(19)
(11)EP 2 703 442 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
27.04.2016 Bulletin 2016/17

(21)Application number: 12777748.0

(22)Date of filing:  27.04.2012
(51)International Patent Classification (IPC): 
C08L 9/00(2006.01)
C08K 3/36(2006.01)
C08L 7/00(2006.01)
C08K 3/04(2006.01)
C08K 5/548(2006.01)
B60C 1/00(2006.01)
(86)International application number:
PCT/JP2012/061490
(87)International publication number:
WO 2012/147976 (01.11.2012 Gazette  2012/44)

(54)

RUBBER COMPOSITION

KAUTSCHUKZUSAMMENSETZUNG

COMPOSITION DE 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: 28.04.2011 JP 2011102334

(43)Date of publication of application:
05.03.2014 Bulletin 2014/10

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

(72)Inventors:
  • HORIE, Satoshi
    Kodaira-shi Tokyo 187-8531 (JP)
  • IGARASHI, Takaaki
    Kodaira-shi Tokyo 187-8531 (JP)

(74)Representative: Oxley, Robin John George et al
Marks & Clerk LLP 90 Long Acre
London WC2E 9RA
London WC2E 9RA (GB)


(56)References cited: : 
EP-A1- 1 380 604
WO-A1-2010/126095
JP-A- 2006 213 858
JP-A- 2007 197 622
WO-A1-2008/123306
JP-A- 2005 075 900
JP-A- 2006 342 262
JP-A- 2011 026 380
  
      
    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 composition containing silica, which has an improved low-heat-generation property.

    Background Art



    [0002] Recently, in association with the movement of global regulation of carbon dioxide emission associated with the increase in attraction to environmental concerns, the demand for low fuel consumption by automobiles is increasing. To satisfy the requirement, it is desired to reduce rolling resistance relating to tire performance. Heretofore, as a means for reducing the rolling resistance of tires, a method of optimizing tire structures has been investigated; however, at present, a technique of using a low-heat-generating rubber composition for tires has become employed as the most common method.

    [0003] For obtaining such a low-heat-generating rubber composition, there is known a method of using an inorganic filler such as silica or the like.

    [0004] However, in the rubber composition containing silica compounded therein, silica aggregates (owing to the hydroxyl group in the surface of silica), and therefore, for preventing the aggregation, a silane coupling agent is used.

    [0005] Accordingly, for successfully solving the above-mentioned problem by incorporation of a silane coupling agent, various trials have been made for increasing the activity of the coupling function of the silane coupling agent.

    [0006] For example, PTL 1 proposes a rubber composition containing, as basic components, at least (i) one diene elastomer, (ii) a white filler as a reinforcing filler and (iii) an alkoxysilane polysulfide as a coupling agent (white filler/diene elastomer) along with (iv) an enamine and (v) a guanidine derivative.

    [0007] PTL 2 discloses a rubber composition containing, as basic components, at least (i) one diene elastomer, (ii) a white filler as a reinforcing filler and (iii) an alkoxysilane polysulfide as a coupling agent (white filler/diene elastomer) along with (iv) zinc dithiophosphate and (v) a guanidine derivative.

    [0008] PTL 3 describes a rubber composition containing, as basic components, at least (i) a diene elastomer, (ii) an inorganic filler as a reinforcing filler and (iii) an alkoxysilane polysulfide (PSAS) as an (inorganic filler/diene elastomer) coupling agent, as combined with (iv) an aldimine (R-CH=N-R) and (v) a guanidine derivative.

    [0009] Further, PTL 4 proposes a rubber composition basically containing at least (i) a diene elastomer, (ii) an inorganic filer as a reinforcing filer and (iii) an alkoxysilane polysulfide as a coupling agent, as combined with (iv) 1,2-dihydropyridine and (v) a guanidine derivative. PTL 5 proposes a technique of increasing the activity of the coupling function of a silane coupling agent in consideration of kneading conditions.

    [0010] PTL 6 describes an invention, in which silica having an average particle diameter of 10 µm or less and a specific silane coupling agent are added to a rubber composition, thereby suppressing aggregation of the silica.

    [0011] PTL 7 proposes a technique, in which silica that preferably has a n-hexadecyltrimethylammonium bromide (CTAB) adsorption specific surface area of from 60 to 250 × 102 m2/kg and an tea extract containing catechin are added to a rubber composition, thereby preventing large aggregates of the silica from being present in the rubber composition.

    [0012] Furthermore, PTL 8 and PTL 9 describe a rubber composition that has such a dispersion state that the area ratio occupied by filler aggregates having a circle-equivalent diameter of 10 µm or more based on the total observed area in a dispersion evaluation method of observing a cut surface of a specimen by a dark field method is 2.0% or less.

    [0013] However, there is a demand of a technique for further enhancing the low-heat-generation property of a rubber composition containing silica.

    Citation List


    Patent Literatures



    [0014] 

    PTL 1: JP-T 2002-521515

    PTL 2: JP-T 2002-521516

    PTL 3: JP-T 2003-530443

    PTL 4: JP-T 2003-523472

    PTL 5: WO2008/123306

    PTL 6: JP-A 2009-256576

    PTL 7: JP-A 2010-031260

    PTL 8: JP-A 2010-248422

    PTL 9: JP-A 2010-248423


    Summary of Invention


    Technical Problem



    [0015] Under the circumstances, an object of the present invention is to provide a rubber composition that is improved in low-heat-generation property.

    Solution to Problem



    [0016] In order to attain the object, the present inventors have paid attention to the dispersion state of silica in a rubber composition, and tried to evaluate the dispersion state of silica by various measurement methods. As a result, it has been found that the low-heat-generation property may be enhanced through reduction of the hysteresis properties (particularly, tanδ) of the rubber composition by making an average aggregated aggregate area according to a particular measurement method to be a particular value or less, and thus the present invention has been completed.

    [0017] The present invention thus relates to a rubber composition containing: (A) a rubber component containing 10% by mass or more of at least one kind of rubber selected from diene rubber synthesized by emulsion polymerization and natural rubber and 90% by mass or less of another kind of diene rubber; (B) silica having a n-hexadecyltrimethylammonium bromide (CTAB) adsorption specific surface area of 140 m2/g or more and less than 180 m2/g measured according to a method described in ASTM D3765-92; (C) at least one silane coupling agent selected from a polysulfide compound and a thioester compound; and (D) a vulcanization accelerator, the rubber composition after vulcanization having an average aggregated aggregate area (nm2) of the silica of 2,300 or less. Measurement method of average aggregated aggregate area:

    an upper surface of a specimen of the rubber composition after vulcanization is cut in a direction making an angle of 38° with respect to the upper surface of the specimen with an focused ion beam; then a smooth surface of the specimen formed by cutting is imaged with a scanning electron microscope at an acceleration voltage of 5 kV in a direction perpendicular to the smooth surface; the resulting image is converted to a binarized image of a rubber portion and a silica portion as a filler of the specimen by the Otsu's method; an aggregated aggregate area of the silica portion is obtained based on the resulting binarized image; and the average aggregated aggregate area of the silica portion is calculated in terms of number average (arithmetic average) per unit area (3 × 3 µm) from a total surface area of the silica portion and the number of aggregated aggregates, provided that in the calculation, a particle that is in contact with an edge of the image is not counted, and a particle of 20 pixels or less is assumed to be noise and is not counted.


    Advantageous Effects of Invention



    [0018] According to the present invention, a rubber composition that is improved in low-heat-generation property may be provided.

    Brief Description of Drawings



    [0019] 

    [Fig. 1]
    Fig. 1 is a photograph showing an example of an FIB-SEM image obtained by imaging aggregated aggregates of silica in the rubber composition of the present invention by the measurement method of an average aggregated aggregate area according to the present invention.

    [Fig. 2]
    Fig. 2 is a photograph showing an example of a binarized image of the image shown in Fig. 1.

    [Fig. 3]
    Fig. 3 is a photograph showing a reference example of an FIB-SEM image obtained by imaging aggregated aggregates of silica by the same method as in Fig. 1.

    [Fig. 4]
    Fig. 4 is a photograph showing an example of a binarized image of the image shown in Fig. 3.


    Description of Embodiments



    [0020] The present invention will be described in detail below.

    [0021] The rubber composition of the present invention contains: (A) a rubber component containing 10% by mass or more of at least one kind of rubber selected from diene rubber synthesized by emulsion polymerization and natural rubber and 90% by mass or less of another kind of diene rubber; (B) silica having a n-hexadecyltrimethylammonium bromide (CTAB) adsorption specific surface area of 140 m2/g or more and less than 180 m2/g measured according to a method described in ASTM D3765-92; (C) at least one silane coupling agent selected from a polysulfide compound and a thioester compound; and (D) a vulcanization accelerator, and the rubber composition after vulcanization has an average aggregated aggregate area (nm2) of the silica of 2,300 or less. For further enhancing the low-heat-generation property of the rubber composition, the average aggregated aggregate area (nm2) of the silica is preferably 2,200 or less, and more preferably 2,150 or less. The average aggregated aggregate area (nm2) of the silica is preferably 300 or more, more preferably from 300 to 2,300, further preferably from 300 to 2,200, and particularly preferably from 300 to 2,150.

    [0022] The measurement method of the average aggregated aggregate area is as follows. An upper surface of a specimen of the rubber composition after vulcanization is cut in a direction making an angle of 38° with respect to the upper surface of the specimen with a focused ion beam, and then a smooth surface of the specimen formed by cutting is imaged with a scanning electron microscope at an acceleration voltage of 5 kV in a direction perpendicular to the smooth surface. The resulting image is converted to a binarized image of a rubber portion and a silica portion as a filler of the specimen by the Otsu's method, an aggregated aggregate area of the silica portion is obtained based on the resulting binarized image, and the average aggregated aggregate area of the silica portion is calculated in terms of number average (arithmetic average) per unit area (3 µm × 3 µm) from the total surface area of the silica portion and the number of aggregated aggregates. In the calculation, a particle that is in contact with an edge of the image is not counted, and a particle of 20 pixels or less is assumed to be noise and is not counted.

    [0023] In the measurement of the average aggregated aggregate area in the present invention, FIB-SEM, which is an integrated equipment of a focused ion beam machining observation device (FIB) and a scanning electron microscope (SEM), is preferably used. The scanning electron microscope (SEM) used is preferably an ultra low acceleration voltage scanning electron microscope.

    [0024] Examples of the FIB-SEM include "NOVA 200", a trade name (registered trademark), produced by FEI Company, and "SMI-3050MS2", a trade name (registered trademark), produced by SII Nano Technology Inc., and "NOVA 200", a trade name (registered trademark), produced by FEI Company, is preferably used.

    [0025] For converting to a binarized image, an image processing device by the Otsu's method may be used.

    [0026] In the measurement of the average aggregated aggregate area in the present invention, The upper surface of the specimen of the rubber composition after vulcanization is cut in a direction making an angle of 38° with respect to the upper surface of the specimen with a focused ion beam, and then a smooth surface of the specimen formed by cutting is imaged with a scanning electron microscope at an acceleration voltage of 5 kV in a direction perpendicular to the smooth surface. In this method, a high precision image of the smooth cross sectional surface of the specimen containing only the surface information of the cross sectional surface without conventional influence of fluctuation in brightness, out of focus and the like. Accordingly, the dispersion state of the filler in the polymer material may be digitalized based on the resulting high precision image, and the average aggregated aggregate area of the rubber composition after vulcanization containing silica may be quantitatively evaluated. In the case where a specimen is cut with FIB, the cut surface that is formed in a direction in parallel to the radiation direction of FIB becomes a smooth surface, and the cut surface that is formed in a direction perpendicular to the radiation direction of FIB becomes a rough surface having unevenness. Accordingly, the smooth surface to be imaged in the present invention means the cut surface that is formed in a direction in parallel to the radiation direction of FIB.

    [0027] Subsequently, the threshold value for binarization of the resulting image is determined by the Otsu's method. The resulting image is converted to a binarized image of the rubber portion and the silica portion as a filler of the specimen with the threshold value, an aggregated aggregate area of the silica portion is obtained based on the resulting binarized image, and the average aggregated aggregate area of the silica portion is calculated in terms of number average (arithmetic average) per unit area (3 µm × 3 µm) from the total surface area of the silica portion and the number of aggregated aggregates. In the calculation, a particle that is in contact with an edge of the image is not counted, and a particle of 20 pixels or less is assumed to be noise and is not counted.

    [0028] Fig. 1 is a photograph showing an example of an FIB-SEM image obtained by imaging aggregated aggregates of silica in the rubber composition of the present invention by the measurement method of an average aggregated aggregate area according to the present invention, and Fig. 2 is a photograph showing an example of a binarized image of the image shown in Fig. 1.

    [0029] Fig. 3 is a photograph showing a reference example of an FIB-SEM image obtained by imaging aggregated aggregates of silica by the same method as in Fig. 1, and Fig. 4 is a photograph showing an example of a binarized image of the image shown in Fig. 3.

    [0030] The aggregated aggregate in the present invention means an agglomerated matter of plural aggregates, and encompasses a single aggregate. The aggregate (i.e., a primary aggregated matter) herein means a complex aggregated form of silica formed by fusing primary particles of silica to form linear or irregularly branched chains, and may have a size of from several ten to several hundred nanometers.

    [0031] The aggregated aggregate in the present invention is far smaller than an agglomerate (i.e., a secondary aggregated matter), which is considered to have, in general, a size of from several ten to several hundred micrometers, and these are concepts that are completely different from each other.

    [0032] The n-hexadecyltrimethylammonium bromide (CTAB) adsorption specific surface area (which may be hereinafter abbreviated as a "CTAB adsorption specific surface area") of silica is measured according to a method described in ASTM D3765-92, as described above. However, small modifications are made in the method since the method described in ASTM D3765-92 is a method of measuring a CTAB adsorption specific surface area of carbon black. Specifically, IRB #3 (83.0 m2/g) as the standard product of carbon black is not used, but a n-hexadecyltrimethylammonium bromide (CTAB) standard solution is separately prepared, with which an Aerosol OT (sodium di-2-ethylhexyl sulfosuccinate) solution is calibrated, and the specific surface area (m2/g) is calculated from the adsorption amount of CTAB assuming that the adsorption cross section per one molecule of CTAB on the surface of hydrated silicic acid is 0.35 nm2. The modifications are made because it is considered that carbon black and hydrated silicic acid have surfaces that are different from each other, and thus there is a difference therebetween in the CTAB adsorption amount on the same surface area.

    [Rubber Component (A)]



    [0033] The rubber component (A) used in the rubber composition of the present invention contains 10% by mass or more of at least one kind of rubber selected from diene rubber synthesized by emulsion polymerization and natural rubber and 90% by mass or less of another kind of diene rubber, and it is preferred that the at least one kind of rubber selected from diene rubber synthesized by emulsion polymerization and natural rubber accounts for more than 10% by mass and the another kind of diene rubber accounts for less than 90% by mass.

