12 111,97,111 Again, high adhesion forces were obtained between the coated experimental cords and the highly filled EPDM rubber.

Example 3

The adhesion between cord and rubber was further investigated by pull-out testing and by peel testing. For the pullout tests the glass cord was: Glass: -1600 filaments, lOp diameter = 330 g/km Twist: 6OtpmZ Cord: 330.1 Z60 For the peel adhesion tests the glass cord was: Glass: -1600 filaments, lOp diameter = 330 g/km Ply: x3 strands 60 tpm Z Cord: 330.1 x3Z60 * * * The cords were treated with the coating composition of the invention as for ** * *.: Example 12 above with a dried coating level of 16-20% by weight of the uncoated cord. As a control, cords were treated with the same level of conventional RFL coating; i.e. a conventional chioroprene resorcinol-formaldehyde latex coating system.

The rubber compounds that were used were based upon two different EPDMs: Buna G 6470 supplied by Lanxess and Nordel 4770 supplied by Dow Chemical Company. The polymer viscosities were measured at 59 and 70 Mooney units respectively for the Buna 59 MU and for the Nordel 70 MU (both ML 1+4 125 C) using a standard Mooney viscometer. A range of compounds were made with increasing levels of filler. The ratios of carbon black to calcium carbonate to oil were kept approximately constant. Three sets of compounds were studied: the Buna EPDM with a sulphur cure system (16.7 phr) and the Nordel EPDM with both a sulphur (16.7 phr) and a peroxide cure system (9.5 phr):

Table 5

Buna G 6470 with sulphur cure Parts per hundred Nordel 4770 with sulphur cure of rubber Nordel 4770 with peroxide cure EPDM 100 100 100 100 100 *...

S... Carbon Black 110 130 150 175 N762 Calcium 60 75 85 100 Carbonate *5 * *. .: ParaffinicOil 60 80 95 115 125 Total Filler 200 250 300 350 400 The pull out test was a U-test geometry. A loop of glass cord was moulded within a rubber strip 10 mm thick and cured for 30 minutes at 149 C. The loop was pulled from the rubber block with a crosshead speed of 50 mm/mm. The side with the weakest adhesion was removed from the block. The maximum force was reported as the pull-out adhesion.

The peel test specimens were prepared by using the larger cord. These were laid parallel, with contact along the length from cord to cord -to form a plane of cords. EPDM was vulcanised on top of the cords, moulded for 30 minutes at 149 C. Peel specimens 25 mm wide were sectioned from the composite.

The rubber was peeled away from the cords using a crosshead speed of 50 mm/mm. Again, the maximum force was reported as the peel adhesion force.

After peeling, the cords were inspected for the percentage area of visible rubber remaining on the cord surface -a visual assessment of the location of the tear path.

The results for pull-out adhesion force (N) are shown in table 6

Table 6

Filler(phr) 59M-S 59M-S 70M-S 70M-S 70M-P 70M-P loading Ex12 RFL Ex12 RFL Ex12 RFL 68 40 68 36 58 9 250 50 28 65 35 47 7 300 67 35 77 34 50 9 350 50 28 78 30 29 7 400 69 33 66 25 29 8 The results for Peel adhesion are shown in table 7 in units of N/25mm

Table 7

Filler(phr) 59M-S 59M-S 70M-S 70M-S 70M-P 70M-P loading Ex12 RFL Ex12 RFL Ex12 RFL 155 55 230 55 165 165 250 250 55 265 50 250 175 300 230 60 230 75 190 165 350 210 65 230 65 180 80 400 215 75 195 75 165 90 The levels of adhesion observed were significantly higher for the EXI 2 coating than the standard RFL. Very good adhesion was obtained to the EPDM compounds with 400 parts of filler.

For the tear path, it was found that for the sulphur cure rubbers, the control samples gave no visible rubber tear, indicating that the rubber had peeled away from the glass indicating poor adhesion. For the cords coated with * * * Example 12 in the sulphur cure rubbers, for filler levels of 300phr and above, 100% visible rubber tear was found, indicating excellent adhesion. For the * peroxide cure, at phr of 300 and above, both the control samples and the * * Example 12 coated samples gave visual rubber tear, but the values were ** * * * 15 100% for the example 12 coating and varied between 0 and 85% for the RFL coating.

