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WO2012147894A1 - Composition de caoutchouc - Google Patents

Composition de caoutchouc Download PDF

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Publication number
WO2012147894A1
WO2012147894A1 PCT/JP2012/061292 JP2012061292W WO2012147894A1 WO 2012147894 A1 WO2012147894 A1 WO 2012147894A1 JP 2012061292 W JP2012061292 W JP 2012061292W WO 2012147894 A1 WO2012147894 A1 WO 2012147894A1
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group
different
same
mass
carbon atoms
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Japanese (ja)
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暁 堀江
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Bridgestone Corp
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Bridgestone Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/548—Silicon-containing compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators

Definitions

  • the present invention relates to a silica-containing rubber composition that reduces rolling resistance of a tire.
  • Patent Document 1 at least (i) one diene elastomer as a basic component, (ii) a white filler as a reinforcing filler, and (iii) a polysulfide as a coupling agent (white filler / diene elastomer). Rubber compositions containing alkoxysilanes together with (iv) enamines and (v) guanidine derivatives have been proposed.
  • Patent Document 2 as a basic component, at least (i) one diene elastomer, (ii) a white filler as a reinforcing filler, and (iii) a polysulfide as a coupling agent (white filler / diene elastomer).
  • a rubber composition comprising an alkoxysilane together with (iv) zinc dithiophosphate and (v) a guanidine derivative is disclosed.
  • Patent Document 3 is based on at least (i) a diene elastomer, (ii) an inorganic filler as a reinforcing filler, and (iii) a polysulfated alkoxysilane (PSAS) as a (inorganic filler / diene elastomer) coupling agent. And (iv) a rubber composition in which aldimine (R—CH ⁇ N—R) and (v) a guanidine derivative are used in combination.
  • PSAS polysulfated alkoxysilane
  • Patent Document 4 based on at least: (i) a diene elastomer, (ii) an inorganic filler as a reinforcing filler, (iii) a polysulfated alkoxysilane as a coupling agent, (iv) 1,2-dihydropyridine and ( v) Rubber compositions with guanidine derivatives have been proposed. However, there is a demand for a technique that can further reduce the rolling resistance of a tire in a rubber composition containing silica.
  • An object of the present invention is to provide a rubber composition having reduced rolling resistance under such circumstances.
  • the present invention relates to a silane cup selected from at least one selected from 100 parts by mass of a rubber component (A) made of a diene rubber, 40 to 75 parts by mass of a filler (B) containing silica and carbon black, a polysulfide compound and a thioester compound.
  • a rubber composition comprising a ring agent (C) and a vulcanization accelerator (D), wherein in the filler (B), the silica is 25% by mass or more and less than 50% by mass, and the carbon black is 50%. More than 75% by mass and 75% by mass or less, and the loss tangent (tan ⁇ ) y of the rubber composition after vulcanization and the filler compounding amount x (part by mass) satisfy the relationship of the following formula [1]. It is a rubber composition characterized by these. y ⁇ 0.0031x ⁇ 0.0006 [1] [Measurement method of loss tangent: The loss tangent (tan ⁇ ) of a sample vulcanized at 160 ° C. for 15 minutes is measured using a dynamic shear modulus measuring device at a temperature of 60 ° C., a dynamic shear strain of 5%, and a frequency of 15 Hz. ]
  • a rubber composition having reduced rolling resistance can be provided.
  • the present invention is described in detail below.
  • the rubber composition of the present invention is at least one selected from 100 parts by mass of a rubber component (A) made of a diene rubber, 40 to 75 parts by mass of a filler (B) containing silica and carbon black, a polysulfide compound and a thioester compound.
  • the loss tangent (tan ⁇ ) y of the rubber composition after vulcanization and the filler compounding amount x (part by mass) preferably satisfy the relationship of the following formula [2]. It is particularly preferable that the relationship of the formula [3] is satisfied.
  • y ⁇ 0.0031x ⁇ 0.0026 [2] y ⁇ 0.0031x ⁇ 0.0046 [3]
  • the loss tangent is measured at a temperature of 60 ° C., a dynamic shear strain of 5%, and a frequency of 15 Hz using a dynamic shear modulus measurement apparatus. tan ⁇ ) is measured.
  • FIG. 1 shows a critical regression in which the loss tangent (tan ⁇ ) y and the filler compounding amount x (part by mass) of the rubber composition of the present invention satisfy the relationships of the equations [1], [2] and [3]. It is a graph which shows a type
  • an example of the relationship between the loss tangent (tan ⁇ ) y and the filler compounding amount x (part by mass) of the rubber composition of the comparative example is represented by the following formula [4].
