Patent Application
20140350173
The present invention relates to a method for producing a rubber composition containing an inorganic filler and having an improved low-heat-generation property.
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 lower-heat-generating rubber composition for tires has become employed as the most common method.
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.
However, in incorporating an inorganic filler such as silica or the like in a rubber composition to prepare an inorganic filler-containing rubber composition, the inorganic filler, especially silica aggregates in the rubber composition (owing to the hydroxyl group in the surface of silica), and therefore, for preventing the aggregation, a silane coupling agent is used.
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.
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.
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.
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.
Further, PTL 4 proposes a rubber composition basically containing at least (i) a diene elastomer, (ii) an inorganic filler as a reinforcing filler and (iii) an alkoxysilane polysulfide as a coupling agent, as combined with (iv) 1,2-dihydropyridine and (v) a guanidine derivative.
However, in these inventions, nothing is taken into consideration relating to kneading conditions.
Furthermore, although PTLs 5 and 6 may be cited as an example of improving the coupling function activity of the silane coupling agent with kneading conditions in consideration, further improving the coupling function activity of the silane coupling agent to thereby enhance the low-heat generation property is desired.
Under such circumstances, the object of the present invention is to provide a method for producing a rubber composition, which enables obtaining a rubber composition capable of suitably improving the low-heat-generation property thereof by further improving the coupling function activity of the silane coupling agent.
In order to accomplish the above object, the present inventors examined various methods of adding each component (A) to (D) in a kneading process for producing a rubber composition provided by compounding a rubber component (A), a filler containing an inorganic filler (B), a silane coupling agent (C), and a vulcanization accelerator (D). As a result, it was found experimentally that improvement of the coupling function activity can be obtained by suitably adding each component (A) to (D) during from the first stage to the final stage of kneading. This finding led to completion of the present invention.
That is, the present invention provides:
[1] a method for producing a rubber composition provided by compounding a rubber component (A) comprising at least one selected from natural rubbers and synthetic diene rubbers, a filler containing an inorganic filler (B), a silane coupling agent (C), and at least one vulcanization accelerator (D) selected from guanidines, sulfenamides, thiazoles, thiurams, dithiocarbamates, thioureas, and xanthates, wherein the rubber composition is kneaded in a plurality of stages and wherein, in the first stage (X) of kneading, a portion (A′) of the rubber component (A), all or a portion of the inorganic filler (B), all or a portion of the silane coupling agent (C), and all or a portion of the vulcanization accelerator (D) are added and kneaded, and, in or after the second stage of kneading, the residual portion (A″) of the rubber component (A) is added and kneaded;
[2] the method for producing a rubber composition according to the above [1], wherein the plural stages of kneading comprise two stages of the first stage (X) and the last stage (Z), in the first stage (X), a portion (A′) of the rubber component (A), all or a portion of the inorganic filler (B), all or a portion of the silane coupling agent (C), and all or a portion of the vulcanization accelerator (D) are added and kneaded, and in the last stage (Z), the residual portion (A″) of the rubber component (A) and a vulcanizing agent are added and kneaded;
[3] a method for producing a rubber composition provided by compounding a rubber component (A) comprising at least one selected from natural rubbers and synthetic diene rubbers, a filler containing an inorganic filler (B), a silane coupling agent (C), and at least one vulcanization accelerator (D) selected from guanidines, sulfenamides, thiazoles, thiurams, dithiocarbamates, thioureas, and xanthates, wherein the rubber composition is kneaded in three or more stages including the first stage (X) and the last stage (Z) and wherein, in the first stage (X), a portion (A′) of the rubber component (A), all or a portion of the inorganic filler (B), and all or a portion of the silane coupling agent (C) are kneaded, in a stage (Y) in or after the second stage but before the last stage (Z) of kneading, all or a portion of the vulcanization accelerator (D) is added and kneaded, in or after the second stage of kneading, the residual portion (A″) of the rubber component (A) is added and kneaded, and in the last stage (Z), a vulcanizing agent is added and kneaded;
[4] the method for producing a rubber composition according to any of the above [1] to [3], wherein the portion (A′) of the rubber component (A) is at least one selected from solution-polymerized diene rubbers, and the residual portion (A″) of the rubber component (A) is at least one selected from natural rubbers and emulsion-polymerized diene rubbers;
[5] a rubber composition produced by the method for producing a rubber composition according to any of the above [1] to [4]; and
[6] a pneumatic tire using the rubber composition according to the above [5], as at least one member of tread parts, base tread parts, sidewall parts, inner liners and side-reinforcing rubber parts.
