POWER TRANSMISSION BELT

Abstract

Power transmission belts have a hydrogenated nitrile-butadiene-PEG acrylate copolymer of 25% to 38% by weight by weight of at least one ,-ethylenically unsaturated nitrile unit, 40% to 60% by weight by weight of at least one conjugated diene unit and 10% to 25% by weight by weight of at least one PEG acrylate unit derived from a PEG acrylate of the general formula (I)

##STR00001##

where R is hydrogen or branched or unbranched C1-C20-alkyl, preferably methyl, ethyl, butyl or ethylhexyl, n is 1 to 8, preferably 2 to 8, more preferably 2 to 5 and most preferably 3 and R1 is hydrogen or CH3-,
where the hydrogenated nitrile-butadiene-PEG acrylate copolymer, if n is 1, does not contain any further copolymerizable monomer unit having a free carboxylic acid group.

Claims

1. A power transmission belt comprising: a hydrogenated nitrile-butadiene-PEG acrylate copolymer comprising: a) 25% to 38% by weight by weight of at least one ,-ethylenically unsaturated nitrile unit, b) 40% to 60% by weight by weight of at least one conjugated diene unit, and c) 10% to 25% by weight by weight of at least one PEG acrylate unit derived from a PEG acrylate of the general formula (I) ##STR00006## where R is hydrogen or branched or unbranched C1-C20-alkyl, preferably methyl, ethyl, butyl or ethylhexyl, n is 1 to 8, preferably 2 to 8, more preferably 2 to 5 and most preferably 3 and R1 is hydrogen or CH3-, where the hydrogenated nitrile-butadiene-PEG acrylate copolymer, if n is 1, does not contain any further copolymerizable monomer unit having a free carboxylic acid group.

2. The power transmission belt according to claim 1, wherein the nitrile units (a) are 29% to 33% by weight.

3. The power transmission belt according to claim 1, wherein the ,-ethylenically unsaturated nitrile units (a) is acrylonitrile, methacrylonitrile, ethacrylonitrile or a mixtures thereof.

4. The power transmission belt according to claim 1, wherein the conjugated diene units (b) are 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene (piperylene) or mixtures thereof.

5. The power transmission belt according to claim 1, wherein the PEG acrylate unit (c) is methoxy, ethoxy, butoxy or ethylhexoxy polyethylene glycol (meth)acrylate having 2 to 8 repeat ethylene glycol units.

6. The power transmission belt according to claim 1, wherein the level of hydrogenation of the conjugated diene units (b) is more than 50%.

7. The power transmission belt according to claim 1, wherein the hydrogenated nitrile-butadiene-PEG acrylate copolymer is within the mixture forming the body of the power transmission belt.

8. The power transmission belt according to claim 1, wherein hydrogenated nitrile-butadiene-PEG acrylate copolymer is constituted by more than 50% by weight, calculated on the total weight of elastomer of the mixture forming the body of the power transmission belt.

9. The power transmission belt according to claim 1, wherein said material is loaded with fibres in a quantity of between 1% and 50% by weight of the total non-elastomeric material.

10. The power transmission belt according to claim 1, wherein the power transmission belt is a toothed power transmission belt.

11. An assembly comprising an engine, a power transmission belt according to claim 1, and oil lubricating the engine; wherein, during operation of the engine, the oil continuously contacts the power transmission belt.

12. A system comprising a power transmission belt according to claim 1 and oil, wherein said power transmission belt is in direct contact with oil or is partially immersed in oil.

13. The power transmission belt according to claim 1, wherein the hydrogenated nitrile-butadiene-PEG acrylate copolymer comprises 27% to 37% by weight by weight of at least one ,-ethylenically unsaturated nitrile unit, 42% to 58% by weight by weight of at least one conjugated diene unit, and 11% to 22% by weight by weight of at least one PEG acrylate unit derived from a PEG acrylate of the general formula (I).

14. The power transmission belt according to claim 1, wherein the hydrogenated nitrile-butadiene-PEG acrylate copolymer comprises 29% to 36% by weight of at least one ,-ethylenically unsaturated nitrile unit, 44% to 59% by weight of at least one conjugated diene unit, and 12% to 20% by weight of at least one PEG acrylate unit derived from a PEG acrylate of the general formula (I).

15. The power transmission belt according to claim 3, wherein the ,-ethylenically unsaturated nitrile units (a) is acrylonitrile.

16. The power transmission belt according to claim 4, wherein the conjugated diene units (b) are 1,3-butadiene.

17. The power transmission belt according to claim 5, wherein the PEG acrylate unit (c) is methoxy or ethoxy polyethylene glycol (meth)acrylate having 2 to 5 repeat ethylene glycol units.

18. The power transmission belt according to claim 5, wherein the PEG acrylate unit (c) is methoxy or ethoxy polyethylene glycol (meth)acrylate having 3 repeat ethylene glycol units.

19. The power transmission belt according to claim 6, wherein the level of hydrogenation of the conjugated diene units (b) is 90% or more.

