• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    utility vehicle tires with a tread The present invention relates to a utility vehicle tire with a tread, in which at least the part of the tread in contact with the road is made up of a mixture of vulcanized rubbers with sulfur. for a high-level solution of the conflicts of objectives between abrasion, rolling resistance and wet grip, it consists at least in the parts that come into contact with the road by a mixture of vulcanized rubbers with sulfur, which comprises 90 to 50 parts in one hundred (parts by weight referred to 100 parts by weight of all rubbers present in the mixture) of natural rubber, 10 to 50 parts by weight of at least one polybutadiene with a glass transition temperature tg of -110 to -65ºc and 5 to 50 parts per hundred of at least one aliphatic and / or aromatic hydrocarbon resin, with a softening point (rim and sphere test according to astm e 28) from 0 to 150ºc and an average molecular weight min 2000 g / mol, as well as with a polydispersity d = mw / mn from 1 to 5.
    公开号:BR112013009296B1
    申请号:R112013009296
    申请日:2011-10-17
    公开日:2020-02-04
    发明作者:Recker Carla；Jocher Christoph；Dettmer Fabian；Daldrup Norbert；Kölle Philipp；Kramer Thomas；Torbrügge Thorsten
    申请人:Continental Reifen Deutschland Gmbh；
    IPC主号:
    专利说明:

    Invention Patent Specification Report for TIRES FOR UTILITY VEHICLES WITH A Treadmill.
    [001] The invention relates to a tire for commercial vehicles with a tread, in which at least the part of the tread in contact with the road is made up of a mixture of vulcanized rubbers with sulfur.
    [002] Since the rolling properties of a tire, especially that of a car tire, depend to a large extent on the composition of the tread rubber, particularly high demands are placed on the composition of the tread mixture. Thus, numerous attempts have been made to positively influence the properties of the tire, by varying the polymeric components and filling materials of the tread mixture. Here it should be noted that an improvement in one property of the tire often brings with it an aggravation of another property. Among the properties, which interact and in which the improvement of one property generally corresponds to the aggravation of another property, includes the trio consisting of abrasion, rolling resistance and wet grip.
    [003] By introducing polybutadiene (BR) in the mixture of rubbers to the tire tread, for example, the behavior regarding abrasion can be improved, however, this happens, at the expense of wet adhesion. In commercial vehicle tires, however, fuel consumption also plays an important role, so tires should have the least possible rolling resistance. Improvements in the field of commercial vehicle tires, for example friction, should therefore occur while maintaining the most uniform level of resistance possible. Petition 870190113268, of 11/05/2019, p. 5/24
    2/13 to the bearing.
    [004] EP 0 899 287 B1 is already known to improve the behavior in relation to abrasion and wet grip, by means of a mixture of rubbers to the tire tread that contains 50 to 90 parts in one hundred (phr [arts per hundred]) of a rubber with a glass transition temperature Tg of -110 to -80 ° C, for example polybutadiene, 10 to 50 parts per hundred of a rubber with a glass transition temperature Tg of -79 to + 20 ° C, for example E-SBR and 15 to 50 parts per hundred of a resin, chosen from the group consisting of hydrocarbon resins, phenol / acetylene resins, resins derived from rosin or mixtures thereof.
    [005] US 7,084,228 B2 describes, for improving the abrasion resistance of vehicle tires, the introduction of resins into the tread mixture, in combination with up to 40 to 100 parts in one hundred of a diene elastomer with a temperature glass transition Tg from -65 to -10 ° C, for example S-SBR and 0 to 60 parts per hundred of a diene elastomer with a glass transition temperature of -110 to -80 ° C, for example polybutadiene.
    [006] Also from WO 02/072688 A1 and WO 02/072689 A1 the combination of special resins with Tg glass transition rubbers in mixtures for tire tracks is already known in order to reduce tire abrasion for vehicles.
    [007] In the aforementioned documents, polybutadiene with a glass transition temperature Tg of -110 to -80 ° C is used as the diene elastomer. Mixture compositions, which are generally used for utility vehicle tire tracks, are not explicitly described in the documents.
