阅读说明：本技术 用于手提便携式交通工具的轮子的轮胎 (Tire for a wheel of a hand-portable vehicle ) 是由 F·勒梅勒 B·沃热 Y·波坦 G·皮布雷 于 2020-04-09 设计创作，主要内容包括：本发明涉及用于手提便携式交通工具的轮子的轮胎,其包含组合物,所述组合物基于至少一种二烯弹性体、至少一种增强填料和交联体系,所述交联体系包含至少一种自由基聚合引发剂和共交联剂,所述共交联剂选自(甲基)丙烯酸酯化合物、马来酰亚胺化合物、烯丙基化合物、乙烯基化合物以及它们的混合物。(The present invention relates to a tyre for wheels of hand-portable vehicles comprising a composition based on at least one diene elastomer, at least one reinforcing filler and a crosslinking system comprising at least one radical polymerization initiator and a co-crosslinking agent selected from (meth) acrylate compounds, maleimide compounds, allyl compounds, vinyl compounds and mixtures thereof.)

1. Tyre for wheels intended to equip portable vehicles, comprising a composition based on at least one diene elastomer, at least one reinforcing filler and a crosslinking system comprising at least one radical polymerization initiator and a co-crosslinking agent chosen from (meth) acrylate compounds, maleimide compounds, allyl compounds, vinyl compounds and mixtures thereof.

2. Tyre according to claim 1, wherein said diene elastomer is selected from the group consisting of polybutadienes, synthetic polyisoprenes, natural rubber, butadiene copolymers, isoprene copolymers and mixtures of these elastomers, preferably from the group consisting of synthetic polyisoprenes, natural rubber and mixtures thereof.

3. Tyre according to any one of the preceding claims, wherein the content of reinforcing filler in said composition is in the range from 1phr to 200phr, preferably from 5phr to 80phr, more preferably from 10phr to 50 phr.

4. Tyre according to any one of the preceding claims, wherein the composition has a content of free-radical polymerization initiator, preferably peroxide, ranging from 0.1phr to 10phr, preferably from 0.5phr to 5 phr.

5. Tyre according to any one of the preceding claims, wherein said radical polymerization initiator is selected from peroxides, azo compounds, redox (oxidation/reduction) systems and mixtures thereof.

6. Tyre according to any one of the preceding claims, wherein the content of co-crosslinking agent in the composition is in the range from 1phr to 150phr, preferably from 20phr to 130 phr.

7. Tyre according to any one of the preceding claims, wherein the amount of radical polymerization initiator in the composition is in the range from 1% to 10% by weight, preferably between 1.25% and 8% by weight, relative to the weight of co-crosslinking agent in the composition.

8. Tyre according to any one of the preceding claims, wherein the co-crosslinking agent comprises an acrylate derivative of formula (I):

[X]_pA (I)

wherein:

-[X]_pa group corresponding to formula (II):

wherein:

°R₁、R₂and R₃Independently represents a hydrogen atom or C₁-C₈A hydrocarbon group of₁-C₈The hydrocarbon radical is chosen from linear, branched or cyclic alkyl, alkylaryl, aryl and arylalkyl radicals, optionally interrupted by one or more heteroatoms, R₂And R₃Can be taken together to form a non-aromatic ring,

(iii) represents the point of attachment of the group of formula (II) to A,

a represents an atom belonging to the alkaline earth metals and to the transition metals, a carbon atom, C optionally interrupted and/or substituted by one or more heteroatoms₁-C₃₀A hydrocarbyl group, and a group comprising 2 to 30 monomeric units selected from the group consisting of epoxy, ester, ether, amine, acrylic, siloxane, and urethane monomeric units,

-A contains p free valences, the value of p ranging from 1 to 20,

it is understood that from 1 to 20X groups are identical or different.

9. Tyre according to any one of the previous claims, wherein said hand-portable vehicle is selected from the group consisting of scooters, roller skates, inline skates, skateboards, unicycles, balance cars and self-balancing scooters; preferably, the hand-portable vehicle is a scooter.

10. Tyre according to any one of the preceding claims, wherein the portable hand-held vehicle has a weight of less than 42kg, preferably in the range of 0.2kg to 30 kg.

11. Tire according to any one of the preceding claims, having a size less than or equal to 16 inches, preferably in the range from 2 inches to 16 inches.

12. Tyre according to any one of the preceding claims, wherein the composition as defined in any one of claims 1 to 8 is present at least in the tread of the tyre.

13. Tyre according to any one of the preceding claims, which is a non-pneumatic or pneumatic tyre, preferably a non-pneumatic tyre.

14. Wheel for a hand-portable vehicle equipped with a tyre according to any one of claims 1 to 13.

15. A hand portable vehicle equipped with at least one wheel according to claim 14.

Technical Field

The present invention relates to a tyre for the wheels of a light vehicle of the scooter, roller skate, inline skate, skateboard or similar type.

For reasons of simplicity of the drawing, the present description describes in particular a tyre for scooter wheels. The tires and wheels described in this specification are not limited to these movement patterns, however, and are also relevant to other types of hand-portable vehicles, such as skates, inline skates, skateboards, and the like.

Background

A scooter wheel is generally composed of a central hub (typically formed of a plastics material) and a tyre (typically solid) the radially outer portion of which (the tread) is intended to be in contact with the ground during rolling. The tire may be placed directly on the hub or on a support located between the tire and the hub. Such wheels have been widely described in the prior art, in particular in documents WO 2005/110558, WO 2018/045225, WO 2003/008050, US 6286907, WO 98/04423, WO 97/01378, EP 0698404 and WO 98/58712.

Generally, tyres for scooters or roller skates are made from compositions based on polyurethane, the high wear resistance of which is known to the person skilled in the art (FR 2831175).

The portable vehicle according to the present invention is used as a simple moving device for leisure and sports. In particular, many users of such vehicles prefer to perform various actions, such as spinning, jumping or controlled skating. Therefore, the tires of these vehicles are required to ensure both the safety of the users and the enjoyment of the use.

In particular in terms of the level of grip of the tread (whether on dry or wet ground) taking into account the safety of the user. In this regard, the enjoyment given to the user can come from a number of parameters, such as the noise of the wheel during rolling, the comfort provided by the wheel, and the rolling resistance. This is because the lower the rolling resistance, the less effort the user needs to move forward. In addition, for motor vehicles, such as electric scooters, lower rolling resistance will result in greater autonomy of use, giving the user less concern about battery charging.

At present, to improve the stability of scooters or inline skates, in particular during skating, solutions have been proposed consisting in creating grooves at the side surfaces of the tires (EP 0962239).

Furthermore, the solutions provided for improving the rolling resistance of such vehicles mainly relate to improving the rolling of the central hub.

The solution currently provided is therefore independent of the composition of the tyre for wheels of hand-portable vehicles within the meaning of the present invention.

Due to the nature of these vehicles (weight, their wheel size, conditions of use, etc.), tires for scooter wheels are subject to very specific limitations. Simply converting the solutions known in other fields, such as for example pneumatic tyres for motorcycles, to the field of tyres for scooter wheels does not solve the compromise of the performance qualities of rolling resistance and grip, without unduly compromising (indeed even maintaining) the other performance qualities (in particular the wear resistance) desired for tyres for scooter wheels.

Therefore, manufacturers of tyres for wheels of hand-portable vehicles are constantly seeking solutions to further improve the compromise of performance, in particular rolling resistance and grip (in particular wet grip).

As a result of continuing research, the applicant company has surprisingly found that the above-mentioned property compromise can be improved by using certain co-crosslinking agents in combination with a radical activator in rubber tyre compositions for wheels of such vehicles.

Disclosure of Invention

The subject of the present invention is therefore in particular a tyre for portable hand-held vehicles or intended for use in a wheel of a portable hand-held vehicle, comprising a composition based on at least one diene elastomer, at least one reinforcing filler and a crosslinking system comprising at least one radical polymerization initiator and a co-crosslinking agent chosen from (meth) acrylate compounds, maleimide compounds, allyl compounds, vinyl compounds and mixtures thereof. Preferably, the present invention relates to a tyre (preferably a non-pneumatic tyre) for scooter wheels (or wheels intended to equip scooters), comprising a composition based on at least one diene elastomer, at least one reinforcing filler and a crosslinking system comprising at least one radical polymerization initiator and a co-crosslinking agent selected from (meth) acrylate compounds, maleimide compounds, allyl compounds, vinyl compounds and mixtures thereof. Preferably, the present invention relates to a tyre (preferably a solid (non-pneumatic) tyre) for scooter wheels (or wheels intended to equip scooters), comprising a composition based on at least one diene elastomer, at least one reinforcing filler and a crosslinking system comprising at least one peroxide and a co-crosslinking agent comprising an acrylate derivative of formula (I):

[X]_pA (I)

wherein:

-[X]_pa group corresponding to formula (II):

wherein:

°R₁、R₂and R₃Independently represents a hydrogen atom or C₁-C₈A hydrocarbon group of₁-C₈The hydrocarbon radical is chosen from linear, branched or cyclic alkyl, alkylaryl, aryl and arylalkyl radicals, optionally interrupted by one or more heteroatoms, R₂And R₃Can be taken together to form a non-aromatic ring,

(iii) represents the point of attachment of the group of formula (II) to A,

a represents an atom belonging to the alkaline earth metals and to the transition metals, a carbon atom, C optionally interrupted and/or substituted by one or more heteroatoms₁-C₃₀A hydrocarbyl group, or a group comprising 2 to 30 monomeric units selected from epoxy, ester, ether, amine, acrylic, siloxane, and urethane monomeric units,

-A contains p free valences, the value of p ranging from 1 to 20,

it is understood that from 1 to 20X groups are identical or different.

Another subject of the invention is a wheel comprising a tyre according to the invention, and a hand-portable vehicle comprising at least one wheel according to the invention.

In this context, unless otherwise indicated, the expression "composition" means a composition intended for tires equipped with wheels of hand-portable vehicles according to the invention.

Detailed Description

I-definition of

The expression "composition based on" is understood to mean that the composition comprises a mixture and/or an in situ reaction product of the various components used, some of which are capable of reacting and/or are intended to react at least partially with each other during the various stages of manufacture of the composition; thus, the composition may be in a fully or partially crosslinked state or a non-crosslinked state.