    [0034] The diene rubber synthesized by emulsion polymerization according to the present invention may be synthesized using an ordinal emulsion polymerization method. For example, a method is exemplified in which a predetermined amount of the monomer described below is emulsified and dispersed in an aqueous medium in the presence of an emulsifier and emulsion polymerization is conducted with a radical polymerization initiator.

    [0035] As an emulsifier, for example, a long chain fatty acid salt having 10 or more carbon atoms and/or rosin acid salt may be used. Specific examples include potassium salt and sodium salt of capric acid, lauric acid, myristic acid, palmitic acid, oleic acid and stearic acid.

    [0036] Examples of the usable radical polymerization initiator include a persulfate salt such as ammonium persulfate and potassium persulfate; and a redox initiator such as a combination of ammonium persulfate and ferric sulfate, a combination of an organic peroxide and ferric sulfate, and a combination of hydrogen peroxide and ferric sulfate.

    [0037] A chain transfer agent may be added for regulating the molecular weight of the diene rubber. Examples of the usable chain transfer agent include a mercaptan such as t-dodecylmercaptan and n-dodecylmercaptan, α-methylstyrene dimer, carbon tetrachloride, thioglycolic acid, diterpene, terpinolene, and γ-terpinenes.

    [0038] The temperature at which the emulsion polymerization is conducted may be appropriately selected depending on the kind of the radical polymerization initiator used, and is typically from 0 to 100°C, and preferably from 0 to 60°C. The mode of the polymerization may be any of continuous polymerization, batch polymerization, and the like.

    [0039] In emulsion polymerization, a larger polymerization conversion tends to result in gelation. Thus, it is preferred that the polymerization conversion is suppressed to 90% or less, and in particular, it is preferred that the polymerization is terminated at a conversion ranging from 50 to 80%. The termination of the polymerization reaction is typically conducted by adding a polymerization terminator to the polymerization system at a time when a predetermined conversion is reached. Examples of the usable polymerization terminator include an amine compound such as diethylhydroxylamine and hydroxylamine, a quinone compound such as hydroquinone and benzoquinone, sodium nitrite, and sodium dithiocarbamate.

    [0040] After the termination of the polymerization reaction, unreacted monomer is removed from the obtained polymerized latex as required, then an acid such as nitric acid and sulfuric acid is added and mixed as required, to adjust the pH of the latex to a predetermined value, and a salt such as sodium chloride, calcium chloride and potassium chloride is added and mixed as an coagulant, thereby solidifying and then collecting the polymer as a crumb. The crumb is washed, dehydrated, and then dried with a band type drier or the like, whereby the target diene rubber can be obtained.

    [0041] Examples of the conjugated diene which is a monomer used for the diene rubber synthesized by emulsion polymerization according to the present invention, include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, and 1,3-pentadiene. Among them, 1,3-butadiene, 2-methyl-1,3-butadiene, etc. are preferable, and 1, 3-butadiene is more preferable. These conjugated dienes may be used alone or in combination of two or more thereof. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-tert-buthylstyrene, and 5-tert-butyl-2-methylstyrene. Among them, styrene is preferable. These aromatic vinyl compounds may be used alone or in combination of two or more thereof.

    [0042] The diene rubber synthesized by emulsion polymerization according to the present invention is preferably a styrene-butadiene copolymer rubber (which may be hereinafter referred to as "emulsion-polymerized SBR").

    [0043] The emulsion-polymerized SBR preferably contains 5 to 50% by mass, more preferably 10 to 50% by mass, and still more preferably 15 to 45% by mass, of styrene component.

    [0044] The another kind of diene rubber in the rubber component (A) used in the rubber composition of the present invention is preferably at least one kind of rubber selected from a solution polymerized styrene-butadiene copolymer rubber (which may be hereinafter referred to as "solution-polymerized SBR"), polybutadiene rubber (which may be hereinafter referred to as "BR"), and synthetic polyisoprene rubber (which may be hereinafter referred to as "IR"). The solution-polymerized SBR is preferably an unmodified styrene-butadiene copolymer rubber (which may be hereinafter referred to as "unmodified solution-polymerized SBR") and/or a modified styrene-butadiene copolymer rubber having molecular chain ends modified with a tin compound (which may be hereinafter referred to as "tin-modified solution-polymerized SBR").

    [0045] For the another kind of diene rubber, one kind may be used alone or two or more kinds may be used in a blend thereof.

    [0046] The unmodified solution-polymerized SBR may be obtained by anionic polymerization or coordination polymerization, and is preferably produced by anionic polymerization.

    [0047] The polymerization initiator used in the anionic polymerization may be an alkali metal compound, and preferably a lithium compound. As the lithium compound, not only an ordinal lithium compound (in particular, hydrocarbyl lithium or lithium amide compound) but also, when a tin-modified solution-polymerized SBR is to be obtained, a lithium compound having a tin atom (for example, triorganotin lithium compound such as tributyltin lithium and trioctyltin lithium) may be used.

    [0048] The tin-modified solution-polymerized SBR may be obtained in such a manner that after completing the polymerization reaction of unmodified solution-polymerized SBR obtained above, a tin compound as a modifier is reacted with the polymerization active end of the styrene-butadiene copolymer before terminating the polymerization.

    [0049] Examples of the tin compound include tin tetrachloride, tributyltin chloride, trioctyltin chloride, dioctyltin dichloride, dibutyltin dichloride and triphenyltin chloride.

    [Silica (B)]



    [0050] The silica (B) used in the rubber composition of the present invention may be any one of commercially available products, and among these, wet method silica, dry method silica and colloidal silica are preferably used, with wet method silica being more preferably used. Wet method silica is classified into precipitation method silica and gel method silica, and precipitation method silica is particularly preferred since it is easily dispersed in the rubber composition under shearing on kneading and is excellent in reinforcing effect due to the surface reaction after dispersion.

    [0051] The silica (B) has a CTAB adsorption specific surface area of 140 m2/g or more and less than 180 m2/g. Preferred examples of the precipitation method silica that has a CTAB adsorption specific surface area within the range include "Nipsil AQ", a trade name (registered trademark) produced by Toso Silica Corporation (CTAB adsorption specific surface area: 160 m2/g), "Zeosil 1165", a trade name (registered trademark), produced by Rhodia, Inc. (CTAB adsorption specific surface area: 160 m2/g).

    [0052] The rubber composition of the present invention may contain carbon black depending on necessity in addition to the silica (B). The use of carbon black contained provides such an effect that the electric resistance is lowered to present static charge. The carbon black is not particularly limited, and examples thereof include high, medium or low structure carbon black, such as SAF, ISAF, IISAF, N339, HAF, FEF, GPF and SRF grades, with carbon black of SAF, ISAF, IISAF, N339, HAF and FEF grades being particularly preferably used. The carbon black used preferably has a nitrogen adsorption specific surface area (N2SA measured according to JIS K6217-2 (2001)) of from 30 to 250 m2/g. The carbon black may be used solely or as a combination of two or more kinds thereof.

    [0053] The rubber composition of the present invention preferably contains the silica (B) in an amount of from 25 to 150 parts by mass per 100 parts by mass of the rubber component (A). The amount of 25 parts by mass or more is preferred from the standpoint of securing the wet capability, and the amount of 150 parts by mass or less is preferred from the standpoint of decreasing the rolling resistance. The silica (B) is more preferably contained in an amount of from 25 to 120 parts by mass, and further preferably in an amount of 30 to 85 parts by mass.

    [0054] The rubber composition of the present invention preferably contains a filler, such as carbon black, that is added depending on necessity in addition to the silica (B) in an amount of from 25 to 170 parts by mass per 100 parts by mass of the rubber component (A). The amount of 25 parts by mass or more is preferred from the standpoint of enhancing the reinforcing property of the rubber composition, and the amount of 170 parts by mass or less is preferred from the standpoint of decreasing the rolling resistance.

    [0055] The amount of the silica (B) in the filler is preferably 40% by mass or more, and more preferably 70% by mass or more, for achieving both the wet capability and the rolling resistance.

    [Silane Coupling Agent (C)]



    [0056] The silane coupling agent (C) used in the rubber composition of the present invention is at least one silane coupling agent that is necessarily selected from a polysulfide compound and a thioester compound. The polysulfide compound and the thioester compound are preferred since they prevent scorch from occurring during kneading, thereby enhancing the processability.

    [0057] The at least one silane coupling agent (C) selected from a polysulfide compound and a thioester compound is preferably at least one compound selected from the compounds represented by the following general formulae (I) to (IV).

    [0058] By using the silane coupling agent (C), the rubber composition according to the method of the present invention is further improved in the workability on processing rubber and may provide a pneumatic tire more excellent in wear resistance.

    [0059] Preferred examples of the polysulfide compound include the compounds represented by the general formula (I) or (III), and preferred examples of the thioester compound include the compounds represented by the general formula (II) or (IV).

    [0060] The general formulae (I) to (IV) are sequentially described below.

    [0061] [Chem. 1]

            (R1O)3-p(R2)pSi-R3-Sa-R3-Si(OR1)3-r(R2),     (I)

    wherein R1, which may be the same or different, each represents a linear, cyclic or branched alkyl group, having from 1 to 8 carbon atoms, or a linear or branched alkoxylalkyl group, having from 2 to 8 carbon atoms; R2, which may be the same or different, each represents a linear, cyclic or branched alkyl group, having from 1 to 8 carbon atoms; R3, which may be the same or different, each represents a linear or branched alkylene group, having from 1 to 8 carbon atoms; a indicates from 2 to 6 as a mean value; p and r, which may be the same or different, each indicates from 0 to 3 as a mean value, provided that both p and r are not 3 at the same time.

    [0062] Specific examples of the silane coupling agent (C) represented by the above-mentioned general formula (I) include bis(3-triethoxysilylpropyl) tetrasulfide, bis(3-trimethoxysilylpropyl) tetrasulfide, bis(3-methyldimethoxysilylpropyl) tetrasulfide, bis(2-triethoxysilylethyl) tetrasulfide, bis(3-triethoxysilylpropyl) disulfide, bis(3-trimethoxysilylpropyl) disulfide, bis(3-methyldimethoxysilylpropyl) disulfide, bis(2-triethoxysilylethyl) disulfide, bis(3-triethoxysilylpropyl) trisulfide, bis(3-trimethoxysilylpropyl) trisulfide, bis(3-methyldimethoxysilylpropyl) trisulfide, bis(2-triethoxysilylethyl) trisulfide, bis(3-monoethoxydimethylsilylpropyl) tetrasulfide, bis(3-monoethoxydimethylsilylpropyl) trisulfide, bis(3-monoethoxydimethylsilylpropyl) disulfide, bis(3-monomethoxydimethylsilylpropyl) tetrasulfide, bis(3-monomethoxydimethylsilylpropyl) trisulfide, bis(3-monomethoxydimethylsilylpropyl) disulfide, bis(2-monoethoxydimethylsilylethyl) tetrasulfide, bis(2-monoethoxydimethylsilylethyl) trisulfide, bis(2-monoethoxydimethylsilylethyl) disulfide.

    wherein R4 represents a monovalent group selected from -C1, -Br, R9O- R9C(=O)O-, R9R10C=NO-, R9R10CNO-, R9R10N-, and -(OSiR9R10)h(OSiR9R10R11) (where R9, R10 and R11, which may be the same or different, each represent a hydrogen atom or a monovalent hydrocarbon group having from 1 to 18 carbon atoms; and h indicates from 1 to 4 as a mean value); R5 represents R4, a hydrogen atom, or a monovalent hydrocarbon group having from 1 to 18 carbon atoms; R6 represents R4, R5, a hydrogen atom, or a group -[O(R12O)j]0.5 (where R12 represents an alkylene group having from 1 to 18 carbon atoms; and j indicates an integer of from 1 to 4); R7 represents a divalent hydrocarbon group having from 1 to 18 carbon atoms; R8 represents a monovalent hydrocarbon group having from 1 to 18 carbon atoms; x, y and z each indicate a number satisfying the relationship of x+y+2z = 3, 0 ≤ x ≤ 3, 0 ≤ y ≤ 2, 0 ≤ z ≤ 1.

    [0063] In the general formula (II), R8, R9, R10 and R11, which may be the same or different, each preferably represents a group selected from the group consisting of a linear, cyclic or branched, alkyl, alkenyl, aryl or aralkyl group, having from 1 to 18 carbon atoms. In case where R5 is a monovalent hydrocarbon group having from 1 to 18 carbon atoms, the group is preferably a group selected from the group consisting of a linear, cyclic or branched, alkyl, alkenyl, aryl or aralkyl group. Preferably, R12 is a linear, cyclic or branched alkylene group, and is more preferably a linear one. R7 is, for example, an alkylene group having from 1 to 18 carbon atoms, an alkenylene group having from 2 to 18 carbon atoms, a cycloalkylene group having from 5 to 18 carbon atoms, a cycloalkylalkylene group having from 6 to 18 carbon atoms, an arylene group having from 6 to 18 carbon atoms, or an aralkylene group having from 7 to 18 carbon atoms. The alkylene group and the alkenylene group may be linear or branched; and the cycloalkylene group, the cycloalkylalkylene group, the arylene group and the aralkylene group may have a substituent such as a lower alkyl group or the like on the ring thereof. Preferably, R7 is an alkylene group having from 1 to 6 carbon atoms, more preferably a linear alkylene group, for example, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group or a hexamethylene group.

    [0064] Specific examples of the monovalent hydrocarbon group having from 1 to 18 carbon atoms of R5, R8, R9, R10 and R11 in the general formula (II) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a cyclopentyl group, a cyclohexyl group, a vinyl group, a propenyl group, an allyl group, a hexenyl group, an octenyl group, a cyclopentenyl group, a cyclohexenyl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, etc.

    [0065] Examples of R12 in the general formula (II) include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, a decamethylene group, a dodecamethylene group, etc.

    [0066] Specific examples of the silane coupling agent (C) represented by the general formula (II) include
    3-hexanoylthiopropyltriethoxysilane,
    3-octanoylthiopropyltriethoxysilane,
    3-decanoylthiopropyltriethoxysilane,
    3-lauroylthiopropyltriethoxysilane,
    2-hexanoylthioethyltriethoxysilane,
    2-octanoylthioethyltriethoxysilane,
    2-decanoylthioethyltriethoxysilane,
    2-lauroylthioethyltriethoxysilane,
    3-hexanoylthiopropyltrimethoxysilane,
    3-octanoylthiopropyltrimethoxysilane,
    3-decanoylthiopropyltrimethoxysilane,
    3-lauroylthiopropyltrimethoxysilane,
    2-hexanoylthioethyltrimethoxysilane,
    2-octanoylthioethyltrimethoxysilane,
    2-decanoylthioethyltrimethoxysilane,
    2-lauroylthioethyltrimethoxysilane, etc. Of those, especially preferred is 3-octanoylthiopropyltriethoxysilane ("NXT Silane" (registered trade name), produced by Momentive Performance Materials Inc.). [Chem. 3]

            (R13O)3-s(R14)sSi-R15-Sk-R16-Sk-R15-Si(OR13)3-t(R14)t     (III)

    wherein R13, which may be the same or different, each represents a linear, cyclic or branched alkyl group, having from 1 to 8 carbon atoms or a linear or branched alkoxylalkyl group, having from 2 to 8 carbon atoms; R14, which may be the same or different, each represents a linear, cyclic or branched alkyl group, having from 1 to 8 carbon atoms; R15, which may be the same or different, each represents a linear or branched alkylene group, having from 1 to 8 carbon atoms; R16 represents a divalent group of a general formula (-S-R17-S-), (-R18-Sm1R19-) or (-R20-Sm2-R21-Sm3-R22-) (where R17 to R22, which may be the same or different, each represents a divalent hydrocarbon group, a divalent aromatic group or a divalent organic group containing a hetero element except sulfur and oxygen, having from 1 to 20 carbon atoms; m1, m2 and m3 may be the same or different, each indicating from 1 to less than 4 as a mean value) ; k, which may be the same or different, each indicates from 1 to 6 as a mean value; s and t, which may be the same or different, each indicate from 0 to 3 as a mean value, provided that both s and t are not 3 at the same time.

