Airsleeve

Field of the Invention

0001The present invention is directed to an airsleeve according to claim 1. The dependent claims cover preferred embodiments of the invention.

Background of the Invention

0002Air springs have been used for motor vehicles and various machines and other equipment for a number of years. The springs are designed to support a suspension load such as a vehicle. The air spring usually consists of a flexible elastomeric reinforced airsleeve that extends between a pair of end members. The airsleeve is attached to end members to form a pressurized chamber therein. The end members mount the air spring on spaced components or parts of the vehicle or equipment on which the air spring is to be mounted. The internal pressurized gas, usually air, absorbs most of the motion impressed upon or experienced by one of the spaced end members. The end members move inwards and towards each other when the spring is in jounce and away and outwards from each other when the spring is in rebound. The design height of the air spring is a nominal position of the spring when the spring is in neither jounce nor rebound.

0003There have been two basic designs of air springs: a rolling lobe air spring, as seen in US-A- 3,043,582 and 5,954,316; and a bellows type air spring, as seen in US-A- 2,999,681 and 3,084,952. In a rolling lobe-type air spring, the airsleeve is a single circular-shaped sleeve secured at both ends. In a bellows-type air spring, the multiple meniscus-shaped portions of the airsleeve extend out radially as the spring is in jounce.

0004Airsleeves have a rubber innerliner, two plies of rubber coated cord fabric, and a rubber cover. These sleeves see their greatest commercial usage in the automotive helper spring market by being mounted as air springs on shock absorbers and struts. Other uses include truck cab suspension springs, truck driver seat springs, automobile air springs, and a variety of industrial air springs.

0005The plies of cord fabric are contained within a reinforcement layer, which along with the cord fabric includes an elastomeric base, or plycoat, made from a rubber compound. The reinforcement layer may be provided from a plurality of different types of materials. The rubber compound of the plycoat is selected from among elastomers conventionally used in manufacturing airsleeves, and blends of such elastomers. Also typically included in the rubber compound are various additives.

0006In the manufacture of fabric-reinforced, molded rubber articles such as airsleeves, it is desirable to obtain strong adhesion between the fabric and the rubber, and also high resistance to deterioration of the bond with flexing of the structure.

0007The adhesion of the plycoat to the cover is essential for acceptable performance of composites in applications such as airsleeves. Further, the adhesion of the reinforcing cord to the plycoat is essential for field performance, especially for its high stress tolerance. An adhesive based on a styrene-butadiene rubber (SBR) latex, a vinylpyridine/styrene/butadiene terpolymer latex, and a resorcinol/formaldehyde condensate is typically used to adhere the cord to the plycoat.

0008The rubber compounds used in the air spring cover are dictated largely by the operating environment to which the air spring is exposed. For airsleeves exposed to a high temperature operating environment, up to about 115°C, an epichlorohydrin rubber (ECO) based compound may be used for the cover, along with a sulfur-cured natural rubber plycoat compound. While this combination of an ECO cover with a sulfur-cured natural rubber plycoat provides adequate service life in some applications, automotive specifications require increasingly better performance from airsleeves.

Description of the Invention

0009In one embodiment, the present invention is directed to an airsleeve comprising an elastomeric liner; a reinforcing layer overlaying the liner; and an elastomeric cover overlaying the reinforcing layer; the reinforcing layer comprising: i) textile fibers having distributed over surface portions thereof an RFL (resorcinol formaldehyde latex) adhesive; and ii) a plycoat formed from a rubber composition comprising: 100 parts by weight of at least one diene-based elastomer selected from natural rubber (NR), synthetic polyisoprene rubber (IR), butadiene rubber (BR) and styrene-butadiene rubber (SBR); from 1 to 40 parts by weight of a metal salt of an α,β-ethylenically unsaturated carboxylic acid, and from 0.2 to 5 parts by weight of an organic peroxide.

0010The reinforcing layer includes a plycoat comprising a curable rubber composition. In one embodiment, the curable or vulcanizable rubber composition may include 100 parts by weight of at least one diene-based elastomer selected from natural rubber (NR), synthetic polyisoprene rubber (IR), butadiene rubber (BR) and styrene-butadiene rubber (SBR). In another embodiment, the rubber composition may include 50 to 95 parts by weight of natural rubber (NR) and 5 to 50 parts by weight of synthetic polyisoprene rubber (IR) or butadiene rubber (BR).

0011The plycoat rubber composition also includes an organic peroxide. Well-known classes of peroxides that may be used include diacyl peroxides, peroxyesters, dialkyl peroxides and peroxyketals. Specific examples include dicumyl peroxide, n-butyl-4,4-di(t-butylperoxy) valerate, 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-butylperoxy) cyclohexane, 1,1-di(t-amylperoxy) cyclohexane, ethyl-3,3-di(t-butylperoxy) butyrate, ethyl-3,3-di(t-amylperoxy) butyrate, 2,5-dimethyl-2,5-di(t-butylperoxy) hexane, t-butyl cumyl peroxide, α,α'-bis(t-butylperoxy)diisopropylbenzene, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy) hexyne-3, t-butyl perbenzoate, 4-methyl-4-t-butylperoxy-2-pentanone and mixtures thereof. The preferred peroxide is dicumyl peroxide. Typical amounts of peroxide ranges from 0.2 to 5 phr (based on active parts of peroxide). Preferably, the amount of peroxide ranges from 0.3 to 3 phr. More preferably, the amount of peroxide ranges from 0.3 to 1.5 phr.

0012The plycoat rubber composition also includes a metal salt of an α,β-ethylenically unsaturated carboxylic acid. The metal salts of α,β-ethylenically unsaturated carboxylic acids include the metal salts of acids including acrylic, methacrylic, maleic, fumaric, ethacrylic, vinyl-acrylic, itaconic, methyl itaconic, aconitic, methyl aconitic, crotonic, alpha-methylcrotonic, cinnamic and 2,4-dihydroxy cinnamic acids. The metals may be zinc, cadmium, calcium, magnesium, sodium or aluminum. In one embodiment, the metal salt of an α,β-ethylenically unsaturated carboxylic acid may be zinc diacrylate or zinc dimethacrylate. In one embodiment, the concentration of metal salt of an α,β-ethylenically unsaturated carboxylic acid is from 1 to 40 phr. In another embodiment, the concentration metal salt of an α,β-ethylenically unsaturated carboxylic acid is from 5 to 20 phr.