    [008] EP 1 526 002 A1 describes, for good buildability, good maintenance and good treatment of tire tracks, a mixture of rubbers intended for the base of tracks, comprising at least
    Petition 870190113268, of 11/05/2019, p. 6/24
    3/13 a diene rubber, at least one filler of 0.5 to 10 parts per hundred of an aromatic hydrocarbon resin and
    1.5 to 10 parts per hundred of a fatty acid and / or a metal salt of a fatty acid and / or a fatty acid derivative. The examples show base mixes for tire tracks with 70 parts in a hundred of natural rubber, 30 parts in a hundred of polybutadiene and 2 parts in a hundred of an aromatic hydrocarbon resin.
    [009] The fundamental object of the invention is to prepare Tires for commercial vehicles, in which the conflict over abrasion, rolling resistance and wet grip is resolved to a higher level.
    [0010] According to the invention, this object is achieved by the fact that at least the parts of the tread of the tires in contact with the highway, are constituted by a mixture of vulcanized rubbers with sulfur, which contains
    - 90 to 50 parts per hundred (parts by weight relative to 100 parts by weight of all the rubber in the mixture) of natural rubber,
    - 10 to 50 parts by weight of at least one polybutadiene with a glass transition temperature Tg of -110 to -65 ° C, and
    - 5 to 50 parts by weight of at least one resin, aliphatic and / or aromatic, of hydrocarbons with a softening temperature (ring and ball test according to ASTM E 28) from 0 to 150 ° C and an average molecular weight Mn less than 2000 g / mol as well as a polydispersity D = Mw / Mn from 1 to 5.
    [0011] The indication parts in hundred (parts in hundred parts of the weight of rubber), used in this document, is here the indication of quantity usual in the rubber industry for the mix recipes. The dosage of parts by weight of each substance is therefore always referred to 100 parts by weight of the mass of all borPetition 870190113268, from 11/05/2019, p. 7/24
    4/13 cracks present in the mixture.
    [0012] Through the special combination of natural rubber, with at least one polybutadiene with a reduced glass transition temperature and at least one special resin with the characteristics mentioned above, in the aforementioned quantities, it is possible to significantly improve the abrasion resistance of a mixture for tire tracks, where simultaneously the deterioration of wet grip, which usually occurs with the introduction of polybutadiene, is not observed and the rolling resistance is reduced in the resulting tires.
    [0013] The mixture of rubbers, for the parts of the tread that come into contact with the highway, comprises 90 to 50 parts per hundred of natural rubber (NR), which, in biochemical terms, refers to polyisoprene synthesized from plants, with a cis-1.4 content greater than 99%.
    [0014] Like another rubber, the rubber mixture contains 10 parts per hundred of at least one polybutadiene (BR) with a glass transition temperature Tg of -110 to -65 ° C. Polybutadienes with glass transition temperatures within this range can, for example, be obtained by solution polymerization in the presence of rare earth type catalysts.
    [0015] In addition to natural rubber and the aforementioned butadienes, the mixture of rubbers in the tire tread may contain other types of rubber, such as polybutadienes with higher glass transition temperatures, synthetic polyisoprene, styrene copolymer -butadiene (SBR), styrene-isoprene-butadiene terpolymer, isoprenobutadiene copolymer, butyl rubber or ethylene-propylene-diene rubber (EPDM). The other types of rubber can also be presented in a functionalized form here.
    Petition 870190113268, of 11/05/2019, p. 8/24
    5/13 [0016] It proved to be particularly advantageous, from the point of view of wet grip, abrasion and rolling resistance, when the tire tread rubber mixture contained 80 to 55 parts per hundred of natural rubber and 20 to 45 parts in one hundred of a polybutadiene with a glass transition temperature Tg of -110 to -65 ° C.
    [0017] According to another advantageous improvement of the invention, the at least one butadiene has a glass transition temperature Tg of -110 to -85 ° C.
    [0018] The mixture of rubbers for the parts in contact with the road of the tire tread contains 5 to 50 parts in a hundred, preferably 5 to 25 parts in a hundred, of at least one aliphatic and / or aromatic hydrocarbon resin , with a softening temperature (rim and ball according to ASTM E 28) from 0 to 150 ° C and an average molecular weight Mn below 2000 g / mol, as well as a polydispersity D = Mw / Mn from 1 to 5 However, several resins can also be used in the mixture.