  • y 0.0031x + 0.0027 (4)
  • the rubber component (A) used in the rubber composition of the present invention is composed of a diene rubber, 90 to 100% by mass of a diene rubber synthesized by at least one solution polymerization, and other diene rubbers 0. Those consisting of ⁇ 10% by weight are preferred.
  • the diene rubber include solution polymerized styrene-butadiene copolymer rubber (hereinafter sometimes referred to as “solution polymerized SBR”) and emulsion polymerized styrene-butadiene copolymer rubber (hereinafter referred to as “emulsion polymerized SBR”).
  • BR polybutadiene rubber
  • IR synthetic polyisoprene rubber
  • SBR solution polymerization SBR
  • non-modified solution polymerization SBR and modified solution polymerization SBR in which the molecular chain terminal is modified with a tin compound are preferable.
  • the unmodified solution polymerization SBR is obtained by anionic polymerization or coordination polymerization, but is preferably produced by anionic polymerization.
  • the polymerization initiator used for the anionic polymerization is an alkali metal compound, but a lithium compound is preferable.
  • the lithium compound not only a normal lithium compound but also a lithium compound having a tin atom may be used when obtaining a tin-modified solution polymerization SBR as described later.
  • hydrocarbyl lithium is preferable.
  • hydrocarbyl lithium a styrene-butadiene copolymer rubber whose polymerization initiation terminal is a hydrocarbyl group can be obtained.
  • hydrocarbyl lithium those having a hydrocarbyl group having 2 to 20 carbon atoms are preferable, for example, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, tert-octyl.
  • any randomizer can be appropriately selected from known compounds that are generally used.
  • the method for producing a styrene-butadiene copolymer by anionic polymerization is not particularly limited, and a conventionally known method can be used.
  • the organic solvent inert to the reaction for example, hydrocarbon solvents such as aliphatic, alicyclic, and aromatic hydrocarbon compounds
  • the above-mentioned randomizer may be used as an organic lithium compound as a polymerization initiator.
  • the target styrene-butadiene copolymer is obtained by anionic polymerization of styrene and 1,3-butadiene in the presence of.
  • the temperature in this polymerization reaction is usually selected in the range of ⁇ 80 to 150 ° C., preferably ⁇ 20 to 100 ° C.
  • the polymerization reaction can be carried out under generated pressure, but it is usually desirable to operate at a sufficient pressure to keep the monomer in a substantially liquid phase. Higher pressures can be used, and such pressures can be obtained by any suitable method, such as pressurizing the reactor with a gas that is inert with respect to the polymerization reaction.
  • Tin-modified solution polymerization SBR reacts with a tin compound as a modifier on the polymerization active terminal of the styrene-butadiene copolymer after completion of the polymerization reaction of the unmodified solution polymerization SBR obtained as described above, and before the termination of the polymerization. Is obtained.
  • the tin compound include tin tetrachloride, tributyltin chloride, trioctyltin chloride, dioctyltin dichloride, dibutyltin dichloride, and triphenyltin chloride.
  • the tin-modified solution polymerization SBR can also be obtained by using a lithium compound having a tin atom as an anionic polymerization initiator.
  • a lithium compound having a tin atom examples include triorganotin lithium compounds such as tributyltin lithium and trioctyltin lithium.
  • the styrene component is preferably contained in the range of 5 to 50% by mass, more preferably in the range of 10 to 50% by mass, and 15 to 45% by mass. More preferably, it is included in the range. Moreover, it is preferable that the vinyl content of a butadiene part is 70 mass% or less.
  • the other diene rubber in the rubber component (A) used in the rubber composition of the present invention is preferably emulsion polymerization SBR and / or natural rubber. These diene rubbers may be used alone or as a blend of two or more.
  • the rubber composition of the present invention contains 40 to 75 parts by mass of a filler (B) containing silica and carbon black with respect to 100 parts by mass of the rubber component (A). If the filler (B) is less than 40 parts by mass, it is difficult to ensure wet performance. Moreover, when a filler (B) exceeds 75 mass parts, it will become difficult to reduce rolling resistance. Furthermore, the filler (B) according to the present invention contains 25% by mass or more and less than 50% by mass of silica, and more than 50% by mass and 75% by mass or less of carbon black.
  • any commercially available silica can be used, among which wet silica, dry silica and colloidal silica are preferably used, and wet silica is more preferably used.
  • Wet silica is classified into precipitated silica and gel silica.