Within the meaning of the present invention, the expression "phr" is understood to mean parts by weight per hundred parts by weight of elastomer.

Herein, all percentages (%) shown are weight percentages (%), unless otherwise indicated.

Furthermore, any interval of values denoted by the expression "between a and b" represents a range of values extending from more than a to less than b (i.e. excluding the limits a and b), whereas any interval of values denoted by the expression "between a and b" means a range of values extending from a up to b (i.e. including the strict limits a and b). Herein, when numerical intervals are represented by the expression "a to b", it is also preferable to represent intervals represented by the expression "between a and b".

When referring to a "primary" compound, within the meaning of the present invention, this is understood to mean that, among the compounds of the same type in the composition, the compound is primary, i.e. the compound which makes up the largest amount among the compounds of the same type. Thus, for example, the predominant elastomer is the elastomer that makes up the maximum weight based on the total weight of elastomers in the composition. In the same manner, the "predominant" filler is the filler that makes up the greatest weight of the fillers in the composition. For example, in a system comprising only one elastomer, this elastomer is predominant within the meaning of the present invention, whereas in a system comprising two elastomers, the predominant elastomer comprises more than half the weight of the elastomer. In contrast, a "minor" compound is a compound that does not account for the greatest weight fraction of the same type of compound. Preferably, the term "primary" is understood to mean present at more than 50%, preferably more than 60%, 70%, 80%, 90%, and more preferably the "primary" compound makes up 100%.

The carbon-containing compounds mentioned in the description may be of fossil or bio-based origin. In the case of bio-based sources, they may be partially or completely produced from biomass, or obtained from renewable feedstocks produced from biomass. Of particular interest are polymers, plasticizers, fillers, and the like.

All values of glass transition temperature ("Tg") described herein are measured in a known manner by DSC (differential scanning calorimetry) according to the standard ASTM D3418 (1999).

II-description of the invention

II-1 Portable hand-held vehicle

The term "hand-portable vehicle" is understood to mean a vehicle that is raised by a person able to use the vehicle, using their own power and without undue effort.

Thus, the hand portable vehicle according to the invention may have a weight of less than 42kg, typically in the range of 0.2kg to 30kg, preferably 0.5kg to 20kg, preferably 1kg to 15 kg.

Preferably, the hand-portable vehicle is selected from the group consisting of a scooter, a roller skate, an inline skate, a skateboard, a unicycle, a balance bike and a self-balancing scooter (also known as a skateboarder), preferably from the group consisting of a scooter and an inline skate.

The composition for tyres for hand-held portable vehicles is particularly suitable for scooters, in particular electric scooters, whose travel speeds can reach, for example, 30km/h, even 45 km/h. Thus, in a particularly advantageous manner, the hand-portable vehicle is a scooter, more preferably an electric scooter.

It is clearly understood by those skilled in the art that the hand portable vehicle according to the present invention does not include, inter alia, automobiles, motorcycles, mopeds, trucks, and the like.

II-2 tyres and wheels for hand-portable vehicles

The tire according to the invention is intended to be fitted to a hub or rim of a hand-portable vehicle, the hub (or rim) and tire assembly thus forming a wheel. Thus, the tire acts as an interface between the hub (or rim) and the ground. The tyre according to the invention may be in the fitted or unassembled state.

The characteristics (in particular the dimensions) of the tyre according to the invention vary according to the portable vehicle, in particular according to the wheel on which the tyre is intended to be placed.

However, those skilled in the art will readily understand how to adjust the characteristics of a tire depending on the wheel for which the tire is intended. As examples of wheels according to the invention, reference may be made to document WO 2018/045225 for scooters and documents WO 2005/110558 and WO 2003/008050 for inline skates.

According to the present invention, the tire may be a non-pneumatic tire or a pneumatic tire. In other words, once fitted to the wheel, the tire may or may not be pressurized with inflation gas (typically air).

In particular, a pneumatic tire is intended to be inflated by gas to be able to carry a load, and a non-pneumatic tire is intended to carry a load only by its structure.

The non-pneumatic tire may be, for example, a solid tire or may also be a hollow tire intended to be placed on a support (or insert) located between the hub (or rim) and the tire. Such supports or inserts are well known to the person skilled in the art (see, for example, WO 2018/045225, WO 97/01378) and are commonly used, in particular in order to reduce the amount of composition used for manufacturing the tyre.

Furthermore, the diameter of a tire intended to equip a wheel of a hand-held portable vehicle is generally much smaller than the diameter of tires of other types of vehicles (e.g., automobiles, motorcycles, etc.). The tyre according to the invention is advantageously intended to be fitted to a hub or rim having an outer diameter of less than or equal to 16 inches, preferably in the range from 2 inches to 16 inches, preferably from 6 inches to 12 inches. Thus, according to the invention, the size of the tyre according to the invention is advantageously less than or equal to 16 inches; preferably in the range of 2 inches to 16 inches, preferably 6 inches to 12 inches.

According to the invention, the whole tyre can be based on the same composition. Since the composition of the tire exhibits very good adhesion performance qualities, the composition of the tire is advantageously present at least (exclusively or not exclusively) in the tread of a tire intended to equip the wheels of a hand-portable vehicle.

II-3 composition for tires

II-3.1 elastomer matrices

The composition of the tyre according to the invention may comprise only one diene elastomer or a mixture of several diene elastomers.

The term "diene" elastomer (or rubber without distinction), whether natural or synthetic, is understood in a known manner to mean an elastomer which is composed at least in part (i.e. a homopolymer or a copolymer) of diene monomer units (monomers bearing two conjugated or non-conjugated carbon-carbon double bonds).

These diene elastomers can be divided into two categories: "substantially unsaturated" or "substantially saturated". The term "essentially unsaturated" is understood to mean in general a diene elastomer resulting at least in part from conjugated diene monomers having a content of units of diene origin (conjugated dienes) which is greater than 15% (mol%); thus diene elastomers such as butyl rubbers or copolymers of dienes and of alpha-olefins of the EPDM type are not included in the preceding definition, but are referred to in particular as "essentially saturated" diene elastomers (low or very low content of units of diene origin, always less than 15%). Advantageously, the diene elastomer is an essentially unsaturated diene elastomer.

Diene elastomers which can be used in the context of the present invention are understood in particular to mean:

a) any homopolymer of a conjugated or non-conjugated diene monomer having from 4 to 18 carbon atoms,

b) any copolymer of a conjugated or non-conjugated diene having from 4 to 18 carbon atoms with at least one other monomer.

The other monomer may be ethylene, an olefin, or a conjugated or non-conjugated diene.

Suitable as conjugated dienes are conjugated dienes having from 4 to 12 carbon atoms, in particular 1, 3-dienes, such as in particular 1, 3-butadiene and isoprene.

Suitable olefins are vinylaromatic compounds having from 8 to 20 carbon atoms and aliphatic alpha-monoolefins having from 3 to 12 carbon atoms.

Suitable as vinylaromatic compounds are, for example, styrene, o-, m-or p-methylstyrene, commercial mixtures of "vinyltoluenes" or p- (tert-butyl) styrene.

Suitable aliphatic alpha-monoolefins are, in particular, acyclic aliphatic alpha-monoolefins having from 3 to 18 carbon atoms.

Preferably, the diene elastomer may be:

a') any homopolymer of a conjugated diene monomer, in particular any homopolymer obtained by polymerization of a conjugated diene monomer having from 4 to 12 carbon atoms;

b') any copolymer obtained by copolymerization of one or more conjugated dienes having from 4 to 12 carbon atoms with each other or with one or more vinyl aromatic compounds having from 8 to 20 carbon atoms;

b') any copolymers obtained by copolymerization of one or more conjugated or non-conjugated dienes with ethylene, alpha-monoolefins or mixtures thereof, such as, for example, elastomers obtained from ethylene, propylene and non-conjugated diene monomers of the type described above.

Preferably, the diene elastomer is selected from the group consisting of polybutadiene (BR), synthetic polyisoprene (IR), Natural Rubber (NR), butadiene copolymers, isoprene copolymers and mixtures thereof.

The butadiene copolymer is preferably selected from butadiene/styrene copolymers (SBR). It should be noted that the SBR may be prepared in Emulsion (ESBR) or in solution (SSBR). Whether ESBR or SSBR. Among the copolymers based on styrene and butadiene, in particular SBR, those can be particularly mentioned which have a styrene content of between 5% and 60% by weight, more particularly between 20% and 50% by weight, a content of 1, 2-bonds (mol%) of the butadiene moiety of between 4% and 75%, and a content of trans-1, 4-bonds (mol%) of between 10% and 80%. Advantageously, the butadiene/styrene copolymer is an SBR made in solution and has a styrene content of between 5% and 60% by weight, preferably between 6% and 30% by weight, and a content of 1, 2-bonds of the butadiene moiety (mol%) of between 4% and 75%, preferably between 15% and 30%, relative to the total weight of the copolymer.

Preferably, the diene elastomer is selected from the group consisting of polybutadiene, synthetic polyisoprene, natural rubber, butadiene/styrene copolymer and mixtures thereof, preferably from the group consisting of synthetic polyisoprene, natural rubber and mixtures thereof. More preferably, the diene elastomer is natural rubber.

The diene elastomer may also advantageously be a blend of polyisoprene and polybutadiene.

The term "polyisoprene" (also referred to as "isoprene elastomer") is understood in a known manner to mean an isoprene homopolymer or copolymer. More preferably, the polyisoprene (diene elastomer) is selected from Natural Rubber (NR), synthetic polyisoprene (IR), isoprene copolymers and mixtures thereof. Mention will in particular be made, among isoprene copolymers, of isobutylene/isoprene (butyl rubber-IIR), isoprene/Styrene (SIR), isoprene/Butadiene (BIR) or isoprene/butadiene/Styrene (SBIR) copolymers. The polyisoprene is preferably natural rubber, synthetic polyisoprene or a mixture of these. Preferably, the synthetic polyisoprene has a content (mol%) of cis-1, 4-bonds greater than 90%, more preferably greater than 98%.

Preferably, the polybutadiene has a glass transition temperature in the range of-90 ℃ to-120 ℃, preferably-100 ℃ to-115 ℃.