Claims

Claims 1. A method for forming by extrusion or moulding a rubber

article comprising reinforcing strands of a strengthening material in a rubber matrix comprising ethylene-propylene-diene monomer rubber, the method comprising the sequential steps of: i) coating the strands with a coating latex curable at the temperature of extrusion, curing or moulding, such that the coating latex remains substantially uncured after coating, ii) drying the coating latex to form a coating film such that the coating film remains substantially uncured after drying, iii) forming the rubber article comprising the reinforcing strands in a rubber matrix comprising ethylene-propylene-diene monomer rubber by extrusion or moulding and curing at a temperature and for a time whereby the coating film on the strands is substantially cured within the rubber article.
2. A method according to claimi wherein the strands are formed into a cord prior to forming the rubber article.

I I * **.

*. . . I*
3. A method according to claim I or claim 2 wherein the strands are 20 formed into a cord prior to coating the strands. I...
4. A method according to any preceding claim wherein the coating latex comprises halogenated rubber, metal oxide, maleimide crosslinking agent, and nitroso-compound dispersed in water.
5. A method according to claim 4 wherein the halogenated rubber is selected from the group consisting of chioroprene rubber, chiorosulphonated polyethylene rubber, and mixtures thereof.
6. A method according to any preceding claim wherein the strands of strengthening material are selected from the group consisting of glass, polyester, aramid, carbon fibres and mixtures thereof.
7. A method according to any preceding claim wherein the rubber matrix comprises a filler.
8. A method according to claim 7 wherein the rubber matrix comprises at least 1 O0phr of filler.
9. A method according to claim 7 or claim 8 wherein the filler is selected from the group consisting of carbon black, calcium carbonate, oil and mixtures thereof. S. * . * ***

*..
10. A method according to any preceding claim wherein the rubber of the * * 20 rubber matrix comprises at least 20% by weight of ethylene-propylene-diene * * monomer rubber. U. * * S *

11. A method according to any preceding claim wherein the rubber matrix comprises at least 50% by weight of ethylene-propylene- diene monomer rubber.

12. A method according to claim 11 wherein the rubber of the rubber matrix comprises at least 90% by weight of ethylene-propylene- diene rubber.

13. A coating latex, for coating filamentary strengthening material for extruded or moulded rubber articles, comprising a metal oxide, a maleimide crosslinking agent, a nitroso-compound, and halogenated rubber, dispersed in water.

14. A coating latex according to claim 13 wherein the nitroso-compound is p-dinitrosobenzene.

15. A coating latex according to claim 13 or claim 14 wherein the metal oxide is zinc oxide.

16. A coating latex according to any one of claims 13 to 15 wherein the halogenated rubber is selected from the group consisting of chloroprene * rubber, chlorosulphonated polyethylene rubber and mixtures thereof.

* I *.

S * S..

* : * 20 17. A coating latex according to any one of claims 13 to 16 wherein the * non-aqueous part of the coating composition comprises from 10 to 80% by weight of halogenated rubber.

IS S

S I * S*

18. A coating latex according to any one of claims 13 to 17 wherein the non-aqueous part of the coating composition comprises from 3 to 50% by weight of nitroso-compound.

19. A coating latex according to any one of claims 13 to 18 wherein the non-aqueous part of the coating composition comprises from 2 to 30% by weight of maleimide crosslinking agent.

20. A coating latex according to any one of claims 13 to 19 wherein the non-aqueous part of the coating composition comprises from I to 25% by weight of metal oxide.

21. A coating latex according to any one of claims 13 to 20 comprising from to 90% by weight of water.

22. A cord for reinforcing rubber articles comprising strands of strengthening material coated with a coating film formed by drying a coating latex according to anyone of claims 13 to 21. *.. a * a...

23. A cord according to claim 22 wherein the strands are glass fibres. S...

24. A cord according to claim 22 or claim 23 wherein the strands have a *..: tex value from 5Oto 1000, preferably 100 to 500 g/km.

25. A rubber article comprising a rubber matrix and a cord according to any one of claims 22 to 24.

26. A rubber article according to claim 25 wherein the rubber matrix comprises ethylene-propylene-diene monomer rubber.

27. A rubber article according to claim 25 or claim 26 wherein the rubber matrix comprises a filler. Ca * a * *.* S. * a * a.. C. * * * . a.. as..

I *5 * * . I * I S* *

S SC

C