  • Precipitated silica is particularly preferable because it is easily dispersed in the rubber composition by kneading shear and has excellent reinforcing properties due to surface reaction after dispersion.
  • the CTAB adsorption specific surface area of silica is preferably 140 m 2 / g or more and less than 180 m 2 / g.
  • CTAB adsorption specific surface area 160 m 2 / g
  • the carbon black used in the rubber composition of the present invention is not particularly limited.
  • the nitrogen adsorption specific surface area (N 2 SA, measured according to JIS K 6217-2: 2001) is preferably 30 to 250 m 2 / g.
  • This carbon black may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the silane coupling agent (C) used in the rubber composition of the present invention is required to be a silane coupling agent selected from at least one selected from a polysulfide compound and a thioester compound. Polysulfide compounds and thioester compounds are preferred because they do not cause scorching during kneading and can improve processability.
  • the silane coupling agent (C) selected from at least one selected from polysulfide compounds and thioester compounds is preferably a compound selected from the group consisting of compounds represented by the following general formulas (I) to (IV). .
  • the rubber composition according to the method of the present invention is further excellent in workability during rubber processing and can provide a pneumatic tire with better wear resistance. it can.
  • a preferred example of the polysulfide compound is a compound represented by the following general formula (I) or (III)
  • a preferred example of the thioester compound is a compound represented by the following general formula (II) or (IV).
  • the following general formulas (I) to (IV) will be described in order.
  • R 1 s may be the same or different and are each a linear, cyclic or branched alkyl group having 1 to 8 carbon atoms or a linear or branched alkoxyalkyl group having 2 to 8 carbon atoms
  • R 2 May be the same or different, each having 1 to 8 carbon straight, cyclic or branched alkyl groups
  • R 3 may be the same or different, each having 1 to 8 carbon straight or branched
  • a is an average value of 2 to 6
  • p and r may be the same or different, and each has an average value of 0 to 3, provided that both p and r are not 3.
  • silane coupling agent (C) represented by the general formula (I) include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, and bis (3-methyl Dimethoxysilylpropyl) 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-trieth
  • R 9 , R 10 and R 11 may be the same or different and each is a hydrogen atom or 1 to 18 is a monovalent hydrocarbon group having an average value of 1 to 4)
  • R 5 is R 4 , a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms
  • R 6 Is R 4 , R 5 a hydrogen atom or a — [O (R 12 O) j ] 0.5 — group
  • R 12 is an alkylene group having 1 to 18 carbon atoms, j is an integer of 1 to 4
  • R 7 Represents a divalent hydrocarbon group having 1 to 18 carbon atoms
  • R 8 represents a monovalent hydrocarbon
  • R 8 , R 9 , R 10 and R 11 may be the same or different and are preferably each a linear, cyclic or branched alkyl group or alkenyl group having 1 to 18 carbon atoms. And a group selected from the group consisting of an aryl group and an aralkyl group.
  • R 5 is a monovalent hydrocarbon group having 1 to 18 carbon atoms, it is a group selected from the group consisting of a linear, cyclic or branched alkyl group, alkenyl group, aryl group and aralkyl group.
  • R 12 is preferably a linear, cyclic or branched alkylene group, particularly preferably a linear one.
  • R 7 is, for example, an alkylene group having 1 to 18 carbon atoms, an alkenylene group having 2 to 18 carbon atoms, a cycloalkylene group having 5 to 18 carbon atoms, a cycloalkylalkylene group having 6 to 18 carbon atoms, or an arylene having 6 to 18 carbon atoms. And an aralkylene group having 7 to 18 carbon atoms.
  • the alkylene group and alkenylene group may be linear or branched, and the cycloalkylene group, cycloalkylalkylene group, arylene group, and aralkylene group may have a substituent such as a lower alkyl group on the ring. You may have.
  • R 7 is preferably an alkylene group having 1 to 6 carbon atoms, particularly preferably a linear alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, or a hexamethylene group. it can.
  • Specific examples of the monovalent hydrocarbon group having 1 to 18 carbon atoms of R 5 , R 8 , R 9 , R 10 and R 11 in the general formula (II) include a methyl group, an ethyl group, and an n-propyl group.
  • R 12 in the general formula (II) examples include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, decamethylene group, dodecamethylene group and the like.