Advantageously, in the composition according to the invention, the polyisoprene content is in the range from 30phr to 100phr and the polybutadiene content is in the range from 0phr to 70 phr. Still more preferably, in the tyre composition according to the present invention, the polyisoprene content is in the range 60phr to 100phr, preferably 80phr to 95phr, and the polybutadiene content is in the range 0 to 40phr, preferably 5phr to 20 phr.

In the composition of the tyre according to the invention, the total content of polyisoprene and polybutadiene may range from 60phr to 100phr, preferably from 70phr to 100 phr. Advantageously, in the composition of the tyre according to the invention, the total content of polyisoprene and polybutadiene is 100 phr. Furthermore, the polyisoprene (preferably natural rubber) may be present in an amount of 100phr, as the sole elastomer of the rubber composition.

II-3.2 reinforcing Filler

The composition of the tire according to the invention additionally comprises a reinforcing filler known for its ability to reinforce rubber compositions.

The reinforcing filler may comprise carbon black, a reinforcing inorganic filler or a mixture thereof. Advantageously, the reinforcing filler mainly, preferably only, comprises carbon black.

The content of reinforcing filler, preferably carbon black, in the composition is preferably in the range from 1phr to 200phr, preferably from 5phr to 80phr, more preferably from 10phr to 50 phr.

The carbon black that may be used in the context of the present invention may be any carbon black conventionally used in pneumatic tires or treads therefor ("tire grade" carbon black). In the latter, mention is made more particularly of reinforcing blacks of the series 100, 200 and 300, or blacks of the series 500, 600 or 700 (ASTM grades), such as, for example, blacks N115, N134, N234, N326, N330, N339, N347, N375, N550, N683 or N772. These carbon blacks may be used in the isolated state, which is commercially available, or in any other form, for example as a carrier for some of the rubber additives used. The carbon black may, for example, have been incorporated in the form of a masterbatch into diene elastomers, in particular isoprene elastomers (see, for example, applications WO 97/36724 or WO 99/16600).

The term "reinforcing inorganic filler" is understood herein to mean any inorganic or mineral filler, whatever its colour and its origin (natural or synthetic), also known as "white" filler, "clear" filler or even "non-black" filler, with respect to carbon black, capable of reinforcing alone the composition without processes other than intermediate coupling agents. In a known manner, some reinforcing inorganic fillers are particularly characterized by the presence of hydroxyl groups (-OH) on their surface.

Mineral fillers of siliceous type, preferably Silica (SiO)₂) Or mineral fillers of the aluminium type, in particular alumina (Al)₂O₃) Particularly suitable as reinforcing inorganic fillers. The silica used may be any reinforcing silica known to the person skilled in the art, in particular having a BET and CTAB specific surface area both of which are less than 450m²A/g, preferably of 30m²G to 400m²In particular 60 m/g²Any precipitated or fumed silica in the range of/g to 300m 2/g. Preferably, the silica exhibits less than 200m²BET specific surface area/g and/or less than 220m²CTAB specific surface area/gVolume, preferably 125m²G to 200m²BET specific surface area in the range of/g and/or in the range of 140m²G to 170m²CTAB specific surface area in the range of/g.

The BET specific surface area of The silica is determined by gas adsorption using The Brunauer-Emmett-Teller method described in "The Journal of The American Chemical Society" (vol 60, p 309, 2p 1938), more specifically according to standard NF ISO 5794-1, june 2010, appendix E [ multipoint (5 points) volumetric method-gas: nitrogen-degassing under vacuum: 1 hour at 160 ℃ relative pressure p/p₀The range is as follows: 0.05 to 0.17]Is determined.

For inorganic fillers such as silica, for example, the CTAB specific surface area value is determined according to standard NF ISO 5794-1, appendix G, 6 months 2010. The method is based on the adsorption of CTAB (N-hexadecyl-N, N, N-trimethylammonium bromide) to the "outer" surface of the reinforcing filler.

As silicas that can be used in the context of the present invention, mention will be made, for example, of highly dispersible precipitated silicas (referred to as "HDS" for "highly dispersible" or "highly dispersible silicas"). These silicas (which may or may not be highly dispersible) are well known to those skilled in the art. Mention may be made, for example, of the silicas described in applications WO03/016215-A1 and WO 03/016387-A1. Among the commercial HDS silicas, from Evonik may be particularly used5000GR and7000GR silica or from Solvay1085GR、1115MP、1165MP、Premium 200MP andHRS 1200MP silica. The following commercial silicas may be used as non-HDS silicas: from EvonikVN2GR andVN3GR silica, from Solvay175GR silica or Hi-Sil EZ120G (-D), Hi-Sil EZ160G (-D), Hi-Sil EZ200G (-D), Hi-Sil 243LD, Hi-Sil 210 and Hi-Sil HDP 320G silicas from PPG.

It is not important in what physical state the reinforcing inorganic filler is provided, whether it be in the form of a powder, microbeads, granules, or beads, or any other suitable densified form. Of course, reinforcing inorganic filler is also understood to mean a mixture of different reinforcing inorganic fillers, in particular of silica as described above.

The person skilled in the art will understand that instead of the reinforcing inorganic filler described above, a reinforcing filler having another property can be used, provided that this reinforcing filler having another property is covered with an inorganic layer, such as silica, or comprises, on its surface, functional sites, in particular hydroxyl sites, which require the use of a coupling agent in order to form bonds between the reinforcing filler and the diene elastomer. By way of example, mention may be made of carbon blacks partially or completely covered with silica or carbon blacks modified with silica, such as, but not limited to, those of the CRX2000 series or CRX4000 series from Cabot corporationA type of filler.

For coupling the reinforcing inorganic filler to the diene elastomer, it is possible, in a known manner, to use an at least bifunctional coupling agent (or bonding agent) aimed at providing a satisfactory chemical and/or physical property of the link between the inorganic filler (the surface of its particles) and the diene elastomer. In particular, at least bifunctional organosilanes or polyorganosiloxanes are used. The term "bifunctional" is understood to mean a compound having a first functional group capable of interacting with the inorganic filler and a second functional group capable of interacting with the diene elastomer. For example, such a bifunctional compound may comprise a first functional group containing a silicon atom, which is capable of interacting with the hydroxyl groups of the inorganic filler, and a second functional group containing a sulfur atom, which is capable of interacting with the diene elastomer.

Preferably, the organosilane is chosen from organosilane polysulfides (symmetrical or asymmetrical), such as bis (3-triethoxysilylpropyl) tetrasulfide, abbreviated to TESPT, sold under the name Si69 by Evonik, or bis (3-triethoxysilylpropyl) disulfide, abbreviated to TESPD, sold under the name Si75 by Evonik, polyorganosiloxanes, mercaptosilanes, blocked mercaptosilanes, such as S- (3- (triethoxysilyl) propyl) thioctate, sold under the name NXT silane by Momentive. More preferably, the organosilane is an organosilane polysulfide.

Of course, mixtures of the above coupling agents may also be used.

In the composition of the invention, the coupling agent is advantageously present in a quantity comprised between 0.5% and 15% by weight with respect to the quantity of reinforcing inorganic filler. The content thereof is preferably in the range of 0.5 to 10phr, more preferably in the range of 1 to 5 phr. The content of reinforcing inorganic filler is used in the composition according to the invention and can be easily adjusted by the person skilled in the art.

II-3.3 Cross-linking System

The composition of the tyre according to the present invention also comprises a crosslinking system comprising at least one radical polymerization initiator and a co-crosslinking agent selected from the group consisting of (meth) acrylate compounds, maleimide compounds, allyl compounds, vinyl compounds and mixtures thereof.

Free radical polymerization initiator

The radical polymerization initiator is a source of radicals necessary for the polymerization of the tire composition according to the present invention. These compounds are well known to the person skilled in the art and are described in particular, for example, in documents WO 2002/22688A1 and FR 2899808A 1 and in document Denisov et al (Handbook of Free radial Initiators, John Wiley & Sons, 2003).

Preferably, according to the present invention, at least the radical polymerization initiator is selected from peroxides, azo compounds, redox (oxidation/reduction) systems and mixtures thereof, preferably from peroxides, azo compounds and mixtures thereof. More preferably, at least the radical polymerization initiator is a peroxide or a mixture of several peroxides. It may be any peroxide known to those skilled in the art. Among the peroxides known to the person skilled in the art, organic peroxides are preferably used in the context of the present invention.

The term "organic peroxide" is understood to mean an organic compound, i.e. a compound containing carbon and comprising an-O-group (two oxygen atoms linked by a single covalent bond). During the crosslinking process, the organic peroxide decomposes at its unstable O-O bond to give a radical. These radicals make it possible to generate cross-links.

The organic peroxide is preferably selected from or includes dialkyl peroxides, monoperoxycarbonates, diacyl peroxides, peroxyketals, and peroxyesters.

Preferably, the dialkyl peroxide is selected from or comprises dicumyl peroxide, di (t-butyl) peroxide, t-butylcumyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, 2, 5-dimethyl-2, 5-di (t-amylperoxy) hexane, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hex-3-yne, 2, 5-dimethyl-2, 5-di (t-amylperoxy) hex-3-yne, α, α '-di [ (t-butylperoxy) isopropyl ] benzene, α, α' -di [ (t-amylperoxy) isopropyl ] benzene, di (t-amyl) peroxide, 1,3, 5-tri [ (t-butylperoxy) isopropyl ] benzene, 1, 3-dimethyl-3- (t-butylperoxy) butanol and 1, 3-dimethyl-3- (tert-amylperoxy) butanol.

Certain monoperoxycarbonates, such as OO-t-butyl-O- (2-ethylhexyl) monoperoxycarbonate, OO-t-butyl-O-isopropyl monoperoxycarbonate, and OO-t-amyl-O- (2-ethylhexyl) monoperoxycarbonate, may also be used.

Among the diacyl peroxides, the preferred peroxide is benzoyl peroxide.

In the peroxyketals, preferred peroxides are selected from or include: 1, 1-di (tert-butylperoxy) -3,3, 5-trimethylcyclohexane, n-butyl 4, 4-di (tert-butylperoxy) valerate, ethyl 3, 3-di (tert-butylperoxy) butyrate, 2-di (tert-amylperoxy) propane, 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane (or methyl ethyl ketone peroxide cyclic trimer), 3,3,5,7, 7-pentamethyl-1, 2, 4-cyclotrioxepane, n-butyl 4, 4-bis (t-amylperoxy) valerate, ethyl 3, 3-di (t-amylperoxy) butyrate, 1-di (t-butylperoxy) cyclohexane, 1-di (t-amylperoxy) cyclohexane and mixtures thereof. Preferably, the peroxyester is selected from the group consisting of tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate and tert-butyl peroxy-3, 5, 5-trimethylhexanoate.

