(19)
(11)EP 3 027 423 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
08.04.2020 Bulletin 2020/15

(21)Application number: 14777806.2

(22)Date of filing:  29.07.2014
(51)Int. Cl.: 
B60C 1/00  (2006.01)
C08K 5/20  (2006.01)
C08J 3/20  (2006.01)
C08K 5/21  (2006.01)
(86)International application number:
PCT/IB2014/063521
(87)International publication number:
WO 2015/015421 (05.02.2015 Gazette  2015/05)

(54)

RUBBER TYRE COMPOUND PRODUCTION METHOD

VERFAHREN ZUR HERSTELLUNG EINES KAUTSCHUKREIFENVERBUNDES

PROCÉDÉ DE PRODUCTION D'UN COMPOSÉ DE PNEU EN CAOUTCHOUC


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 29.07.2013 IT RM20130442

(43)Date of publication of application:
08.06.2016 Bulletin 2016/23

(73)Proprietor: Bridgestone Corporation
Tokyo 104-8340 (JP)

(72)Inventors:
  • GRENCI, Valeria
    I-00124 Roma (IT)
  • AGORETTI, Pasquale
    I-00040 Ariccia (IT)

(74)Representative: Marchetti, Alessio 
Bridgestone Technical Center Europe S.p.A. Via Fosso del Salceto, 13/15
00128 Roma
00128 Roma (IT)


(56)References cited: : 
WO-A1-03/091324
US-A- 5 674 932
WO-A1-2012/164002
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    TECHNICAL FIELD



    [0001] The present invention relates to a rubber tyre compound production method.

    BACKGROUND ART



    [0002] One goal on which research in the tyre industry is constantly focused is in improving tyre rolling and abrasion resistance.

    [0003] In this regard, silica has long been used as a reinforcing filler in tread compounds. Silica is used instead of carbon black and together with special chemical substances (silanes) which interact with the silanol groups of silica to prevent its particles from forming hydrogen bonds. With the right functionality, silanes may also interact with the polymer base to form a chemical bridge between it and the silica and so improve affinity of the polymer with the reinforcing filler. Silica is employed for the advantages it affords in terms of rolling resistance and wet-road-holding performance.

    [0004] As anyone skilled in the art knows, the better the silica interacts with the polymer base, the better the resulting compound is in terms of rolling and abrasion resistance. WO 03/091324 A1 discloses a tire comprising structural tread band including crosslinked elastomeric material obtained by crosslinking an elastomeric composition containing diene elastomer polymers, reinforcing fillers, zinc oxide , fatty acid amide, and zinc salt of carboxylic acid.

    [0005] The Applicant has surprisingly discovered a rubber compound production method, in which silica as a reinforcing filler interacts better with the polymer base.

    DISCLOSURE OF INVENTION



    [0006] The object of the present invention is a rubber tyre compound production method, characterized by comprising a mixing step, in which at least one cross-linking, unsaturated-chain polymer base, silica, a silane bonding agent, and 0.6 to less than 5 phr of a chemical of general formula (I) are mixed with one another; and a following mixing step, in which at least stearic acid and a curing system are added to and mixed with the compound being prepared;

    wherein:
    R1, R2 and R3, which are the same or different, are chosen from the group consisting of: hydrogen and groups in the alkane, alkene, cycloalkane, heterocyclic compound, aromatic compound, amine, imine, amide, sulphide, alcohol, aldehyde, ketone, ether, ester, nitrile, nitro-derivative, and isocyanate families.

    [0007] Tests show that using over 5 phr of the chemical of general formula (I) may cause premature curing problems when extruding the compound. Other potential problems resulting from using over 5 phr of the chemical of general formula (I) include increased viscosity of the compound being produced; and reduced adhesion of the rubber to the metal cords, due to the chemical of general formula (I) migrating in compounds incorporating metal cords.

    [0008] To safely eliminate one of the above drawbacks, less than 5 phr of the chemical of general formula (I) should be preferably used.