  • silane coupling agent (C) represented by the general formula (II) include 3-hexanoylthiopropyltriethoxysilane, 3-octanoylthiopropyltriethoxysilane, 3-decanoylthiopropyltri Ethoxysilane, 3-lauroylthiopropyltriethoxysilane, 2-hexanoylthioethyltriethoxysilane, 2-octanoylthioethyltriethoxysilane, 2-decanoylthioethyltriethoxysilane, 2-lauroylthioethyltriethoxysilane 3-hexanoylthiopropyltrimethoxysilane, 3-octanoylthiopropyltrimethoxysilane, 3-decanoylthiopropyltrimethoxysilane, 3-decanoylthiopropyltrimethoxysi
  • R 13 may be the same or different and each is a linear, cyclic or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkoxyalkyl group having 2 to 8 carbon atoms
  • R 14 May be the same or different, each having a straight chain, cyclic or branched alkyl group having 1 to 8 carbon atoms
  • R 15 may be the same or different, each having a straight chain or branched structure having 1 to 8 carbon atoms.
  • R 16 is an alkylene group of the general formula (—S—R 17 —S—), (—R 18 —S m1 —R 19 —) and (—R 20 —S m2 —R 21 —S m3 —R 22 —).
  • Any one of divalent groups (R 17 to R 22 may be the same or different and each is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent aromatic group, or other than sulfur and oxygen) It is a divalent organic group containing a hetero element, and m1, m2, and m3 may be the same or different and each has an average value of 1 or more Less than 4), k may be the same or different and each is an average value of 1 to 6, and s and t may be the same or different, and each is an average value of 0 to 3, provided that Both s and t are not 3.
  • silane coupling agent (C) represented by the general formula (III), Average composition formula (CH 3 CH 2 O) 3 Si— (CH 2 ) 3 —S 2 — (CH 2 ) 6 —S 2 — (CH 2 ) 3 —Si (OCH 2 CH 3 ) 3 , Average composition formula (CH 3 CH 2 O) 3 Si— (CH 2 ) 3 —S 2 — (CH 2 ) 10 —S 2 — (CH 2 ) 3 —Si (OCH 2 CH 3 ) 3 , Average composition formula (CH 3 CH 2 O) 3 Si— (CH 2 ) 3 —S 3 — (CH 2 ) 6 —S 3 — (CH 2 ) 3 —Si (OCH 2 CH 3 ) 3 , Average composition formula (CH 3 CH 2 O) 3 Si— (CH 2 ) 3 —S 4 — (CH 2 ) 6 —S 4 — (CH 2 ) 3 —Si (OCH 2 CH 3 ) 3 ,
  • R 23 is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms
  • G may be the same or different, and each is an alkanediyl group or alkenediyl group having 1 to 9 carbon atoms
  • Z a may be the same or different, each being a group capable of bonding to two silicon atoms, and [ ⁇ 0 ⁇ ] 0.5 , [ ⁇ 0 ⁇ G ⁇ ] 0.5 or [—O—G—O— ]
  • a group selected from 0.5 , Z b may be the same or different, each being a group capable of bonding to two silicon atoms, and a functional group represented by [—O—G—O—] 0.5
  • Z c may be the same or different and each represents —Cl, —Br, —OR a , R a C ( ⁇ O) O—, R a R b C ⁇ NO—, R a R b N -, R a -, HO- G-O- (.
  • R a and R b are good be the same or different Are each straight-chain, branched or cyclic alkyl group having 1 to 20 carbon atoms.
  • each of Z a u , Z b v and Z c w in the plurality of A parts may be the same or different.
  • Z a in a plurality of B parts Each of u , Z b v and Z c w may be the same or different.
  • silane coupling agent (C) represented by the general formula (IV) include chemical formula (V), chemical formula (VI), and chemical formula (VII).
  • silane coupling agent represented by the chemical formula (V) ⁇ trade name “NXT Low-V Silane” (registered trademark) ⁇ manufactured by Momentive Performance Materials Inc. is commercially available. Further, as the silane coupling agent represented by the chemical formula (VI), ⁇ Momentive Performance Materials Inc., trade name “NXT Ultra Low-V Silane” (registered trademark) ⁇ can be obtained as a commercial product. it can. Furthermore, examples of the silane coupling agent represented by the chemical formula (VII) include ⁇ Mentive Performance Materials Inc., trade name “NXT-Z” (registered trademark) ⁇ .
  • silane coupling agent obtained by the above general formula (II), chemical formula (V) and chemical formula (VI) has a protected mercapto group, initial vulcanization (scorch) during processing in the process prior to the vulcanization process. ) Can be prevented, so that workability is improved.