In general, the organic peroxide is particularly preferably selected from dicumyl peroxide, aryl or diaryl peroxide, diacetyl peroxide, benzoyl peroxide, dibenzoyl peroxide, di (tert-butyl) peroxide, tert-butylcumyl peroxide, 2, 5-bis (tert-butylperoxy) -2, 5-dimethylhexane, n-butyl 4, 4-di (tert-butylperoxy) valerate, OO- (tert-butyl) O- (2-ethylhexyl) monoperoxycarbonate, tert-butylperoxyisopropyl carbonate, tert-butyl peroxybenzoate, tert-butyl peroxy-3, 5, 5-trimethylhexanoate, 1,3(4) -bis (tert-butylperoxyisopropyl) benzene and mixtures thereof. More preferably, the organic peroxide is selected from dicumyl peroxide, n-butyl 4, 4' -di (t-butylperoxy) valerate, OO- (t-butyl) O- (2-ethylhexyl) monoperoxycarbonate, t-butylperoxyisopropyl carbonate, t-butyl peroxybenzoate, t-butyl peroxy-3, 5, 5-trimethylhexanoate, 1,3(4) -bis (t-butylperoxyisopropyl) benzene, and mixtures thereof.

As examples of peroxides which can be used in the context of the present invention and are commercially available, Dicup from Hercules Powder co., Perkadox Y12 from Noury van der Lande, Peroximon F40 from monteationi Edison s.p.a., Trigonox from Noury van der Lande, Varox from r.t.vanderbilt co., or Luperko from Wallace & tiennan Inc.

The term "azo compound" is understood to mean a compound whose molecular structure comprises at least one-N ═ N-bond (two nitrogen atoms are linked by a covalent double bond).

Preferably, the azo compound is selected from the group consisting of 2,2 '-azobis (isobutyronitrile), 2' -azobis (2-butyronitrile), 4 '-azobis (4-pentanoic acid), 1' -azobis (cyclohexanecarbonitrile), 2- (tert-butylazo) -2-cyanopropane, 2 '-azobis [ 2-methyl-N- (1,1) -bis (hydroxymethyl) -2-hydroxyethyl ] propionamide, 2' -azobis (2-methyl-N-hydroxyethyl) propionamide, 2 '-azobis (N, N' -dimethyleneisobutyramidine) dichloride, 2 '-azobis (2-amidinopropane) dichloride, 2' -azobis (N, n ' -dimethyleneisobutyramide), 2 ' -azobis (2-methyl-N- [1, 1-bis (hydroxymethyl) -2-hydroxyethyl ] propionamide), 2 ' -azobis (2-methyl) -N- [1, 1-bis (hydroxymethyl) ethyl ] propionamide), 2 ' -azobis [ 2-methyl-N- (2-hydroxyethyl) propionamide ], 2 ' -azobis (isobutyramide) dihydrate, and mixtures thereof.

As an example of a commercially available azo compound which can be used in the context of the present invention, mention may be made of 2, 2' -azobis (isobutyronitrile) from Sigma-Aldrich.

The term "redox system" is understood to mean a combination of compounds which causes oxidation/reduction reactions and generates free radicals.

For example, they may be a combination of a peroxide and a tertiary amine (e.g., p: benzoyl peroxide plus dimethylaniline); a combination of a hydroperoxide and a transition metal (e.g., cumene hydroperoxide plus cobalt naphthenate mixture).

Advantageously, in the composition of the tyre according to the invention, the content of free radical initiator (preferably peroxide) is in the range from 0.1phr to 10phr, preferably from 0.5phr to 5phr, more preferably from 1phr to 4 phr.

Co-crosslinking agent

According to the present invention, the co-crosslinking agent is selected from the group consisting of (meth) acrylate compounds, maleimide compounds, allyl compounds, vinyl compounds, and mixtures thereof.

Preferably, the co-crosslinking agent comprises a (meth) acrylate compound in the form of a metal salt or an ester or a polymer.

More preferably, the co-crosslinking agent comprises an acrylate derivative of formula (I):

[X]_pA (I)

wherein:

-[X]_pa group corresponding to formula (II):

wherein:

°R₁、R₂and R₃Independently represents a hydrogen atom or C₁-C₈A hydrocarbon group of₁-C₈The hydrocarbon radical is chosen from linear, branched or cyclic alkyl, alkylaryl, aryl and arylalkyl radicals, optionally interrupted by one or more heteroatoms, R₂And R₃Can be taken together to form a non-aromatic ring,

(iii) represents the point of attachment of the group of formula (II) to A,

a represents an atom belonging to the alkaline earth metals and to the transition metals, a carbon atom, C optionally interrupted and/or substituted by one or more heteroatoms₁-C₃₀A hydrocarbyl group, and a group comprising 2 to 30 monomeric units selected from the group consisting of epoxy, ester, ether, amine, acrylic, siloxane, and urethane monomeric units,

-A contains p free valences, the value of p ranging from 1 to 20,

it is understood that from 1 to 20X groups are identical or different.

According to the invention, the bond between X and A may be an ionic or covalent bond. As is clearly understood by those skilled in the art,when A represents an atom belonging to the alkaline earth metals and transition metals, in particular Zn or Mg, the bond between X and A is an ionic bond. Furthermore, when A represents a carbon atom or C₁-C₃₀When hydrocarbyl, the bond between X and A is clearly understood by those skilled in the art to be a covalent bond.

Cyclic alkyl is understood to mean alkyl comprising one or more rings.

A hydrocarbon group or chain interrupted by one or more heteroatoms is understood to mean a group or chain comprising one or more heteroatoms, each heteroatom being between two carbon atoms of the group or the chain, or between a carbon atom of the group or the chain and another heteroatom of the group or the chain, or between two other heteroatoms of the group or the chain.

A hydrocarbyl group or chain substituted by one or more heteroatoms is understood to mean a group or chain comprising one or more heteroatoms, each heteroatom being bonded to the hydrocarbyl group or chain by a covalent bond without interrupting the hydrocarbyl group or chain.

"monomeric unit" is understood to mean the reacted form of at least one monomer of the acrylate derivative of the formula (I).

When a comprises a cyclic hydrocarbon group, it may be a non-aromatic hydrocarbon group or an aromatic cyclic hydrocarbon group.

R₁、R₂、R₃And the heteroatoms of the A group may, independently of one another, be an oxygen atom, a sulfur atom, a nitrogen atom, a phosphorus atom or a silicon atom, preferably an oxygen atom or a nitrogen atom.

Irrespective of the nature of the group A, R₁、R₂And R₃May represent, independently of one another, a hydrogen atom, a methyl group or an ethyl group; preferably, R₁、R₂And R₃Independently of one another, represents a hydrogen atom or a methyl group.

Advantageously, R₁May represent methyl and R₂And R₃May each represent a hydrogen atom. Or, R₁、R₂And R₃May each represent a hydrogen atom.

The valence p depends on the nature of the A radical. According to the invention, p may have a value of 1 to 20; for example, it may be 1; alternatively, it may be 2 to 6, preferably 2 to 4.

According to a first embodiment of the invention, R is either₁、R₂And R₃What is the radical:

o A represents an atom belonging to the alkaline earth metals and transition metals, a carbon atom and C₁-C₁₃Hydrocarbyl, preferably C₁-C₈A hydrocarbon group,

a comprises p free valences, the value of p ranges from 2 to 4,

o is understood that the 2 to 4X groups of the acrylate derivative of formula (I) are the same or different, preferably the same.

According to the invention, when A represents an atom belonging to the alkaline earth metals and to the transition metals, it may be, for example, an atom chosen from Zn and Mg. Preferably, the acrylate derivative of formula (I) is preferably a zinc diacrylate derivative in the form of a zinc salt of formula (III):

wherein R is₁、R₂And R₃Independently of one another, represents a hydrogen atom or C₁-C₇A hydrocarbon group of₁-C₇The hydrocarbon radical is selected from the group consisting of linear, branched or cyclic alkyl, aralkyl, alkylaryl and aryl radicals, optionally interrupted by one or more heteroatoms, R₂And R₃Can together form a non-aromatic ring.

When A represents C₁-C₈Preferably C₁-C₈When it is a hydrocarbon group, it may be, for example, C₁-C₇Preferably C₁-C₆Preferably C₁-C₅A hydrocarbyl group.

E.g. C₁-C₁₃The hydrocarbyl group is selected from the following groups:

wherein m is an integer ranging from 1 to 13, preferably from 6 to 10, () represents the point of attachment of a to the group of formula (II).

E.g. C₁-C₈The hydrocarbyl group is selected from the following groups:

wherein (—) represents the point of attachment of the group of formula (II) to a.

Thus, according to the present invention, the acrylate derivative of formula (I) may be selected from Zinc Dimethacrylate (ZDMA), magnesium dimethacrylate (MgDMA), Zinc Diacrylate (ZDA), magnesium diacrylate (MgDA), trimethylolpropane trimethacrylate (TMPTMA), trimethylolpropane triacrylate (TMPTA) and mixtures thereof. Preferably, the acrylate derivative of formula (I) is ZDMA, MgDMA or a mixture thereof.

Commercially available examples are diacrylate derivatives such as Zinc Diacrylate (ZDA), Dymalink 633 from Cray Valley, Zinc Dimethacrylate (ZDMA), Dymalink 634 from Cray Valley or trimethylolpropane trimethacrylate (TMPTMA), SR351 from Sartomer.

According to a second embodiment of the invention, either R or R₁、R₂And R₃What is the radical:

o A may be C selected from linear, branched or cyclic alkyl₁-C₃₀A hydrocarbyl group optionally interrupted and/or substituted by one or more heteroatoms,

a comprises p free valences, the value of p being 1.