    [0019] Preferably, the aliphatic and / or aromatic hydrocarbon resin is chosen from the group consisting of terpene, C5, C9, benzofuran-indene and dicyclopentadiene (DCPD) resins, aromatic resins produced from α-methylstyrene, as well as copolymers of the monomers of these types of resin. Resins not according to the invention, which are suitable, are polar resins, such as phenol resin, which do not cause any improvement in abrasion.
    [0020] C5 or C9 resins are hydrocarbon resins, which are based on different C5 or C9 monomers.
    [0021] According to a preferred improvement of the invention, the hydrocarbon resin is an aromatic hydrocarbon resin, preferably an aromatic resin produced
    Petition 870190113268, of 11/05/2019, p. 9/24
    6/13 from α-methylstyrene. This resin produces particularly good abrasion resistance.
    [0022] The rubber mixture may contain filling materials, and different filling materials known to those skilled in the art may be used, such as carbon black, silica, aluminum silicate, chalk, starch, magnesium oxide, titanium oxide or gel. eraser. [0023] In order to optimize the abrasion and wear of Commercial Vehicle Tires, it proved to be advantageous when the tire tread rubber mixture contained less than 60 parts in a hundred, especially less than 50 parts in a hundred. silica.
    [0024] As for silicas, these are common silicas, used for tire rubber mixtures. It is particularly preferred to use a precipitated silica, finely crushed, with a nitrogen surface (Surface-BET) (according to DIN 66131 and 66132) from 35 to 350m 2 / gram, preferably from 145 to 270m 2 / g and a CTAB surface (according to ASTM D 3765) from 30 to 350 m 2 / g, preferably from 100 to 285 m 2 / g. These types of silicas lead, for example in rubber mixtures for tire tracks, to particularly good physical properties of the vulcanized material. In addition, advantages in the treatment of the mixture can be obtained by reducing the mixing time, while maintaining product properties, which leads to an improvement in productivity. As silicas can be used, for example, both any of the VN3 types (trademark) of Firma Degussa, as well as highly soluble silicas, the so-called HD silicas (for example, Ultrasil 7000 by Firma Degussa).
    [0025] In order to improve the treatment and to bind silica and other polar fillers possibly provided to the diene rubber, silane binding agents can be added to the mixture of rubbers. Silane binding agents react with the groups
    Petition 870190113268, of 11/05/2019, p. 10/24
    7/13 surface silanol of silica, or with other polar groups, during mixing with the rubber or rubber mixture, (on site) or even before the introduction of the filler in the rubber, in the sense of a pre-treatment ( previous modification). As silane binders, all the silane binders known to those skilled in the art can be used here in the rubber mixture. Such silane binding agents, known in the art, are the bifunctional organosilane, which has at least one alkoxy, cycloalkoxy or phenoxy group, as the starting group on the silicon atom and those with a group as another functionality, which eventually it can react, after the split of a chemical reaction, with the double bond of the polymer. As for the group mentioned last, it can, for example, be the following chemical groups: -SCN, -SH, -NH2 or -Sx- (with x = 28). Thus, as silane binding agents, for example, 3-mercaptopropyltriethoxysilane, propyltrimethoxysilane 3-thiocyanate or 3,3'-bis (triethoxysilylpropyl) polysulfide with 2 to 8 sulfur atoms, for example, 3-tetrasulfide , 3'-bis (triethoxysilylpropyl) (TESPT), the corresponding disulfide or also mixtures of sulfides with 1 to 8 sulfur atoms, with different levels of the different sulfides. TESPT can be used here, for example, also in a mixture with industrial carbon black (trade name X50S from Firma Degussa). Also blocked mercaptosilanes, as they are known, for example, from WO 99/09036, can be used as silane binding agents. Silanes as described in WO 2008/083241 A1, WO 2008/083242 A1, WO 2008/083243 A1 and WO 2008/083244 A1 can also be used. Usable are, for example, silanes, which can be obtained, under the name NXT, in several variants, from Firma Momentive Performance Materials, USA, or, under the name VP Si 363, from Firma Evonik Industries, Germany.
    [0026] Silane binding agents are introduced in quanti
    Petition 870190113268, of 11/05/2019, p. 11/24
    8/13 between 0.2 and 30 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of filler material, especially silica, since this way an optimal bonding of the filling material to rubber or rubbers.