    [0009] Preferably, R1, R2 and R3, which are the same or different, are chosen from the group consisting of: H, CH3, CH3CH2, CH3CH2CH2, CH3CH2CH2CH2, CH2CHCHCH, CH3CH3CH, C6H5, C6H11, C10H7, CH3C6H4CH3, CH3CH2C6H5, C6H4OH, C4H5O2, CH3C6H4OCH3, CH3OC6H4OCH3, NH2, C6H4NH2, C4H7NH, C6H10NH2, C(CH3)2OH, C5H9NH, NH2CH2C7H12, CHCHOCH2C6H5, C6H10OH, CH2C6H3C3H2NH, SO3C6H4CH3, C6H4NO2, C6H11, C10H7, C6H4OH, CH3OC6H4, (CH3)3CC6H4, CH3C6H3NO2, (CH2)3Cl, CH3X, CH3CH2X, CH3CH2CH2X, CH3CH2CH2CH2X, C6H5X, C6H5CH2X, (CH3)3CX, C4H3X, CH2CHCH2X, C6H4SO3CH3X, C6H4NO2X, C6H11X, C10H7X, OHCH2CH2X, OHC4H4X, CH3OC6H4X, (CH3)3CC6H4X, CH2C6H4CHX, NH2C6H10X, OHC (CH3)2X, NHC5H9X, NHC5H9NC5H9X, NH2CH2C7H12X, OHC6H10X, NHCH2C6H3C3H2X, wherein X may be O or S.

    [0010] Preferably, R1 and R2 are H, and R3 is NH2.

    [0011] Preferably, 20 phr or more of silica is used in the first mixing step.

    [0012] Preferably, the polymer base is chosen from the group comprising styrene-butadiene rubber, butadiene rubber, natural rubber, or mixtures thereof.

    [0013] Preferably, 1 to 6 phr of stearic acid is used in the final mixing step.

    [0014] A further object of the present invention is a tread compound produced using the method according to the present invention.

    [0015] A further object of the present invention is a tread made from the compound produced using the method according to the present invention.

    [0016] A further object of the present invention is a tyre, at least one part of which is made from the compound produced using the method according to the present invention.

    BEST MODE FOR CARRYING OUT THE INVENTION



    [0017] The following are non-limiting examples for a clearer understanding of the present invention.

    [0018] Two compounds (E1, E2) were produced using the method according to the present invention.

    [0019] At the first mixing step, the polymer base is mixed with silica, the silane bonding agent, and a chemical of general formula (I). More specifically, the chemical used in example compounds E1, E2 was urea. Stearic acid and the curing system were added at the final mixing step. The compounds produced using the method according to the present invention differ from each other as regards the amount of urea added at the first mixing step, and the type of polymer base.

    [0020] To correctly evaluate the advantages of the present invention, five control compounds (Ctrl 1 - Ctrl 5) were produced. The first two control compounds (Ctrl 1, Ctrl 2) differ from the compounds produced according to the invention by containing no urea, and differ from each other as to the step in which the stearic acid is added: in the first control compound (Ctrl 1), stearic acid is added at the first mixing step, as in a standard method; whereas, in the second control compound (Ctrl 2), it is added at the final step, together with the curing system.

    [0021] Control compounds Ctrl 3 and Ctrl 4 differ from the compounds produced according to the invention by the stearic acid being added at the first mixing step according to the standard method.

    [0022] Control compound Ctrl 5 differs from compound E1 produced according to the invention by simply substituting thiourea for the chemical of general formula (I).

    [0023] The example compounds were produced as follows:

    - compound preparation -


    (first mixing step)



    [0024] Prior to mixing, a 230-270-litre, tangential-rotor mixer was loaded with the ingredients in Tables I and II to a fill factor of 66-72%.

    [0025] The mixer was operated at a speed of 40-60 rpm, and the resulting mixture unloaded on reaching a temperature of 140-160°C.

    (second mixing step)



    [0026] The resulting mixture was mixed again in the mixer operated at a speed of 40-60 rpm, and the compound unloaded on reaching a temperature of 130-150°C.