Preferably, A represents a linear or branched C optionally interrupted and/or substituted by one or more oxygen or nitrogen atoms, preferably oxygen atoms₃-C₃₀An alkyl group. More preferably, A represents a linear or branched C optionally interrupted and/or substituted by one or more oxygen or nitrogen atoms, preferably oxygen atoms₅-C₂₀Alkyl, preferably C₆-C₁₆An alkyl group. According to this embodiment, a is advantageously not interrupted and/or substituted by one or more heteroatoms. Alternatively, according to this embodiment, AInterrupted and/or substituted by one or more heteroatoms, preferably one or more oxygen or nitrogen atoms (preferably oxygen atoms).

According to this second embodiment, the acrylate derivative of formula (I) may be selected from lauryl (meth) acrylate, stearyl (meth) acrylate, polycaprolactone (meth) acrylate, isophoryl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 4-acetoxyphenethyl (meth) acrylate, 4-acryloylmorpholine, butyl (meth) acrylate, t-butyl (meth) acrylate, benzyl 2-propyl (meth) acrylate, 2- [ [ (butylamino) carbonyl ] oxy ] ethyl (meth) acrylate, 2-carboxyethyl (meth) acrylate, oligo-2-carboxyethyl (meth) acrylate, 2- (diethylamino) ethyl (meth) acrylate, di (ethylene glycol) ethyl ether (meth) acrylate, 2- (dimethylamino) ethyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, and mixtures thereof, 3- (dimethylamino) propyl (meth) acrylate, ethylene glycol dicyclopentenyl ether (meth) acrylate, ethylene glycol methyl ether (meth) acrylate, ethylene glycol phenyl ether (meth) acrylate, 2-ethylhexyl (meth) acrylate, hexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, hydroxypropyl (meth) acrylate, isobornyl (meth) acrylate, isobutyl (meth) acrylate, isodecyl (meth) acrylate, isooctyl (meth) acrylate, stearyl (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, poly (propylene glycol) (meth) acrylate, N-propyl (meth) acrylamide, N-butyl (meth) acrylate, N-butyl acrylate, and (meth) acrylate, Tetrahydrofurfuryl (meth) acrylate, 2-tetrahydropyranyl (meth) acrylate, 3,5, 5-trimethylhexyl (meth) acrylate, 10-undecyl (meth) acrylate, ethoxylated nonylphenol (meth) acrylate, propoxylated nonylphenol (meth) acrylate, phenoxyethyl (meth) acrylate, ethoxylated nonylphenol mono (meth) acrylate, propoxylated nonylphenol mono (meth) acrylate, o-phenylphenoxyethyl (meth) acrylate, 2- [ [ (butylamino) carbonyl ] oxy ] ethyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, octyldecyl (meth) acrylate, isodecyl (meth) acrylate, propoxylated neopentyl glycol monomethyl ether (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, and mixtures thereof, Tricyclodecane methanol (meth) acrylate and mixtures thereof.

As examples of commercially available acrylate derivatives of formula (I) corresponding to this embodiment, mention may be made of, for example, those from Sigma-Aldrich: lauryl Acrylate (LA); those from Rahn AG under the name Genomer 1120 or Miramer M140; those from IGM Resins under the names Photomer 4135 or 4211; or from those named Sartomer SR217, SR335, or SR 531.

According to a third embodiment of the invention, R is either₁、R₂And R₃What is the radical:

o A represents a linear, branched or cyclic C interrupted and/or substituted by one or more heteroatoms₄-C₃₀A hydrocarbon group,

a comprises p free valences, the value of p ranges from 2 to 6,

o is understood that the 2 to 6X groups of the acrylate derivative of formula (I) are the same or different, preferably the same.

According to this third embodiment, the heteroatoms of a may advantageously be selected from oxygen atoms, sulphur atoms, nitrogen atoms, silicon atoms and phosphorus atoms, and combinations thereof. Preferably, the heteroatoms of a are selected from oxygen atoms and sulfur atoms. More preferably, the heteroatom of a is an oxygen atom.

In other words, according to this third embodiment, a advantageously represents a linear, branched or cyclic C interrupted and/or substituted by one or more heteroatoms (preferably chosen from oxygen atoms and sulfur atoms) chosen from oxygen atoms, sulfur atoms, nitrogen atoms, silicon atoms or phosphorus atoms, and combinations thereof₄-C₃₀A hydrocarbyl group. More preferably, A advantageously represents a linear, branched or cyclic, preferably linear or branched C interrupted and/or substituted by one or more oxygen and/or sulfur atoms, preferably by one or more oxygen atoms₄-C₃₀A hydrocarbyl group.

Preferably, according to this third embodiment, a represents a linear, branched or cyclic, preferably linear, branched or cyclic, interrupted by one or more oxygen and/or sulphur atoms, preferably interrupted by one or more oxygen atomsSelected from straight or branched chain C₄-C₃₀A hydrocarbyl group. More preferably, A represents a linear or branched C interrupted by one or more oxygen atoms₄-C₃₀A hydrocarbyl group.

According to this third embodiment, when A represents C₄-C₃₀When it is a hydrocarbon group, it may be, for example, C₅-C₂₀A hydrocarbon group, preferably C₆-C₁₆A hydrocarbyl group.

According to the present invention, according to this third embodiment, the polyfunctional acrylate derivative of formula (I) is preferably selected from the group consisting of dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, ethoxylated hexanediol di (meth) acrylate, propoxylated hexanediol di (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, propoxylated pentaerythritol tetra (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, propoxylated bisphenol A di (meth) acrylate, ethoxylated hexanediol di (meth) acrylate, propoxylated hexanediol di (meth) acrylate, propylene glycol di (meth) acrylate, propylene glycol (meth) acrylate, propylene glycol di (meth) acrylate, propylene glycol (meth) acrylate, propylene glycol (meth) acrylate, propylene glycol di (meth) acrylate, propylene glycol acrylate, propylene, Ethoxylated neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxylated glycerol tri (meth) acrylate, propoxylated glycerol tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, ester diol di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, hydroxypivalate bis [6- (acryloyloxy) hexanoate ], and mixtures thereof.

As examples of polyfunctional acrylate derivatives of formula (I) corresponding to this third embodiment, mention may be made of those from Sartomer, named SR264 (polyethylene glycol (300) diacrylate) or SR454 (ethoxylated (3) trimethylolpropane triacrylate); the designation Miramer M340, M410, M500, M600, or M231 from Miwon Specialty Chemical; or those from IGM Resins under the names Photomer 4050, 4226 or 4600, and those from Sigma-Aldrich: diethylene glycol diacrylate, dipropylene glycol diacrylate, dipentaerythritol pentaacrylate (DPPA), or dipentaerythritol hexaacrylate (DPHA).

According to a fourth embodiment of the invention, R is either₁、R₂And R₃What is the radical:

o A represents a group comprising 2 to 30 monomer units selected from epoxy, ester, ether, amine, acrylic, siloxane and urethane monomer units,

a comprises p free valences, the value of p ranging from 1 to 20,

o is understood that 1 to 20X groups of the acrylate derivative of formula (I) are the same or different, preferably the same.

Particularly advantageously, according to this fourth embodiment, the monomer units constitute more than 50 mol% of a, preferably more than 60 mol% of a. The monomer units may also constitute 100 mol% of A. Furthermore, the monomer units of a are advantageously identical within the acrylate derivative of formula (I).

Advantageously, according to this fourth embodiment, a represents a linear group. However, a may have a branch, preferably when the monomer unit is a urethane monomer unit.

According to this fourth embodiment, a may advantageously represent a group comprising from 2 to 16, preferably from 3 to 10, monomeric units chosen from monomeric units consisting of epoxy, ester, ether, amine, acrylic, siloxane and urethane.

Advantageously, according to this fourth embodiment, a comprises p free valences, the value of p ranging from 2 to 20, preferably from 2 to 15, preferably from 2 to 10, preferably from 2 to 8, preferably from 2 to 6. In other words, the acrylate derivative preferably comprises 2 to 20, preferably 2 to 15, preferably 2 to 10, preferably 2 to 8, preferably 2 to 6X groups.

According to this fourth embodiment, the molecular weight of the acrylate derivative of formula (I) is advantageously in the range of 250 to 15000g/mol, preferably 500 to 10000g/mol, more preferably 800 to 8000 g/mol.

When the monomer units of a are epoxy monomer units, the acrylate derivative of formula (I) is advantageously an "epoxy (meth) acrylate". A description of such compounds can be found in the following works: radiation Curing, Coatings and Printing Inks, Technical bases, Applications and reliable Shooting, ISBN 3-86630-: vincentz Network GmbH&Co eKG, Hanover, author: and P.Jung, s.struck and k.studer,2008, pages 60-62. These compounds may be bisphenol epoxides, epoxy novolacs, derivatives of epoxidized fatty acids or oils (e.g., epoxidized soybean oil, epoxidized castor oil, etc.), or derivatives of any other oligomer or polymer having an epoxy functional group that is functionalized with (meth) acrylic acid to obtain the epoxy (meth) acrylic acid described above, and may or may not be modified.

When the monomer units of a are ester monomer units, the acrylate derivative of formula (I) is advantageously a "(meth) acrylate". Such compounds are described in Radiation Curing: Coatings and Printing Inks, Technical bases, Applications and reliable Shooting, ISBN3-86630-907-4, publishers: vincentz Network GmbH&Co eKG, Hanover, author: and P.Jung, s.struck and k.studer,2008, page 65. These compounds are characterized by the presence of ester-C (O) -O-units and by the presence of two or more (meth) acrylate functions in their structure. They may contain alkyl or aryl units. In most cases, these molecules are prepared by esterification of the hydroxyl functions carried by the polyester polyols or their derivatives with acrylic acid. Another route involves the reaction of the carboxyl groups carried by the polyester with hydroxyalkyl acrylates.

When the monomer units of a are ether monomer units, the acrylate derivative of formula (I) is advantageously an "ether (meth) acrylate". Description of such CompoundsThe method can be described in the publication of publication documents, Technical bases, Applications and reliable Shooting, ISBN 3-86630-: vincentz Network GmbH&Co eKG, Hanover, author: and P.Jung, s.struck and k.studer,2008, pages 65-67. These compounds are characterized by the presence of ether-C-O-units in their structure. They may result, for example, from the polymerization of ethylene oxide or propylene oxide polymerized with, for example, a molecule containing one, two or more hydroxyl functions as a base molecule (e.g., trimethylolpropane polymerization). These ether (meth) acrylates can be modified by amine functions, in most cases by a Michael reaction between the (meth) acrylate functions and a primary or secondary amine.