    [0067] Preferred examples of the silane coupling agent (C) represented by the above-mentioned general formula (III) are compounds represented by an average compositional formula (CH3CH2O)3Si-(CH2)3-S2-(CH2)6-S2-(CH2)3-Si(OCH2CH3)3,
    an average compositional formula (CH3CH2O)3Si-(CH2)3-S2-(CH2)10-S2-(CH2)3-Si(OCH2CH3)3,
    an average compositional formula (CH3CH2O3Si-(CH2)3-S3-(CH2)6-S3-(CH2)3-Si(OCH2CH3)3,
    an average compositional formula (CH3CH2O)3Si-(CH2)3-S4-(CH2)6-S4-(CH2)3-Si(OCH2CH3)3,
    an average compositional formula (CH3CH2O)3Si-(CH2)3-S-(CH2)6-S2-(CH2)6-S-(CH2)3-Si-(OCH2CH3)3,
    an average compositional formula (CH3CH2O)3Si-(CH2)3-S-(CH2)6-S2.5-(CH2)6-S-(CH2)3-Si(OCH2CH3)3,
    an average compositional formula (CH3CH2O)3Si-(CH2)3-S-(CH2)6-(CH2)6-S-(CH2)3-Si(OCH2CH3)3,
    an average compositional formula (CH3CH2O)3Si-(CH2)3-S-(CH2)6-S4-(CH2)6-S-(CH2)3-Si(OCH2CH3)3,
    an average compositional formula (CH3CH2O)3Si-(CH2)-3-S-(CH2)10-S2-(CH2)10-S-(CH2)3-Si(OCH2CH3)3,
    an average compositional formula (CH3CH2O)3Si-(CH2)3-S4-(CH2)6-S4-(CH2)6-S4-(CH2)3-Si(OCH2CH3)3,
    an average compositional formula (CH3CH2O)3Si-(CH2)3-S2-(CH2)6-S2-(CH2)6-S2-(CH2)3-Si(OCH2CH3)3,
    an average compositional formula (CH3CH2O)3Si-(CH2)3-S-(CH2)6-S2-(CH2)6-S2-(CH2)6-S-(CH2)3-Si(OC H2CH3)3, etc.

    [0068] The synthetic example of the silane coupling agent (C) represented by the above general formula (III) is described, for example, in WO2004/000930.

    wherein R23 represents a linear, branched or cyclic alkyl group, having from 1 to 20 carbon atoms; G, which may be the same or different, each represents an alkanediyl group or an alkenediyl group, having from 1 to 9 carbon atoms; Za, which may be the same or different, each represents a group capable of bonding to the two silicon atoms and selected from [-O-]0.5, [-O-G-]0.5 and [-O-G-O-]0.5; Zb, which may be the same or different, each represents a group which is capable of bonding to the two silicon atoms and is the functional group represented by [-O-G-O-]0.5; Zc, which may be the same or different, each represents a functional group selected from -Cl, -Br, -ORa, RaC(=O)O-, RaRbC=NO-, RaRbN-, Ra- and HO-G-O- (where G is the same as above) ; Ra and Rb, which may be the same or different, each represent a linear, branched or cyclic alkyl group, having from 1 to 20 carbon atoms; m, n, u, v and w, which may be the same or different, each are 1 ≤ m ≤ 20, 0 ≤ n ≤ 20, 0 ≤ u ≤ 3, 0 ≤ v ≤ 2, 0 ≤ w ≤ 1, and (u/2)+v+2w is 2 or 3; in case where the formula has multiple A's, then Zau, Zbv and Zcw may be the same or different in those multiple A's; in case where the formula has multiple B's, then Zau, Zbv and Zcw may be the same or different in those multiple B's.

    [0069] Specific examples of the silane coupling agent (C) represented by the general formula (IV) include the following chemical formula (V), chemical formula (VI) and chemical formula (VII):





    In the formula, L each independently represents an alkanediyl group or an alkenediyl group having from 1 to 9 carbon atoms; and x = m and y = n.

    [0070] As the silane coupling agent represented by the chemical formula (V), a commercial product is available as "NXT Low-V Silane", a trade name (registered trademark), produced by Momentive Performance Materials Inc.

    [0071] As the silane coupling agent represented by the chemical formula (VI), a commercial product is available as "NXT Ultra Low-V Silane", a trade name (registered trademark), produced by Momentive Performance Materials Inc.

    [0072] Further, as the silane coupling agent represented by the chemical formula (VII), there is mentioned a commercial product of "NXT-Z", a trade name (registered trademark), produced by Momentive Performance Materials Inc.

    [0073] The silane coupling agent represented by the general formula (II), the chemical formula (V) or the chemical formula (VI) has a protected mercapto group, and is therefore effective for preventing initial scorching in the processing process before the vulcanization step, and accordingly, the processability thereof is good.

    [0074] In the silane coupling agent represented by the general formula (V), (VI) or (VII), the carbon number of the alkoxysilane is large, and therefore the amount of the volatile compound VOC (especially alcohol) to be generated from the agent is small, and accordingly, the agent is favorable in point of working environment. Further, the silane coupling agent of the chemical formula (VII) provides a low-heat-generation property as tire performance, and is therefore more preferred.

    [0075] The silane coupling agent (C) in the present invention is particularly preferably the compound represented by the general formula (I) among the compounds represented by the general formulae (I) to (IV). This is because in the case where the vulcanization accelerator (D) is added in the first step of kneading for enhancing the activity of the silane coupling agent (C), the activation of the polysulfide-bonding site to be reacted with the rubber component is facilitated.

    [0076] In the present invention, the silane coupling agent (C) may be used solely or as a combination of two or more kinds thereof.

    [0077] The mixing amount of the silane coupling agent (C) in the rubber composition of the present invention is preferably from 1 to 20% by mass based on the silica. This is because when the amount is less than 1% by mass, it may be difficult to enhance the low-heat-generation property of the rubber composition, and when the amount exceeds 20% by mass, the cost of the rubber composition may be too increased to lower the economical efficiency. The amount is more preferably from 3 to 20% by mass based on the silica, and particularly preferably from 4 to 10% by mass based on the silica.

    [0078] In the case where the silica (B) having a CTAB adsorption specific surface area of 140 m2/g or more and less than 180 m2/g is used in the rubber composition of the present invention, for providing an average aggregated aggregate area (nm2) of the silica in the rubber composition after vulcanization of 2, 300 or less, the production method of the rubber composition is not limited, and the rubber composition may be produced by any kneading method, but the following production methods (1) to (5) are preferred since the rubber composition may be produced with an ordinary equipment with high productivity.
    1. (1) A production method of the rubber composition by kneading the rubber composition through plural steps, in which the rubber component (A), the whole or a part of the silica (B), the whole or a part of the silane coupling agent (C) and the vulcanization accelerator (D) are kneaded in the first step of kneading, where the molar amount of the organic acid compound in the rubber composition in the first step is limited to 1.5 times or less the molar amount of the vulcanization accelerator (D). In this case, the vulcanization accelerator (D) is preferably at least one selected from a guanidine compound, a sulfenamide compound and a thiazole compound.
    2. (2) A production method of the rubber composition by kneading the rubber composition through plural steps, in which the rubber component (A), the whole or a part of the silica (B) and the whole or a part of the silane coupling agent (C) are kneaded in the first step of kneading, and the vulcanization accelerator (D) is added in the course of the first step, followed by further kneading. In this case, the vulcanization accelerator (D) is preferably at least one selected from a guanidine compound, a sulfenamide compound, a thiazole compound, a thiram compound, a dithiocarbamate salt compound, a thiourea compound and a xanthate salt compound.
    3. (3) A production method of the rubber composition by kneading the rubber composition through three or more steps, in which the rubber component (A), the whole or a part of the silica (B) and the whole or a part of the silane coupling agent (C) are kneaded in the first step (X) of kneading; the vulcanization accelerator (D) is added and kneaded in the step (Y) that is the second or later step and before the final step of kneading; and the vulcanization agent is added and kneaded in the final step (Z) of kneading. In this case, the vulcanization accelerator (D) is preferably at least one selected from a guanidine compound, a sulfenamide compound, a thiazole compound, a thiram compound, a dithiocarbamate salt compound, a thiourea compound and a xanthate salt compound.
    4. (4) A production method of the rubber composition by kneading the rubber composition through plural steps, in which the rubber component (A), the whole or a part of the silica (B), the whole or a part of the silane coupling agent (C) and the vulcanization accelerator (D) are kneaded in the first step of kneading. In this case, the vulcanization accelerator (D) is preferably at least one selected from a guanidine compound, a sulfenamide compound, a thiazole compound, a thiram compound, a dithiocarbamate salt compound, a thiourea compound and a xanthate salt compound. In the method (4), the following production method (5) is preferably performed.
    5. (5) A production method of the rubber composition by kneading the rubber composition through plural steps, in which the rubber component (A), the whole or a part of the silica (B), the whole or a part of the silane coupling agent (C) and the vulcanization accelerator (D) are kneaded in the first step of kneading, where the molar amount of the organic acid compound in the rubber composition in the first step is limited to 1.5 times or less the molar amount of the vulcanization accelerator (D). In this case, the vulcanization accelerator (D) is preferably at least one selected from a guanidine compound, a sulfenamide compound, a thiazole compound, a thiram compound, a dithiocarbamate salt compound, a thiourea compound and a xanthate salt compound.


    [0079] In the production methods (1) to (5), the step of kneading before the final step, such as the first step and the second step, is a process step where the raw materials other than the reagents that contribute to crosslinking (e.g., the vulcanizing agent and vulcanization accelerator) are mixed and kneaded, and is a process step for performing dispersion of the filler to the rubber composition for reinforcing the rubber component. The step of kneading that is second or later step and before the final step does not include a step of kneading that performs only kneading without addition of any raw material and does not include a special mixing method, such as a wet master batch.

    [0080] The maximum temperature of the rubber composition in the step of kneading before the final step, such as the first step and the second step, is preferably from 120 to 190°C, more preferably from 130 to 175°C, and further preferably from 150 to 170°C. The kneading time is preferably from 0.5 to 20 minutes, more preferably from 0.5 to 10 minutes, and further preferably from 0.5 to 5 minutes.

    [0081] The final step of kneading is a process step where the reagents that contribute to crosslinking (e.g., the vulcanizing agent and vulcanization accelerator) are mixed and kneaded. The maximum temperature of the rubber composition in the final step is preferably from 60 to 140°C, more preferably from 80 to 120°C, and further preferably from 100 to 120°C. The kneading time is preferably from 0.5 to 20 minutes, more preferably from 0.5 to 10 minutes, and further preferably from 0.5 to 5 minutes.

    [Vulcanization accelerator (D)]



    [0082] As the vulcanization accelerator (D) which can be used for the rubber composition of the present invention, preferred examples include guanidines, sulfenamides, thiazoles, thiurams, dithiocarbamate salts, thioureas and xanthate salts.

    [0083] Examples of the guanidines for use in the rubber composition of the present invention include 1,3-diphenylguanidine, 1,3-di-o-tolylguanidine, 1-o-tolylbiguanide, dicatechol borate di-o-tolylguanidine salt, 1,3-di-o-cumenylguanidine, 1,3-di-o-biphenylguanidine, 1,3-di-o-cumenyl-2-propionylguanidine, etc. Preferred are 1,3-diphenylguanidine, 1,3-di-o-tolylguanidine and 1-o-tolylbiguanide as having high reactivity.

    [0084] Examples of the sulfenamides for use in the rubber composition of the present invention include
    N-cyclohexyl-2-benzothiazolylsulfenamide,
    N,N-dicyclohexyl-2-benzothiazolylsulfenamide,
    N-tert-butyl-2-benzothiazolylsulfenamide,
    N-oxydiethylene-2-benzothiazolylsulfenamide,
    N-methyl-2-benzothiazolylsulfenamide,
    N-ethyl-2-benzothiazolylsulfenamide,
    N-propyl-2-benzothiazolylsulfenamide,
    N-butyl-2-benzothiazolylsulfenamide,
    N-pentyl-2-benzothiazolylsulfenamide,
    N-hexyl-2-benzothiazolylsulfenamide,
    N-pentyl-2-benzothiazolylsulfenamide,
    N-octyl-2-benzothiazolylsulfenamide,
    N-2-ethylhexyl-2-benzothiazolylsulfenamide,
    N-decyl-2-benzothiazolylsulfenamide,
    N-dodecyl-2-benzothiazolylsulfenamide,
    N-stearyl-2-benzothiazolylsulenamide,
    N,N-dimethyl-2-benzothiazolylsulenamide,
    N,N-diethyl-2-benzothiazolylsulenamide,
    N,N-dipropyl-2-benzothiazolylsulenamide,
    N,N-dibutyl-2-benzothiazolylsulenamide,
    N,N-dipentyl-2-benzothiazolylsulenamide,
    N,N-dihexyl-2-benzothiazolylsulenamide,
    N,N-dipentyl-2-benzothiazolylsulenamide,
    N,N-dioctyl-2-benzothiazolylsulenamide,
    N,N-di-2-ethylhexylbenzothiazolylsulfenamide,
    N-decyl-2-benzothiazolylsulenamide,
    N,N-didodecyl-2-benzothiazolylsulenamide,
    N,N-distearyl-2-benzothiazolylsulenamide, etc. Of those, preferred are N-cyclohexyl-2-benzothiazolylsulenamide and N-tert-butyl-2-benzothiazolylsulenamide, as having high reactivity.

    [0085] Examples of the thiazoles for use in the rubber composition of the present invention include 2-mercaptobenzothiazole, di-2-benzothiazolyl disulfide, 2-mercaptobenzothiazole zinc salt, 2-mercaptobenzothiazole cyclohexylamine salt, 2-(N,N-diethylthiocarbamoylthio)benzothiazole, 2-(4'-morpholinodithio)benzothiazole, 4-methyl-2-mercaptobenzothiazole, di-(4-methyl-2-benzothiazolyl) disulfide, 5-chloro-2-mercaptobenzothiazole, 2-mercaptobenzothiazole sodium, 2-mercapto-6-nitrobenzothiazole, 2-mercapto-naphtho[1,2-d]thiazole, 2-mercapto-5-methoxybenzothiazole, 6-amino-2-mercaptobenzothiazole, etc. Of those, preferred are 2-mercaptobenzothiazole and di-2-benzothiazolyl disulfide, as having high reactivity.