0013As will be demonstrated, the presence of sulfur in the plycoat may interfere with adhesion of the plycoat to the cover. For this reason, it is generally preferable to have no sulfur in the plycoat. However, small amounts of sulfur and usual cure accelerators may be used in the plycoat to assist in curing. The amount of sulfur should be low enough not to interfere with the adhesion of the plycoat to the cover. Preferably, the amount of sulfur in the plycoat is less than 1 phr and more preferably less than 0.5 phr, and even more preferably to have no sulfur.

0014The term "phr" as used herein, and according to conventional practice, refers to "parts by weight of a respective material per 100 parts by weight of rubber, or elastomer".

0015It is readily understood by those having skill in the art that the plycoat rubber composition would be compounded by methods generally known in the rubber compounding art, such as mixing the rubbers with various commonly used additive materials such as, for example, curing aids, activators, retarders, processing oils, resins, reinforcing resins, tackifying resins, plasticizers, fillers, pigments, fatty acids, zinc oxide, magnesium oxide, waxes, antioxidants, antiozonants and peptizing agents. As known to those skilled in the art, the additives mentioned above are selected and commonly used in conventional amounts. Typical amounts of reinforcing-type carbon blacks(s) comprise 20 to 100 phr. Representative examples of such carbon blacks include N110, N121, N220, N231, N234, N242, N293, N299, N330, N339, N343, N347, N351, N358, N375, N550, N660, N683, N754, N762, N765, N774, N907, N908, N990 and N991. Various non-carbon black fillers and/or reinforcing agents may be added to the plycoat composition. An example of a reinforcing agent is silica. Silica may be used in the present composition in amounts from 0 to 80 parts, and preferably 10 to 20 parts, by weight based on 100 parts of rubber. In one embodiment, the plycoat composition may include from 30 to 60 phr of filler selected from carbon black and silica. Typical amounts of processing oils comprise 1 to 50 phr. Such processing oils can include, for example, aromatic, napthenic, and/or paraffinic processing oils. Typical amounts of antioxidants comprise 1 to 5 phr. Representative antioxidants may be, for example, diphenyl-p-phenylenediamine and others, such as, for example, those disclosed in <u>The Vanderbilt Rubber Handbook</u> (1978), pages 344-346. Typical amounts of antiozonants comprise 1 to 5 phr. Typical amounts of fatty acids (such as stearic acid and oleic acid) are used in an amount ranging from 0.2 to 3 phr. Typical amounts of zinc oxide comprise 0.5 to 8 phr. Typical amounts of magnesium oxide ranges from 0 to 1.0 phr. Typical amounts of waxes comprise 1 to 5 phr. Often microcrystalline waxes are used.

0016The mixing of the plycoat rubber composition can be accomplished by methods known to those having skill in the rubber mixing art. For example, the ingredients are typically mixed in at least two stages, namely at least one non-productive stage followed by a productive mix stage. The final curatives including peroxides and co-agents are typically mixed in the final stage which is conventionally called the "productive" mix stage in which the mixing typically occurs at a temperature, or ultimate temperature, lower than the mix temperature(s) of the preceding non-productive mix stage(s). The rubber and carbon black, if used, may be mixed in one or more non-productive mix stages.

0017The reinforcing layer includes, along with the plycoat, textile fibers treated with an RFL type adhesive dip. Textile fibers in the form of suitable cord or fabric may be in various forms, including woven fabrics, knitted fabric, or spun bonded fabric, and fiber cord. The cord or fabric may be comprised of various materials typically used as reinforcement in composite materials, including rayon, nylon, polyester, aramid, cotton, and combinations thereof. In one embodiment, the cord or fabric is nylon or polyester.

0018The reinforcing layer includes an adhesive composition useful in adhering textile fibers to the plycoat. In one embodiment, the so-called RFL adhesive composition may be comprised of resorcinol, formaldehyde, and one or more polymer latexes. In one embodiment, the polymer latex may include one or more of styrene-butadiene copolymer latex, vinylpyridine-styrene-butadiene terpolymer latex, or latexes made from polymers included in the plycoat, liner, or cover compositions.

0019The RFL adhesive dip is, in general, used in the form of an aqueous latex. The latices are prepared by free radical emulsion polymerization of styrene and butadiene to form a copolymer latex, and free radical emulsion polymerization of styrene, butadiene, and vinylpyridine to form a terpolymer latex. The charge compositions used in the preparation of the latices contain monomers, at least one surfactant, and at least one free radical initiator. Such latices are well known, and a suitable RFL dip may be made by any of various methods as are known in the art, for example, following the teaching of US-A 3,525,703.

0020The RFL adhesive may optionally include a blocked isocyanate. In one embodiment from 1 to 20 parts by solid of blocked isocyanate is added to the adhesive. The blocked isocyanate may be any suitable blocked isocyanate known to be used in RFL adhesive dips including, but not limited to, caprolactam blocked methylene-bis-(4-phenylisocyanate), such as Grilbond-IL6 available from EMS American Grilon, Inc, and phenolformaldehyde blocked isocyanates as disclosed in US-A- 3,226,276; 3,268,467; and 3,298,984.

0021In accordance with this invention, the cord or fabric to be treated is dipped for one to three minutes in the RFL dip, and dried at a temperature within the range of 75°C to 265°C for 0.5 minutes to 20 minutes, and thereafter calendered into the plycoat rubber compound and cured therewith. The dip process may be carried out in one or two steps. Adjustment of the solids content of the dips for a one or two-step dipping process is done as required, as is known to one skilled in the art.