    (final mixing step)



    [0027] The ingredients in Tables I and II were added to the mixture from the first mixing step to a fill factor of 63-67%.

    [0028] The mixer was operated at a speed of 20-40 rpm, and the resulting mixture unloaded on reaching a temperature of 100-110°C.

    [0029] Table I shows the compositions in phr of the two compounds produced in accordance with the teachings of the present invention.
    TABLE I
     E1E2
    First mixing step
    S-SBR 80.0 80.0
    BR 20.0 20.0
    Carbon Black 8.0 8,0
    Silica 80.0 80.0
    Silane bonding agent 8.0 8.0
    Urea 1.0 3.0
    Final mixing step
    Stearic acid 2.0 2.0
    Sulphur 1.5 1.5
    Accelerant 1 1.0 1.0
    Accelerant 2 1.0 1.0
    Antioxidant 2.0 2.0
    ZnO 1.0 1.0


    [0030] Table II shows the compositions in phr of the five control compounds.
    TABLE II
     Ctrl.1Ctrl.2Ctrl.3Ctrl.4Ctrl.5
    First mixing step
    S-SBR 80.0 80.0 80.0 80.0 80.0
    BR 20.0 20.0 20.0 20.0 20.0
    Carbon Black 8.0 8.0 8.0 8.0 8.0
    Silica 80.0 80.0 80.0 80.0 80.0
    Silane bonding agent 8.0 8.0 8.0 8.0 8.0
    Urea -- -- 1.0 3.0 --
    Thiourea -- -- -- -- 1.0
    Stearic acid 2.0 -- 2.0 2.0 --
    Final mixing step
    Stearic acid -- 2.0 -- -- 2.0
    Sulphur 1.5 1.5 1.5 1.5 1.5
    Accelerant 1 1.0 1.0 1.0 1.0 1.0
    Accelerant 2 1.0 1.0 1.0 1.0 1.0
    Antioxidant 2.0 2.0 2.0 2.0 2.0
    ZnO 1.0 1.0 1.0 1.0 1.0


    [0031] S-SBR is a polymer base produced by solution polymerization, with a mean molecular weight of 800-1500x103 and 500-900x103 respectively, a 10 to 45% styrene content, and a 20 to 70% vinyl content.

    [0032] BR is a butadiene rubber.

    [0033] The silica used is marketed by EVONIK under the trade name Ultrasil VN3 GR, and has a surface area of roughly 170 m2/g.

    [0034] The silane bonding agent used is in the polysulphide organosilane class, is of formula (CH3CH2O)3Si(CH2)3SS(CH2)3Si(OCH2CH3)3 and is marketed by EVONIK under the trade name SI75.

    [0035] The Accelerant 1 used is mercaptobenzothiazol-disulphide (MBTS).

    [0036] The Accelerant 2 used is diphenyl-guanidine (DPG) .

    [0037] The antioxidant used is a mixture of polymerized 1,2-di-hydro-2,2,4-trimethylquinoline (TMQ) and N-1,3-dimethylbutyl-N'-phenyl-paraphenylenediamine (6PPD).

    [0038] The compounds in Tables I and II were tested to determine their properties related to effective chemical bonding of the silica and the polymer base.

    [0039] Dynamic properties were measured as per ISO Standard 4664 (as anyone skilled in the art knows, 60°C tanĪ“ values are closely related to rolling resistance properties: the lower the 60°C tanĪ“ value, the better the rolling resistance); and abrasion resistance was measured as per ISO Standard 4649. The parameter indicated 'BOUND RUBBER' is commonly used in literature to indicate the chemical-physical interaction of the polymer and filler. The test is carried out on green samples, and normally determines the fraction of the compound not solubilised after treatment in THF (24 hours at ambient temperature).