  • the silane coupling agent obtained by chemical formula (V), (VI) and (VII) has many alkoxysilane carbon number, there is little generation
  • the silane coupling agent (C) according to the present invention is particularly preferably a compound represented by the above general formula (I) among the compounds represented by the above general formulas (I) to (IV).
  • a silane coupling agent (C) may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the blending amount of the silane coupling agent (C) in the rubber composition of the present invention is preferably 1 to 20% by mass of silica. If the amount is less than 1% by mass, the effect of improving the low heat build-up of the rubber composition is difficult to be exhibited. Further, it is more preferably 3 to 20% by mass of silica, and particularly preferably 4 to 10% by mass of silica.
  • the production method of the rubber composition is not limited and may be produced by any kneading method, but the following production methods (1) to (5) It is preferable from the viewpoint of being able to be produced with high productivity.
  • the rubber composition is kneaded in a plurality of stages, and in the first stage of kneading, the rubber component (A), all or part of silica, all or part of the silane coupling agent (C), and a vulcanization accelerator ( D) is added and kneaded, and production of a rubber composition in which the molar amount of the organic acid compound in the rubber composition in the first stage is limited to 1.5 times or less the molar amount of the vulcanization accelerator (D).
  • Method The rubber composition is kneaded in a plurality of stages, and in the first stage of kneading, the rubber component (A), all or part of silica, all or part of the silane coupling agent (C), and a vulcanization accelerator ( D) is
  • the vulcanization accelerator (D) is preferably at least one selected from guanidines, sulfenamides and thiazoles.
  • the rubber composition was kneaded in a plurality of stages, and in the first stage of kneading, all or part of the rubber component (A), silica, and all or part of the silane coupling agent (C) were kneaded. Then, the manufacturing method of the rubber composition which knead
  • the vulcanization accelerator (D) is preferably at least one selected from guanidines, sulfenamides, thiazoles, thiurams, dithiocarbamates, thioureas and xanthates.
  • the rubber composition is kneaded in three or more stages of kneading, and in the first stage (X) of kneading, the rubber component (A), all or part of silica, and all or part of the silane coupling agent (C) Part of the mixture is kneaded, the vulcanization accelerator (D) is added after the second stage of the kneading and before the final stage (Y), and the vulcanizing agent is added at the final stage (Z) of the kneading.
  • a method for producing a rubber composition to be kneaded is kneaded.
  • the vulcanization accelerator (D) is preferably at least one selected from guanidines, sulfenamides, thiazoles, thiurams, dithiocarbamates, thioureas and xanthates.
  • the rubber composition is kneaded in a plurality of stages, and in the first stage of kneading, the rubber component (A), all or part of the silica, and all or part of the silane coupling agent (C) and vulcanized.
  • the vulcanization accelerator (D) is preferably at least one selected from guanidines, sulfenamides, thiazoles, thiurams, dithiocarbamates, thioureas and xanthates.
  • the following (5) is desirable.
  • the rubber composition is kneaded in a plurality of stages, and in the first stage of kneading, the rubber component (A), all or part of silica, all or part of the silane coupling agent (C), and the vulcanization accelerator.
  • the vulcanization accelerator (D) is preferably at least one selected from guanidines, sulfenamides, thiazoles, thiurams, dithiocarbamates, thioureas and xanthates.
  • the kneading stage before the final stage such as the first stage and the second stage refers to chemicals related to crosslinking, such as rubber components, fillers, and coupling agents ( This is a step of blending and kneading raw materials other than vulcanizing agents and vulcanization accelerators, and is a step for reinforcing the rubber component by dispersing the filler into the rubber composition.
  • a kneading process in which only the kneading is performed without adding the raw materials is not included, and a special mixing method such as a wet masterbatch is not included.
  • the maximum temperature of the rubber composition in the kneading stage prior to the final stage such as the first stage and the second stage is preferably 120 to 190 ° C, more preferably 130 to 175 ° C, and 150 to 170 ° C. More preferably it is.
  • the kneading time is preferably from 0.5 minutes to 20 minutes, more preferably from 0.5 minutes to 10 minutes, and further preferably from 0.5 minutes to 5 minutes.
  • the final stage of kneading refers to a step of blending and kneading chemicals related to crosslinking (vulcanizing agent, vulcanization accelerator).
  • the maximum temperature of the rubber composition in this final stage is preferably 60 to 140 ° C, more preferably 80 to 120 ° C, and further preferably 100 to 120 ° C.
  • the kneading time is preferably from 0.5 minutes to 20 minutes, more preferably from 0.5 minutes to 10 minutes, and further preferably from 0.5 minutes to 5 minutes.