0022The airsleeve further includes an elastomeric liner and an elastomeric cover. The liner and cover may each comprise vulcanizable rubber compounds; the compounds used in the liner may be the same as that used in the cover, or it may be different. Elastomers that may be used in the liner and cover compounds include at least one elastomer selected from among elastomers conventionally used in manufacturing airsleeves included, but not limited to, elastomers such as epichlorohydrin rubber, polyisobutylene, halogenated butyl rubbers, natural rubber, polyisoprene, polybutadiene, styrene-butadiene, and blends of such elastomers. In one embodiment, the liner or cover compounds may include epichlorohydrin rubber, chlorinated butyl rubber, or brominated butyl rubber. In another embodiment, the liner or cover may include epichlorohydrin rubber and a halogenated rubber selected from chlorinated butyl rubber and brominated butyl rubber. The liner and cover compounds may include any of various additives and fillers as in the plycoat compound.

0023Epichlorohydrin rubber suitable for use includes (1) homopolymers of epichlorohydrin, (2) copolymers of an epiochlorohydrin with less than 30% of saturated epoxy monomers or with an unsaturated epoxy monomer, and (3) terpolymers of an epichlorohydrin with (a) less than 30 % of a saturated epoxy monomer or mixtures thereof, (b) an unsaturated epoxy monomer or mixtures thereof, or (c) mixtures of (a) and (b). The epichlorohydrin polymers are prepared by polymerizing a monomeric epichlorohydrin alone or together with one or more of the aforementioned epoxy monomers with a suitable catalyst, such as an organometallic catalyst. For example, a reaction product of water with an alkyl aluminum compound is a suitable organometallic catalyst. Typical saturated epoxy monomers include alkylene oxides, such as ethylene oxide, and typical unsaturated epoxy monomers include allylglycidyl ether. The properties and the preparation of epichlorohydrin polymers suitable for use in the practice of this invention are known in the art and are described, for example, in US-A- 3,158,500, the disclosure of which is incorporated herein by reference.

0024Suitable chlorinated butyl rubber may be considered part of a larger group of halogenated isobutylene rubbers. By the term "halogenated isobutylene rubber" is meant a halogenated polymer comprising isobutylene sub-units. Halogens include chlorine and bromine. The halogenated rubbers used in this invention include polymers bearing halogen atoms incorporated before or after polymerization.

0025The halogenated isobutylene rubbers used in this invention include, but are not limited to, brominated butyl rubber (commonly called bromobutyl and abbreviated BIIR where isoprene is the diene copolymerized with isobutylene; as used herein, the term "butyl rubber" means a copolymer of isobutylene and a diene such as isoprene); chlorinated butyl rubber (commonly called chlorobutyl and abbreviated CIIR where isoprene is the diene copolymerized with isobutylene); so-called star-branched polyisobutylene comprising branched or star-shaped polyisobutylene sub-units, such as star-branched bromobutyl and star-branched chlorobutyl; isobutylene-bromomethylstyrene copolymers such as isobutylene/meta-bromomethylstyrene and isobutylene/para-bromomethylstyrene, isobutylene/chloromethylstyrene copolymers such as isobutylene/meta-chloromethylstyrene and isobutylene/parachloromethylstyrene, and the like, including and mixtures thereof.

0026The halogenated isobutylene rubbers also include halogenated isobutylene containing terpolymers, such as halogenated isobutylene/styrene/dienes; e.g., isobutylene/styrene/isoprene and halogenated isobutylene/methylstyrene/dienes; e.g., isobutylene/methylstyrene/isoprene; isobutylene/halomethylstyrene/diene terpolymers including isobutylene/bromomethylstyrene/isoprene; isobutylene/haloisobutylene/ dienes, including isobutylene/bromobutylene/isoprene; and the like, and mixtures thereof with other halogenated isobutylene rubbers.

0027Vulcanization of the airsleeve is generally carried out at conventional temperatures ranging from 100°C to 200°C. Preferably, the vulcanization is conducted at temperatures ranging from 110°C to 180°C. Any of the usual vulcanization processes may be used such as heating in a press or mold, heating with superheated steam or hot air. Such composites can be built, shaped, molded and cured by various methods which are known and will be readily apparent to those having skill in such art. Methods for making airsleeves are described in US-A- 3,794,538 and 6,264,178.

0028The airsleeve may be used in any of various airspring applications including truck cab suspension springs, truck driver seat springs, automobile air springs, and a variety of industrial air springs. These air springs may be of various designs including, but not limited to, a rolling lobe air spring, for example as in US-A- 3,043,582 and 5,954,316, and a bellows type air spring, for example as in US-A- 2,999,681 and 3,084,952.

0029The invention is further illustrated by the following example.