20. The power transmission belt according to claim 6, wherein the level of hydrogenation of the conjugated diene units (b) is 99% or more.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0033] For a better understanding of the present invention, it will now be described with reference to the attached figure, in which:

[0034] FIG. 1 is a side view of a portion of toothed power transmission belt according to the present invention;

[0035] FIG. 2 a rig for a flexibility test of a power transmission belt according to the present invention;

[0036] FIG. 3 a rig for an oil swelling test of a power transmission belt according to the present invention;

[0037] FIG. 4 a graph showing the result of a flexibility test according to the present invention; and

[0038] FIG. 5 a graph showing the result of a swelling in oil test according to the present invention.

DESCRIPTION

[0039] FIG. 1 shows a power transmission belt, indicated as a whole by reference numeral 1. The power transmission belt 1 comprises a body 2 made of elastomeric material comprising a hydrogenated nitrile-butadiene-PEG acrylate copolymer in which is a plurality of longitudinal filiform resistant inserts 3 are embedded. In a preferred alternative, the body 2 has a toothing 4, which is covered by a covering fabric 8.

[0040] The power transmission belt also comprises a back 7 opposite to the working surface 5.

[0041] Hereinafter, by the expression power transmission belt is intended not only a toothed belt but also all kind of known power transmission belts as V-belts, poly-V belts, trapezoidal belts, flat belts.

[0042] Hereinafter, by the expression the elastomeric material is basically constituted it is meant that the elastomeric material can comprise small percentages of other polymers or copolymers, which can be added to the elastomeric material without varying the chemical-physical characteristics of the mixture and hence without departing from the scope of the present invention. Hereinafter, it is understood that additive for elastomeric material means some kind of material that is added to the elastomeric material to change its chemical and physical characteristics.

[0043] Use in oil or in an oil mist means that the power transmission belt is used partially immersed in an oil bath or is in direct contact with oil, generally the power transmission belt in use is within the engine block, for instance as a replacement of chain or gear systems.

[0044] Use in dry conditions means that the power transmission belts are outside the engine block and are only accidentally in contact with the engine oil and are not generally in contact with fuel-mixed oil.

[0045] Use in fuel-mixed oil means that the power transmission belt is used in a mixture of oil with percentages even over 30%.

[0046] The power transmission belt comprises a hydrogenated nitrile-butadiene-PEG acrylate copolymer containing

[0047] a) 25% to 38% by weight, preferably 27% to 37% by weight and more preferably 29% to 36% by weight of at least one ,-ethylenically unsaturated nitrile unit,

[0048] b) 40% to 60% by weight, preferably 42% to 58% by weight and

[0049] more preferably 44% to 56% by weight of at least one conjugated diene unit and [0050] c) 10% to 25% by weight, preferably 11% to 22% by weight and more preferably 12% to 20% by weight of at least one PEG acrylate unit derived from a PEG acrylate of the general formula (I)

##STR00002##

[0051] where

[0052] R is hydrogen or branched or unbranched C1-C20-alkyl, preferably methyl, ethyl, butyl or ethylhexyl,

[0053] n is 1 to 8, preferably 2 to 8, more preferably 2 to 5 and most preferably 3 and

[0054] R1 is hydrogen or CH3-,

[0055] where the hydrogenated nitrile-butadiene-PEG acrylate copolymer, if n is 1, does not contain any further copolymerizable monomer unit having a free carboxylic acid group.

[0056] Preferably the above elastomer is used within the body 2, but it can be used also in any other portion of the power transmission belt as for example in the fabric treatment composition, in the compound forming the teeth, in a further compound forming only the back of the power transmission belt and not the full body. Preferably the body or also any further elastomeric mixture within the power transmission belt is made of a compound comprising one or more elastomeric materials as the main elastomer and numerous additives.

[0057] The main elastomer is intended as being present in the compound that constitutes the body for more than 50% by weight, calculated on the total weight of all the elastomers in the compound and therefore excluding all other non-elastomeric components of the power transmission belt.

[0058] Preferably the invention elastomer is the main elastomer.

[0059] In an embodiment of the invention, at least some of the conjugated diene units have been hydrogenated. Preferably, the level of hydrogenation is 50% or more, more preferably 90% or more, most preferably 99% or more.

[0060] It should be noted that the scope of the invention includes any and all possible combinations of the components, ranges of values and/or process parameters mentioned above and cited hereinafter, in general terms or within areas of preference.

[0061] The term nitrile-butadiene-PEG acrylate copolymer in the context of this invention concerns a copolymer containing at least one ,-ethylenically unsaturated nitrile monomer unit, at least one conjugated diene monomer unit and at least one PEG acrylate unit derived from a PEG acrylate of the general formula (I).