    [0027] As a filling material, the mixture of rubbers for the parts of the tread, which come into contact with the road, according to a preferred improvement of the invention, contains 30 to 60 parts in one hundred, preferably 45 to 55 parts in one hundred carbon black, for example soot which, according to the ASTM classification, belongs to the 100 or 200 series, such as carbon black type N121, for optimal tearing and tearing properties for use in utility vehicles.
    [0028] The rubber mixture for the tracks may, in addition to the substances mentioned, also have other additional materials, such as softener (for example, mineral, aromatic, naphthenic or paraffinic softener oil, MES (mild extraction solvate ), RAE oils, TDAE (treated distillate aromatic extract), oils based on renewable sources (such as rapeseed oil or factices), so-called BTL oils (as described in the order with the number of order DE 10 2008 035962.9) or liquid polymers (such as liquid polybutadiene)).
    [0029] In addition, the rubber mixture may contain, in the tread, additional usual materials, in usual weight parts. These additional materials include anti-aging media, such as B.N-phenyl-N '- (1,3-dimethylbutyl) -pphenylenediamine (6PPD), N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD),
    2,2,4-trimethyl-1,2-dihydroquinoline (TMQ) and other substances as are known, for example, J.Schnetger, Lexicon der Kautschuktechnik, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1991
    Petition 870190113268, of 11/05/2019, p. 12/24
    9/13 pages 42-48, activators, such as fatty acids (eg stearic acid), waxes, resins and chewing aids, such as B.2,2'-dibenzamidodiphenyl disulfide (DBD).
    [0030] Vulcanization is performed in the presence of sulfur or sulfur donors, in which any sulfur donor can also act as a vulcanization accelerator. Sulfur or sulfur donor is introduced into the rubber mixture in the last step of the mixture and in the quantities known to those skilled in the art (0.4 to 4 parts per hundred sulfur, preferably in amounts of 1.5 to 2.5 hundred parts).
    [0031] In addition, the mixture of rubbers for tire tracks may contain substances that influence vulcanization, such as vulcanization accelerators, vulcanization repressors and vulcanization activators, in the usual amounts, in order to control the required time and / or the required temperature of the vulcanization and improve the properties of the vulcanization. Here, vulcanization accelerators can be chosen, for example, from the following groups of accelerators: thiazole accelerators, such as B. 2-mercaptobenzothiazole, sulfenamide accelerators, such as B. benzothiazil-2-cyclohexylsulfenamide (CBS ), guanidine accelerators, such as B. N, N'-diphenylguanidine (DPG), dithiocarbamate accelerators, such as B. zincodibenzyldithiocarbamate, disulfide, thiophosphate, thiurame accelerators. Accelerators can also be used in combination with one another, where synergistic effects can be produced.
    [0032] The production of the mixture of rubbers for the part of the tread of the tires, which comes into contact with the highway, takes place in a usual way and by a technique, in which it is usually, firstly, created, in a or more steps and in connection with the introduction
    Petition 870190113268, of 11/05/2019, p. 13/24
    10/13 tion of the vulcanization system, a crushed mixture, which comprises all the components, with the exception of the vulcanization system (sulfur and materials influencing vulcanization), and then the finished mixture is produced. The mixture is then further worked on, for example through an extrusion step and taken to take the form of a tire track roller. The tire track roller is known to be used for the construction of the track roller for commercial vehicle tires. The tire tracks can, however, be applied to a track roller, which already contains all parts of the tire up to the track, and is rolled up in the form of a small strip of rubber mixture. After placing the tire roll for commercial vehicles in the manufacturing position, it is vulcanized in a form of vulcanization. The resulting utility vehicle tires are characterized by less abrasion, less rolling resistance and better wet grip.
    [0033] The invention will now be described in more detail, with the help of comparative examples and embodiments, which are summarized in Table 1.
    [0034] In all the examples of mixtures contained in the Table, all indications of quantity supplied are of parts by weight, referred to 100 parts by weight of all rubbers (parts in hundred phr - parts per hundred). Comparative mixtures are indicated by V, mixtures for commercial vehicle tires according to the invention are indicated by E. Mixture 1 (V) is a mixture for tire tracks without resin. Mixtures V (4) to V (9) are comparison mixtures which, instead of natural rubber, contain styrene-butadiene copolymer. In mixtures containing resin, the degrees of filling, as well as the amounts of sulfur and accelerator, have been adapted in order to constitute the mixtures with approximately the same hardness, that is, in order to balance the dilution due to
    Petition 870190113268, of 11/05/2019, p. 14/24
    11/13 resin.