<u>EXAMPLE</u>

0030Plycoat compounds were prepared according to Table 1 and a cover compound containing epichlorohydrin rubber and chlorobutyl rubber was prepared as indicated in Table 2, with amounts in parts per hundred rubber (phr). Plycoat test samples were prepared using samples 1-8 and tested for physical properties as indicated in Table 3. Plycoat/cover samples and plycoat/fabric samples were prepared using samples 1-8, and tested for adhesion as indicated in Table 3. Tests were done according to the following protocols: <u>Rheometer</u> ODR at 150°C (302°F), ASTM D2048 Mooney Scorch at 121°C (250°F), ASTM D1646 <u>Tensile, Elongation, and Hardness</u> Original, ASTM D412, dumbbell specimens <u>Adhesion to ECO/CIIR cover compound, ASTM D413</u> Original, using machine method with type A, 180° peel, strip specimens. <u>Adhesion to RFL-Dipped nylon fabric, ASTM D413</u> Original, using machine method with type A, 180° peel, strip specimens. <u>Other</u> Die C tear, ASTM D624 <tables id="tabl0001" num="0001"><table frame="all"><title>Table 1</title><tgroup cols="9" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="17.50mm" /><colspec colnum="2" colname="col2" colwidth="17.50mm" /><colspec colnum="3" colname="col3" colwidth="17.50mm" /><colspec colnum="4" colname="col4" colwidth="17.50mm" /><colspec colnum="5" colname="col5" colwidth="17.50mm" /><colspec colnum="6" colname="col6" colwidth="17.50mm" /><colspec colnum="7" colname="col7" colwidth="17.50mm" /><colspec colnum="8" colname="col8" colwidth="17.50mm" /><colspec colnum="9" colname="col9" colwidth="17.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="left">Sample</entry><entry namest="col2" nameend="col2" align="center">1</entry><entry namest="col3" nameend="col3" align="center">2</entry><entry namest="col4" nameend="col4" align="center">3</entry><entry namest="col5" nameend="col5" align="center">4</entry><entry namest="col6" nameend="col6" align="center">5</entry><entry namest="col7" nameend="col7" align="center">6</entry><entry namest="col8" nameend="col8" align="center">7</entry><entry namest="col9" nameend="col9" align="center">8</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Natural Rubber¹</entry><entry namest="col2" nameend="col2" align="right">50</entry><entry namest="col3" nameend="col3" align="right">90</entry><entry namest="col4" nameend="col4" align="right">50</entry><entry namest="col5" nameend="col5" align="right">90</entry><entry namest="col6" nameend="col6" align="right">50</entry><entry namest="col7" nameend="col7" align="right">90</entry><entry namest="col8" nameend="col8" align="right">50</entry><entry namest="col9" nameend="col9" align="right">90</entry></row><row><entry namest="col1" nameend="col1" align="left">Polybutadiene²</entry><entry namest="col2" nameend="col2" align="right">50</entry><entry namest="col3" nameend="col3" align="right">0</entry><entry namest="col4" nameend="col4" align="right">50</entry><entry namest="col5" nameend="col5" align="right">0</entry><entry namest="col6" nameend="col6" align="right">50</entry><entry namest="col7" nameend="col7" align="right">0</entry><entry namest="col8" nameend="col8" align="right">50</entry><entry namest="col9" nameend="col9" align="right">0</entry></row><row><entry namest="col1" nameend="col1" align="left">Synthetic polyisoprene³</entry><entry namest="col2" nameend="col2" align="right">0</entry><entry namest="col3" nameend="col3" align="right">10</entry><entry namest="col4" nameend="col4" align="right">0</entry><entry namest="col5" nameend="col5" align="right">10</entry><entry namest="col6" nameend="col6" align="right">0</entry><entry namest="col7" nameend="col7" align="right">10</entry><entry namest="col8" nameend="col8" align="right">0</entry><entry namest="col9" nameend="col9" align="right">10</entry></row><row><entry namest="col1" nameend="col1" align="left">Carbon black⁴</entry><entry namest="col2" nameend="col2" align="right">45</entry><entry namest="col3" nameend="col3" align="right">45</entry><entry namest="col4" nameend="col4" align="right">25</entry><entry namest="col5" nameend="col5" align="right">25</entry><entry namest="col6" nameend="col6" align="right">45</entry><entry namest="col7" nameend="col7" align="right">45</entry><entry namest="col8" nameend="col8" align="right">25</entry><entry namest="col9" nameend="col9" align="right">25</entry></row><row><entry namest="col1" nameend="col1" align="left">Silica</entry><entry namest="col2" nameend="col2" align="right">0</entry><entry namest="col3" nameend="col3" align="right">0</entry><entry namest="col4" nameend="col4" align="right">15</entry><entry namest="col5" nameend="col5" align="right">15</entry><entry namest="col6" nameend="col6" align="right">0</entry><entry namest="col7" nameend="col7" align="right">0</entry><entry namest="col8" nameend="col8" align="right">15</entry><entry namest="col9" nameend="col9" align="right">15</entry></row><row><entry namest="col1" nameend="col1" align="left">Napthenic oil</entry><entry namest="col2" nameend="col2" align="right">4</entry><entry namest="col3" nameend="col3" align="right">4</entry><entry namest="col4" nameend="col4" align="right">4</entry><entry namest="col5" nameend="col5" align="right">4</entry><entry namest="col6" nameend="col6" align="right">4</entry><entry namest="col7" nameend="col7" align="right">4</entry><entry namest="col8" nameend="col8" align="right">4</entry><entry namest="col9" nameend="col9" align="right">4</entry></row><row><entry namest="col1" nameend="col1" align="left">Stearic acid</entry><entry namest="col2" nameend="col2" align="right">1</entry><entry namest="col3" nameend="col3" align="right">1</entry><entry namest="col4" nameend="col4" align="right">1</entry><entry namest="col5" nameend="col5" align="right">1</entry><entry namest="col6" nameend="col6" align="right">1</entry><entry namest="col7" nameend="col7" align="right">1</entry><entry namest="col8" nameend="col8" align="right">1</entry><entry namest="col9" nameend="col9" align="right">1</entry></row><row><entry namest="col1" nameend="col1" align="left">Zinc oxide</entry><entry namest="col2" nameend="col2" align="right">5</entry><entry namest="col3" nameend="col3" align="right">5</entry><entry