[0062] The term copolymer encompasses polymers having more than one monomer unit. In one embodiment of the invention, the copolymer is derived preferably, for example, from the three monomer types (a), (b) and (c) described, and is therefore a terpolymer. The term copolymer likewise encompasses, for example, additionally quaterpolymers, derived from the three monomer types (a), (b) and (c) described and a further monomer unit (d). ,-Ethylenically unsaturated nitrile

[0063] The ,-ethylenically unsaturated nitrile used, which forms the ,-ethylenically unsaturated nitrile units (a), may be any known ,-ethylenically unsaturated nitrile. Preference is given to (C3-C5)-,-ethylenically unsaturated nitriles such as acrylonitrile, -haloacrylnitrile, for example -chloroacrylnitrile and -bromoacrylnitrile, -alkylacrylonitrile, for example methacrylonitrile, ethacrylonitrile or mixtures of two or more ,-ethylenically unsaturated nitriles. Particular preference is given to acrylonitrile, methacrylonitrile, ethacrylonitrile or mixtures thereof. Very particular preference is given to acrylonitrile. The amount of ,-ethylenically unsaturated nitrile units (a) is typically in the range from 25% to 38% by weight, preferably 27% to 37% by weight, more preferably from 29% to 36% by weight, based on the total amount of 100% by weight of all the monomer units. The best preferred range is 29% to 33% by weight.

[0064] Conjugated Diene

[0065] The conjugated diene, which forms the conjugated diene unit (b), may be of any type, especially conjugated C4-C12 dienes. Particular preference is given to 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene (piperylene) or mixtures thereof. Especially preferred are 1,3-butadiene and isoprene or mixtures thereof. Very particular preference is given to 1,3-butadiene.

[0066] The amount of conjugated diene is typically in the range from 40% to 60% by weight, preferably 42% to 58% by weight and more preferably 44% to 56% by weight, based on the total amount of 100% by weight of all the monomer units.

[0067] PEG Acrylate

[0068] In addition to the ,-ethylenically unsaturated nitrile units and the conjugated diene units, the hydrogenated nitrile-butadiene-PEG acrylate copolymer contains, as a third unit, at least one PEG acrylate unit derived from PEG acrylates of the general formula (I)

##STR00003##

[0069] where

[0070] R is hydrogen or branched or unbranched C1-C20-alkyl, preferably methyl, ethyl, butyl or ethylhexyl,

[0071] n is 1 to 8, preferably 2 to 8, more preferably 2 to 5 and most preferably 3 and

[0072] R1 is hydrogen or CH3-.

[0073] The term (meth)acrylate in the context of this invention represents acrylate and methacrylate. When the R1 radical in the general formula (I) is CH3-, the molecule is a methacrylate.

[0074] The term polyethylene glycol or the abbreviation PEG in the context of this invention represents both monoethylene glycol sections having one repeat ethylene glycol unit (PEG-1; n=1) and polyethylene glycol sections having 2 to 8 repeat ethylene glycol units (PEG-2 to PEG-8; n=2 to 8).

[0075] The term PEG acrylate is also abbreviated to PEG-X-(M)A where X represents the number of repeat ethylene glycol units, MA represents methacrylate and A represents acrylate.

[0076] Acrylate units derived from PEG acrylates of the general formula (I) are referred to in the context of this invention as PEG acrylate unit.

[0077] Preferred PEG acrylate units are derived from the PEG acrylates of the following formulae no. 1 to no. 10, where n is 1, 2, 3, 4, 5, 6, 7 or 8, preferably 2, 3, 4, 5, 6, 7 or 8, more preferably 3, 4, 5, 6, 7 or 8 and most preferably 3:

##STR00004## ##STR00005##

[0078] Other commonly used names for methoxy polyethylene glycol acrylate (formula no. 3) are, for example, poly(ethylene glycol) methyl ether acrylate, acryloyl-PEG, methoxy-PEG acrylate, methoxy poly(ethylene glycol) monoacrylate, poly(ethylene glycol) monomethyl ether monoacrylate or mPEG acrylate.

[0079] These PEG acrylates can be purchased commercially, for example from Arkema under the Sartomer trade name, from Evonik under the Visiomer trade name, or from Sigma Aldrich.

[0080] The amount of the PEG acrylate units in copolymers of the invention is in the range from 10% to 25% by weight, preferably 11% to 22% by weight and more preferably 12% to 20% by weight, based on the total amount of 100% by weight of all the monomer units.

[0081] In a preferred hydrogenated nitrile-butadiene-PEG acrylate copolymer of the invention, the ,-ethylenically unsaturated nitrile unit (a) is derived from acrylonitrile or methacrylonitrile, more preferably from acrylonitrile, the conjugated diene unit (b) from isoprene or 1,3-butadiene, more preferably from 1,3-butadiene, and the PEG acrylate unit (c) is derived from PEG acrylate of the general formula (I) where n is 3 to 8, more preferably from PEG acrylate of the general formula (I) with n=3.