    [0086] Examples of the thiurams for use in the rubber composition of the present invention include tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrapropylthiuram disulfide, tetraisopropylthiuram disulfide, tetrabutylthiuram disulfide, tetrapentylthiuram disulfide, tetrahexylthiuram disulfide, tetraheptylthiuram disulfide, tetraoctylthiuram disulfide, tetranonylthiuram disulfide, tetradecylthiuram disulfide, tetradodecylthiuram disulfide, tetrastearylthiuram disulfide, tetrabenzylthiuram disulfide, tetrakis(2-ethylhexyl)thiuram disulfide, tetramethylthiuram monosulfide, tetraethylthiuram monosulfide, tetrapropylthiuram monosulfide, tetraisopropylthiuram monosulfide, tetrabutylthiuram monosulfide, tetrapentylthiuram monosulfide, tetrahexylthiuram monosulfide, tetraheptylthiuram monosulfide, tetraoctylthiuram monosulfide, tetranonylthiuram monosulfide, tetradecylthiuram monosulfide, tetradodecylthiuram monosulfide, tetrastearylthiuram monosulfide, tetrabenzylthiuram monosulfide, dipentamethylenethiuram tetrasulfide, etc. Of those, preferred are tetrakis(2-ethylhexyl)thiuram disulfide and tetrabenzylthiuram disulfide, as having high reactivity.

    [0087] Examples of the dithiocarbamate salts for use in the rubber composition of the present invention include zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dipropyldithiocarbamate, zinc diisopropyldithiocarbamate, zinc dibutyldithiocarbamate, zinc dipentyldithiocarbamate, zinc dihexyldithiocarbamate, zinc diheptyldithiocarbamate, zinc dioctyldithiocarbamate, zinc di(2-ethylhexyl)dithiocarbamate, zinc didecyldithiocarbamate, zinc didodecyldithiocarbamate, zinc N-pentamethylenedithiocarbamate, zinc N-ethyl-N-phenyldithiocarbamate, zinc dibenzyldithiocarbamate, copper dimethyldithiocarbamate, copper diethyldithiocarbamate, copper dipropyldithiocarbamate, copper diisopropyldithiocarbamate, copper dibutyldithiocarbamate, copper dipentyldithiocarbamate, copper dihexyldithiocarbamate, copper diheptyldithiocarbamate, copper dioctyldithiocarbamate, copper di(2-ethylhexyl)dithiocarbamate, copper didecyldithiocarbamate, copper didodecyldithiocarbamate, copper N-pentamethylenedithiocarbamate, copper dibenzyldithiocarbamate, sodium dimethyldithiocarbamate, sodium diethyldithiocarbamate, sodium dipropyldithiocarbamate, sodium diisopropyldithiocarbamate, sodium dibutyldithiocarbamate, sodium dipentyldithiocarbamate, sodium dihexyldithiocarbamate, sodium diheptyldithiocarbamate, sodium dioctyldithiocarbamate, sodium di(2-ethylhexyl)dithiocarbamate, sodium didecyldithiocarbamate, sodium didodecyldithiocarbamate, sodium N-pentamethylenedithiocarbamate, sodium dibenzyldithiocarbamate, ferric dimethyldithiocarbamate, ferric diethyldithiocarbamate, ferric dipropyldithiocarbamate, ferric diisopropyldithiocarbamate, ferric dibutyldithiocarbamate, ferric dipentyldithiocarbamate, ferric dihexyldithiocarbamate, ferric diheptyldithiocarbamate, ferric dioctyldithiocarbamate, ferric di(2-ethylhexyl)dithiocarbamate, ferric didecyldithiocarbamate, ferric didodecyldithiocarbamate, ferric N-pentamethylenedithiocarbamate, ferric dibenzyldithiocarbamate, etc. Of those, preferred are zinc dibenzyldithiocarbamate, zinc N-ethyl-N-phenyldithiocarbamate, zinc dimethyldithiocarbamate and copper dimethyldithiocarbamate, as having high reactivity.

    [0088] Examples of the thioureas for use in the rubber composition of the present invention include N,N'-diphenylthiourea, trimethylthiourea, N,N'-diethylthiourea, N,N'-dimethylthiourea, N,N'-dibutylthiourea, ethylenethiourea, N,N'-diisopropyithiourea, N,N'-dicyclohexylthiourea, 1,3-di(o-tolyl)thiourea, 1,3-di(p-tolyl)thiourea, 1,1-diphenyl-2-thiourea, 2,5-dithiobiurea, guanylthiourea, 1-(1-naphthyl)-2-thiourea, 1-phenyl-2-thiourea, p-tolylthiourea, o-tolylthiourea, etc. Of those, preferred are N,N'-diethylthiourea, trimethylthiourea, N,N'-diphenylthiourea and N,N'-dimethylthiourea, as having high reactivity.

    [0089] Examples of the xanthate salts for use in the rubber composition of the present invention include zinc methylxanthate, zinc ethylxanthate, zinc propylxanthate, zinc isopropylxanthate, zinc butylxanthate, zinc pentylxanthate, zinc hexylxanthate, zinc heptylxanthate, zinc octylxanthate, zinc 2-ethylhexylxanthate, zinc decylxanthate, zinc dodecylxanthate, potassium methylxanthate, potassium ethylxanthate, potassium propylxanthate, potassium isopropylxanthate, potassium butylxanthate, potassium pentylxanthate, potassium hexylxanthate, potassium heptylxanthate, potassium octylxanthate, potassium 2-ethylhexylxanthate, potassium decylxanthate, potassium dodecylxanthate, sodium methylxanthate, sodium ethylxanthate, sodium propylxanthate, sodium isopropylxanthate, sodium butylxanthate, sodium pentylxanthate, sodium hexylxanthate, sodium heptylxanthate, sodium octylxanthate, sodium 2-ethylhexylxanthate, sodium decylxanthate, sodium dodecylxanthate, etc. Of those, preferred is zinc isopropylxanthate, as having high reactivity.

    [0090] The rubber composition of the present invention preferably contains the vulcanization accelerator (D) in an amount of from 0.1 to 10 parts by mass, and more preferable from 0.2 to 7 parts by mass, per 100 parts by mass of the rubber component (A). From 0.1 to 5 parts by mass of the vulcanization accelerator (D) thereof is preferably added in the step before the final step of kneading, and from 0.1 to 5 parts by mass thereof is preferably added in the final step of kneading.

    [Organic Acid Compound]



    [0091] Examples of the organic acid compound added to the rubber composition of the present invention include an organic acid selected from a saturated fatty acid or an unsaturated fatty acid, such as stearic acid, palmitic acid, lauric acid, arachidinic acid, behenic acid, lignoceric acid, capric acid, pelargonic acid, caprylic acid, enanthic acid, caproic acid, oleic acid, vaccenic acid, linoleic acid, linolenic acid and nervonic acid, and a resin acid, such as rosin acid and modified rosin acid, a metal salt and an ester of the organic acid, and a phenol derivative.

    [0092] In the present invention, it is necessary to exhibit the function of the vulcanization accelerator sufficiently, and therefore, 50% by mol or more of the organic acid compound is preferably stearic acid.

    [0093] In the rubber composition of the present invention, various additives that are generally incorporated in a rubber composition, for example, a vulcanization activator such as zinc flower or the like, an antioxidant and others may be optionally added and kneaded in the first stage or the final stage of kneading, or in the intermediate stage between the first stage and the final stage.

    [0094] As the kneading apparatus for the present invention, usable is any of a Banbury mixer, a roll, an intensive mixer, etc.

    Example



    [0095] The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the examples.

    [0096] The average aggregated aggregate area and the low-heat-generation property (tanδ index) of the vulcanized rubber composition were evaluated in the following manners.

    <Average Aggregated Aggregate Area of Vulcanized Rubber Composition>



    [0097] A specimen of the vulcanized rubber composition was produced by cutting a vulcanized rubber sheet with a razor. The size of the specimen was 5 mm × 5 mm × 1mm (thickness).

    [0098] The upper surface of the specimen was cut in a direction making an angle of 38° with respect to the upper surface of the specimen with an focused ion beam under condition of a voltage of 30 kV by using FIB-SEM (NOVA 200, produced by FEI Company). The smooth surface of the specimen formed by cutting was imaged with an SEM at an acceleration voltage of 5 kV in a direction perpendicular to the smooth surface. The resulting image was converted to a binarized image of the rubber portion and the silica portion as a filler of the specimen by the Otsu' s method, an aggregated aggregate area of the silica portion was obtained based on the resulting binarized image, and the average aggregated aggregate area of the silica portion was calculated in terms of number average (arithmetic average) per unit area (3 µm × 3 µm) from the total surface area of the silica portion and the number of aggregated aggregates. In the calculation, a particle that was in contact with an edge of the image was not counted, and a particle of 20 pixels or less was assumed to be noise and was not counted.

    <Low-Heat-Generation Property (tanδ index)>



    [0099] Using a viscoelasticity measuring device (produced by Rheometric), tanδ.of the rubber composition sample was measured at a temperature of 60°C, at a dynamic strain of 5% and at a frequency of 15 Hz. Based on the reciprocal of tanδ in Comparative Example 1, 6, 11, 15, 20, 25, 30, 35, 39, 43 or 47 as referred to 100, the data were expressed as index indication according to the following formula. The samples having a larger index value have a better low-heat-generation property and have a smaller hysteresis loss. Low-Heat-Generation Index



    [0100] The raw materials used in Examples 1 to 44 and Comparative Examples 1 to 50 described later are abbreviated as follows.
    1. (1) Emulsion-polymerized SBR-1: emulsion-polymerized styrene-butadiene copolymer rubber (SBR), "#1500", a trade name, produced by JSR Corporation
    2. (2) Solution-polymerized SBR-2: unmodified solution-polymerized styrene-butadiene copolymer rubber (SBR), "Tufdene 2000", a trade name, produced by Asahi Kasei Corporation
    3. (3) Natural rubber: RSS#3
    4. (4) Carbon black N220: "#80", a trade name, produced by Asahi Carbon Co., Ltd.
    5. (5) Silica-1: "Zeosil 1165", a trade name (registered trademark), produced by Rhodia, Inc. (CTAB adsorption specific surface area: 160 m2/g)
    6. (6) Silica-2: "Nipsil AQ", a trade name (registered trademark), produced by Toso Silica Corporation, (CTAB adsorption specific surface area: 160 m2/g)
    7. (7) Silane coupling agent Si75: bis(3-triethoxysilylpropyl) disulfide (average sulfur chain length: 2.35), silane coupling agent, "Si75", a trade name (registered trademark), produced by Evonik Industries AG
    8. (8) Anti-aging agent 6PPD: N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, "Nocrac 6C", a trade name, produced by Ouchi Shinko Chemical Industrial Co., Ltd.
    9. (9) 1,3-Diphenylguanidine: "Sanceler D", a trade name, produced by Sanshin Chemical Industry Co., Ltd.
    10. (10) Anti-aging agent TMDQ: polymerized 2,2,4-trimethyl-1,2-dihydroquinoline, "Nocrac 224", a trade name, produced by Ouchi Shinko Chemical Industrial Co., Ltd.
    11. (11) Vulcanization accelerator MBTS: di-2-benzothiazolyl disulfide, "Sanceler DM", a trade name, produced by Sanshin Chemical Industry Co., Ltd.
    12. (12) Vulcanization accelerator TBBS: N-tert-butyl-2-benzothiazolylsulfenamide, "Sanceler NS", a trade name, produced by Sanshin Chemical Industry Co., Ltd.

    Example 1



    [0101] In the first step of kneading, with a Banbury mixer, 25 parts by mass of the emulsion-polymerized SBR-1 and 75 parts by mass of solution-polymerized SBR-2 as the rubber component (A), 10 parts by mass of the carbon black N220, 50 parts by mass of the silica-1 as the silica (B), 4 parts by mass of the silane coupling agent Si75 as the silane coupling agent (C) and 30 parts by mass of an aromatic oil were kneaded for 60 seconds, and then 1 part by mass of 1,3-diphenylguanidine, which is a guanidine compound, as the vulcanization accelerator (D) was added and further kneaded, in which the maximum temperature of the rubber composition in the first step of kneading was regulated to 150°C.

    [0102] Subsequently, in the final step of kneading, 2 parts by mass of stearic acid, 1 part by mass of the anti-aging agent 6PPD, 1 part by mass of the anti-aging agent TMDQ, 2.5 parts by mass of zinc flower, 0.6 part by mass of 1,3-diphenylguanidine, 1 part by mass of the vulcanization accelerator MBTS, 0.6 part by mass of the vulcanization accelerator TBBS and 1.5 parts by mass of sulfur were added, in which the maximum temperature of the rubber composition in the final step of kneading was regulated to 110°C.

    [0103] The vulcanized rubber composition obtained from the rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 1.

    Example 2



    [0104] The kneading operation was performed in the same manner as in Example 1, except that 50 parts by mass of the emulsion-polymerized SBR-1 and 50 parts by mass of solution-polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 1.

    Example 3



    [0105] The kneading operation was performed in the same manner as in Example 1, except that 67 parts by mass of the emulsion-polymerized SBR-1 and 33 parts by mass of the solution-polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 1.

    Example 4



    [0106] The kneading operation was performed in the same manner as in Example 1, except that 100 parts by mass of the emulsion-polymerized SBR-1 was used as the rubber component (A) and the maximum temperature of the rubber composition in the first step of kneading was regulated to 170°C. The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 1.

    Comparative Example 1



    [0107] The kneading operation was performed in the same manner as in Example 1, except that 1 part by mass of 1,3-diphenylguanidine was not added in the first step of kneading, 2 parts by mass of stearic acid and 1 part by mass of the anti-aging agent 6PPD were not added in the final step of kneading, and in the first step of kneading, 100 parts mass of the solution-polymerized SBR-2 was used as the rubber component (A) and 2 parts by mass of stearic acid and 1 part by mass of the anti-aging agent 6PPD were added. The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 1.

    Comparative Example 2



    [0108] The kneading operation was performed in the same manner as in Comparative Example 1, except that 40 parts by mass of the emulsion-polymerized SBR-1 and 60 parts by mass of the solution-polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 1.

    Comparative Example 3



    [0109] The kneading operation was performed in the same manner as in Comparative Example 1, except that 50 parts by mass of the emulsion-polymerized SBR-1 and 50 parts by mass of the solution-polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 1.

    Comparative Example 4



    [0110] The kneading operation was performed in the same manner as in Comparative Example 1, except that 67 parts by mass of the emulsion-polymerized SBR-1 and 33 parts by mass of the solution-polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 1.

    Comparative Example 5



    [0111] The kneading operation was performed in the same manner as in Comparative Example 1, except that 100 parts by mass of the emulsion-polymerized SBR-1 was used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 1.