When the monomer units of a are amine monomer units, the acrylate derivative of formula (I) is advantageously an "amine (meth) acrylate". Such compounds are described in Radiation Curing: Coatings and Printing Inks, Technical bases, Applications and reliable Shooting, ISBN3-86630-907-4, publishers: vincentz Network GmbH&Co eKG, Hanover, author: and P.Jung, s.struck and k.studer,2008, page 66. These compounds may be oligomers containing one amine function and one, two or more acrylic functions per repeating unit, or oligomers based on repeating units of the ester, ether, acrylic, silicone or urethane type with grafted acrylic functions, some of which have been modified by compounds with amine functions. Examples of the preparation of such compounds can be found in documents WO2000044734, FR3022544 or WO 2008000696.

When the monomer units of a are acrylate monomer units, the acrylate derivative of formula (I) is advantageously an "acrylate (meth) acrylate". Such compounds may be described at RaCatalysis Curing, Coatings and Printing Inks, Technical bases, Applications and reliable Shooting, ISBN 3-86630-: vincentz Network GmbH&Co eKG, Hanover, author: and P.Jung, s.struck and k.studer,2008, page 67. These compounds are characterized in that they are obtained by polymerization of acrylic monomers to obtain oligomers, polymers or copolymers and subsequent post-grafting thereof to carry one, two or more (meth) acrylic functions on their structure. The structure in question may be linear, branched or star-branched and thus comprise a-CH₂-C (R) (C (O) -O-R ') -type of repeating unit wherein R is hydrogen or alkyl or aryl and R' is a group of a (meth) acrylic functional support or a group not of a (meth) acrylic functional support. Examples of the preparation of such compounds can be found in document WO 201293465.

When the monomeric units of a are siloxane monomeric units, the acrylate derivative of formula (I) is advantageously a "silicone (meth) acrylate". Such compounds are described in Radiation Curing: Coatings and Printing Inks, Technical bases, Applications and reliable Shooting, ISBN3-86630-907-4, publishers: vincentz Network GmbH&Co eKG, Hanover, author: and P.Jung, s.struck and k.studer,2008, pages 67-68. These compounds are characterized by the presence of siloxane-Si (R) in their structure₂-O-units and the presence of one, two or more (meth) acrylate functions (R may be alkyl or aryl). Several preparative routes are described in the literature, in particular in documents CA 2288384 and EP 1595909.

When the monomer units of a are urethane monomer units, the acrylate derivative of formula (I) is advantageously a "urethane (meth) acrylate". Such compounds can be described in Radiation Curing, Coatings and Printing Inks, Technical Basics, Applications and Trouble Shooting, ISBN 3-86630-: vincentz Network GmbH&Co eKG, Hanover, author: and P.Jung, s.struck and k.studer,2008, pages 62-64. These compounds are characterized by the presence of urethane-N (H) -C (O) -O-units and by the presence of one, two or more (meth) acrylate functions in their structure. A simple route of preparation involves the reaction of a molecule containing two or more isocyanate functional groups with a molecule of the hydroxyalkyl acrylate type. For example, more structurally complex molecules may be obtained by reaction of polyols which may themselves include alkyl groups, aryl groups, esters, ethers, etc., may be straight, branched or star branched, and include diisocyanate molecules in the presence of hydroxyalkyl acrylates.

A number of acrylate derivatives of formula (I) corresponding to this fourth embodiment are commercially available. For example, when the monomer units of a of the acrylate derivative of formula (I) are epoxy monomer units, mention may be made of those from Sartomer, named CN109 or CN186, or one of those from Rahn AG, named Genomer2253 or 2281, or those from Miwon, named Miramer PE210 or PE310, or those from IGM Resins, named Photomer 3015, 3620 or 3660. When the monomeric units of a of the acrylate derivative of formula (I) are ester monomeric units, mention may be made of those from Sartomer under the names CN203, CN291 or CH2562, or from Rahn AG under the names Genomer 3485 or 3611, or from Miwon under the names Miramer PS3010, PS4500 or P261, or from IGM Resins under the names Photomer 5432 or 5450. When the monomer units of a of the acrylate derivative of formula (I) are ether monomer units, mention may be made of those from Sartomer with the designation tripropylene glycol diacrylate (SR306), triethylene glycol diacrylate (SR272) or dipropylene glycol diacrylate (SR508), or one of those from Rahn AG with the designation Genomer 3364, 3480 or 3457, or those from IGM Resins with the designation Photomer 5662 or 5010. When the monomeric units of a of the acrylate derivative of formula (I) are amine monomeric units, mention may be made of one of those from Rahn AG, named Genomer 5271, 5275 or 5695, or one of those from Sartomer, named CN890, or one of those from Miwon, named Miramer AS1000, LR3600 or a 102. When the monomeric units of a of the acrylate derivative of formula (I) are acrylic monomeric units, mention may be made of one of those from Sartomer, named CN820, or one of those from Miwon, named Miramer SC9060, SC9211 or S5242. When the monomeric units of A of the acrylate derivative of formula (I) are siloxane monomeric units, mention may be made of one of those from Sartomer with the name CN9800, or one of those from Elkem Silicones with the names Silcolease UV POLY 110, UV ADD 150 or UV RCA170, or one of those from Evonik with the names Tego RC902, RC711, RC722 or RC922, or one of those from Shin-Etsu with the names X-22-164, X-22-2445 or X-22-174. When the monomeric units of a of the acrylate derivative of formula (I) are urethane monomeric units, mention may be made of those from Sartomer, under the names CN965 or CN9002, or one of those from Miwon, under the names Miramer PU2100, PU2560 or PU256NT, or one of those from IGM Resins, under the names Photomer 6010, 6019 or 6720.

Advantageously, regardless of the embodiment of the invention, the co-crosslinking agent is selected from the group consisting of zinc dimethacrylate, magnesium dimethacrylate, zinc diacrylate, magnesium diacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, 1, 6-hexanediol diacrylate, 3-methyl-1, 5-pentanediol diacrylate, 1, 10-decanediol diacrylate, tricyclodecane dimethanol diacrylate, pentaerythritol tetraacrylate, ethylene glycol dimethacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, 1, 10-decanediol dimethacrylate, 1, 3-butanediol dimethacrylate, tricyclodecane dimethanol dimethacrylate and mixtures thereof, preferably from the group consisting of zinc dimethacrylate, magnesium dimethacrylate, zinc diacrylate, magnesium diacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, 1, 6-hexanediol diacrylate, 1, 10-decanediol dimethacrylate, 1, 3-butanediol dimethacrylate, tricyclodecane dimethanol dimethacrylate and mixtures thereof, Magnesium dimethacrylate, zinc diacrylate, magnesium diacrylate and mixtures thereof.

Alternatively or additionally, the co-crosslinking agent may also comprise a vinyl compound, which may be, for example, a vinyl ether compound. Preferably, the vinyl compound is selected from the group consisting of trans-stilbene, divinylbenzene, trans-2, 6-dimethyl-2, 4, 6-octatriene, dicyclopentadiene, 3, 7-dimethyl-1, 3, 6-octatriene (ocimene), a compound represented by the general formula (IV):

wherein R is^xRepresents a hydrogen atom or an alkyl group of 1 to 9 carbon atoms, and o is an integer between 1 and 3,

and a compound represented by the general formula (V):

wherein R is^yAnd R^zMay be the same or different and represents an alkyl group of 1 to 4 carbon atoms.

As the compound represented by the general formula (IV), there may be mentioned α -methylstyrene, o-, m-or p-di (isopropenyl) benzene, 1,2, 4-tri (isopropenyl) benzene, 1,3, 5-tri (isopropenyl) benzene, 3-isopropyl-o-di (isopropenyl) benzene, 4-isopropyl-m-di (isopropenyl) benzene, 5-isopropyl-m-di (isopropenyl) benzene or 2-isopropyl-p-di (isopropenyl) benzene.

As the compound represented by the general formula (V), there may be mentioned 2, 4-bis (3-isopropylphenyl) -4-methyl-1-pentene, 2, 4-bis (4-isopropylphenyl) -4-methyl-1-pentene, 2- (3-isopropylphenyl) -4- (4-isopropylphenyl) -4-methyl-1-pentene, 2- (4-isopropylphenyl) -4- (3-isopropylphenyl) -4-methyl-1-pentene, 2, 4-bis (3-methylphenyl) -4-methyl-1-pentene or 2, 4-bis (4-methylphenyl) -4-methyl-1-pentene.

Methyl methacrylate, lauryl methacrylate, allyl methacrylate, trimethylolpropane triacrylate, triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), triallyl phosphate, tetraallyloxyethane, allyl diglycol carbonate, triallyl trimellitate, triallyl citrate, diallyl adipate, diallyl terephthalate, diallyl oxalate, diallyl fumarate, ethylene glycol dimethacrylate, 2-hydroxyethyl methacrylate are also suitable as co-crosslinking agents.

Alternatively or additionally, the co-crosslinking agent may also comprise a maleimide compound, for example selected from compounds of general formula (VI):

wherein q is equal to 1 or 2, R is divalent or trivalent and is selected from the group consisting of acyclic aliphatic groups having 2 to 16 carbon atoms, cycloaliphatic groups having 5 to 20 carbon atoms, aromatic groups having 6 to 18 carbon atoms and alkylaromatic (alkylaryl) groups having 7 to 24 carbon atoms, and these divalent or trivalent groups may contain one or more heteroatoms of oxygen, nitrogen and/or sulfur in place of one or more carbon atoms, each R being₄Are identical and represent a hydrogen atom or an alkyl group having from 1 to 18 carbon atoms.

Among the compounds of the general formula (VI), bismaleimides and biscitraconimides are advantageously chosen.