  • Vulcanization accelerator (D) As the vulcanization accelerator (D) used in the rubber composition of the present invention, at least one vulcanization selected from guanidines, sulfenamides, thiazoles, thiurams, dithiocarbamates, thioureas and xanthates An accelerator is preferred.
  • guanidines used 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-cumenyl guanidine, 1,3-di-o-biphenyl guanidine, 1,3-di-o-cumenyl-2-propionyl guanidine, and the like can be mentioned.
  • 1,3-diphenyl guanidine, 1,3-di-o-tolylguanidine and 1-o-tolylbiguanide are preferred because of their high reactivity.
  • Examples of the sulfenamide used 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-octy -2-Benz
  • Examples of thiazoles used 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-me Mercaptobenzothiazole, and the like. Of these, 2-mercapto
  • Thiurams used in the rubber composition of the present invention include tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrapropylthiuram disulfide, tetraisopropylthiuram disulfide, tetrabutylthiuram disulfide, tetrapentylthiuram disulfide, tetrahexylthiuram disulfide, tetraheptyl Thiuram disulfide, tetraoctyl thiuram disulfide, tetranonyl thiuram disulfide, tetradecyl thiuram disulfide, tetradodecyl thiuram disulfide, tetrastearyl thiuram disulfide, tetrabenzyl thiuram disulfide, tetrakis (2-ethylhexyl)
  • dithiocarbamate used in the rubber composition of the present invention examples include zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dipropyldithiocarbamate, zinc diisopropyldithiocarbamate, zinc dibutyldithiocarbamate, zinc dipentyldithiocarbamate, and zinc dihexyldithiocarbamate.
  • zinc dibenzyldithiocarbamate zinc N-ethyl-N-phenyldithiocarbamate, zinc dimethyldithiocarbamate and copper dimethyldithiocarbamate are preferred because of their high reactivity.
  • thioureas used in the rubber composition of the present invention include N, N′-diphenylthiourea, trimethylthiourea, N, N′-diethylthiourea, N, N′-dimethylthiourea, and N, N′-dibutylthiourea.
  • Ethylenethiourea N, N'-diisopropylthiourea, 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.
  • N, N'-diethylthiourea, trimethylthiourea, N, N'-diphenylthiourea and N, N'-dimethylthiourea are preferred because of their high reactivity.
  • Examples of xanthates used 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, butylxanthate Potassium, potassium pentylxanthate, potassium hexylxanthate, potassium heptylxanthate, octyl chloride Potassium tonate, potassium 2-ethylhexyl
  • the rubber composition of the present invention preferably contains 0.1 to 10 parts by mass, preferably 0.2 to 7 parts by mass of the vulcanization accelerator (D) with respect to 100 parts by mass of the rubber component (A). More preferably. Among these, it is preferable to add 0.1 to 5 parts by mass of the vulcanization accelerator (D) before the final stage of kneading, and it is preferable to add 0.1 to 5 parts by mass at the final stage of kneading. .
  • Organic acid compound optionally blended in the rubber composition of the present invention includes stearic acid, palmitic acid, myristic acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, capric acid, pelargonic acid, caprylic acid, enanthic acid , Organic acids selected from saturated fatty acids such as caproic acid, oleic acid, vaccenic acid, linoleic acid, linolenic acid, nervonic acid, and resin acids such as rosin acid and modified rosin acid, and metal salts of the above organic acids Or ester, a phenol derivative, etc. are mentioned.
  • 50 mol% or more in the organic acid compound is preferably stearic acid because it is necessary to sufficiently exhibit the function as a vulcanization acceleration aid.
  • various compounding agents such as a vulcanization activator such as zinc white and an anti-aging agent blended in the rubber composition are mixed in the first stage or the final stage of kneading, if necessary. It is kneaded in an intermediate stage between the first stage and the final stage.
  • a Banbury mixer, a roll, an intensive mixer or the like is used as the kneading apparatus in the present invention.
  • the loss tangent (tan ⁇ ) and low rolling resistance of the vulcanized rubber composition were evaluated by the following methods.
  • ⁇ Loss tangent (tan ⁇ )> Using a vulcanized rubber composition sample obtained by vulcanization at 160 ° C. for 15 minutes, using a dynamic shear modulus measurement apparatus (manufactured by Rheometrics), at a temperature of 60 ° C., a dynamic shear strain of 5%, and a frequency of 15 Hz. Tan ⁇ was measured.