namest="col4" nameend="col4" align="right">5</entry><entry namest="col5" nameend="col5" align="right">5</entry><entry namest="col6" nameend="col6" align="right">5</entry><entry namest="col7" nameend="col7" align="right">5</entry><entry namest="col8" nameend="col8" align="right">5</entry><entry namest="col9" nameend="col9" align="right">5</entry></row><row><entry namest="col1" nameend="col1" align="left">40% dicumyl peroxide</entry><entry namest="col2" nameend="col2" align="right">2</entry><entry namest="col3" nameend="col3" align="right">2</entry><entry namest="col4" nameend="col4" align="right">2</entry><entry namest="col5" nameend="col5" align="right">2</entry><entry namest="col6" nameend="col6" align="right">2</entry><entry namest="col7" nameend="col7" align="right">2</entry><entry namest="col8" nameend="col8" align="right">2</entry><entry namest="col9" nameend="col9" align="right">2</entry></row><row><entry namest="col1" nameend="col1" align="left">75% zinc diacrylate</entry><entry namest="col2" nameend="col2" align="right">9.33</entry><entry namest="col3" nameend="col3" align="right">13.33</entry><entry namest="col4" nameend="col4" align="right">13.33</entry><entry namest="col5" nameend="col5" align="right">9.33</entry><entry namest="col6" nameend="col6" align="right">13.33</entry><entry namest="col7" nameend="col7" align="right">9.33</entry><entry namest="col8" nameend="col8" align="right">9.33</entry><entry namest="col9" nameend="col9" align="right">13.33</entry></row><row><entry namest="col1" nameend="col1" align="left">Sulfur</entry><entry namest="col2" nameend="col2" align="right">0</entry><entry namest="col3" nameend="col3" align="right">0</entry><entry namest="col4" nameend="col4" align="right">0</entry><entry namest="col5" nameend="col5" align="right">0</entry><entry namest="col6" nameend="col6" align="right">1.4</entry><entry namest="col7" nameend="col7" align="right">1.4</entry><entry namest="col8" nameend="col8" align="right">1.4</entry><entry namest="col9" nameend="col9" align="right">1.4</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">TBBS</entry><entry namest="col2" nameend="col2" align="right">0</entry><entry namest="col3" nameend="col3" align="right">0</entry><entry namest="col4" nameend="col4" align="right">0</entry><entry namest="col5" nameend="col5" align="right">0</entry><entry namest="col6" nameend="col6" align="right">1</entry><entry namest="col7" nameend="col7" align="right">1</entry><entry namest="col8" nameend="col8" align="right">1</entry><entry namest="col9" nameend="col9" align="right">1</entry></row></tbody></tgroup><tgroup cols="9" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="17.50mm" /><colspec colnum="2" colname="col2" colwidth="17.50mm" /><colspec colnum="3" colname="col3" colwidth="17.50mm" /><colspec colnum="4" colname="col4" colwidth="17.50mm" /><colspec colnum="5" colname="col5" colwidth="17.50mm" /><colspec colnum="6" colname="col6" colwidth="17.50mm" /><colspec colnum="7" colname="col7" colwidth="17.50mm" /><colspec colnum="8" colname="col8" colwidth="17.50mm" /><colspec colnum="9" colname="col9" colwidth="17.50mm" /><tbody valign="top"><row><entry namest="col1" nameend="col9" align="justify">¹ SMR20</entry></row><row><entry namest="col1" nameend="col9" align="justify">² Budene® 1207, high cis-polybutadiene from The Goodyear Tire &amp; Rubber Company</entry></row><row><entry namest="col1" nameend="col9" align="justify">³ Natsyn® 2200, from The Goodyear Tire &amp; Rubber Company</entry></row><row><entry namest="col1" nameend="col9" align="justify">⁴ N550</entry></row></tbody></tgroup></table></tables><tables id="tabl0002" num="0002"><table frame="all"><title>Table 2</title><tgroup cols="2" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">ECO¹</entry><entry namest="col2" nameend="col2" align="center">70</entry></row><row><entry namest="col1" nameend="col1" align="left">CIIR²</entry><entry namest="col2" nameend="col2" align="center">30</entry></row><row><entry namest="col1" nameend="col1" align="left">Carbon black³</entry><entry namest="col2" nameend="col2" align="center">40</entry></row><row><entry namest="col1" nameend="col1" align="left">Stearic acid</entry><entry namest="col2" nameend="col2" align="center">2</entry></row><row><entry namest="col1" nameend="col1" align="left">Resins⁴</entry><entry namest="col2" nameend="col2" align="center">6</entry></row><row><entry namest="col1" nameend="col1" align="left">Process aids⁵</entry><entry namest="col2" nameend="col2" align="center">3</entry></row><row><entry namest="col1" nameend="col1" align="left">Zinc oxide</entry><entry namest="col2" nameend="col2" align="center">2.25</entry></row><row><entry namest="col1" nameend="col1" align="left">Sulfur</entry><entry namest="col2" nameend="col2" align="center">0.7</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Accelerators⁶</entry><entry namest="col2" nameend="col2" align="center">2.54</entry></row></tbody></tgroup><tgroup cols="2" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><tbody valign="top"><row><entry namest="col1" nameend="col2" align="justify">¹ Hydrin T3000L, Zeon Chemical Co.</entry></row><row><entry namest="col1" nameend="col2" align="justify">² HT-10-66, ExxonMobil Chemical Co.</entry></row><row><entry namest="col1" nameend="col2" align="justify">³ N550</entry></row><row><entry namest="col1" nameend="col2" align="justify">⁴ aromatic hydrocarbon and non-reactive phenol-formaldehyde types</entry></row><row><entry namest="col1" nameend="col2" align="justify">⁵ fatty acid derivative type</entry></row><row><entry namest="col1" nameend="col2" align="justify">⁶ thiazole and thiuram types</entry></row></tbody></tgroup></table></tables><tables id="tabl0003" num="0003"><table frame="all"><title>Table 3</title><tgroup cols="9" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="17.50mm" /><colspec colnum="2" colname="col2" colwidth="17.50mm" /><colspec colnum="3" colname="col3" colwidth="17.50mm" /><colspec colnum="4" colname="col4" colwidth="17.50mm" /><colspec colnum="5" colname="col5" colwidth="17.50mm" /><colspec colnum="6" colname="col6" colwidth="17.50mm" /><colspec colnum="7" colname="col7" colwidth="17.50mm" /><colspec colnum="8" colname="col8" colwidth="17.50mm" /><colspec colnum="9" colname="col9" colwidth="17.