    [0040] Tables III and IV show the above test results for the compounds produced using the method according to the present invention and for the control compounds respectively. To show more clearly the advantages of the compounds according to the present invention, the test results are indexed on the basis of the results of control compound Ctrl 1 representing the standard methodology.
    TABLE III
     E1E2
    Rolling resistance 110 120
    Bound rubber 115 125
    Abrasion resistance 120 140
    TABLE IV
     Ctrl.1Ctrl.2Ctrl.3Ctrl.4Ctrl.5
    Rolling resistance 100 100 102 104 105
    Bound rubber 100 102 105 108 110
    Abrasion resistance 100 100 105 107 110


    [0041] As shown clearly in Tables III and IV, the compounds produced using the method according to the present invention have better rolling resistance, better interaction between the silica and the polymer base, and better abrasion resistance.

    [0042] More specifically, as shown by the control compound Ctrl 2, Ctrl 3 and Ctrl 4 figures, simply shifting the stearic acid to the final mixing step or simply using a chemical of general formula (I) is not enough to achieve the advantages achieved by the compounds according to the present invention.

    [0043] Moreover, as shown by the control compound Ctrl 5 figures, other chemicals of other than general formula (I), even though structurally similar, are not as effective in terms of silica and polymer base interaction.


    Claims

    1. A rubber tyre compound production method, characterized by comprising a mixing step, in which at least one cross-linking, unsaturated-chain polymer base, silica, a silane bonding agent, and 0.6 to less than 5 phr of a chemical of general formula (I) are mixed with one another; and a following mixing step, in which at least stearic acid and a curing system are added to and mixed with the compound being prepared;

    wherein:
    R1, R2 and R3, which are the same or different, are chosen from the group consisting of: hydrogen and groups in the alkane, alkene, cycloalkane, heterocyclic compound, aromatic compound, amine, imine, amide, sulphide, alcohol, aldehyde, ketone, ether, ester, nitrile, nitro-derivative, and isocyanate families.
     
    2. A rubber tyre compound production method as claimed in Claim 1, characterized in that R1, R2 and R3, which are the same or different, are chosen from the group consisting of: H, CH3, CH3CH2, CH3CH2CH2, CH3CH2CH2CH2, CH2CHCHCH, CH3CH3CH, C6H5, C6H11, C10H7, CH3C6H4CH3, CH3CH2C6H5, C6H4OH, C4H5O2, CH3C6H4OCH3, CH3OC6H4OCH3, NH2, C6H4NH2, C4H7NH, C6H10NH2, C (CH3)2OH, C5H9NH, NH2CH2C7H12, CHCHOCH2C6H5, C6H10OH, CH2C6H3C3H2NH, SO3C6H4CH3, C6H4NO2, C6H11, C10H7, C6H4OH, CH3OC6H4, (CH3)3CC6H4, CH3C6H3NO2, (CH2)3Cl, CH3X, CH3CH2X, CH3CH2CH2X, CH3CH2CH2CH2X, C6H5X, C6H5CH2X, (CH3)3CX, C4H3X, CH2CHCH2X, C6H4SO3CH3X, C6H4NO2X, C6H11X, C10H7X, OHCH2CH2X, OHC4H4X, CH3OC6H4X, (CH3)3CC6H4X, CH2C6H4CHX, NH2C6H10X, OHC (CH3)2X, NHC5H9X, NHC5H9NC5H9X, NH2CH2C7H12X, OHC6H10X, NHCH2C6H3C3H2X, wherein X may be O or S.
     
    3. A rubber tyre compound production method as claimed in Claim 2, characterized in that R1 and R2 are H, and R3 is NH2.
     
    4. A rubber tyre compound production method as claimed in one of the foregoing Claims, characterized in that 20 phr or more of silica is used in the first mixing step.
     
    5. A rubber tyre compound production method as claimed in one of the foregoing Claims, characterized in that the polymer base is chosen from the group comprising styrene-butadiene rubber, butadiene rubber, natural rubber, or mixtures thereof.
     
    6. A rubber tyre compound production method as claimed in one of the foregoing Claims, characterized in that 1 to 6 phr of stearic acid is used in the final mixing step.
     