    Example 5



    [0112] The kneading operation was performed in the same manner as in Example 1, except that 50 parts by mass of the silica-2 was used as the silica (B) in the first step of kneading. The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 2.

    Example 6



    [0113] The kneading operation was performed in the same manner as in Example 5, except that 50 parts by mass of the emulsion-polymerized SBR-1 and 50 parts by mass of solution-polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 2.

    Example 7



    [0114] The kneading operation was performed in the same manner as in Example 5, except that 67 parts by mass of the emulsion-polymerized SBR-1 and 33 parts by mass of the solution-polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 2.

    Example 8



    [0115] The kneading operation was performed in the same manner as in Example 5, except that 100 parts by mass of the emulsion-polymerized SBR-1 was used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 2.

    Comparative Example 6



    [0116] The kneading operation was performed in the same manner as in Example 5, except that 1 part by mass of 1,3-diphenylguanidine was not added in the first step of kneading, 2 parts by mass of stearic acid and 1 part by mass of the anti-aging agent 6PPD were not added in the final step of kneading, and in the first step of kneading, 100 parts mass of the solution-polymerized SBR-2 was used as the rubber component (A) and 2 parts by mass of stearic acid and 1 part by mass of the anti-aging agent 6PPD were added. The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 2.

    Comparative Example 7



    [0117] The kneading operation was performed in the same manner as in Comparative Example 6, except that 40 parts by mass of the emulsion-polymerized SBR-1 and 60 parts by mass of the solution-polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 2.

    Comparative Example 8



    [0118] The kneading operation was performed in the same manner as in Comparative Example 6, except that 50 parts by mass of the emulsion-polymerized SBR-1 and 50 parts by mass of the solution-polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 2.

    Comparative Example 9



    [0119] The kneading operation was performed in the same manner as in Comparative Example 6, except that 67 parts by mass of the emulsion-polymerized SBR-1 and 33 parts by mass of the solution-polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 2.

    Comparative Example 10



    [0120] The kneading operation was performed in the same manner as in Comparative Example 6, except that 100 parts by mass of the emulsion-polymerized SBR-1 was used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 2.

    Example 9



    [0121] The kneading operation was performed in the same manner as in Example 1, except that 25 parts by mass of the natural rubber and 75 parts by mass of the solution polymerized SBR-2 were used as the rubber component (A) in the first step of kneading. The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 3.

    Example 10



    [0122] The kneading operation was performed in the same manner as in Example 1, except that 50 parts by mass of the natural rubber and 50 parts by mass of the solution-polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 3.

    Example 11



    [0123] The kneading operation was performed in the same manner as in Example 1, except that 67 parts by mass of the natural rubber and 33 parts by mass of the solution-polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 3.

    Example 12



    [0124] The kneading operation was performed in the same manner as in Example 1, except that 100 parts by mass of the natural rubber was used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 3.

    Comparative Example 11



    [0125] The kneading operation was performed in the same manner as in Comparative Example 1, except that 100 parts by mass of the natural rubber was used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 3.

    Comparative Example 12



    [0126] The kneading operation was performed in the same manner as in Comparative Example 1, except that 25 parts by mass of the natural rubber and 75 parts by mass of the solution-polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 3.

    Comparative Example 13



    [0127] The kneading operation was performed in the same manner as in Comparative Example 1, except that 50 parts by mass of the natural rubber and 50 parts by mass of the solution-polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 3.

    Comparative Example 14



    [0128] The kneading operation was performed in the same manner as in Comparative Example 1, except that 67 parts by mass of the natural rubber and 33 parts by mass of the solution-polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 3.

    [0129] [Table 1]
    Table 1
     ExampleComparative Example
    123412345
    Average aggregated aggregate area of vulcanized rubber composition (nm2) 2,000 2,100 2,100 2,050 2,400 2,400 2,400 2,400 2,400
    Vulcanization property: low-heat-generation property (tanδ index) 115 113 112 114 100 100 100 100 100
    Table 2
     ExampleComparative Example
    5678678910
    Average aggregated aggregate area of vulcanized rubber composition (nm2) 1, 950 2,050 2,050 2,000 2,500 2,500 2,500 2,500 2,500
    Vulcanization property: low-heat-generation property (tanδ index) 120 118 117 119 100 100 100 100 100
    Table 3
     ExampleComparative Example
    910111211121314
    Average aggregated aggregate area of vulcanized rubber composition (nm2) 2,000 2,100 2,100 2,150 2,400 2,400 2,400 2,400
    Vulcanization property: low-heat-generation property (tanδ index) 116 114 113 111 100 100 100 100

    Example 13



    [0130] In the first step of kneading, with a Banbury mixer, 25 parts by mass of the emulsion-polymerized SBR-1 and 75 parts by mass of the solution-polymerized SBR-2 as the rubber component (A), 30 parts by mass of the carbon black N220, 30 parts by mass of the silica-1 as the silica (B), 2.4 parts by mass of the silane coupling agent Si75 as the silane coupling agent (C) and 30 parts by mass of an aromatic oil were kneaded for 60 seconds, and then 1 part by mass of 1, 3-diphenylguanidine, which is a guanidine compound, as the vulcanization accelerator (D) was added and further kneaded, in which the maximum temperature of the rubber composition in the first step of kneading was regulated to 150°C.

    [0131] Subsequently, in the final step of kneading, 2 parts by mass of stearic acid, 1 part by mass of the anti-aging agent 6PPD, 1 part by mass of the anti-aging agent TMDQ, 2.5 parts by mass of zinc flower, 1 part by mass of the vulcanization accelerator MBTS, 0.6 part by mass of the vulcanization accelerator TBBS and 1.5 parts by mass of sulfur were added, in which the maximum temperature of the rubber composition in the final step of kneading was regulated to 110°C.

    [0132] The vulcanized rubber composition obtained from the rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 4.

    Example 14



    [0133] The kneading operation was performed in the same manner as in Example 13, except that 50 parts by mass of the emulsion-polymerized SBR-1 and 50 parts by mass of the solution-polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 4.

    Example 15



    [0134] The kneading operation was performed in the same manner as in Example 13, except that 67 parts by mass of the emulsion-polymerized SBR-1 and 33 parts by mass of the solution-polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 4.

    Example 16



    [0135] The kneading operation was performed in the same manner as in Example 13, except that 100 parts by mass of the emulsion-polymerized SBR-1 was used as the rubber component (A) and the maximum temperature of the rubber composition in the first step of kneading was regulated to 170°C. The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 4.

    Comparative Example 15



    [0136] The kneading operation was performed in the same manner as in Example 13, except that 1 part by mass of 1,3-diphenylguanidine was not added in the first step of kneading, 2 parts by mass of stearic acid and 1 part by mass of the anti-aging agent 6PPD were not added in the final step of kneading, and in the first step of kneading, 100 parts mass of the solution-polymerized SBR-2 was used as the rubber component (A) and 2 parts by mass of stearic acid and 1 part by mass of the anti-aging agent 6PPD were added. The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 4.

    Comparative Example 16



    [0137] The kneading operation was performed in the same manner as in Comparative Example 15, except that 40 parts by mass of the emulsion-polymerized SBR-1 and 60 parts by mass of the solution-polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 4.

    Comparative Example 17



    [0138] The kneading operation was performed in the same manner as in Comparative Example 15, except that 50 parts by mass of the emulsion-polymerized SBR-1 and 50 parts by mass of the solution-polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 4.

    Comparative Example 18



    [0139] The kneading operation was performed in the same manner as in Comparative Example 15, except that 67 parts by mass of the emulsion-polymerized SBR-1 and 33 parts by mass of the solution-polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 4.

    Comparative Example 19



    [0140] The kneading operation was performed in the same manner as in Comparative Example 15, except that 100 parts by mass of the emulsion-polymerized SBR-1 was used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 4.

    Example 17



    [0141] In the first step of kneading, with a Banbury mixer, 25 parts by mass of the emulsion-polymerized SBR-1 and 75 parts by mass of the solution-polymerized SBR-2 as the rubber component (A), 10 parts by mass of the carbon black N220, 75 parts by mass of the silica-1 as the silica (B), 6 parts by mass of the silane coupling agent Si75 as the silane coupling agent (C) and 30 parts by mass of an aromatic oil were kneaded for 60 seconds, and then 1 part by mass of 1, 3-diphenylguanidine, which is a guanidine compound, as the vulcanization accelerator (D) was added and further kneaded, in which the maximum temperature of the rubber composition in the first step of kneading was regulated to 150°C.

    [0142] Subsequently, in the final step of kneading, 2 parts by mass of stearic acid, 1 part by mass of the anti-aging agent 6PPD, 1 part by mass of the anti-aging agent TMDQ, 2.5 parts by mass of zinc flower, 0.6 parts by mass of 1,3-diphenylguanidine, 1 part by mass of the vulcanization accelerator MBTS, 0.6 part by mass of the vulcanization accelerator TBBS and 1.5 parts by mass of sulfur were added, in which the maximum temperature of the rubber composition in the final step of kneading was regulated to 110°C.

    [0143] The vulcanized rubber composition obtained from the rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 5.

    Example 18



    [0144] The kneading operation was performed in the same manner as in Example 17, except that 50 parts by mass of the emulsion-polymerized SBR-1 and 50 parts by mass of the solution-polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 5.

    Example 19



    [0145] The kneading operation was performed in the same manner as in Example 17, except that 67 parts by mass of the emulsion-polymerized SBR-1 and 33 parts by mass of the solution-polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 5.

    Example 20



    [0146] The kneading operation was performed in the same manner as in Example 17, except that 100 parts by mass of the emulsion-polymerized SBR-1 was used as the rubber component (A) and the maximum temperature of the rubber composition in the first step of kneading was regulated to 170°C. The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 5.

    Comparative Example 20



    [0147] The kneading operation was performed in the same manner as in Example 17, except that 1 part by mass of 1,3-diphenylguanidine was not added in the first step of kneading, 2 parts by mass of stearic acid and 1 part by mass of the anti-aging agent 6PPD were not added in the final step of kneading, and in the first step of kneading, 100 parts mass of the solution-polymerized SBR-2 was used as the rubber component (A) and 2 parts by mass of stearic acid and 1 part by mass of the anti-aging agent 6PPD were added. The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 5.

    Comparative Example 21



    [0148] The kneading operation was performed in the same manner as in Comparative Example 20, except that 40 parts by mass of the emulsion-polymerized SBR-1 and 60 parts by mass of the solution-polymerized SBR-2 were used as the rubber component. The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 5.

    Comparative Example 22



    [0149] The kneading operation was performed in the same manner as in Comparative Example 20, except that 50 parts by mass of the emulsion-polymerized SBR-1 and 50 parts by mass of the solution-polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 5.

    Comparative Example 23



    [0150] The kneading operation was performed in the same manner as in Comparative Example 20, except that 67 parts by mass of the emulsion-polymerized SBR-1 and 33 parts by mass of the solution-polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 5.

    Comparative Example 24



    [0151] The kneading operation was performed in the same manner as in Comparative Example 20, except that 100 parts by mass of the emulsion-polymerized SBR-1 was used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 5.

    Example 21



    [0152] In the first step of kneading, with a Banbury mixer, 25 parts by mass of the emulsion-polymerized SBR-1 and 75 parts by mass of the solution-polymerized SBR-2 as the rubber component (A), 5 parts by mass of the carbon black N220, 100 parts by mass of the silica-1 as the silica (B), 8 parts by mass of the silane coupling agent Si75 as the silane coupling agent (C) and 40 parts by mass of an aromatic oil were kneaded for 60 seconds, and then 1 part by mass of 1, 3-diphenylguanidine, which is a guanidine compound, as the vulcanization accelerator (D) was added and further kneaded, in which the maximum temperature of the rubber composition in the first step of kneading was regulated to 150°C.

    [0153] Subsequently, in the final step of kneading, 2 parts by mass of stearic acid, 1 part by mass of the anti-aging agent 6PPD, 1 part by mass of the anti-aging agent TMDQ, 2.5 parts by mass of zinc flower, 0.9 part by mass of 1,3-diphenylguanidine, 1 part by mass of the vulcanization accelerator MBTS, 0.6 part by mass of the vulcanization accelerator TBBS and 1.5 parts by mass of sulfur were added, in which the maximum temperature of the rubber composition in the final step of kneading was regulated to 110°C.

    [0154] The vulcanized rubber composition obtained from the rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 6.

    Example 22



    [0155] The kneading operation was performed in the same manner as in Example 21, except that 50 parts by mass of the emulsion-polymerized SBR-1 and 50 parts by mass of the solution-polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 6.

    Example 23



    [0156] The kneading operation was performed in the same manner as in Example 21, except that 67 parts by mass of the emulsion-polymerized SBR-1 and 33 parts by mass of the solution-polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 6.

    Example 24



    [0157] The kneading operation was performed in the same manner as in Example 21, except that 100 parts by mass of the emulsion-polymerized SBR-1 was used as the rubber component (A) and the maximum temperature of the rubber composition in the first step of kneading was regulated to 170°C. The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 6.

    Comparative Example 25



    [0158] The kneading operation was performed in the same manner as in Example 21, except that 1 part by mass of 1,3-diphenylguanidine was not added in the first step of kneading, 2 parts by mass of stearic acid and 1 part by mass of the anti-aging agent 6PPD were not added in the final step of kneading, and in the first step of kneading, 100 parts mass of the solution-polymerized SBR-2 was used as the rubber component (A) and 2 parts by mass of stearic acid and 1 part by mass of the anti-aging agent 6PPD were added. The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 6.

    Comparative Example 26



    [0159] The kneading operation was performed in the same manner as in Comparative Example 25, except that 40 parts by mass of the emulsion-polymerized SBR-1 and 60 parts by mass of the solution-polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 6.

    Comparative Example 27



    [0160] The kneading operation was performed in the same manner as in Comparative Example 25, except that 50 parts by mass of the emulsion-polymerized SBR-1 and 50 parts by mass of the solution-polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 6.

    Comparative Example 28



    [0161] The kneading operation was performed in the same manner as in Comparative Example 25, except that 67 parts by mass of the emulsion-polymerized SBR-1 and 33 parts by mass of the solution-polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 6.

    Comparative Example 29



    [0162] The kneading operation was performed in the same manner as in Comparative Example 25, except that 100 parts by mass of the emulsion-polymerized SBR-1 was used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 6.

    Example 25



    [0163] In the first step of kneading, with a Banbury mixer, 25 parts by mass of the emulsion-polymerized SBR-1 and 75 parts by mass of the solution-polymerized SBR-2 as the rubber component (A), 5 parts by mass of the carbon black N220, 125 parts by mass of the silica-1 as the silica (B), 9.6 parts by mass of the silane coupling agent Si75 as the silane coupling agent (C) and 50 parts by mass of an aromatic oil were kneaded for 60 seconds, and then 1 part by mass of 1, 3-diphenylguanidine, which is a guanidine compound, as the vulcanization accelerator (D) was added and further kneaded, in which the maximum temperature of the rubber composition in the first step of kneading was regulated to 150°C.