    [0035] The production of the mixtures was carried out under usual conditions, in several steps, in a tangential laboratory mixer. Samples were extracted from all mixtures, produced by vulcanization for 20 minutes, under pressure, at 160 ° C and with these samples the typical properties of the material for the rubber industry were determined, with the following test method.
    • Shore A hardness at room temperature, according to DIN 53 505 • Rebound elasticity at room temperature and 70 ° C, according to DIN 53 512, • Tensile strength at room temperature, according to DIN 53 504 • Elongation at break, according to DIN 53 504 • Expansion value (module) with an elongation of 50 and 300%, at room temperature, according to DIN 53 504 • Tear resistance according to Graves, at temperature environment, according to DIN 53 515 • Tangential loss factor õmax at 55 ° C, with the maximum value, through the scanning voltage of the dynamic mechanical measurement, according to DIN 53 513 • Abrasion at room temperature, according to with DIN 53 516
    Petition 870190113268, of 11/05/2019, p. 15/24
    12/13
    Table 1
    Component unity 1 (V) 2 (E) 5 (E) 4iV) SfV) <RV) 7 (V) »V) W) Natural rubber ptC tin ¢ 0 60 O 0 0 0 l> 0 Poly butadiene 1 [XX 40 40 40 40 40 40 40 40 40 S-SDiC [H C 0 0 0 60 60 60 0 0 0 E-SBR 1 pí'C 0 0 0 0 0 0 60 60 60 Soot N121 per 4S 50 50 45 50 50 45 only 50 RcmiA ^ pcc 0 0 14 0 0 14 0 0 14 * Aroma resin. pee 0 14 0 0 14 0 0 14 0 Mfioproteíüo cl pec 3 3 3 3 3 3 3 3 3 aging Protective wax. ozone pec 2 2 2 2 2 2 2 2 2 Zinc oxide pec 3 3 3 3 3 3 3 3 3 Theoretical c * acid pê € 2 2 2 2 2 2 2 2 2 Accelerator pre 1.3 1.4 1.4 1.3 1.4 1.4 1.3 1.4 1.4 Sulfur pec 1.3 1.4 ) .4 1.3 1.4 1.4 I.J 1.4 1.4 properties Shore A hardness Yes it is 63 60 60 65 62 63 63 59 61 Temp.Aintiientc THEElastic rebound going to TA % 55 48 46 47 41 41 44 39 3 « Rebound Elasticity at 70 * C % 64 61 60 67 52 51 54 51 49 Fractional resistance to TA MPa 2i, 8 22.0 20.7 19.3 19.5 18.9 19.9 20.1 18.6 Stretching up464 532 522 499 527 544 489 555 547 Rolling to MTExp. Val. 50% MPa 1.5 U M 1.4 1.4 J.4 1.4 1.2 1.2 Exp. Value.300% MPa 15.2 U.l 10.5 10.1 9.8 9.2 1U 9.4 9.1 Resistance to N / mm 46 50 48 34 33 32 29 36 32 tan ãmax raKgimimnt 11 - 0.120 $ 0.13 0.142 0.174 0.190 0202 0.184 0.195 0.215 The coat of arms mm 1 14 $ 1 24 39 36 23 36 43 32
    a cis-high polybutadiene, T g = -105 ° C b Styrene-butadiene copolymer polymerized in the solution, styrene content: 25% by weight, vinyl content, about 11%, T g = -69 ° C c Copolymer styrene-butadiene, styrene content: 23.5% by weight, vinyl content about 16%, T g = -55 ° C d Cs aliphatic resin, softening point about 100 ° C, M n = 1200 g / mol, D = 2.9, Scoring 1102, ExxonMobil Central Europe Holding GmbH and Aromatic a-methylstyrene resin, softening point
    Petition 870190113268, of 11/05/2019, p. 16/24
    13/13 about 85 ° C, Mn = 648 g / mol, D = 1.88, Sylvares SA 85, Arizona Chemical.