[0082] In addition, the hydrogenated nitrile-butadiene-PEG acrylate copolymer may contain one or more further copolymerizable monomers in an amount of 0.1% by weight to 10% by weight, preferably 0.1% by weight to 5% by weight, based on the total amount of 100% by weight of all monomer units. In that case, the amounts of the other monomer units are reduced in a suitable manner, such that the sum total is always 100% by weight. Further preferred copolymerizable monomers which may be used are, for example: [0083] aromatic vinyl monomers, preferably styrene, -methylstyrene and vinylpyridine, [0084] fluorinated vinyl monomers, preferably fluoroethyl vinyl ether, fluoropropyl vinyl ether, o-fluoromethylstyrene, vinyl pentafluorobenzoate, difluoroethylene and tetrafluoroethylene, or else [0085] -olefins, preferably C2-C12 olefins, for example ethylene, 1-butene, 4-butene, 4-methyl-1-pentene, 1-hexene or 1-octene, [0086] non-conjugated dienes, preferably C4-C12 dienes such as 1,4-pentadiene, 1,4-hexadiene, 4-cyanocyclohexene, 4-vinylcyclohexene, vinylnorbornene, dicyclopentadiene or else, [0087] alkynes such as 1- or 2-butyne, [0088] ,-ethylenically unsaturated monocarboxylic acids, preferably acrylic acid, methacrylic acid, crotonic acid or cinnamic acid, [0089] ,-ethylenically unsaturated monocarboxylic acid esters, preferably butyl acrylate, [0090] ,-ethylenically unsaturated dicarboxylic acids, preferably maleic acid, fumaric acid, citraconic acid, itaconic acid, [0091] ,-ethylenically unsaturated dicarboxylic acid monoesters, for example: [0092] alkyl, especially C4-C18-alkyl, preferably n-butyl, tert-butyl, n-pentyl or n-hexyl, more preferably mono-n-butyl maleate, mono-n-butyl fumarate, mono-n-butyl citraconate, mono-n-butyl itaconate; [0093] alkoxyalkyl, especially C4-C18-alkoxyalkyl, preferably C4-C12-alkoxyalkyl, [0094] hydroxyalkyl, especially C4-C18-hydroxyalkyl, preferably C4-C12-hydroxyalkyl, [0095] cycloalkyl, especially C5-C18-cycloalkyl, preferably C6-C12-cycloalkyl, more preferably monocyclopentyl maleate, monocyclohexyl maleate, monocycloheptyl maleate, monocyclopentyl fumarate, monocyclohexyl fumarate, monocycloheptyl fumarate, monocyclopentyl citraconate, monocyclohexyl citraconate, monocycloheptyl citraconate, monocyclopentyl itaconate, monocyclohexyl itaconate and monocycloheptyl itaconate, [0096] alkylcycloalkyl, especially C6-C12-alkylcycloalkyl, preferably C7-C10-alkylcycloalkyl, more preferably monomethylcyclopentyl maleate and monoethylcyclohexyl maleate, monomethylcyclopentyl fumarate and monoethylcyclohexyl fumarate, monomethylcyclopentyl citraconate and monoethylcyclohexyl citraconate; monomethylcyclopentyl itaconate and monoethylcyclohexyl itaconate; [0097] aryl, especially C6-C14-aryl, monoester, preferably monoaryl maleate, monoaryl fumarate, monoaryl citraconate or monoaryl itaconate, more preferably monophenyl maleate or monobenzyl maleate, monophenyl fumarate or monobenzyl fumarate, monophenyl citraconate or monobenzyl citraconate, monophenyl itaconate or monobenzyl itaconate or mixtures thereof, [0098] unsaturated polyalkyl polycarboxylates, for example dimethyl maleate, dimethyl fumarate, dimethyl itaconate or diethyl itaconate; or [0099] ,-ethylenically unsaturated carboxylic esters containing amino groups, for example dimethylaminomethyl acrylate or diethylaminoethyl acrylate [0100] copolymerizable antioxidants, for example N-(4-anilinophenyl)acrylamide, N-(4-anilinophenyl)methacrylamide, N-(4-anilinophenyl)cinnamide, N-(4-anilinophenyl)crotonamide, N-phenyl-4-(3-vinylbenzyloxy)aniline, N-phenyl-4-(4-vinylbenzyloxy) aniline or [0101] crosslinkable monomers, for example divinyl components, for example divinylbenzene; di(meth)acrylic esters, for example ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, butanediol di(meth)acrylate or polyethylene glycol di(meth)acrylate, or tri(meth)acrylic esters, for example trimethylolpropane tri(meth)acrylate; self-crosslinkable monomers, for example dimethylol(meth)acrylamide.

[0102] Some further copolymerizable monomers affect the physical properties of the hydrogenated nitrile-butadiene-PEG acrylate copolymer of the invention.

[0103] Copolymerized monomer units having at least one free carboxylic acid group, for example acrylic acid, methacrylic acid, ethylenically unsaturated dicarboxylic monoesters or ethylenically unsaturated dicarboxylic acids, generally lead to a deterioration in the ageing properties. As a result of free acid groups in the polymer, a drop in extension after ageing at elevated temperatures was detectable. At the same time, a rise in the glass transition temperature was observable, which has adverse effects on the demand for excellent low-temperature flexibility which has been made here. The effect on the ageing properties depends upon factors including the length of the copolymerized PEG acrylate unit, with particular deterioration in the ageing properties especially in the case of a copolymerized PEG-1 unit, i.e. in the case of PEG acrylate units derived from (alkoxy) monoethylene glycol (meth)acrylate.