    7. A tyre portion compound produced using the method as claimed in one of the foregoing Claims.
     
    8. A tread made from the compound as claimed in Claim 7.
     
    9. A tyre, at least one part of which is made from the compound as claimed in Claim 7.
     


    Ansprüche

    1. Verfahren zur Herstellung eines Kautschukreifenverbundes, dadurch gekennzeichnet, dass es einen Mischungsschritt, in dem mindestens eine vernetzende, ungesättigte Polymerkettenbasis, Kieselerde, ein Silanhaftmittel und 0,6 bis weniger als 5 phr einer Chemikalie der allgemeinen Formel (I) miteinander vermischt werden; und einen folgenden Mischungsschritt umfasst, in dem mindestens Stearinsäure und ein Vulkanisierungssystem hinzufügt und mit dem erzeugten Verbund vermischt werden;

    worin:
    R1, R2 und R3, die gleich oder verschieden sind, ausgewählt sind aus der Gruppe bestehend aus: Wasserstoff und Gruppen in den Familien Alkan, Alken, Cycloalkan, heterocyclische Verbindung, aromatische Mischung, Amin, Imin, Amid, Sulfid, Alkohol, Aldehyd, Keton, Ether, Ester, Nitril, Nitroderivat und Isocyanat.
     
    2. Verfahren zur Herstellung eines Kautschukreifenverbundes nach Anspruch 1, dadurch gekennzeichnet, dass R1, R2 und R3, die gleich oder verschieden sind, ausgewählt sind aus der Gruppe bestehend aus: H, CH3, CH3CH2, CH3CH2CH2, CH3CH2CH2CH2, CH2CHCHCH, CH3CH3CH, C6H5, C6H11, C10H7, CH3C6H4CH3, CH3CH2C6H5, C6H4OH, C4H5O2, CH3C6H4OCH3, CH3OC6H4OCH3, NH2, C6H4NH2, C4H7NH, C6H10NH2, C(CH3)2OH, C5H9NH, NH2CH2C7H12, CHCHOCH2C6H5, C6H10OH, CH2C6H3C3H2NH, SO3C6H4CH3, C6H4NO2, C6H11, C10H7, C6H4OH, CH3OC6H4, (CH3)3CC6H4, CH3C6H3NO2, (CH2)3Cl, CH3X, CH3CH2X, CH3CH2CH2X, CH3CH2CH2CH2X, C6H5X, C6H5CH2X, (CH3)3CX, C4H3X, CH2CHCH2X, C6H4SO3CH3X, C6H4NO2X, C6H11X, C10H7X, OHCH2CH2X, OHC4H4X, CH3OC6H4X, (CH3)3CC6H4X, CH2C6H4CHX, NH2C6H10X, OHC(CH3)2X, NHC5H9X, NHC5H9NC5H9X, NH2CH2C7H12X, OHC6H10X, NHCH2C6H3C3H2X, worin X O oder S sein kann.
     
    3. Verfahren zur Herstellung eines Kautschukreifenverbundes nach Anspruch 2, dadurch gekennzeichnet, dass R1 und R2 H sind und R3 NH2 ist.
     
    4. Verfahren zur Herstellung eines Kautschukreifenverbundes nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass im ersten Mischungsschritt 20 phr oder mehr Kieselerde verwendet wird.
     
    5. Verfahren zur Herstellung eines Kautschukreifenverbundes nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die Polymerbasis ausgewählt ist aus der Gruppe bestehend aus Styrol-Butadien-Kautschuk, Butadien-Kautschuk, Naturkautschuk oder Mischungen davon.
     
    6. Verfahren zur Herstellung eines Kautschukreifenverbundes nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass 1 bis 6 phr Stearinsäure im finalen Mischungsschritt verwendet wird.
     