As bismaleimides there may be mentioned N, N ' - (m-phenylene) bismaleimide, N ' -ethylenebismaleimide, N ' -hexamethylenebismaleimide, N ' -dodecamethylenebismaleimide, N ' - (2,2, 4-trimethylhexamethylene) bismaleimide, N ' - (dipropylene oxide) bismaleimide, N ' - (aminodipropylene oxide) bismaleimide, N ' - (ethylenedipropylene oxide) bismaleimide, N ' - (1, 4-cyclohexylene) bismaleimide, N ' - (1, 3-cyclohexylene) bismaleimide, N ' - (methylenebis (1, 4-cyclohexylene)) bismaleimide, N, N '- (isopropylidenedi (1, 4-cyclohexylidene)) bismaleimide, N' - (oxydi (1, 4-cyclohexylidene)) bismaleimide, N '- (p-phenylene) bismaleimide, N' - (o-phenylene) bismaleimide, N '- (1, 3-naphthylene) bismaleimide, N' - (1, 4-naphthylene) bismaleimide, N '- (1, 5-naphthylene) bismaleimide, N' - (3,3 '-dimethyl-4, 4' -diphenylene) bismaleimide, N '- (3, 3' -dichloro-4, 4 '-phenylene) bismaleimide, N' -bis (1, 4-phenylene) bismaleimide, N '-maleimide, N' - (3,3 '-dichloro-4, 4' -phenylene) bismaleimide, N '-bis (N, N' - (3,3 '-dichloro-4, 4' -phenylene) bismaleimide, N '-bis (N, N' - (3 '-naphthalene) bismaleimide, N' - (1, 4-phenylene) bismaleimide, N '-bismaleimide, N' -maleimide, N '-bismaleimide, N' -maleimide, N, and a mixture thereof, N, N ' - (2, 4-pyridyl) bismaleimide, N ' - (2, 6-pyridyl) bismaleimide, N ' - (1, 4-anthraquinone diyl) bismaleimide, N ' - (m-benzylidene) bismaleimide, N ' - (p-benzylidene) bismaleimide, N ' - (4, 6-dimethyl-1, 3-phenylene) bismaleimide, N ' - (2, 3-dimethyl-1, 4-phenylene) bismaleimide, N ' - (4, 6-dichloro-1, 3-phenylene) bismaleimide, N ' - (5-chloro-1, 3-phenylene) bismaleimide, N, N '- (5-hydroxy-1, 3) -phenylene) bismaleimide, N' - (5-methoxy-1, 3-phenylene) bismaleimide, N '- (m-xylylene) bismaleimide, N' - (p-xylylene) bismaleimide, N '- (methylenedi (p-phenylene)) bismaleimide, N' - (isopropylidenedi (p-phenylene)) bismaleimide, N '- (oxydiphenylene) bismaleimide, N' - (thiodi (p-phenylene)) bismaleimide, N '- (dithiodi (p-phenylene)) bismaleimide, N' - (sulfodi (p-phenylene)) bismaleimide, N, N '- (carbonyldi (p-phenylene)) bismaleimide, α' -bis (4-maleimidophenyl) -m-diisopropylbenzene, α '-bis (4-p-phenylene) bismaleimide, and α, α' -bis (4-maleimidophenyl) -p-diisopropylbenzene.

As biscitraconimides, mention may be made of 1,2-N, N '-dimethylenebiscitraconimide, 1,2-N, N' -trimethylenebiscitraconimide, 1,5-N, N '- (2-methylpentamethylene) biscitraconimide and N, N' -methylphenylenebiscitraconimide.

Advantageously, in the composition for a tire according to the present invention, the content of co-crosslinking agent, preferably the total content of co-crosslinking agent, ranges from 1phr to 150phr, preferably from 20phr to 130phr, more preferably from 40phr to 100phr, preferably from 50phr to 80 phr.

Particularly advantageously, the amount of radical polymerization initiator in the composition is in the range from 1% to 10% by weight, preferably between 1.25% and 8% by weight, preferably between 2% and 5% by weight, preferably between 3% and 4% by weight, relative to the weight of co-crosslinker in the composition.

Sulfur

Furthermore, the composition of the tyre according to the invention advantageously contains no sulphur as vulcanizing agent, or less than 0.5phr, preferably less than 0.3phr, preferably less than 0.2phr and preferably less than 0.1phr of sulphur. The sulfur may be molecular sulfur or may be sourced from a sulfur donor, such as alkylphenol disulfide (APDS).

II-3.4 various additives

The rubber composition of the tyre according to the invention may also optionally comprise all or part of the usual additives normally used in rubber tyre elastomer compositions, such as, for example, plasticizers (for example plasticizing oils and/or plasticizing resins), fillers (reinforcing or non-reinforcing fillers other than those described above), pigments, protective agents (for example antiozone waxes), chemical antiozonants or antioxidants, antifatigue agents or reinforcing resins (as described, for example, in application WO 02/10269).

II-4 preparation of rubber composition and tire

The composition of the tyre according to the invention can be prepared in a suitable mixer using two successive preparation stages known to those skilled in the art:

the first stage of thermomechanical working or kneading (the "non-productive" stage), which can be carried out in a single thermomechanical step in which all the necessary components (in particular the elastomeric matrix, the reinforcing filler and optionally other various additives, with the exception of the crosslinking system) are introduced into a suitable mixer, for example a standard internal mixer (for example of the "banbury" type). The incorporation of the optional fillers into the elastomer can be carried out one or more times by thermomechanical kneading. In the case where the filler has been incorporated into the elastomer in whole or in part in the form of a masterbatch, as described for example in applications WO 97/36724 and WO 99/16600, the masterbatch is kneaded directly and, if appropriate, incorporated into the other elastomer or filler present in the composition which is not in the form of a masterbatch, and optionally further additives other than the crosslinking system. The non-preparation phase is carried out at an elevated temperature up to a maximum temperature of between 110 ℃ and 200 ℃, preferably between 130 ℃ and 185 ℃, for a period of time generally between 2 minutes and 10 minutes.

A second stage of mechanical processing ("productive" stage), which is carried out in an external mixer (such as an open mill) after cooling the mixture obtained in the first non-productive stage to a lower temperature (generally less than 120 ℃, for example between 40 ℃ and 100 ℃). The crosslinking system is then incorporated and the combined mixture is then mixed for several minutes, for example between 5 and 15 minutes.

These stages are described, for example, in applications EP 0501227A, EP 0735088A, EP 0810258A, WO 00/05300 or WO 00/05301.

The final composition thus obtained is then calendered, for example in the form of sheets or plates, in particular for laboratory characterization.

The composition of the tire may be in the green state (before crosslinking or vulcanization) or in the cured state (after crosslinking or vulcanization).

The crosslinking of the composition can be carried out in a manner known to the person skilled in the art, for example at a temperature between 130 ℃ and 200 ℃ under pressure.

In particular, the tyre intended to equip the wheel of a hand-portable vehicle can be manufactured according to any method known to the person skilled in the art. Preferably, the tyre can be manufactured under pressure by compression moulding at a pressure between 12 and 24 bar and a temperature between 130 ℃ and 200 ℃. The tire is then mounted to a wheel hub or rim according to techniques known to those skilled in the art, thereby forming a wheel that is then mounted to a scooter.

Other methods for manufacturing the wheel according to the invention can be found in particular in documents US 3548812, FR 2800295 or CN 104816592, for example.

III-preparation of the embodiments

In view of the above, preferred embodiments of the present invention are described below:

A. tyre for wheels intended to equip portable vehicles, comprising a composition based on at least one diene elastomer, at least one reinforcing filler and a crosslinking system comprising at least one radical polymerization initiator and a co-crosslinking agent chosen from (meth) acrylate compounds, maleimide compounds, allyl compounds, vinyl compounds and mixtures thereof.

B. Tire according to embodiment a, wherein the diene elastomer is chosen from polybutadienes, synthetic polyisoprenes, natural rubber, butadiene copolymers, isoprene copolymers and mixtures of these elastomers, preferably from synthetic polyisoprenes, natural rubber and mixtures thereof.

C. The tire according to any one of the preceding embodiments, wherein the amount of reinforcing filler in the composition is in the range of 1phr to 200phr, preferably 5phr to 80phr, more preferably 10phr to 50 phr.

D. The tire of any of the preceding embodiments, wherein the reinforcing filler comprises one of carbon black, an inorganic reinforcing filler, or a mixture thereof.

E. The tire according to embodiment 4, wherein the reinforcing filler comprises mainly, preferably only, carbon black.

F. The tire according to any one of the preceding embodiments, wherein the content of free radical polymerization initiator (preferably peroxide) in the composition is in the range of 0.1phr to 10phr, preferably in the range of 0.5phr to 5phr, more preferably in the range of 1phr to 4 phr.

G. The tire of any one of the preceding embodiments, wherein the free radical polymerization initiator is selected from the group consisting of peroxides, azo compounds, redox (oxidation/reduction) systems, and mixtures thereof.

H. The tire of any one of the preceding embodiments, wherein the free radical polymerization initiator is an organic peroxide selected from the group consisting of dicumyl peroxide, aryl or diaryl peroxides, diacetyl peroxide, benzoyl peroxide, dibenzoyl peroxide, di (t-butyl) peroxide, t-butylcumyl peroxide, 2, 5-bis (t-butylperoxy) -2, 5-dimethylhexane, n-butyl 4, 4' -di (t-butylperoxy) valerate, OO- (t-butyl) -O- (2-ethylhexyl) monoperoxycarbonate, t-butylperoxyisopropyl carbonate, t-butyl peroxybenzoate, t-butyl peroxy-3, 5, 5-trimethylhexanoate, 1,3(4) -bis (t-butylperoxyisopropyl) benzene, and mixtures thereof, preferably selected from dicumyl peroxide, n-butyl 4, 4' -di (t-butylperoxy) valerate, OO- (t-butyl) -O- (2-ethylhexyl) monoperoxycarbonate, t-butylperoxyisopropyl carbonate, t-butyl peroxybenzoate, t-butyl peroxy-3, 5, 5-trimethylhexanoate, 1,3(4) -bis (t-butylperoxyisopropyl) benzene, and mixtures thereof.

I. The tire according to any one of the preceding embodiments, wherein the content of co-crosslinking agent in the composition is in the range of 1phr to 150phr, preferably in the range of 20phr to 130phr, more preferably in the range of 40phr to 100phr, preferably in the range of 50phr to 80 phr.

J. The tire according to any one of the preceding embodiments, wherein the amount of the radical polymerization initiator in the composition is in the range of 1 to 10% by weight, preferably between 1.25 to 8% by weight, preferably between 2 to 5% by weight, preferably between 3 to 4% by weight, relative to the weight of the co-crosslinking agent in the composition.