[0104] In one embodiment, the hydrogenated nitrile-butadiene-PEG acrylate copolymer of the invention contains, aside from the ,-ethylenically unsaturated nitrile unit, the conjugated diene unit and the PEG acrylate unit derived from a PEG acrylate of the general formula (I) where n is 1, no monomer units having a free carboxylic acid group.

[0105] Even more preferably, the hydrogenated nitrile-butadiene-PEG acrylate copolymer contains, aside from the ,-ethylenically unsaturated nitrile unit, the conjugated diene unit and the PEG acrylate unit derived from a PEG acrylate of the general formula (I), no monomer units having a free carboxylic acid group.

[0106] Most preferably, the hydrogenated nitrile-butadiene-PEG acrylate copolymer contains, aside from the ,-ethylenically unsaturated nitrile unit, the conjugated diene unit and the PEG acrylate unit derived from a PEG acrylate of the general formula (I), no further monomer units. This means that this embodiment consists solely of ,-ethylenically unsaturated nitrile units, conjugated diene units and PEG acrylate units derived from a PEG acrylate of the general formula (I).

[0107] The hydrogenated nitrile-butadiene-PEG acrylate copolymer of the invention typically has a number-average molecular weight (Mn) of 10 000 to 2 000 000 g/mol, preferably 50 000 to 1 000 000 g/mol, more preferably 100 000 to 500 000 g/mol and most preferably 150 000 to 300 000 g/mol.

[0108] The hydrogenated nitrile-butadiene-PEG acrylate copolymer of the invention typically has a polydispersity index (PDI=Mw/Mn where Mw is the weight-average molecular weight) of 1.5 to 6, preferably 2 to 5 and more preferably 2.5 to 4.

[0109] The hydrogenated nitrile-butadiene-PEG acrylate copolymer of the invention typically has a Mooney viscosity (ML1+4@100 C.) of 10 to 150, preferably of 20 to 120 and more preferably of 25 to 100.

[0110] A power transmission belt comprising the hydrogenated nitrile-butadiene-PEG acrylate copolymer of the invention has obtained optimal result in term of high temperature resistance, but in particular in term of low oil swell and low-temperature characteristics.

[0111] Advantageously, the hydrogenated nitrile-butadiene-PEG acrylate copolymer used for making the transmission systems in which the power transmission belt is partially in an oil bath or in direct contact with oil and impurities has a high level of hydrogenation, for example so-called fully saturated hydrogenated nitrile-butadiene-PEG acrylate copolymer can be used. These hydrogenated nitrile-butadiene-PEG acrylate copolymers have a percentage of residual double bonds of 0.9% at most. Hydrogenated nitrile-butadiene-PEG acrylate copolymer with a lower level of unsaturation can also be used in alternative, such as, for example, so-called partially saturated hydrogenated nitrile-butadiene-PEG acrylate copolymer having a saturation level of 4% or 5.5%.

[0112] Process for Preparing Hydrogenated Nitrile-Butadiene-PEG Acrylate Copolymers

[0113] The preparation of the nitrile-butadiene-PEG acrylate copolymers required for the hydrogenation can be done by polymerization of the aforementioned monomers which has been described extensively in the literature (e.g. Houben-Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry], vol. 14/1, 30 Georg Thieme Verlag Stuttgart 1961) and is not particularly restricted. In general, the process is one in which ,-ethylenically unsaturated nitrile units, conjugated diene units and PEG acrylate units are copolymerized as desired. The polymerization process used may be any known emulsion polymerization process, suspension polymerization process, bulk polymerization process and solution polymerization process. Emulsion polymerization is especially understood to mean a process known per se in which the reaction medium used is usually water (see, inter alia, Rmpp Lexikon der Chemie [Rmpp's Chemistry Lexicon], volume 2, 10th edition 1997; P. A. Lovell, M. S. El-Aasser, Emulsion Polymerization and Emulsion Polymers, John Wiley & Sons, ISBN: 0471 96746 7; H. Gerrens, Fortschr. Hochpolym. Forsch. 1, 234 (1959)). The incorporation rate of the termonomer can be adjusted directly by the person skilled in the art, such that a hydrogenated nitrile-butadiene-PEG acrylate copolymer of this invention is obtained. The monomers can be initially charged or converted by incrementation in a number of steps.

[0114] After the copolymerization of the nitrile-butadiene-PEG acrylate copolymers, they are at least partly hydrogenated (hydrogen addition reaction). In the at least partly hydrogenated nitrile-butadiene-PEG acrylate copolymers, at least some of the CC double bonds of the repeat unit derived from the conjugated diene have been specifically hydrogenated. The level of hydrogenation of the conjugated diene units (b) in hydrogenated nitrile-butadiene-PEG acrylate copolymers of the invention is preferably 50% or more, more preferably 90% or more, most preferably 99% or more.

[0115] The hydrogenation of nitrile-butadiene copolymers is known, for example from U.S. Pat. No. 3,700,637, DE-A-2 539 132, DE-A-3 046 008, DE-A-3 046 251, DE-A-3 227 650, DE-A-3 329 974, EP-A-111 412, FR-B 2 540 503. Hydrogenated nitrile-butadiene copolymers are notable for high breaking strength, low abrasion, consistently low deformation after pressure and tensile stress, and good oil resistance, but in particular for remarkable stability against thermal and oxidative influences.