    7. Reifenabschnittverbund, hergestellt unter Verwendung des Verfahrens nach einem der vorstehenden Ansprüche.
     
    8. Lauffläche, gefertigt aus einem Verbund nach Anspruch 7.
     
    9. Reifen, von welchem mindestens ein Teil aus dem Verbund nach Anspruch 7 gefertigt ist.
     


    Revendications

    1. Procédé de production d'un composé pour pneumatique en caoutchouc, caractérisé en ce qu'il comprend une étape de mélange, dans laquelle on mélange au moins une base polymère à chaîne insaturée, de réticulation, de la silice, un agent liant de silane, et de 0,6 à moins de 5 phr d'un composé chimique de formule générale (I) les uns avec les autres ; et une étape de mélange suivante, dans laquelle on ajoute au moins de l'acide stéarique et un système de durcissement et on les mélange au composé préparé ;

    dans lequel :
    R1, R2 et R3, qui sont identiques ou différents, sont choisis dans le groupe constitué de : hydrogène et des groupes des familles alcane, alcène, cycloalcane, composé hétérocyclique, composé aromatique, amine, imine, amide, sulfure, alcool, aldéhyde, cétone, éther, ester, nitrile, dérivé nitro, et isocyanate.
     
    2. Procédé de production d'un composé pour pneumatique en caoutchouc selon la revendication 1, caractérisé en ce que R1, R2 et R3, qui sont identiques ou différents, sont choisis dans le groupe constitué de : H, CH3, CH3CH2, CH3CH2CH2, CH3CH2CH2CH2, CH2CHCHCH, CH3CH3CH, C6H5, C6H11, C10H7, CH3C6H4CH3, CH3CH2C6H5, C6H4OH, C4H5O2, CH3C6H4OCH3, CH3OC6H4OCH3, NH2, C6H4NH2, C4H7NH, C6H10NH2, C(CH3)2OH, C5H9NH, NH2CH2C7H12, CHCHOCH2C6H5, C6H10OH, CH2C6H3C3H2NH, SO3C6H4CH3, C6H4NO2, C6H11, C10H7, C6H4OH, CH3OC6H4, (CH3)3CC6H4, CH3C6H3NO2, (CH2)3Cl, CH3X, CH3CH2X, CH3CH2CH2X, CH3CH2CH2CH2X, C6H5X, C6H5CH2X, (CH3)3CX, C4H3X, CH2CHCH2X, C6H4SO3CH3X, C6H4NO2X, C6H11X, C10H7X, OHCH2CH2X, OHC4H4X, CH3OC6H4X, (CH3)3CC6H4X, CH2C6H4CHX, NH2C6H10X, OHC(CH3)2X, NHC5H9X, NHC5H9NC5H9X, NH2CH2C7H12X, OHC6H10X, NHCH2C6H3C3H2X, dans lequel X peut être O ou S.
     
    3. Procédé de production d'un composé pour pneumatique en caoutchouc selon la revendication 2, caractérisé en ce que R1 et R2 sont H, et R3 est NH2.
     
    4. Procédé de production d'un composé pour pneumatique en caoutchouc selon l'une des revendications précédentes, caractérisé en ce que l'on utilise 20 phr ou plus de silice dans la première étape de mélange.
     
    5. Procédé de production d'un composé pour pneumatique en caoutchouc selon l'une des revendications précédentes, caractérisé en ce que la base polymère est choisie dans le groupe comprenant le caoutchouc styrène-butadiène, le caoutchouc butadiène, le caoutchouc naturel, ou leurs mélanges.
     
    6. Procédé de production d'un composé pour pneumatique en caoutchouc selon l'une des revendications précédentes, caractérisé en ce que l'on utilise de 1 à 6 phr d'acide stéarique dans l'étape de mélange finale.
     
    7. Composé pour partie de pneumatique produit en utilisant le procédé selon l'une des revendications précédentes.
     
    8. Bande de roulement fabriquée à partir du composé selon la revendication 7.
     
    9. Pneumatique, dont au moins une partie est fabriquée à partir du composé selon la revendication 7.
     




    REFERENCES CITED IN THE DESCRIPTION



    This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

    Patent documents cited in the description