According to the present invention, there can be provided methods for producing a rubber composition, which enable production of a rubber composition excellent in low-heat-generation property by further improving the coupling function activity of the silane coupling agent.
Hereinafter, the present invention will be explained in detail.
The first invention is a method for producing a rubber composition provided by compounding a rubber component (A) comprising at least one selected from natural rubbers and synthetic diene rubbers, a filler containing an inorganic filler (B), a silane coupling agent (C), and at least one vulcanization accelerator (D) selected from guanidines, sulfenamides, thiazoles, thiurams, dithiocarbamates, thioureas, and xanthates, wherein the rubber composition is kneaded in a plurality of stages and wherein, in the first stage (X) of kneading, a portion (A′) of the rubber component (A), all or a portion of the inorganic filler (B), all or a portion of the silane coupling agent (C), and all or a portion of the vulcanization accelerator (D) are added and kneaded, and in or after the second stage of kneading, the residual portion (A″) of the rubber component (A) is added and kneaded.
In the first stage (X) of kneading in the present invention, a portion (A′) of the rubber component (A), all or a portion of the inorganic filler (B), all or a portion of the silane coupling agent (C), and all or a portion of the vulcanization accelerator (D) are added and kneaded, and this is for the purpose of enhancing the dispersibility of a portion (A′) of the rubber component (A) and the inorganic filler (B), and in addition, by adding and kneading the residual portion (A″) of the rubber component (A) in or after the second stage of kneading, it becomes possible to control the dispersion condition of each rubber component in the rubber component (A) and the inorganic filler (B) thereby to further enhance the low-heat-generation property.
In addition, in the first stage of kneading, all or a portion of the vulcanization accelerator (D) is added and kneaded, and this is for the purpose of enhancing the coupling function activity of the silane coupling agent (C).
In that manner, the first invention of the method for producing a rubber composition comprising a rubber component (A) comprising at least one selected from natural rubbers and synthetic diene rubbers, a filler containing an inorganic filler (B), a silane coupling agent (C), and at least one vulcanization accelerator (D) selected from guanidines, sulfenamides, thiazoles, thiurams, dithiocarbamates, thioureas, and xanthates makes it possible to impart an excellent low-heat-generation property to the rubber composition.
Preferably in the first invention, the plural stages of kneading comprise two stages of the first stage (X) and the last stage (Z), in the first stage (X), a portion (A′) of the rubber component (A), all or a portion of the inorganic filler (B), all or a portion of the silane coupling agent (C), and all or a portion of the vulcanization accelerator (D) are added and kneaded, and in the last stage (Z), the residual portion (A″) of the rubber component (A) is added and kneaded. This is because the dispersion condition of each rubber component in the rubber component (A) and the inorganic filler (B) can be more suitably controlled.
In the first stage of kneading in the first invention, preferably, the number of molecules X of an organic acid compound (E) in the rubber composition is in the relationship represented by the following formula [A] relative to the number of molecules Y of the vulcanization accelerator (D) therein.
0≦X≦1.5×Y [A]
Making the relationship between the number of molecules (number of moles) X of the organic acid compound (E) and the number of molecules (number of moles) Y of the vulcanization accelerator (D) represented by the above-mentioned formula [A] can favorably prevent the effect of enhancing the coupling function activity of the silane coupling agent (C) by incorporation of the vulcanization accelerator (D) from being reduced.
The second invention of the method for producing a rubber composition of the present invention is a method for producing a rubber composition provided by compounding a rubber component (A) comprising at least one selected from natural rubbers and synthetic diene rubbers, a filler containing an inorganic filler (B), a silane coupling agent (C), and at least one vulcanization accelerator (D) selected from guanidines, sulfenamides, thiazoles, thiurams, dithiocarbamates, thioureas, and xanthates, wherein the rubber composition is kneaded in three or more stages including the first stage (X) and the last stage (Z) and wherein, in the first stage (X), a portion (A′) of the rubber component (A), all or a portion of the inorganic filler (B), and all or a portion of the silane coupling agent (C) are added and kneaded, in a stage (Y) in or after the second stage but before the last stage (Z) of kneading, all or a portion of the vulcanization accelerator (D) is added and kneaded, in or after the second stage of kneading, the residual portion (A″) of the rubber component (A) is added and kneaded, and in the last stage (Z), a vulcanizing agent is added and kneaded.