[0116] The body of the power transmission belt may advantageously comprise one or more further elastomers that is chosen from the group constituted by natural rubber (NR), polychloroprene (CR), acrylonitrile butadiene (NBR) and associated hydrogenated elastomers known as hydrogenated acrylonitrile butadiene (HNBR) or zinc salts of hydrogenated acrylonitrile butadiene seamed with esters of unsaturated carboxylic acid, polyisoprene, styrene-butadiene rubbers, ethylene-alpha-olefin elastomers, EPDM, polyurethane, fluoroelastomers, ethylene-acrylic elastomers (AEM), bromobutyls, chlorosulphonated polythene (CSM) or chlorosulphonated alkyl, chlorinated polythene, epoxidized natural rubber, SBR, NBR carboxylates, HNBR carboxylates, ACM and mixtures of these compounds.

[0117] Some examples of HNBR copolymers that can be used as further elastomers in the body compound, but also in the different treatments of the various elements forming the power transmission belt, include copolymers belonging to the THERBAN family made by ARLANXEO, such as THERBAN 3407 with 34% nitrile groups and a hydrogenation level of 0.9% at most, THERBAN 3406 with 34% nitrile groups and an unsaturation level of 0.9% at most, THERBAN 3607 with 36% nitrile groups and an unsaturation level of 0.9% at most, THERBAN 3446 with 34% nitrile groups and an unsaturation level of 4% at most, THERBAN 3447 with 34% nitrile groups and an unsaturation level of 5.5% at most, THERBAN 3627 with 36% nitrile groups and an unsaturation level of 2% at most, THERBAN 3629 with 36% nitrile groups and an unsaturation level of 2% at most, and THERBAN 3907 with 39% nitrile groups and an unsaturation level of 0.9% at most.

[0118] Alternatively, it is also possible to use HNBRs made by Nippon Zeon as further elastomers with the name ZETPOL. In particular, ZETPOL 2000 with 36% nitrile groups and an unsaturation level of 0.9% at most, ZETPOL 2000L with 36% nitrile groups and an unsaturation level of 0.9% at most, ZETPOL 2010 with 36% nitrile groups and an unsaturation level of 4% at most, ZETPOL 2010L with 36% nitrile groups and an unsaturation level of 4% at most, ZETPOL 2010H with 36% nitrile groups and an unsaturation level of 4% at most, ZETPOL 2020 with 36% nitrile groups and an unsaturation level of 5.5% at most, and ZETPOL 2020L with 36% nitrile groups and an unsaturation level of 5.5% at most.

[0119] More advantageously, the acrylonitrile units in the further elastomer for applications in oil are between 33% and 51%, for example 50% by weight, while for dry applications they are between 15% and 25% by weight, for example 21% by weight.

[0120] Even more advantageously, a polymer formed by a mixture of one or more copolymers, obtained starting from a diene monomer and a monomer containing nitrile groups where an acid or salt of an unsaturated carboxylic acid is added to one or more of these copolymers, is used in combination with a first polymer. More advantageously, the unsaturated carboxylic acid is methacrylic or acrylic acid and said salt is a zinc salt of the methacrylic or acrylic acid. Even more advantageously, a zinc salt of methacrylic acid is used. Even more advantageously, the zinc salt of methacrylic acid is added in a quantity in the range between 10 and 60 phr.

[0121] For example, the elastomers sold by Zeon under the following names can be used advantageously: ZSC 1295, ZSC 2095, ZSC 2195, ZSC 2295, ZSC 2295L, ZSC 2295R and ZSC 2395. More advantageously ZSC 2095 is used.

[0122] In particular, it is possible to partially replace the previously mentioned HNBRs, namely ZETPOL and/or THERBAN with a ZSC that comprises an unsaturated carboxylic acid and zinc oxide and/or with THERBAN ART that comprises an unsaturated carboxylic acid salt.

[0123] Mixed compounds of polyolefin and rubber containing acrylonitrile units are also preferred, more preferably compounds containing a copolymer of ethylene with NBRs or HNBRs or the above-mentioned modified HNBRs. For example, rubbers containing EPDM (ethylene-propylene diene monomer) or EPM (ethylene-propylene monomer) can be added to polymers containing acrylonitrile units, in quantities preferably in the range between 1% and 30%.

[0124] In addition to the elastomeric materials, the body compound can comprise conventional additives such as, for example, reinforcement agents, extenders, pigments, stearic acid, accelerators, vulcanization agents, antioxidants, activators, initiators, plasticizers, waxes, pre-vulcanization inhibitors, anti-degradants, process oils and similar.

[0125] The skilled person may vary the quantity of the various additives according to the specific needs.

[0126] Advantageously, carbon black can be employed as a filler, being advantageously added in quantities in the range between 0 and 80 phr, more advantageously about 40 phr. Advantageously, light-coloured reinforcing filers such as talc, calcium carbonate, silica and silicates are added in quantities advantageously in the range between 0 and 80 phr, advantageously about 40 phr. It is also possible to advantageously use silanes in quantities in the range between 0 and 5 phr.