    [0164] Subsequently, in the final step of kneading, 2 parts by mass of stearic acid, 1 part by mass of the anti-aging agent 6PPD, 1 part by mass of the anti-aging agent TMDQ, 2.5 parts by mass of zinc flower, 1.2 parts by mass of 1,3-diphenylguanidine, 1.2 parts by mass of the vulcanization accelerator MBTS, 0.7 part by mass of the vulcanization accelerator TBBS and 1.7 parts by mass of sulfur were added, in which the maximum temperature of the rubber composition in the final step of kneading was regulated to 110°C.

    [0165] The vulcanized rubber composition obtained from the rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 7.

    Example 26



    [0166] The kneading operation was performed in the same manner as in Example 25, except that 50 parts by mass of the emulsion-polymerized SBR-1 and 50 parts by mass of the solution-polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 7.

    Example 27



    [0167] The kneading operation was performed in the same manner as in Example 25, except that 67 parts by mass of the emulsion-polymerized SBR-1 and 33 parts by mass of the solution-polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 7.

    Example 28



    [0168] The kneading operation was performed in the same manner as in Example 25, except that 100 parts by mass of the emulsion-polymerized SBR-1 was used as the rubber component (A) and the maximum temperature of the rubber composition in the first step of kneading was regulated to 170°C. The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 7.

    Comparative Example 30



    [0169] The kneading operation was performed in the same manner as in Example 25, except that 1 part by mass of 1,3-diphenylguanidine was not added in the first step of kneading, 2 parts by mass of stearic acid and 1 part by mass of the anti-aging agent 6PPD were not added in the final step of kneading, and in the first step of kneading, 100 parts mass of the solution-polymerized SBR-2 was used as the rubber component (A) and 2 parts by mass of stearic acid and 1 part by mass of the anti-aging agent 6PPD were added. The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 7.

    Comparative Example 31



    [0170] The kneading operation was performed in the same manner as in Comparative Example 30, except that 40 parts by mass of the emulsion-polymerized SBR-1 and 60 parts by mass of the solution-polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 7.

    Comparative Example 32



    [0171] The kneading operation was performed in the same manner as in Comparative Example 30, except that 50 parts by mass of the emulsion-polymerized SBR-1 and 50 parts by mass of the solution-polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 7.

    Comparative Example 33



    [0172] The kneading operation was performed in the same manner as in Comparative Example 30, except that 67 parts by mass of the emulsion-polymerized SBR-1 and 33 parts by mass of the solution-polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 7.

    Comparative Example 34



    [0173] The kneading operation was performed in the same manner as in Comparative Example 30, except that 100 parts by mass of the emulsion-polymerized SBR-1 was used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 7.

    [0174] [Table 2]
    Table 4
     ExampleComparative Example
    131415161516171819
    Average aggregated aggregate area of vulcanized rubber composition (nm2) 1,850 1,900 1, 930 1,930 2,430 2,430 2,430 2,450 2,450
    Vulcanization property: low-heat-generation property (tanδ index) 116 114 113 113 100 100 100 100 100
    Table 5
     ExampleComparative Example
    171819202021222324
    Average aggregated aggregate area of vulcanized rubber composition (nm2) 2,000 2,030 2,040 2,040 2,600 2, 600 2,600 2, 600 2, 600
    Vulcanization property: low-heat-generation property (tanδ index) 124 119 118 118 100 100 100 100 100
    Table 6
     ExampleComparative Example
    212223242526272829
    Average aggregated aggregate area of vulcanized rubber composition (nm2) 2,100 2,140 2,150 2,160 2,700 2,700 2,700 2,700 2,700
    Vulcanization property: low-heat-generation property (tanδ index) 123 117 116 115 100 100 100 100 100
    Table 7
     ExampleComparative Example
    252627283031323334
    Average aggregated aggregate area of vulcanized rubber composition (nm2) 2,190 2,230 2,240 2,240 2,780 2,780 2,780 2,780 2,800
    Vulcanization property: low-heat-generation property (tanδ index) 120 116 115 114 100 100 100 100 100

    Example 29



    [0175] The kneading operation was performed in the same manner as in Example 13, except that 25 parts by mass of the natural rubber and 75 parts by mass of the solution polymerized SBR-2 were used as the rubber component (A) in the first step of kneading. The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 8.

    Example 30



    [0176] The kneading operation was performed in the same manner as in Example 13, except that 50 parts by mass of the natural rubber and 50 parts by mass of the solution polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 8.

    Example 31



    [0177] The kneading operation was performed in the same manner as in Example 13, except that 67 parts by mass of the natural rubber and 33 parts by mass of the solution polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 8.

    Example 32



    [0178] The kneading operation was performed in the same manner as in Example 13, except that 100 parts by mass of the natural rubber was used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 8.

    Comparative Example 35



    [0179] The kneading operation was performed in the same manner as in Comparative Example 15, except that 100 parts by mass of the natural rubber was used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 8.

    Comparative Example 36



    [0180] The kneading operation was performed in the same manner as in Comparative Example 15, except that 25 parts by mass of the natural rubber and 75 parts by mass of the solution polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 8.

    Comparative Example 37



    [0181] The kneading operation was performed in the same manner as in Comparative Example 15, except that 50 parts by mass of the natural rubber and 50 parts by mass of the solution polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 8.

    Comparative Example 38



    [0182] The kneading operation was performed in the same manner as in Comparative Example 15, except that 67 parts by mass of the natural rubber and 33 parts by mass of the solution polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 8.

    Example 33



    [0183] The kneading operation was performed in the same manner as in Example 17, except that 25 parts by mass of the natural rubber and 75 parts by mass of the solution polymerized SBR-2 were used as the rubber component (A) in the first step of kneading. The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 9.

    Example 34



    [0184] The kneading operation was performed in the same manner as in Example 17, except that 50 parts by mass of the natural rubber and 50 parts by mass of the solution polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 9.

    Example 35



    [0185] The kneading operation was performed in the same manner as in Example 17, except that 67 parts by mass of the natural rubber and 33 parts by mass of the solution polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 9.

    Example 36



    [0186] The kneading operation was performed in the same manner as in Example 17, except that 100 parts by mass of the natural rubber was used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 9.

    Comparative Example 39



    [0187] The kneading operation was performed in the same manner as in Comaparative Example 20, except that 100 parts by mass of the natural rubber was used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 9.

    Comparative Example 40



    [0188] The kneading operation was performed in the same manner as in Comparative Example 20, except that 25 parts by mass of the natural rubber and 75 parts by mass of the solution polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 9.

    Comparative Example 41



    [0189] The kneading operation was performed in the same manner as in Comparative Example 20, except that 50 parts by mass of the natural rubber and 50 parts by mass of the solution polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 9.

    Comparative Example 42



    [0190] The kneading operation was performed in the same manner as in Comparative Example 20, except that 67 parts by mass of the natural rubber and 33 parts by mass of the solution polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 9.

    Example 37



    [0191] The kneading operation was performed in the same manner as in Example 21, except that 25 parts by mass of the natural rubber and 75 parts by mass of the solution polymerized SBR-2 were used as the rubber component (A) in the first step of kneading. The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 10.

    Example 38



    [0192] The kneading operation was performed in the same manner as in Example 21, except that 50 parts by mass of the natural rubber and 50 parts by mass of the solution polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 10.

    Example 39



    [0193] The kneading operation was performed in the same manner as in Example 21, except that 67 parts by mass of the natural rubber and 33 parts by mass of the solution polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 10.

    Example 40



    [0194] The kneading operation was performed in the same manner as in Example 21, except that 100 parts by mass of the natural rubber was used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 10.

    Comparative Example 43



    [0195] The kneading operation was performed in the same manner as in Comparative Example 25, except that 100 parts by mass of the natural rubber was used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 10.

    Comparative Example 44



    [0196] The kneading operation was performed in the same manner as in Comparative Example 25, except that 25 parts by mass of the natural rubber and 75 parts by mass of the solution polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 10.

    Comparative Example 45



    [0197] The kneading operation was performed in the same manner as in Comparative Example 25, except that 50 parts by mass of the natural rubber and 50 parts by mass of the solution polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 10.

    Comparative Example 46



    [0198] The kneading operation was performed in the same manner as in Comparative Example 25, except that 67 parts by mass of the natural rubber and 33 parts by mass of the solution polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 10.

    Example 41



    [0199] The kneading operation was performed in the same manner as in Example 25, except that 25 parts by mass of the natural rubber and 75 parts by mass of the solution polymerized SBR-2 were used as the rubber component (A) in the first step of kneading. The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 11.

    Example 42



    [0200] The kneading operation was performed in the same manner as in Example 25, except that 50 parts by mass of the natural rubber and 50 parts by mass of the solution polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 11.

    Example 43



    [0201] The kneading operation was performed in the same manner as in Example 25, except that 67 parts by mass of the natural rubber and 33 parts by mass of the solution polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 11.

    Example 44



    [0202] The kneading operation was performed in the same manner as in Example 25, except that 100 parts by mass of the natural rubber was used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 11.

    Comparative Example 47



    [0203] The kneading operation was performed in the same manner as in Comparative Example 30, except that 100 parts by mass of the natural rubber was used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 11.

    Comparative Example 48



    [0204] The kneading operation was performed in the same manner as in Comparative Example 30, except that 25 parts by mass of the natural rubber and 75 parts by mass of the solution polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 11.

    Comparative Example 49



    [0205] The kneading operation was performed in the same manner as in Comparative Example 30, except that 50 parts by mass of the natural rubber and 50 parts by mass of the solution polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 11.

    Comparative Example 50



    [0206] The kneading operation was performed in the same manner as in Comparative Example 30, except that 67 parts by mass of the natural rubber and 33 parts by mass of the solution polymerized SBR-2 were used as the rubber component (A). The resulting vulcanized rubber composition was evaluated for the average aggregated aggregate area and the low-heat-generation property (tanδ index) according to the aforementioned manners. The results are shown in Table 11.

    [0207]  [Table 3]
    Table 8
     ExampleComparative Example
    2930313235363738
    Average aggregated aggregate area of vulcanized rubber composition (nm2) 1,900 1,950 1,960 1,970 2,350 2,350 2,350 2,360
    Vulcanization property: low-heat-generation property (tanδ index) 113 111 111 109 100 100 100 100
    Table 9
     ExampleComparative Example
    3334353639404142
    Average aggregated aggregate area of vulcanized rubber composition (nm2) 2,020 2,040 2,040 2,050 2,470 2,470 2,470 2,470
    Vulcanization property: low-heat-generationproperty (tanδ index) 115 112 110 109 100 100 100 100
    Table 10
     ExampleComparative Example
    3738394043444546
    Average aggregated aggregate area of vulcanized rubber composition (nm2) 2,150 2,180 2,190 2,190 2,550 2,550 2,550 2,550
    Vulcanization property: Low-heat-generation property (tanδ index) 115 112 110 110 100 100 100 100
    Table 11
     ExampleComparative Example
    4142434447484950
    Average aggregated aggregate area of vulcanized rubber composition (nm2) 2,240 2,260 2,270 2,270 2,610 2,610 2, 610 2, 610
    Vulcanization property: low-heat-generation property (tanδ index) 114 110 109 108 100 100 100 100


    [0208] As apparent from Tables 1 to 3, each of the rubber compositions of Examples 1 to 12 has good low-heat-generation property (tanδ index) as compared to the rubber composition to be compared among Comparative Examples 1 to 14.

    [0209] As apparent from Tables 4 to 11, each of the rubber compositions of Examples 13 to 44 has good low-heat-generation property (tanδ index) as compared to the rubber composition to be compared among Comparative Examples 15 to 50.

    [Industrial Applicability]



    [0210] The rubber composition of the present invention is excellent in low-heat-generation property, and thus is favorably used as members of pneumatic tires for a passenger car, a pickup truck, a kei car, a kei truck and a heavy vehicle (such as a truck, a bus and a construction vehicle), and particularly a tread member of a pneumatic radial tire.


    Claims

    1. A rubber composition comprising: (A) a rubber component containing 10% by mass or more of at least one kind of rubber selected from diene rubber synthesized by emulsion polymerization and natural rubber and 90% by mass or less of another kind of diene rubber; (B) a silica having a n-hexadecyltrimethylammonium bromide (CTAB) adsorption specific surface area of 140 m2/g or more and less than 180 m2/g measured according to a method described in ASTM D3765-92; (C) at least one silane coupling agent selected from a polysulfide compound and a thioester compound; and (D) a vulcanization accelerator, the rubber composition after vulcanization having an average aggregated aggregate area (nm2) of the silica of 2,300 or less, measurement method of average aggregated aggregate area:
    an upper surface of a specimen of the rubber composition after vulcanization is cut in a direction making an angle of 38° with respect to the upper surface of the specimen with an focused ion beam; then a smooth surface of the specimen formed by cutting is imaged with a scanning electron microscope at an acceleration voltage of 5 kV in a direction perpendicular to the smooth surface; the resulting image is converted to a binarized image of a rubber portion and a silica portion as a filler of the specimen by the Otsu's method; an aggregated aggregate area of the silica portion is obtained based on the resulting binarized image; and the average aggregated aggregate area of the silica portion is calculated in terms of number average (arithmetic average) per unit area (3 µm × 3 µm) from a total surface area of the silica portion and the number of aggregated aggregates, provided that in the calculation, a particle that is in contact with an edge of the image is not counted, and a particle of 20 pixels or less is assumed to be noise and is not counted.
     
    2. The rubber composition according to claim 1, wherein the another kind of diene rubber is at least one kind of rubber selected from solution polymerized styrene-butadiene copolymer rubber, polybutadiene rubber and synthetic polyisoprene rubber.
     