  • ⁇ Low rolling resistance (index)> A pneumatic radial tire for a passenger car having a tire size of 225 / 50R17 in which the test rubber composition was disposed in the tread grounding portion (cap tread portion) was produced.
  • Emulsion polymerization SBR-1 Emulsion polymerization styrene-butadiene copolymer rubber (SBR) manufactured by JSR Corporation, trade name “# 1500”
  • Solution polymerization SBR-2 Asahi Kasei Corporation, unmodified solution polymerization styrene-butadiene copolymer rubber (SBR), trade name “Toughden 2000”
  • Emulsion polymerization SBR-3 manufactured by JSR Corporation, emulsion polymerization styrene-butadiene copolymer rubber (SBR), trade name “# 1712” (37.5 parts by mass of oil-extended oil with respect to 100 parts by mass of SBR) is there.
  • Solution polymerization SBR-4 Solution polymerization styrene-butadiene copolymer rubber (SBR) manufactured by Asahi Kasei Co., Ltd.,
  • Example 1 In the first stage of kneading, in a Banbury mixer, 100 parts by mass of solution polymerization SBR-2 as the rubber component (A), 18 parts by mass of silica-1 and 27 parts by mass of carbon black N220 as the filler (B), 1 part by mass of guanidine as vulcanization accelerator (D) after kneading 1.4 parts by mass of silane coupling agent Si75 as silane coupling agent (C) and 30 parts by mass of aromatic oil for 60 seconds 1,3-diphenylguanidine was added and further kneaded, and the maximum temperature of the rubber composition in the first stage of kneading was adjusted to 150 ° C.
  • the maximum temperature of the rubber composition at the final stage of kneading is The temperature was adjusted to 110 ° C.
  • the loss tangent (tan ⁇ ) of the vulcanized rubber composition obtained from this rubber composition and the low rolling resistance of the passenger car pneumatic radial tire were evaluated by the above methods. The results are shown in Table 1.
  • Example 2 the filler (B) was changed to 22 parts by mass of silica-1 and 33 parts by mass of carbon black N220, and the silane coupling agent (C) was changed to 1.8 parts by mass of the silane coupling agent Si75.
  • Example 3 the filler (B) was changed to 26 parts by mass of silica-1 and 39 parts by mass of carbon black N220, and the silane coupling agent (C) was changed to 2.1 parts by mass of the silane coupling agent Si75.
  • Example 5 28 parts by mass of silica-1 and 42 parts by mass of carbon black N220 as filler (B) and 2.2 parts by mass of silane coupling agent Si75 as silane coupling agent (C) were changed.
  • Comparative Examples 2-5 In Comparative Example 2, the filler (B) was changed to 22 parts by mass of silica-1 and 33 parts by mass of carbon black N220, and the silane coupling agent (C) was changed to 1.8 parts by mass of the silane coupling agent Si75. In Example 3, the filler (B) was changed to 26 parts by mass of silica-1 and 39 parts by mass of carbon black N220, and the silane coupling agent (C) was changed to 2.1 parts by mass of the silane coupling agent Si75. In Comparative Example 5, the filler (B) was changed to 28 parts by mass of silica-1 and 42 parts by mass of carbon black N220 and the silane coupling agent (C) to 2.2 parts by mass of silane coupling agent Si75.
  • Examples 6 to 38 and Comparative Examples 6 to 38 66 types of rubber compositions of Examples 6 to 38 and Comparative Examples 6 to 38 were prepared according to the blending contents and kneading methods shown in Tables 2 to 8.
  • the rubber component (A), the filler (B), the silane coupling agent (C), and the aromatic oil were used in the first stage of kneading in the Banbury mixer. After kneading for 60 seconds, 1 part by mass of 1,3-diphenylguanidine, which is a guanidine, is added as a vulcanization accelerator (D) and further kneaded.
  • the maximum temperature of the rubber composition in the first stage of kneading is All were adjusted so that it might become 150 degreeC.
  • various compounding agents having the blending contents shown in Tables 2 to 8 were added to adjust the maximum temperature of the rubber composition at 110 ° C. in the final stage of kneading.
  • Comparative Examples 6 to 38 as in Comparative Example 1, 1 part by weight of 1,3-diphenylguanidine was not added in the first stage of kneading, and 2 parts by weight of stearic acid and 1 part by weight of the final stage of kneading were not added.
  • each of the rubber compositions of Examples 1 to 5 has a low loss tangent compared to the rubber compositions having the same filler content in Comparative Examples 1 to 5, Low rolling resistance was good.