[0127] Advantageously, zinc and magnesium oxides are added in a quantity ranging between 0 and 15 phr.

[0128] Advantageously, ester plasticizers such as trimellitates or ethyl esters or ethylene glycol ether esters (e.g. ADK sizer 700 or ADK sizer 735) are added in a quantity advantageously ranging between 0 and 20 phr.

[0129] Advantageously, pre-vulcanization coagents such as triallyl cyanurates and organic or inorganic methacrylates such as metal salts are advantageously added in a quantity ranging between 0 and 20 phr, or organic peroxides, such as isopropyl benzene peroxide for example, in a quantity advantageously ranging between 0 and 15 phr.

[0130] Advantageously, the mixture in the elastomeric material moreover comprises reinforcement fibres, more advantageously in an amount comprised between 2 and 40 phr, even more advantageously 20 phr. Advantageously, the reinforcement fibres have a length comprised between 0.1 and 10 mm.

[0131] The use of fibres enables a further increase in the mechanical characteristics of the mixture constituting the body.

[0132] Advantageously, the reinforcement fibres comprise aromatic polyamides, more advantageously aramides, for example Technora fibres can be advantageously used, which can be adhered to the mixture by means of an RFL-based treatment. For example, the lattice used can have a base of VP-SBR, i.e., a copolymer of vinylpiridine and styrenebutadiene.

[0133] Particularly effective have proven aramidic fibres, such as, for example, Technora fibres of Teijn having a length of 1 mm.

[0134] Preferably, the power transmission belt is a toothed power transmission belt.

[0135] Preferably, the pitch of the toothed belts is between 5 and 10 mm, more preferably between 8 and 10 mm.

[0136] A power transmission belt according to the present invention is made by using the known manufacturing processes.

[0137] The manufacturing process for the power transmission belt comprises a step during which the compound loaded with fibres is passed through a calender so as to form a strip of material in which the fibres are arranged in the direction of calendering. The compound with fibres oriented in the direction of calendering is then collected on a roller.

[0138] The power transmission belts of the present invention are particularly indicated for use in vehicle transmission systems. More preferably, the power transmission belts according to the present invention are also suitable for being used in transmission systems in which, in use, they are in direct contact with or partially immersed in oil.

[0139] In particular, excellent results have been achieved in the case where the power transmission belt is used as a replacement for traditional gear or chain systems inside the crankcase, systems in which the power transmission belt is exposed for its entire working life to means that continuously place it in contact with oil or, if necessary, is partially immersed in an oil bath.

[0140] In particular, the power transmission belt of the present invention has proved to be particularly effective when used in a transmission system commonly known as balance shaft.

[0141] In use, the power transmission belts in the respective control systems are in direct contact with oil.

[0142] Alternatively, the power transmission belts according to the present invention can also be used as dry timing belts. Furthermore, it is also possible to use the power transmission belt of the present invention in the main transmission for driving cams and also for driving the injection pump in diesel engines.

[0143] From an examination of the characteristics of the power transmission belt produced according to the present invention, the advantages that can be achieved with it are evident.

[0144] It has been experimentally verified that the use of the power transmission belt according to the present invention comprising the hydrogenated nitrile-butadiene-PEG acrylate copolymer ensures a significant improvement in low-temperature characteristics whilst maintaining an high temperature resistance, and the same or lower swell in oil as compared to known power transmission belts.

[0145] In this way, the power transmission belts according to the invention assures that the power transmission belt does not need to be replaced for the entire working life of the vehicle.

[0146] It has also been verified that the power transmission belts according to the present invention also allow achieving effective oil resistance even at high temperatures and consequently pass the durability tests to which power transmission belts are subjected in order to be used in motor vehicles and therefore avoid all the power transmission belt problems when used continuously in contact with oil and, in particular, the fall-off in mechanical characteristics, less adhesion, worse meshing and less wear resistance.

[0147] Furthermore, it has also been verified that the power transmission belts of the present invention can be used as dry power transmission belts in high-operating temperature timing systems, where high operating temperature is intended as a temperature greater than 130 C.

[0148] Furthermore, the power transmission belts according to the present invention have a very low swelling, in particular in the use in fuel-mixed oil.

[0149] While some embodiments have been disclosed by way of illustration of the invention, it is apparent that the skilled in the art may make modifications to the kind of fibres and to the materials forming it, as well as to the materials of the body compound and of the other components of the power transmission belt without departing from the scope of the present invention.

Example 1 and Comparative Example 2Cold Temperature Flexibility Test

[0150] Four toothed belts have been tested with different tests.

[0151] Two toothed belts (A) and (B) comprise the full body comprising a compound having as elastomeric material HNBR THERBAN 3907. Two further toothed belts (C) and (D) are identical to the previous toothed belts but comprise a body having as elastomeric material the hydrogenated nitrile-butadiene-PEG acrylate copolymer according to the invention.

[0152] More precisely the hydrogenated nitrile-butadiene-PEG acrylate copolymer is an hydrogenated nitrile-butadiene-PEG acrylate copolymer having 31% acrylonitrile (ACN) content, 54.9% in weight of butadiene and 14.1% in weight of a PEG with n=3, R=ethyl and R1=CH3.