    3. The rubber composition according to claim 1 or 2, wherein the silane coupling agent (C) is at least one compound selected from the compounds represented by the following general formulae (I) to (IV):
    [Chem. 1]

            (R1O)3-p(R2)pSi-R3-Sa-R3-Si(OR1)3-r(R2)r     (I)

    wherein R1, which may be the same or different, each represents a linear, cyclic or branched alkyl group, having from 1 to 8 carbon atoms, or a linear or branched alkoxylalkyl group, having from 2 to 8 carbon atoms; R2, which may be the same or different, each represents a linear, cyclic or branched alkyl group, having from 1 to 8 carbon atoms; R3, which may be the same or different, each represents a linear or branched alkylene group, having from 1 to 8 carbon atoms; a indicates from 2 to 6 as a mean value; p and r, which may be the same or different, each indicates from 0 to 3 as a mean value, provided that both p and r are not 3 at the same time,

    wherein R4 represents a monovalent group selected from -Cl, -Br, R9O-, R9C(=O)O-, R9R10C=NO-, R9R11CNO-, R9R10N-, and -(OSiR9R10)h(OSiR9R10R11) (where R9, R10 and R11, which may be the same or different, each represent a hydrogen atom or a monovalent hydrocarbon group having from 1 to 18 carbon atoms; and h indicates from 1 to 4 as a mean value); R5 represents R4, a hydrogen atom, or a monovalent hydrocarbon group having from 1 to 18 carbon atoms; R6 represents R4, R5, a hydrogen atom, or a group -[O(R12O)j]0.5 (where R12 represents an alkylene group having from 1 to 18 carbon atoms; and j indicates an integer of from 1 to 4); R7 represents a divalent hydrocarbon group having from 1 to 18 carbon atoms; R8 represents a monovalent hydrocarbon group having from 1 to 18 carbon atoms; x, y and z each indicate a number satisfying the relationship of x+y+2z = 3, 0 ≤ x ≤ 3, 0 ≤ y ≤ 2, 0 ≤ z ≤ 1,
    [Chem. 3]

            (R13O)3-s(R14)sSi-R15-Sk-R16-Sk-R15-Si(OR13)3-t(R14)t     (III)

    wherein R13, which may be the same or different, each represents a linear, cyclic or branched alkyl group, having from 1 to 8 carbon atoms or a linear or branched alkoxylalkyl group, having from 2 to 8 carbon atoms; R14, which may be the same or different, each represents a linear, cyclic or branched alkyl group, having from 1 to 8 carbon atoms; R15, which may be the same or different, each represents a linear or branched alkylene group, having from 1 to 8 carbon atoms; R16 represents a divalent group of a general formula (-S-R17-S-), (-R18-Sm1-R19-) or (-R20-Sm2-R21-Sm3-R22-) (where R17 to R22, which may be the same or different, each represents a divalent hydrocarbon group, a divalent aromatic group or a divalent organic group containing a hetero element except sulfur and oxygen, having from 1 to 20 carbon atoms; m1, m2 and m3 may be the same or different, each indicating from 1 to less than 4 as a mean value) ; k, which may be the same or different, each indicates from 1 to 6 as a mean value; s and t, which may be the same or different, each indicate from 0 to 3 as a mean value, provided that both s and t are not 3 at the same time,

    wherein R23 represents a linear, branched or cyclic alkyl group, having from 1 to 20 carbon atoms; G, which may be the same or different, each represents an alkanediyl group or an alkenediyl group, having from 1 to 9 carbon atoms; Za, which may be the same or different, each represents a group capable of bonding to the two silicon atoms and selected from [-O-]0.5, [-O-G-]0.5 and [-O-G-O-]0.5; Zb, which may be the same or different, each represents a group which is capable of bonding to the two silicon atoms and is the functional group represented by [-O-G-O-]0.5; Zc, which may be the same or different, each represents a functional group selected from -Cl, -Br, -ORa, RaC(=O)O-, RaRbC=NO-, RaRbN-, Ra- and HO-G-O- (where G is the same as above) ; Ra and Rb, which may be the same or different, each represent a linear, branched or cyclic alkyl group, having from 1 to 20 carbon atoms; m, n, u, v and w, which may be the same or different, each are 1 ≤ m ≤ 20, 0 ≤ n ≤ 20, 0 ≤ u ≤ 3, 0 ≤ v ≤ 2, 0 ≤ w ≤ 1, and (u/2)+v+2w is 2 or 3; in case where the formula has multiple A's, then Zau, Zbv and Zcw may be the same or different in those multiple A's; in case where the formula has multiple B's, then Zau, Zbv and Zcw may be the same or different in those multiple B's.
     
    4. The rubber composition according to claim 3, wherein the silane coupling agent (C) is a compound represented by the general formula (I).
     
    5. The rubber composition according to any one of claims 1 to 4, wherein the rubber composition contains the silica (B) in an amount of from 25 to 150 parts by mass per 100 parts by mass of the rubber component (A).
     
    6. The rubber composition according to any one of claims 1 to 5, wherein the silica (B) is precipitation method silica.
     
    7. The rubber composition according to any one of claims 1 to 6, wherein the rubber composition further comprises carbon black.
     
    8. A production method of the rubber composition of claim 1 comprising kneading the rubber composition through plural steps, in which the rubber component (A), the whole or a part of the silica (B) and the whole or a part of the silane coupling agent (C) are kneaded in a first step of kneading, and the vulcanization accelerator (D) is added in the course of the first step, followed by further kneading.
     
    9. A production method of the rubber composition of claim 1 comprising kneading the rubber composition through three or more steps, in which the rubber component (A), the whole or a part of the silica (B) and the whole or a part of the silane coupling agent (C) are kneaded in a first step (X) of kneading; the vulcanization accelerator (D) is added and kneaded in a step (Y) that is the second or later step and before a final step of kneading; and the vulcanization agent is added and kneaded in the final step (Z) of kneading.
     
    10. A production method of the rubber composition of claim 1 comprising kneading the rubber composition through plural steps, in which the rubber component (A), the whole or a part of the silica (B), the whole or a part of the silane coupling agent (C) and the vulcanization accelerator (D) are kneaded in a first step of kneading.
     
    11. A production method of claim 10, where the molar amount of an organic acid compound in the rubber composition in the first step is limited to 1.5 times or less the molar amount of the vulcanization accelerator (D).
     
    12. A production method of any of claims 8 to 11, where the vulcanization accelerator (D) is at least one selected from a guanidine compound, a sulfenamide compound, a thiazole compound, a thiram compound, a dithiocarbamate salt compound, a thiourea compound and a xanthate salt compound.
     
    13. A pneumatic tire for a passenger car, a pickup truck, a kei car, a kei truck and a heavy vehicle comprising a member comprising the rubber composition of any of claims 1 to 7.
     
    14. The tire of claim 13, wherein the rubber composition of any of claims 1 to 7 is present in a tread member of a pneumatic radial tire.
     


    Ansprüche

    1. Kautschukzusammensetzung umfassend: (A) eine Kautschukkomponente enthaltend 10 Masse-% oder mehr mindestens einer Art von Kautschuk ausgewählt unter Dienkautschuk, der durch Emulsionspolymerisation synthetisiert worden ist, und Naturkautschuk und 90 Masse-% oder weniger einer anderen Art von Dienkautschuk; (B) ein Siliciumdioxid, das einen n-Hexadecyltrimethylammoniumbromid- (CTAB-) adsorptionsspezifischen Oberflächenbereich von 140 m2/g oder mehr und weniger als 180 m2/g, einem in ASTM D3765-92 beschriebenen Verfahren gemäß gemessen, aufweist; (C) mindestens ein Silankopplungsmittel, ausgewählt von einer Polysulfidverbindung und einer Thioesterverbindung; und (D) einen Vulkanisationsbeschleuniger, wobei die Kautschukzusammensetzung nach dem Vulkanisieren einen durchschnittlichen aggregierten Aggregatbereich (nm2) des Siliciumdioxids von 2.300 oder weniger, dem Verfahren des durchschnittlichen aggregierten Aggregatsbereichs entsprechend gemessen, aufweist:

    eine obere Fläche einer Probe der Kautschukzusammensetzung wird nach dem Vulkanisieren mit einem fokussierten Ionenstrahl in einer Richtung geschnitten, die einen Winkel von 38° mit Bezug auf die obere Fläche der Probe bildet; dann wird eine glatte Fläche der Probe, die durch Schneiden gebildet worden ist, mit einem Rasterelektronenmikroskop mit einer Beschleunigungsspannung von 5 kV in einer Richtung senkrecht zu der glatten Fläche abgebildet; das resultierende Bild wird in ein binarisiertes Bild eines Kautschukteils und eines Siliciumdioxidteils als Füllstoff der Probe durch das Otsu-Verfahren umgewandelt; ein aggregierter Aggregatbereich des Siliciumdioxidteils wird auf der Basis des resultierenden binarisierten Bilds erhalten; und der durchschnittliche aggregierte Aggregatbereich des Siliciumdioxidteils wird als Zahlenmittel (arithmetischer Mittelwert) pro Einheitsbereich (3 µm x 3 µm) von einem gesamten Flächenbereich des Siliciumdioxidteils und der Anzahl aggregierter Aggregate berechnet, vorausgesetzt, dass bei der Berechnung ein Teilchen, das in Kontakt mit einer Kante des Bilds steht, nicht gezählt wird und von einem Teilchen von 20 Pixeln oder weniger angenommen wird, dass es Geräusch ist und nicht gezählt wird.


     
    2. Kautschukzusammensetzung nach Anspruch 1, wobei die andere Art von Dienkautschuk mindestens eine Art von Kautschuk ist ausgewählt unter lösungspolymerisiertem Styrol-Butadien-Copolymerkautschuk, Polybutadienkautschuk und synthetischem Polyisoprenkautschuk.
     
    3. Kautschukzusammensetzung nach Anspruch 1 oder 2, wobei das Silankopplungsmittel (C) mindestens eine Verbindung ist ausgewählt von den Verbindungen, die durch die folgenden allgemeinen Formeln (I) bis (IV) dargestellt sind:
    [Chem. 1]

            (R1O)3-p(R2)pSi-R3-Sa-R3-Si(OR1)3-r(R2)r     (I)

    wobei R1, die gleich oder verschieden sein können, jeweils eine lineare, cyclische oder verzweigte Alkylgruppe, die 1 bis 8 Kohlenstoffatome aufweist, oder eine lineare oder verzweigte Alkoxyalkylgruppe darstellen, die 2 bis 8 Kohlenstoffatome aufweist; R2, die gleich oder verschieden sein können, jeweils eine lineare, cyclische oder verzweigte Alkylgruppe darstellen, die 1 bis 8 Kohlenstoffatome aufweist; R3, die gleich oder verschieden sein können, jeweils eine lineare oder verzweigte Alkylengruppe darstellen, die 1 bis 8 Kohlenstoffatome aufweist; a 2 bis 6 als Mittelwert angibt; p und r, die gleich oder verschieden sein können, jeweils 0 bis 3 als Mittelwert angeben, vorausgesetzt, dass sowohl p als auch r nicht gleichzeitig 3 betragen,

    wobei R4 eine einwertige Gruppe darstellt ausgewählt von -Cl, Br, R9O-, R9C(=O)O-, R9R10C=NO-, R9R10CNO-, R9R10N- und -(OSiR9R10)h(OSiR9R10R11) (wobei R9, R10 und R11, die gleich oder verschieden sein können, jeweils ein Wasserstoffatom oder eine einwertige Kohlenwasserstoffgruppe darstellen, die 1 bis 18 Kohlenstoffatome aufweist; und h 1 bis 4 als Mittelwert angibt); R5 R4, ein Wasserstoffatom oder eine einwertige Kohlenwasserstoffgruppe darstellt, die 1 bis 18 Kohlenstoffatome aufweist; R6 R4, R5, ein Wasserstoffatom oder eine Gruppe -[O(R12O)j]0,5 darstellt (wobei R12 eine Alkylengruppe darstellt, die 1 bis 18 Kohlenstoffatome aufweist; und j eine ganze Zahl von 1 bis 4 anzeigt); R7 eine zweiwertige Kohlenwasserstoffgruppe darstellt, die 1 bis 18 Kohlenstoffatome aufweist; R8 eine einwertige Kohlenwasserstoffgruppe darstellt, die 1 bis 18 Kohlenstoffatome aufweist; x, y und z jeweils eine Zahl angeben, die dem Verhältnis x+y+2z = 3, 0 ≤ x ≤ 3, 0 ≤ y ≤ 2, 0 ≤ z ≤ 1 entspricht,
    [Chem. 3]

            (R13O)3-s(R14)sSi-R15-Sk-R16-Sk-R15-Si(OR13)3-t(R14)t     (III)

    wobei R13, die gleich oder verschieden sein können, jeweils eine lineare, cyclische oder verzweigte Alkylgruppe, die 1 bis 8 Kohlenstoffatome aufweist, oder eine lineare oder verzweigte Alkoxyalkylgruppe darstellen, die 2 bis 8 Kohlenstoffatome aufweist; R14, die gleich oder verschieden sein können, jeweils eine lineare, cyclische oder verzweigte Alkylgruppe darstellen, die 1 bis 8 Kohlenstoffatome aufweist; R15, die gleich oder verschieden sein können, jeweils eine lineare oder verzweigte Alkylengruppe darstellen, die 1 bis 8 Kohlenstoffatome aufweist; R16 eine zweiwertige Gruppe einer allgemeinen Formel (-S-R17-S-), (R18-Sm1-R19-) oder (R20-Sm2-R21-Sm3-R22-) darstellt (wobei R17 bis R22, die gleich oder verschieden sein können, jeweils eine zweiwertige Kohlenwasserstoffgruppe, eine zweiwertige aromatische Gruppe oder eine zweiwertige organische Gruppe darstellen, die ein Heteroelement ausschließlich Schwefel und Sauerstoff enthält, die 1 bis 20 Kohlenstoffatome aufweist; m1, m2 und m3 gleich oder verschieden sein können, wobei jedes 1 bis weniger als 4 als Mittelwert angibt); k, die gleich oder verschieden sein können, jeweils 1 bis 6 als Mittelwert angeben; s und t, die gleich oder verschieden sein können, jeweils 0 bis 3 als Mittelwert angeben, vorausgesetzt, dass beide, s und t, nicht gleichzeitig 3 betragen,

    wobei R23 eine lineare, verzweigte oder cyclische Alkylgruppe, die 1 bis 20 Kohlenstoffatome aufweist, darstellt; G, die gleich oder verschieden sein können, jeweils eine Alkandiylgruppe oder eine Alkendiylgruppe darstellen, die 1 bis 9 Kohlenstoffatome aufweist; Za, die gleich oder verschieden sein können, jeweils eine Gruppe darstellen, die dazu fähig ist, an die zwei Siliciumatome zu binden und aus [-O]0,5, [-O-G-]0,5 und [-O-G-O]0,5 ausgewählt werden; Zb, die gleich oder verschieden sein können, jeweils eine Gruppe darstellen, die dazu fähig ist, an die zwei Siliciumatome zu binden und die funktionelle Gruppe ist, die durch [-O-G-O]0,5 dargestellt ist; Zc, die gleich oder verschieden sein können, jeweils eine funktionelle Gruppe darstellen, ausgewählt von -Cl, -Br, -ORa, RaC (=O)O-, RaRbC=NO-, RaRbN-, Ra- und HO-G-O- (wobei G gleich wie oben ist); Ra und Rb, die gleich oder verschieden sein können, jeweils eine lineare, verzweigte oder cyclische Alkylgruppe, die 1 bis 20 Kohlenstoffatome aufweist, darstellen; m, n, u, v und w, die gleich oder verschieden sein können jeweils 1 ≤ m ≤ 20, 0 ≤ n ≤ 20, 0 ≤ u ≤ 3, 0 ≤ v ≤ 2, 0 ≤ w ≤ 1 und (u/2)+v+2w 2 oder 3 sind; im Fall, wo die Formel mehrere As aufweist, können Zau, Zbv und Zcw in diesen mehreren As gleich oder verschieden sein; und im Fall, wo die Formel mehrere Bs aufweist, können Zau, Zbv und Zcw in diesen mehreren Bs gleich oder verschieden sein.
     