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="left">Sample</entry><entry namest="col2" nameend="col2" align="left">1</entry><entry namest="col3" nameend="col3" align="left">2</entry><entry namest="col4" nameend="col4" align="left">3</entry><entry namest="col5" nameend="col5" align="left">4</entry><entry namest="col6" nameend="col6" align="left">5</entry><entry namest="col7" nameend="col7" align="left">6</entry><entry namest="col8" nameend="col8" align="left">7</entry><entry namest="col9" nameend="col9" align="left">8</entry></row><row><entry namest="col1" nameend="col9" align="left"><u>Mooney Scorch, MS@121°C, 30 minutes</u></entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Minimum Viscosity</entry><entry namest="col2" nameend="col2" align="center">27.7</entry><entry namest="col3" nameend="col3" align="center">22.8</entry><entry namest="col4" nameend="col4" align="center">27.2</entry><entry namest="col5" nameend="col5" align="center">22.4</entry><entry namest="col6" nameend="col6" align="center">27.1</entry><entry namest="col7" nameend="col7" align="center">22.8</entry><entry namest="col8" nameend="col8" align="center">27.2</entry><entry namest="col9" nameend="col9" align="center">21.4</entry></row><row><entry namest="col1" nameend="col1" align="left">Time to 5 pt. Rise, Mins.</entry><entry namest="col2" nameend="col2" align="center">12.9</entry><entry namest="col3" nameend="col3" align="center">17.4</entry><entry namest="col4" nameend="col4" align="center">13.7</entry><entry namest="col5" nameend="col5" align="center">17.3</entry><entry namest="col6" nameend="col6" align="center">20.1</entry><entry namest="col7" nameend="col7" align="center">21.7</entry><entry namest="col8" nameend="col8" align="center">18.6</entry><entry namest="col9" nameend="col9" align="center">25.8</entry></row></tbody></tgroup><tgroup cols="9" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="17.50mm" /><colspec colnum="2" colname="col2" colwidth="17.50mm" /><colspec colnum="3" colname="col3" colwidth="17.50mm" /><colspec colnum="4" colname="col4" colwidth="17.50mm" /><colspec colnum="5" colname="col5" colwidth="17.50mm" /><colspec colnum="6" colname="col6" colwidth="17.50mm" /><colspec colnum="7" colname="col7" colwidth="17.50mm" /><colspec colnum="8" colname="col8" colwidth="17.50mm" /><colspec colnum="9" colname="col9" colwidth="17.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col9" align="left"><u>Rheometer, ODR, 150°C</u></entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">T₅₀</entry><entry namest="col2" nameend="col2" align="center">10.6</entry><entry namest="col3" nameend="col3" align="center">14.0</entry><entry namest="col4" nameend="col4" align="center">12.3</entry><entry namest="col5" nameend="col5" align="center">12.0</entry><entry namest="col6" nameend="col6" align="center">12.7</entry><entry namest="col7" nameend="col7" align="center">9.4</entry><entry namest="col8" nameend="col8" align="center">12.5</entry><entry namest="col9" nameend="col9" align="center">12.5</entry></row><row><entry namest="col1" nameend="col1" align="left">T₉₀</entry><entry namest="col2" nameend="col2" align="center">32.5</entry><entry namest="col3" nameend="col3" align="center">38.0</entry><entry namest="col4" nameend="col4" align="center">35.4</entry><entry namest="col5" nameend="col5" align="center">35.9</entry><entry namest="col6" nameend="col6" align="center">36.8</entry><entry namest="col7" nameend="col7" align="center">28.3</entry><entry namest="col8" nameend="col8" align="center">36.5</entry><entry namest="col9" nameend="col9" align="center">36.2</entry></row><row><entry namest="col1" nameend="col1" align="left">Time to 1 pt. Rise, Mins.</entry><entry namest="col2" nameend="col2" align="center">1.7</entry><entry namest="col3" nameend="col3" align="center">2.4</entry><entry namest="col4" nameend="col4" align="center">2.0</entry><entry namest="col5" nameend="col5" align="center">2.3</entry><entry namest="col6" nameend="col6" align="center">2.6</entry><entry namest="col7" nameend="col7" align="center">2.7</entry><entry namest="col8" nameend="col8" align="center">2.7</entry><entry namest="col9" nameend="col9" align="center">3.1</entry></row><row><entry namest="col1" nameend="col1" align="left">Maximum Torque</entry><entry namest="col2" nameend="col2" align="center">52.7</entry><entry namest="col3" nameend="col3" align="center">40.7</entry><entry namest="col4" nameend="col4" align="center">53.6</entry><entry namest="col5" nameend="col5" align="center">36.1</entry><entry namest="col6" nameend="col6" align="center">44.7</entry><entry namest="col7" nameend="col7" align="center">37.8</entry><entry namest="col8" nameend="col8" align="center">41.8</entry><entry namest="col9" nameend="col9" align="center">34.5</entry></row><row><entry namest="col1" nameend="col1" align="left">Minimum Torque</entry><entry namest="col2" nameend="col2" align="center">8.5</entry><entry namest="col3" nameend="col3" align="center">6.7</entry><entry namest="col4" nameend="col4" align="center">8.9</entry><entry namest="col5" nameend="col5" align="center">6.6</entry><entry namest="col6" nameend="col6" align="center">8.5</entry><entry namest="col7" nameend="col7" align="center">6.1</entry><entry namest="col8" nameend="col8" align="center">8.5</entry><entry namest="col9" nameend="col9" align="center">6.0</entry></row></tbody></tgroup><tgroup cols="9" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="17.50mm" /><colspec colnum="2" colname="col2" colwidth="17.50mm" /><colspec colnum="3" colname="col3" colwidth="17.50mm" /><colspec colnum="4" colname="col4" colwidth="17.50mm" /><colspec colnum="5" colname="col5" colwidth="17.50mm" /><colspec colnum="6" colname="col6" colwidth="17.50mm" /><colspec colnum="7" colname="col7" colwidth="17.50mm" /><colspec colnum="8" colname="col8" colwidth="17.50mm" /><colspec colnum="9" colname="col9" colwidth="17.