  • each of the rubber compositions of Examples 6 to 38 was compared with the rubber composition having the same silica compounding amount in the same table in Comparative Examples 6 to 38. Also, the loss tangent was low, and the low rolling resistance was good.
  • the rubber composition of the present invention has low rolling resistance and excellent low heat build-up, it is used for passenger cars, small trucks, light passenger cars, light trucks and large vehicles (for trucks, buses, construction vehicles, etc.), etc. It is used suitably as each member of these various pneumatic tires, in particular, as a tread member (particularly a cap tread member) of a pneumatic radial tire.

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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

L'invention concerne une composition de caoutchouc qui contient : 100 parties en masse d'un composant caoutchouc (A) constitué de caoutchouc diénique; 40 à 75 parties en masse d'une matière de remplissage (B) contenant une silice et un noir de carbone; au moins une sorte d'agent adhésif au silane (C) choisie parmi un composé polysulfure et un composé thioester; et un accélérateur de vulcanisation (D). Dans la matière de remplissage (B), la silice représente au moins 25% en masse, et moins de 50% en masse, et le noir de carbone représente plus de 50% en masse et au plus 75% en masse. Cette composition de caoutchouc est caractéristique en ce que son facteur de dissipation diélectrique (tanδ) y, et sa quantité de matière de remplissage mélangée x (en parties en masse) après vulcanisation, satisfont la relation de la formule (1). Ainsi, l'invention fournit une composition de caoutchouc dont la résistance au roulement est réduite. y≦0,0031x-0,0006…(1)
PCT/JP2012/061292 2011-04-28 2012-04-26 Composition de caoutchouc Ceased WO2012147894A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014162897A (ja) * 2013-02-27 2014-09-08 Bridgestone Corp ゴム組成物の製造方法

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JP2005075900A (ja) * 2003-08-29 2005-03-24 Mitsubishi Chemicals Corp シリカマスターバッチ及びその製造方法
JP2007154130A (ja) * 2005-12-08 2007-06-21 Yokohama Rubber Co Ltd:The タイヤ用ゴム組成物及びその製造方法
WO2008102513A1 (fr) * 2007-02-21 2008-08-28 The Yokohama Rubber Co., Ltd. Composition de caoutchouc
WO2008123306A1 (fr) * 2007-03-27 2008-10-16 Bridgestone Corporation Procédé de fabrication d'une composition de caoutchouc pour une bande de roulement de pneumatique
WO2009158604A2 (fr) * 2008-06-26 2009-12-30 Bridgestone Corporation Compositions de caoutchouc comportant des dérivés de polyisobutylène fonctionnalisés par métal et procédés de préparation de telles compositions
JP2010168528A (ja) * 2008-10-09 2010-08-05 Ube Ind Ltd 共役ジエン重合体変性物及びその製造方法、その共役ジエン重合体変性物が含まれたゴム補強剤配合ゴム組成物及びその製造方法、並びにそのゴム補強剤配合ゴム組成物が含まれたタイヤ
JP2011026380A (ja) * 2009-07-22 2011-02-10 Bridgestone Corp タイヤ

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005075900A (ja) * 2003-08-29 2005-03-24 Mitsubishi Chemicals Corp シリカマスターバッチ及びその製造方法
JP2007154130A (ja) * 2005-12-08 2007-06-21 Yokohama Rubber Co Ltd:The タイヤ用ゴム組成物及びその製造方法
WO2008102513A1 (fr) * 2007-02-21 2008-08-28 The Yokohama Rubber Co., Ltd. Composition de caoutchouc
WO2008123306A1 (fr) * 2007-03-27 2008-10-16 Bridgestone Corporation Procédé de fabrication d'une composition de caoutchouc pour une bande de roulement de pneumatique
WO2009158604A2 (fr) * 2008-06-26 2009-12-30 Bridgestone Corporation Compositions de caoutchouc comportant des dérivés de polyisobutylène fonctionnalisés par métal et procédés de préparation de telles compositions
JP2010168528A (ja) * 2008-10-09 2010-08-05 Ube Ind Ltd 共役ジエン重合体変性物及びその製造方法、その共役ジエン重合体変性物が含まれたゴム補強剤配合ゴム組成物及びその製造方法、並びにそのゴム補強剤配合ゴム組成物が含まれたタイヤ
JP2011026380A (ja) * 2009-07-22 2011-02-10 Bridgestone Corp タイヤ

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014162897A (ja) * 2013-02-27 2014-09-08 Bridgestone Corp ゴム組成物の製造方法

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