    4. Kautschukzusammensetzung nach Anspruch 3, wobei das Silankopplungsmittel (C) eine Verbindung ist, die durch die allgemeine Formel (I) dargestellt ist.
     
    5. Kautschukzusammensetzung nach einem der Ansprüche 1 bis 4, wobei die Kautschukzusammensetzung das Siliciumdioxid (B) in einer Menge von 25 bis 150 Masseteilen pro 100 Masseteilen der Kautschukkomponente (A) enthält.
     
    6. Kautschukzusammensetzung nach einem der Ansprüche 1 bis 5, wobei das Siliciumdioxid (B) Ausfällungsverfahrensiliciumdioxid ist.
     
    7. Kautschukzusammensetzung nach einem der Ansprüche 1 bis 6, wobei die Kautschukzusammensetzung ferner Ruß umfasst.
     
    8. Herstellungsverfahren für die Kautschukzusammensetzung nach Anspruch 1, umfassend das Kneten der Kautschukzusammensetzung durch mehrere Schritte, wobei die Kautschukkomponente (A), das gesamte oder ein Teil des Siliciumdioxids (B) und das gesamte oder ein Teil des Silankopplungsmittels (C) in einem ersten Schritt des Knetens geknetet werden und der Vulkanisationsbeschleuniger (D) im Laufe des ersten Schritts zugegeben wird, gefolgt von weiterem Kneten.
     
    9. Herstellungsverfahren für die Kautschukzusammensetzung nach Anspruch 1, umfassend das Kneten der Kautschukzusammensetzung durch drei oder mehr Schritte, wobei die Kautschukkomponente (A), das gesamte oder ein Teil des Siliciumdioxids (B) und das gesamte oder ein Teil des Silankopplungsmittels (C) in einem ersten Schritt (X) des Knetens geknetet werden; der Vulkanisationsbeschleuniger (D) in einem Schritt (Y), der der zweite oder letzte Schritt ist, und vor dem letzten Schritt des Knetens zugegeben und geknetet wird; und das Vulkanisationsmittel im letzten Schritt (Z) des Knetens zugegeben und geknetet wird.
     
    10. Herstellungsverfahren für die Kautschukzusammensetzung nach Anspruch 1, umfassend das Kneten der Kautschukzusammensetzung durch mehrere Schritte, wobei die Kautschukkomponente (A), das gesamte oder ein Teil des Siliciumdioxids (B) und das gesamte oder ein Teil des Silankopplungsmittels (C) und der Vulkanisationsbeschleuniger (D) in einem ersten Schritt des Knetens geknetet werden.
     
    11. Herstellungsverfahren nach Anspruch 10, wobei die molare Menge einer organischen Säureverbindung in der Kautschukzusammensetzung im ersten Schritt auf 1,5-mal oder weniger der molaren Menge des Vulkanisationsbeschleunigers (D) beschränkt ist.
     
    12. Herstellungsverfahren nach einem der Ansprüche 8 bis 11, wobei der Vulkanisationsbeschleuniger (D) mindestens einer ist ausgewählt unter einer Guanidinverbindung, einer Sulfenamidverbindung, einer Thiazolverbindung, einer Thiramverbindung, einer Dithiocarbamatsalzverbindung, einer Thioharnstoffverbindung und einer Xanthatsalzverbindung.
     
    13. Luftreifen für einen Personenkraftwagen, einen offenen Kleinlaster, ein Kei-Car, einen Kei-Truck und einen Schwerlastwagen, umfassend ein Element umfassend die Kautschukzusammensetzung nach einem der Ansprüche 1 bis 7.
     
    14. Reifen nach Anspruch 13, wobei die Kautschukzusammensetzung nach einem der Ansprüche 1 bis 7 in einem Laufflächenelement eines Radialluftreifens vorliegt.
     


    Revendications

    1. Composition de caoutchouc comprenant: (A) un composant de caoutchouc contenant 10 % en masse ou plus d'au moins un type de caoutchouc sélectionné parmi le caoutchouc diène synthétisé par polymérisation en émulsion et le caoutchouc naturel et 90 % en masse ou moins d'un autre type de caoutchouc diène; (B) une silice ayant une surface spécifique d'adsorption du bromure de n-hexadécyltriméthylammonium (CTAB) de 140 m2/g ou plus et inférieure à 180 m2/g mesurée selon le procédé décrit dans la norme ASTM D3765-92; (C) au moins un agent de couplage de type silane sélectionné parmi un composé polysulfure et un composé thioester; et (D) un accélérateur de vulcanisation, la composition de caoutchouc après vulcanisation ayant une surface moyenne des agrégats agrégés (nm2) de la silice de 2 300 ou moins, procédé de mesure de la surface moyenne des agrégats agrégés:

    une surface supérieure d'un échantillon de la composition de caoutchouc après vulcanisation est coupée dans un sens constituant un angle de 38° par rapport à la surface supérieure de l'échantillon avec un faisceau d'ions focalisé; ensuite une surface lisse de l'échantillon formé par découpe est imagée avec un microscope électronique à balayage à une tension d'accélération de 5 kV dans un sens perpendiculaire à la surface lisse; l'image résultante est convertie en une image binarisée d'une partie du caoutchouc et d'une partie de la silice en tant que charge de l'échantillon selon le procédé d'Otsu; une surface des agrégats agrégés de la partie silice est obtenue sur la base de l'image binarisée résultante; et la surface moyenne des agrégats agrégés de la partie silice est calculée en termes de moyenne en nombre (moyenne arithmétique) par unité de surface (3 µm x 3 µm) à partir d'une surface totale de la partie silice et du nombre d'agrégats agrégés, à condition que dans le calcul, une particule qui se trouve au contact d'un bord de l'image ne soit pas comptée, et qu'une particule de 20 pixels ou moins soit considérée comme bruit parasite et ne soit pas comptée.


     
    2. Composition de caoutchouc selon la revendication 1, l'autre type de caoutchouc diène est au moins un type de caoutchouc sélectionné parmi le caoutchouc copolymère de styrène-butadiène polymérisé en solution, le caoutchouc de polybutadiène et le caoutchouc de polyisoprène synthétique.
     
    3. Composition de caoutchouc selon la revendication 1 ou 2, l'agent de couplage silane (C) étant au moins un composé sélectionné parmi les composés représentés par les formules générales suivantes (I) à (IV):
    [Chem. 1]

            (R1O)3-p(R2)pSi-R3-Sa-R3-Si(OR1)3-r(R2)r     (I)

    où R1, qui peuvent être identiques ou différents, représentent chacun un groupe alkyle linéaire, cyclique ou ramifié, ayant de 1 à 8 atomes de carbone, ou un groupe alcoxyalkyle linéaire ou ramifié, ayant de 2 à 8 atomes de carbone; R2, qui peuvent être identiques ou différents, représentent chacun un groupe alkyle linéaire, cyclique ou ramifié, ayant de 1 à 8 atomes de carbone; R3, qui peuvent être identiques ou différents, représentent chacun un groupe alcylène linéaire ou ramifié, ayant de 1 à 8 atomes de carbone; a indique une valeur de 2 à 6 comme valeur moyenne; p et r, qui peuvent être identiques ou différents, indiquent chacun une valeur de 0 à 3 comme valeur moyenne, à condition qu'à la fois p et r ne soient pas 3 au même moment,

    dans laquelle R4 représente un groupe monovalent sélectionné parmi -Cl, -Br, R9O-, R9C(=O)O-, R9R10C=NO-, R9R10CNO-, R9R10N-, et -(OSiR9R10)h(OSiR9R10R11) (où R9, R10 et R11, qui peuvent être identiques ou différents, représentent chacun un atome d'hydrogène ou un groupe hydrocarbure monovalent ayant de 1 à 18 atomes de carbone; et h indique une valeur de 1 à 4 comme valeur moyenne); R5 représente R4, un atome d'hydrogène, ou un groupe hydrocarbure monovalent ayant de 1 à 18 atomes de carbone; R6 représente R4, R5, un atome d'hydrogène, ou un groupe -[O(R12O)j]0,5 (où R12 représente un groupe alcylène ayant de 1 à 18 atomes de carbone; et j indique un nombre entier d'une valeur de 1 à 4); R7 représente un groupe hydrocarbure divalent ayant de 1 à 18 atomes de carbone; R8 représente un groupe hydrocarbure monovalent ayant de 1 à 18 atomes de carbone; x, y et z indiquent chacun un nombre satisfaisant la relation de x + y + 2z = 3, 0 ≤ x ≤ 3, 0 ≤ y ≤ 2, 0 ≤ z ≤ 1,
    [Chem. 3]

            (R13O)3-s(R14)sSi-R15-Sk-R16-Sk-R15-Si(OR13)3-t(R14)t     (III)

    dans laquelle R13, qui peuvent être identiques ou différents, représentent chacun un groupe alkyle linéaire, cyclique ou ramifié, ayant de 1 à 8 atomes de carbone ou un groupe alcoxyalkyle linéaire ou ramifié, ayant de 2 à 8 atomes de carbone; R14, qui peuvent être identiques ou différents, représentent chacun un groupe alkyle linéaire, cyclique ou ramifié, ayant de 1 à 8 atomes de carbone; R15, qui peuvent être identiques ou différents, représentent chacun un groupe alcylène linéaire ou ramifié, ayant de 1 à 8 atomes de carbone; R16 représente un groupe divalent de formule générale (-S-R17-S-), (-R18-Sm1-R19-) ou (-R20-Sm2-R21-Sm3-R22-) (où R17 à R22, qui peuvent être identiques ou différents, représentent chacun un groupe hydrocarbure divalent, un groupe aromatique divalent ou un groupe organique divalent contenant un hétéro élément excepté le soufre et l'oxygène, ayant de 1 à 20 atomes de carbone; m1, m2 et m3 peuvent être identiques ou différents, indiquant chacun de 1 à moins de 4 comme valeur moyenne); k, qui peuvent être identiques ou différents, indiquent chacun de 1 à 6 comme valeur moyenne; s et t, qui peuvent être identiques ou différents, indiquent chacun de 0 à 3 comme valeur moyenne, à condition qu'à la fois s et t ne soient pas 3 au même moment,

    dans laquelle R23 représente un groupe alkyle linéaire, ramifié ou cyclique, ayant de 1 à 20 atomes de carbone; G, qui peuvent être identiques ou différents, représentent chacun un groupe alcanediyle ou un groupe alcènediyle, ayant de 1 à 9 atomes de carbone; Za, qui peuvent être identiques ou différents, représentent chacun un groupe capable de liaison à deux atomes de silicium et sélectionnés parmi [-O-]0,5, [-O-G-]0,5 et [-O-G-O-]0,5; Zb, qui peuvent être identiques ou différents, représentent chacun un groupe qui est capable de liaison aux deux atomes de silicium et qui est le groupe fonctionnel représenté par [-O-G-O-]0,5; Zc, qui peuvent être identiques ou différents, représentent chacun un groupe fonctionnel sélectionné parmi -Cl, -Br, -ORa, RaC(=O)O-, RaRbC=NO-, RaRbN-, Ra- et HO-G-O- (où G est le même que ci-dessus); Ra et Rb, qui peuvent être identiques ou différents, représentent chacun un groupe alkyle linéaire, ramifié ou cyclique, ayant de 1 à 20 atomes de carbone; m, n, u, v et w, qui peuvent être identiques ou différents, sont chacun 1 ≤ m ≤ 20, 0 ≤ n ≤ 20, 0 ≤ u ≤ 3, 0 ≤ v ≤ 2, 0 ≤ w ≤ 1, et (u/2) + v + 2w est 2 ou 3; dans le cas où la formule possède de multiple A, alors Zau, Zbv et Zcw peuvent être identiques ou différents dans ces multiple A; dans le cas où la formule possède de multiple B, alors Zau, Zbv et Zcw peuvent être identiques ou différents dans ces multiple B.
     
    4. Composition de caoutchouc selon la revendication 3, l'agent de couplage silane (C) étant un composé représenté par la formule générale (I).
     
    5. Composition de caoutchouc selon l'une quelconque des revendications 1 à 4, la composition de caoutchouc contenant de la silice (B) en une quantité de 25 à 150 parties en masse pour 100 parties en masse du composant de caoutchouc (A).
     
    6. Composition de caoutchouc selon l'une quelconque des revendications 1 à 5, la silice (B) étant une silice obtenue par un procédé de précipitation.
     
    7. Composition de caoutchouc selon l'une quelconque des revendications 1 à 6, la composition de caoutchouc comprenant en outre du noir de carbone.
     
    8. Procédé de production de la composition de caoutchouc selon la revendication 1 comprenant le malaxage de la composition de caoutchouc à travers des étapes multiples, dans lesquelles le composant de caoutchouc (A), la totalité ou une partie de la silice (B) et la totalité ou une partie de l'agent de couplage silane (C) sont malaxés dans une première étape de malaxage, et l'accélérateur de vulcanisation (D) est ajouté durant la première étape, suivi du malaxage supplémentaire.
     
    9. Procédé de production de la composition de caoutchouc selon la revendication 1 comprenant le malaxage de la composition de caoutchouc à travers trois étapes ou plus, dans lequel le composant de caoutchouc (A), la totalité ou une partie de la silice (B) et la totalité ou une partie de l'agent de couplage silane (C) sont malaxés dans une première étape (X) de malaxage; l'accélérateur de vulcanisation (D) est ajouté et malaxé dans une étape (Y) qui est la seconde ou la dernière étape et avant une étape finale de malaxage; et l'agent de vulcanisation est ajouté et malaxé dans l'étape finale (Z) de malaxage.
     
    10. Procédé de production de la composition de caoutchouc selon la revendication 1 comprenant le malaxage de la composition de caoutchouc à travers des étapes multiples, le composant de caoutchouc (A), la totalité ou une partie de la silice (B), la totalité ou une partie de l'agent de couplage silane (C) et l'accélérateur de vulcanisation (D) étant malaxés dans une première étape de malaxage.
     
    11. Procédé de production selon la revendication 10, où la quantité molaire d'un composé d'acide organique dans la composition de caoutchouc dans la première étape est limitée à 1,5 fois ou moins la quantité molaire de l'accélérateur de vulcanisation (D).
     
    12. Procédé de production selon l'une quelconque des revendications 8 à 11, où l'accélérateur de vulcanisation (D) est au moins l'un sélectionné parmi un composé guanidine, un composé sulfénamide, un composé thiazole, un composé thirame, un composé sel dithiocarbamate, un composé thiourée et un composé sel xanthate.
     
    13. Bandage pneumatique pour un véhicule de passager, un camion pickup, une mini-citadine (kei car), une mini-camionnette (kei truck) et un véhicule poids lourd comprenant un élément comprenant la composition de caoutchouc selon l'une quelconque des revendications 1 à 7.
     
    14. Pneumatique selon la revendication 13, la composition de caoutchouc selon l'une quelconque des revendications 1 à 7 étant présente dans un élément de bande de roulement à carcasse radiale de pneumatique.
     




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    Cited references

    REFERENCES CITED IN THE DESCRIPTION



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    Patent documents cited in the description