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col9" align="left"><u>Rheometer, MDR, 191°C</u></entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">T₅₀</entry><entry namest="col2" nameend="col2" align="center">0.44</entry><entry namest="col3" nameend="col3" align="center">0.44</entry><entry namest="col4" nameend="col4" align="center">0.45</entry><entry namest="col5" nameend="col5" align="center">0.46</entry><entry namest="col6" nameend="col6" align="center">0.59</entry><entry namest="col7" nameend="col7" align="center">0.56</entry><entry namest="col8" nameend="col8" align="center">0.59</entry><entry namest="col9" nameend="col9" align="center">0.6</entry></row><row><entry namest="col1" nameend="col1" align="left">T₉₀</entry><entry namest="col2" nameend="col2" align="center">0.87</entry><entry namest="col3" nameend="col3" align="center">0.76</entry><entry namest="col4" nameend="col4" align="center">0.88</entry><entry namest="col5" nameend="col5" align="center">0.82</entry><entry namest="col6" nameend="col6" align="center">1.15</entry><entry namest="col7" nameend="col7" align="center">0.93</entry><entry namest="col8" nameend="col8" align="center">1.1</entry><entry namest="col9" nameend="col9" align="center">1.05</entry></row><row><entry namest="col1" nameend="col1" align="left">Time to 2 pt. Rise, Mins.</entry><entry namest="col2" nameend="col2" align="center">0.29</entry><entry namest="col3" nameend="col3" align="center">0.34</entry><entry namest="col4" nameend="col4" align="center">0.3</entry><entry namest="col5" nameend="col5" align="center">0.37</entry><entry namest="col6" nameend="col6" align="center">0.38</entry><entry namest="col7" nameend="col7" align="center">0.41</entry><entry namest="col8" nameend="col8" align="center">0.39</entry><entry namest="col9" nameend="col9" align="center">0.45</entry></row><row><entry namest="col1" nameend="col1" align="left">Maximum Torque</entry><entry namest="col2" nameend="col2" align="center">18.9</entry><entry namest="col3" nameend="col3" align="center">10.9</entry><entry namest="col4" nameend="col4" align="center">20.3</entry><entry namest="col5" nameend="col5" align="center">9.6</entry><entry namest="col6" nameend="col6" align="center">14.8</entry><entry namest="col7" nameend="col7" align="center">11.7</entry><entry namest="col8" nameend="col8" align="center">13.9</entry><entry namest="col9" nameend="col9" align="center">10.5</entry></row><row><entry namest="col1" nameend="col1" align="left">Minimum Torque</entry><entry namest="col2" nameend="col2" align="center">2.15</entry><entry namest="col3" nameend="col3" align="center">1.65</entry><entry namest="col4" nameend="col4" align="center">2.07</entry><entry namest="col5" nameend="col5" align="center">1.68</entry><entry namest="col6" nameend="col6" align="center">1.95</entry><entry namest="col7" nameend="col7" align="center">1.6</entry><entry namest="col8" nameend="col8" align="center">1.96</entry><entry namest="col9" nameend="col9" align="center">1.49</entry></row></tbody></tgroup><tgroup cols="9" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="17.50mm" /><colspec colnum="2" colname="col2" colwidth="17.50mm" /><colspec colnum="3" colname="col3" colwidth="17.50mm" /><colspec colnum="4" colname="col4" colwidth="17.50mm" /><colspec colnum="5" colname="col5" colwidth="17.50mm" /><colspec colnum="6" colname="col6" colwidth="17.50mm" /><colspec colnum="7" colname="col7" colwidth="17.50mm" /><colspec colnum="8" colname="col8" colwidth="17.50mm" /><colspec colnum="9" colname="col9" colwidth="17.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col9" align="left"><u>Original Properties</u></entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Tensile (MPa)</entry><entry namest="col2" nameend="col2" align="center">13.0</entry><entry namest="col3" nameend="col3" align="center">20.8</entry><entry namest="col4" nameend="col4" align="center">15.1</entry><entry namest="col5" nameend="col5" align="center">21.5</entry><entry namest="col6" nameend="col6" align="center">17.2</entry><entry namest="col7" nameend="col7" align="center">21.2</entry><entry namest="col8" nameend="col8" align="center">16.4</entry><entry namest="col9" nameend="col9" align="center">23.1</entry></row><row><entry namest="col1" nameend="col1" align="left">Elongation (%)</entry><entry namest="col2" nameend="col2" align="center">204</entry><entry namest="col3" nameend="col3" align="center">327</entry><entry namest="col4" nameend="col4" align="center">253</entry><entry namest="col5" nameend="col5" align="center">392</entry><entry namest="col6" nameend="col6" align="center">462</entry><entry namest="col7" nameend="col7" align="center">484</entry><entry namest="col8" nameend="col8" align="center">530</entry><entry namest="col9" nameend="col9" align="center">558</entry></row><row><entry namest="col1" nameend="col1" align="left">Modulus @ 50%</entry><entry namest="col2" nameend="col2" align="center">2.01</entry><entry namest="col3" nameend="col3" align="center">1.54</entry><entry namest="col4" nameend="col4" align="center">2.16</entry><entry namest="col5" nameend="col5" align="center">1.23</entry><entry namest="col6" nameend="col6" align="center">1.48</entry><entry namest="col7" nameend="col7" align="center">1.35</entry><entry namest="col8" nameend="col8" align="center">1.27</entry><entry namest="col9" nameend="col9" align="center">1.18</entry></row><row><entry namest="col1" nameend="col1" align="left">Modulus @ 100%</entry><entry namest="col2" nameend="col2" align="center">4.72</entry><entry namest="col3" nameend="col3" align="center">3.78</entry><entry namest="col4" nameend="col4" align="center">4.70</entry><entry namest="col5" nameend="col5" align="center">2.63</entry><entry namest="col6" nameend="col6" align="center">2.67</entry><entry namest="col7" nameend="col7" align="center">2.65</entry><entry namest="col8" nameend="col8" align="center">2.02</entry><entry namest="col9" nameend="col9" align="center">2.01</entry></row><row><entry namest="col1" nameend="col1" align="left">Modulus @ 200%</entry><entry namest="col2" nameend="col2" align="center">12.74</entry><entry namest="col3" nameend="col3" align="center">12.13</entry><entry namest="col4" nameend="col4" align="center">11.97</entry><entry namest="col5" nameend="col5" align="center">8.54</entry><entry namest="col6" nameend="col6" align="center">6.54</entry><entry namest="col7" nameend="col7" align="center">6.93</entry><entry namest="col8" nameend="col8" align="center">4.39</entry><entry