K. The tire of any of the preceding embodiments, wherein the co-crosslinker comprises an acrylate derivative of formula (I):

[X]_pA (I)

wherein:

-[X]_pa group corresponding to formula (II):

wherein:

°R₁、R₂and R₃Independently represent a hydrogen atomOr C₁-C₈A hydrocarbon group of₁-C₈The hydrocarbon radical is chosen from linear, branched or cyclic alkyl, alkylaryl, aryl and arylalkyl radicals, optionally interrupted by one or more heteroatoms, R₂And R₃Can be taken together to form a non-aromatic ring,

(iii) represents the point of attachment of the group of formula (II) to A,

a represents an atom belonging to the alkaline earth metals and to the transition metals, a carbon atom, C optionally interrupted and/or substituted by one or more heteroatoms₁-C₃₀A hydrocarbyl group, and a group comprising 2 to 30 monomeric units selected from the group consisting of epoxy, ester, ether, amine, acrylic, siloxane, and urethane monomeric units,

-A contains p free valences, the value of p ranging from 1 to 20,

it is understood that from 1 to 20X groups are identical or different.

L. tire according to embodiment K, wherein R₁、R₂And R₃Independently represents a hydrogen atom or a methyl group.

M. the tire according to any one of embodiments K and L, wherein R₁、R₂And R₃Each represents a hydrogen atom.

N. the tire according to any one of embodiments K and L, wherein R₁Represents methyl, R₂And R₃Each represents a hydrogen atom.

O. the tire according to any one of embodiments K to N, wherein, in the acrylate derivative of formula (I):

a represents an atom belonging to the alkaline earth metals and transition metals, a carbon atom or C₁-C₁₃A hydrocarbon group,

-A contains p free valences, the value of p ranging from 2 to 4,

it is understood that 2 to 4X groups are identical or different.

P. the tire according to any one of embodiments K to O, wherein a represents an atom selected from Zn and Mg.

Q. the tire of any one of embodiments K to P, wherein the acrylate derivative of formula (I) is a zinc diacrylate derivative in the form of a zinc salt of formula (III):

wherein R is₁、R₂And R₃Independently of one another, represents a hydrogen atom or C₁-C₇A hydrocarbon group of₁-C₇The hydrocarbon radical is selected from the group consisting of linear, branched or cyclic alkyl, aralkyl, alkylaryl and aryl radicals, optionally interrupted by one or more heteroatoms, R₂And R₃Can together form a non-aromatic ring.

R. tire according to any one of embodiments K to O, wherein a represents C selected from the group consisting of₁-C₁₃Hydrocarbyl group:

wherein m is an integer ranging from 1 to 13, preferably from 6 to 10, () represents the point of attachment of a to the group of formula (II).

S. the tire according to any one of embodiments K to N, wherein, in the acrylate derivative of formula (I):

-A represents a C selected from linear, branched or cyclic alkyl₁-C₃₀A hydrocarbyl group optionally interrupted and/or substituted by one or more heteroatoms,

a contains p free valences, p having the value 1.

T. the tire according to any one of embodiments K to N, wherein, in the acrylate derivative of formula (I):

-A represents a linear, branched or cyclic C interrupted and/or substituted by one or more heteroatoms₄-C₃₀A hydrocarbon group,

-A contains p free valences, the value of p ranging from 2 to 6,

it is understood that 2 to 6X groups are identical or different.

U. the tire of any one of embodiments K to N, wherein, in the acrylate derivative of formula (I):

-A represents a group comprising from 2 to 30 monomer units selected from epoxy, ester, ether, amine, acrylic, siloxane and urethane monomer units,

-A contains p free valences, the value of p ranging from 1 to 20,

it is understood that from 1 to 20X groups are identical or different.

V. the tire according to any one of embodiments K to N, wherein the co-crosslinking agent is selected from the group consisting of zinc dimethacrylate, magnesium dimethacrylate, zinc diacrylate, magnesium diacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, 1, 6-hexanediol diacrylate, 3-methyl-1, 5-pentanediol diacrylate, 1, 10-decanediol diacrylate, tricyclodecane dimethanol diacrylate, pentaerythritol tetraacrylate, ethylene glycol dimethacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, 1, 10-decanediol dimethacrylate, 1, 3-butanediol dimethacrylate, tricyclodecane dimethanol dimethacrylate, and mixtures thereof, preferably selected from the group consisting of zinc dimethacrylate, magnesium dimethacrylate, zinc diacrylate, magnesium diacrylate and mixtures thereof.

W. the tire of any one of the preceding embodiments, wherein the composition contains no or less than 0.5phr of molecular sulfur or sulfur donor agent as a vulcanizing agent.

X. the tire according to any one of the preceding embodiments, wherein the hand portable vehicle is selected from the group consisting of a scooter, a skate, an inline skate, a skateboard, a unicycle, a balance bike, and a self-balancing scooter; preferably, the hand-portable vehicle is a scooter.

Y. the tire according to any one of the preceding embodiments, wherein the portable vehicle has a weight of less than 42kg, preferably in the range of 0.2kg to 30kg, preferably 0.5kg to 20kg, preferably 1kg to 15 kg.

Z. a tire according to any one of the preceding embodiments having a size of less than or equal to 16 inches, preferably in the range of 2 inches to 16 inches, preferably in the range of 6 inches to 12 inches.

A tire according to any one of the preceding embodiments, wherein the composition according to any one of embodiments a to Z is present at least in the tread of the tire.

BB. A tire according to any one of the preceding embodiments, the tire being a non-pneumatic or pneumatic tire, preferably a non-pneumatic tire.

A wheel for a hand-portable vehicle equipped with a tire according to any one of embodiments a to BB.

DD. hand portable vehicle equipped with at least one wheel according to embodiment CC.

A hand-portable vehicle according to embodiment DD, the vehicle being a scooter.

IV-examples

IV-1 composition and preparation of tires

In the following examples, rubber compositions were prepared as described above at point II.4. In particular, the "non-productive" phase was carried out in a 7.8 liter mixer for 4.5 minutes with an average blade speed of 50 revolutions per minute until a maximum discharge temperature of 160 ℃ was reached. The "production" stage was carried out in an open mill at 30 ℃ for 5 minutes.

Crosslinking of the composition was carried out by compression molding at a temperature of 160 ℃ and a pressure of 16 bar to obtain a non-pneumatic tire having an outer diameter of 200mm, a width of 40mm and a thickness of 25mm at the center of the profile. The tire is then mounted to a wheel according to techniques known to those skilled in the art before various tests and measurements are made.

Measurement and test used for IV-2

Grip performance was evaluated by measuring the time of a single turn on a circular track defined by two concentric rings of 5m and 7m diameter with a pre-sprayed polished concrete floor to obtain a 1mm water film. The test was carried out on a 350W electric scooter equipped with wheels having tires made in point IV-1 above. The shorter the single-turn time, the better the grip performance.

The rolling resistance performance was evaluated by measuring the stopping distance of the drum on which the wheel with the tire mounted was placed. For this measurement, the tread was in contact with a roller of diameter 1m, with a supporting force of 500N. The drum was rotated until a steady speed of 40km/h was reached. Then the motor off the drum: the distance the tread travels without applied torque is measured until the drum comes to a complete stop. The greater the travel distance, the better the rolling resistance performance.

IV-3 testing on rubber compositions

The examples given below are intended to compare the performance compromise between rolling resistance and wet grip of four compositions according to the invention (C1 to C4) and two control compositions (T1 and T2).

Control composition T1 was used as reference. With respect to the control composition T1, the results of rolling resistance and wet grip performance are expressed as the base 100%. Results above 100 indicate improved performance, i.e. reduced rolling resistance and better wet grip, respectively.

Control composition T2 is a control composition giving details of the results known to the person skilled in the art, according to which the improvement in rolling resistance is generally accompanied by a deterioration in wet grip.

Compositions C1 to C4, all according to the invention, are different compositions, it having been unexpectedly observed that the improvement in rolling resistance is not accompanied by a worsening of grip. The compromise between rolling resistance and wet grip performance is thus greatly improved.

The compositions tested (in phr) and the results obtained are listed in table 1.

TABLE 1

(1) SBR 1: SBR having 27% of styrene units, a butadiene portion having 17.5% of 1, 2-units and 22% of cis-1, 4-units (Tg-44 ℃ C.)

(2) SBR 2: SBR functionalized at the chain end with a silanol SiOH function, having 15% of styrene units, a butadiene moiety having 20% of 1, 2-units and 26% of cis-1, 4-units (Tg of-65 ℃ C.)

(3) Natural rubber

(4) Butadiene copolymer having 0.5% of 1, 2-units and 97% of cis-1, 4- (Tg-108 ℃ C.)

(5) Dicumyl peroxide (Dicup DCP from Arkema)

(6) Zinc Dimethacrylate (ZDMA) (Dymalink 634 from Cray Valley)

(7) Zinc Diacrylate (ZDA) (Dymalink 633 from Cray Valley)

(8) Silica (Zeosil 1165MP from Solvay)

(9) Silane triethoxysilylpropyl tetrasulfide (Si 69 from Evonik)

(10) 1, 3-Diphenylguanidine (DPG) from Konimpex

(11) Carbon Black N234 (named according to Standard ASTM D-1765)

(12) Carbon Black N650 (named according to Standard ASTM D-1765)

(13) Carbon black N683 (named according to the standard ASTM D-1765)

(14) Paraffin oil (Tudalen 1968 from Klaus Dahleke)

(15) Oleic sunflower oil (Agripure-80 from Cargill)

(16) MES/HPD Paraffin extender oil present in SBR1 (Tg-60 ℃ C.)

(17) Petroleum Hydrocarbon resins (Tg 52 ℃, Escorez 5000 series from Exxon Mobil)

(18) Oxidation resistant Wax (Cera SER AO 32 from SER Wax Industry)

(19)2,2, 4-trimethyl-1, 2-dihydroquinoline (Pilnox TDQ from Nocil)

(20) N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine (Vulkanox 4020/LG from Lanxess)

(21) Zinc oxide (Industrial grade-Umicore)

(22) Stearin (Pristerene 4931 from Uniqema)

(23) N-Cyclohexylbenzothiazole-2-sulfenamide (Rubenamid C from General Quimica).