[0153] To this hydrogenated nitrile-butadiene-PEG acrylate copolymer the usual additives are added in the quantities known to the skilled person both to the comparison power transmission belts and to the power transmission belts according to the invention. A toothed power transmission belt is formed having a standard glass fibre cord for automotive use and a standard fabric for toothed belts as the one known for the automotive use and previously described in other examples of EP0965771. A resistance layer having the composition as in the example of EP1157813 is also added.

[0154] The toothed belts are 15 mm width, have the known RPP plus profile as tooth profile, i.e. a standard geometry of the teeth. The pitch is 9.525 mm and the belt has 118 teeth.

[0155] Cold properties performance were measured as a variation of Tg after 100 hours intervals. The higher Tg correspond to lower performances.

[0156] This flex or flexibility test as measure of Tg gives indication on the low temperature flexibility of the toothed belt and this latter is known to prevent the rupture of the toothed belt when the engine is started at low temperatures.

[0157] The low temperature flexibility is measured in term of Tg variation, i.e. glass transition temperature variation. Usually at an higher Tg corresponds a lower performance at low temperature.

[0158] The measurements were conducted with the rig illustrated in FIG. 2 and the toothed belts were running always in direct contact with oil.

[0159] The test conditions of this dynamic test are reported in the table 1 below.

TABLE-US-00001 TABLE 1 FLEX TEST TESTING CONDITION: Constant speed: 6000 rpm Constant tension: 300 N Pulleys teeth: 19 Pulleys diameter: 57.6 mm Idlers diameter: 31 mm Oil: ENI I-sint MS 5W40 Oil temperature: 140 C.

[0160] The load as depicted in the rig was 300 N.

[0161] The Tg value was tested on a DSC TA instrument Q200 with the following testing condition

TABLE-US-00002 DSC TA Instruments - Q200 TESTING CONDITION: 40 C. .fwdarw. 90 C. 90 C. .fwdarw. 40 C. Scan rate: 10 C./min

[0162] A small sample of 5-10 mg is taken from the back of the toothed belt and scanned with the DSC without compromising the subsequent performance of the toothed belt.

[0163] As it can be read in the graph of FIG. 4 the Tg of the toothed belt comprising the hydrogenated nitrile-butadiene-PEG acrylate copolymer according to the present invention is always much lower than the comparison toothed belt.

[0164] The numerical results obtained are also reported in the table 2 below:

TABLE-US-00003 TABLE 2 Comparative Example 1 Example 2 H Tg [ C.] H Tg [ C.] Belt A Belt C Invention Comparison 0 33.7 0 24 100 26.85 100 19.43 200 26.44 200 15.93 300 25.01 300 14.2 400 23.16 400 12.94 500 21.06 500 13.5 Belt B Belt D Invention Comparison 0 33.7 0 24 100 27.4 100 17.61 200 25.95 200 15.47 300 24.61 300 14.5 400 23.34 400 14 500 21.8 500 13.8

Example 3 and Comparative Example 4Oil Swelling Test

[0165] Four toothed belts (Belt 1 to 4) were tested, two having a composition as the inventive toothed belts of example 1 (Belt 1 and Belt 2) and two as the comparative toothed belts of example 2 (Belt 3 and Belt 4).

[0166] The differences are only in the dimension of the toothed belt: for this test the toothed belts have 10 mm width, RPP plus profile, pitch 9.525, 43 teeth.

[0167] The swelling properties have been measured by measuring the toothed belt width with the following test conditions.

TABLE-US-00004 SWELLING TEST TESTING CONDITION: Speed: 2500/4500 rpm Pulleys teeth: 19 Pulleys diameter: 57.6 mm Blend of oil/diesel/rme (80/10/10) Oil: ENI I-sint MS 5W40 Oil temperature: 120 C.

[0168] The speed of the engine is set at 2500 rpm for 10 sec and then is increased up to 4500 rpm during 90 sec. After this second step the engine remains at 4500 rpm for 10 sec and successively the speed drops to 2500 rpm again during 90 sec and then the cycle starts again.

[0169] The oil swelling was measured as a relative difference in width of the toothed belt. As it can be seen in FIG. 5, the oil swelling remains at least equal or is lower than the swelling on the comparative toothed belts using the standard HNBR THERBAN 3907. The results obtained are also reported in the table 3 below:

TABLE-US-00005 TABLE 3 Belt 1 Belt 2 Invention Invention [h] Oil swell [%] Oil swell [%] 0.1 0.01 0.01 299 2.40 2.10 645 4.62 4.43 935 6.40 6.30 1308 8.60 8.44 Belt 3 Belt 4 Comparison Comparison [h] Oil swell [%] Oil swell [%] 0.1 0.01 0.01 299 2.90 2.60 645 4.83 5.07 935 6.80 7.00 1308 8.07 8.70

[0170] It can be concluded from the examples that the toothed belt comprising a body with the terpolymer of the invention is able to achieve the best balance of the properties of oil swelling and low temperature flexibility.