namest="col9" nameend="col9" align="center">4.97</entry></row><row><entry namest="col1" nameend="col1" align="left">Modulus @300%</entry><entry namest="col2" nameend="col2" align="center">-</entry><entry namest="col3" nameend="col3" align="center">19.70</entry><entry namest="col4" nameend="col4" align="center">-</entry><entry namest="col5" nameend="col5" align="center">15.57</entry><entry namest="col6" nameend="col6" align="center">10.88</entry><entry namest="col7" nameend="col7" align="center">12.80</entry><entry namest="col8" nameend="col8" align="center">7.58</entry><entry namest="col9" nameend="col9" align="center">9.13</entry></row><row><entry namest="col1" nameend="col1" align="left">Hardness (Shore A)</entry><entry namest="col2" nameend="col2" align="center">69</entry><entry namest="col3" nameend="col3" align="center">64</entry><entry namest="col4" nameend="col4" align="center">70</entry><entry namest="col5" nameend="col5" align="center">58</entry><entry namest="col6" nameend="col6" align="center">65</entry><entry namest="col7" nameend="col7" align="center">63</entry><entry namest="col8" nameend="col8" align="center">62</entry><entry namest="col9" nameend="col9" align="center">60</entry></row></tbody></tgroup><tgroup cols="9" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="17.50mm" /><colspec colnum="2" colname="col2" colwidth="17.50mm" /><colspec colnum="3" colname="col3" colwidth="17.50mm" /><colspec colnum="4" colname="col4" colwidth="17.50mm" /><colspec colnum="5" colname="col5" colwidth="17.50mm" /><colspec colnum="6" colname="col6" colwidth="17.50mm" /><colspec colnum="7" colname="col7" colwidth="17.50mm" /><colspec colnum="8" colname="col8" colwidth="17.50mm" /><colspec colnum="9" colname="col9" colwidth="17.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col9" align="left"><u>Fabric Adhesion, RFL-Dipped Nylon Fabric</u></entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Adhesion 1(N / 25mm)</entry><entry namest="col2" nameend="col2" align="center">205</entry><entry namest="col3" nameend="col3" align="center">325</entry><entry namest="col4" nameend="col4" align="center">76</entry><entry namest="col5" nameend="col5" align="center">231</entry><entry namest="col6" nameend="col6" align="center">102</entry><entry namest="col7" nameend="col7" align="center">125</entry><entry namest="col8" nameend="col8" align="center">343</entry><entry namest="col9" nameend="col9" align="center">147</entry></row><row><entry namest="col1" nameend="col1" align="left">Adhesion 2</entry><entry namest="col2" nameend="col2" align="center">223</entry><entry namest="col3" nameend="col3" align="center">360</entry><entry namest="col4" nameend="col4" align="center">116</entry><entry namest="col5" nameend="col5" align="center">209</entry><entry namest="col6" nameend="col6" align="center">107</entry><entry namest="col7" nameend="col7" align="center">120</entry><entry namest="col8" nameend="col8" align="center">396</entry><entry namest="col9" nameend="col9" align="center">151</entry></row><row><entry namest="col1" nameend="col1" align="left">Avg. Adhesion</entry><entry namest="col2" nameend="col2" align="center">214</entry><entry namest="col3" nameend="col3" align="center">343</entry><entry namest="col4" nameend="col4" align="center">96</entry><entry namest="col5" nameend="col5" align="center">220</entry><entry namest="col6" nameend="col6" align="center">105</entry><entry namest="col7" nameend="col7" align="center">122</entry><entry namest="col8" nameend="col8" align="center">369</entry><entry namest="col9" nameend="col9" align="center">149</entry></row></tbody></tgroup><tgroup cols="9" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="17.50mm" /><colspec colnum="2" colname="col2" colwidth="17.50mm" /><colspec colnum="3" colname="col3" colwidth="17.50mm" /><colspec colnum="4" colname="col4" colwidth="17.50mm" /><colspec colnum="5" colname="col5" colwidth="17.50mm" /><colspec colnum="6" colname="col6" colwidth="17.50mm" /><colspec colnum="7" colname="col7" colwidth="17.50mm" /><colspec colnum="8" colname="col8" colwidth="17.50mm" /><colspec colnum="9" colname="col9" colwidth="17.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col9" align="left"><u>Compound Adhesion, ECO/CIIR Blend</u></entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Adhesion 1 (N / 25mm)</entry><entry namest="col2" nameend="col2" align="center">240</entry><entry namest="col3" nameend="col3" align="center">320</entry><entry namest="col4" nameend="col4" align="center">236</entry><entry namest="col5" nameend="col5" align="center">169</entry><entry namest="col6" nameend="col6" align="center">116</entry><entry namest="col7" nameend="col7" align="center">165</entry><entry namest="col8" nameend="col8" align="center">102</entry><entry namest="col9" nameend="col9" align="center">160</entry></row><row><entry namest="col1" nameend="col1" align="left">Adhesion 2</entry><entry namest="col2" nameend="col2" align="center">231</entry><entry namest="col3" nameend="col3" align="center">307</entry><entry namest="col4" nameend="col4" align="center">316</entry><entry namest="col5" nameend="col5" align="center">165</entry><entry namest="col6" nameend="col6" align="center">111</entry><entry namest="col7" nameend="col7" align="center">174</entry><entry namest="col8" nameend="col8" align="center">98</entry><entry namest="col9" nameend="col9" align="center">169</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Avg. Adhesion</entry><entry namest="col2" nameend="col2" align="center">236</entry><entry namest="col3" nameend="col3" align="center">314</entry><entry namest="col4" nameend="col4" align="center">276</entry><entry namest="col5" nameend="col5" align="center">167</entry><entry namest="col6" nameend="col6" align="center">113</entry><entry namest="col7" nameend="col7" align="center">169</entry><entry namest="col8" nameend="col8" align="center">100</entry><entry namest="col9" nameend="col9" align="center">165</entry></row></tbody></tgroup></table></tables>

0031The data of Tables 1, 2 and 3 illustrate that samples made according to the present invention surprisingly and unexpectedly showed significantly higher adhesion to an elastomeric cover compound than did samples made otherwise.