    [0036] It can be seen from Table 1 that, through the combination of natural rubber with polybutadiene and resin, a mixture is obtained, which in tires provides reduced abrasion (so-called DIN abrasion), reduced rolling resistance, which reflected in a high bounce elasticity at 70 ° C and a reduced tangential loss factor õmax at 55 ° C and a good wet grip, which is reflected in a reduced bounce elasticity at room temperature. If, instead of natural rubber, styrene-butadiene copolymers (mixtures 4 (V) to 9 (V)) are introduced, the worst values are observed in terms of rolling resistance and abrasion.
    [0037] It should also be noted that mixtures 2 (E) and 3 (E) are distinguished by a high resistance to tearing, which, especially in commercial vehicle tires, leads to a longer duration, because tears in the track due to corrosion do not reach the steel cord belt as quickly.
    [0038] Particularly good values, with regard to abrasion, are achieved with aromatic hydrocarbon resins, as shown in mixture 2 (E).
    权利要求:
    Claims (9)
    [1]
    1/2
    1. Commercial vehicle tires with a tread, characterized by the fact that at least the part of the tread that comes into contact with the road is composed of a mixture of vulcanised rubbers with sulfur comprising:
    - 90 to 50 parts per hundred (parts by weight, based on 100 parts by weight of all rubbers present in the mixture) of natural rubber,
    - 10 to 50 parts per hundred of at least one polybutadiene with a glass transition temperature Tg of -110 to -65 ° C, and
    - 5 to 50 parts per hundred of an aliphatic and / or aromatic hydrocarbon resin, with a softening point (rim and ball test according to ASTM E 28) from 0 to 150 ° C and a lower average molecular weight Mn at 2000 g / mol, and with a polydispersity D = Mw / Mn of 1 to 5.
    [2]
    2. Commercial vehicle tires according to claim 1, characterized by the fact that the tread rubber mixture contains 80 to 55 parts per hundred of natural rubber and 20 to 45 parts per hundred of at least one polybutadiene with a glass transition temperature Tg of -110 to -65 ° C.
    [3]
    Commercial vehicle tires according to claim 1 or 2, characterized by the fact that at least one polybutadiene has a glass transition temperature Tg of -110 to 85 ° C.
    [4]
    4. Commercial vehicle tires according to any one of claims 1 to 3, characterized by the fact that the aliphatic and / or aromatic hydrocarbon resin is selected from the group consisting of terpene resins, C5 resins, C9 resins , coumarone-indene resins and dicyclopentadiene resins (DCPD), aromatic resin produced from α-methylstyrene and copolymers
    Petition 870190113268, of 11/05/2019, p. 18/24
    2/2 obtained from the monomers of these types of resins.
    [5]
    5. Commercial vehicle tires according to claim 4, characterized by the fact that the hydrocarbon resin is an aromatic hydrocarbon resin.
    [6]
    6. Commercial vehicle tires, according to claim 5, characterized by the fact that the aromatic hydrocarbon resin is a resin produced from α-methylstyrene.
    [7]
    Utility vehicle tires according to any one of claims 1 to 6, characterized in that the tread rubber mixture comprises 5 to 25 parts per hundred of aliphatic and / or aromatic hydrocarbon resin.
    [8]
    Commercial vehicle tires according to any one of claims 1 to 7, characterized in that the tread rubber mixture comprises less than 60 parts in a hundred, preferably less than 50 parts in a hundred, of silica.
    [9]
    Commercial vehicle tires according to any one of claims 1 to 8, characterized in that the tread rubber mixture comprises 30 to 60 parts in a hundred, preferably 45 to 55 parts in a hundred, of carbon black.
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    同族专利:
    公开号 | 公开日
    US20130237659A1|2013-09-12|
    EP2452972A1|2012-05-16|
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    CN103201335B|2015-09-16|
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-08-13| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2019-11-26| B09A| Decision: intention to grant|
    2020-02-04| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 17/10/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP10190627.9A|EP2452972B1|2010-11-10|2010-11-10|Commercial vehicle pneumatic tyre|
    PCT/EP2011/068075|WO2012062534A1|2010-11-10|2011-10-17|Pneumatic tyres for utility vehicles|
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