In the present invention, the rubber composition is kneaded in three or more kneading stages, and this is for securing the reaction between the silane coupling agent and silica and the reaction between the silane coupling agent and the polymer. Further, the above is effective for preventing the molecular weight of the rubber component (A) from being lowered owing to long-term high-temperature kneading thereof. That is, if the time of one kneading stage is made longer in order to decrease the number of stages of kneading, the rubber component (A) becomes exposed to high temperature for a long time and results in a possible decrease in the molecular weight thereof. It is important to avoid this.
The rubber component (A), all or a portion of the inorganic filler (B), and all or a portion of the silane coupling agent (C) are kneaded in the first stage (X) of kneading, and this is for making the reaction of the inorganic filler (B) and the silane coupling agent (C) proceed sufficiently.
In the stage (Y) in or after the second stage but before the last stage (Z) of kneading in the second invention, all or a portion of the vulcanization accelerator (D) is added and kneaded. This is for the purpose of further enhancing the coupling function activity of the silane coupling agent (C) by the vulcanization accelerator (D) after sufficient development of the reaction between the inorganic filler (B) and the silane coupling agent (C) to thereby make the reaction between the silane coupling agent (C) and the rubber component (A) proceed more favorably, whereby the low-heat-generation property can be improved further more.
The number of the kneading stages in the second invention may be 3 or more, and the upper limit thereof is not specifically defined, but is, in consideration of the productivity, preferably 8 stages or less, more preferably 6 stages or less, even more preferably 4 stages or less.
In that manner, the second invention of the method for producing a rubber composition comprising a rubber component (A) comprising at least one selected from natural rubbers and synthetic diene rubbers, a filler containing an inorganic filler (B), a silane coupling agent (C), and at least one vulcanization accelerator (D) selected from guanidines, sulfenamides, thiazoles, thiurams, dithiocarbamates, thioureas, and xanthates makes it possible to impart an excellent low-heat-generation property to the rubber composition.
In or after the second stage of kneading in the present invention, preferably, the residual portion (B″) of the inorganic filler (B), or the residual portion (B″) of the inorganic filler (B) and the residual portion (C″) of the silane coupling agent (C) are added and kneaded. It becomes possible to favorably disperse the inorganic filler (B) even in the residual portion (A″) of the rubber component (A) and to further suitably control the dispersion condition of each rubber component in the rubber component (A) and the inorganic filler (B) to thereby further enhance the low-heat-generation property.
In the present invention, preferred is adding the organic acid compound (E) in or after the second stage of kneading for more favorably exhibiting the effect of enhancing the coupling function activity of the silane coupling agent (C) by adding the vulcanization accelerator (D) in the first stage of kneading.
In the present invention, the maximum temperature of the rubber composition in the first stage (X) of kneading is preferably from 120 to 190° C., more preferably from 130 to 190° C., even more preferably from 140 to 180° C. Falling within the range of from 120 to 190° C., the coupling function activity of the silane coupling agent (C) can be favorably enhanced and the reaction between the silane coupling agent (C) and the rubber component (A) can be thereby made to further favorably proceed.
Similarly, the maximum temperature of the rubber composition in the kneading stage (Y) is preferably from 120 to 190° C., more preferably from 125 to 175° C.
The first stage of kneading in the present invention is the first stage of kneading the rubber component (A), the inorganic filler (B) and the silane coupling agent (C), but does not include a case of kneading the rubber component (A) and another filler than the inorganic filler (B) in the initial stage and a case of pre-kneading the rubber component (A) alone.
The maximum temperature of the rubber composition in the kneading stage before the last stage such as the first stage, the second stage and others is preferably from 120 to 190° C., more preferably from 130 to 175° C., even more preferably from 150 to 170° C. The kneading time is preferably from 0.5 minutes to 20 minutes, more preferably from 0.5 minutes to 10 minutes, even more preferably from 0.5 minutes to 5 minutes.
The last stage of kneading is a step of incorporating the chemicals participating in crosslinking (vulcanizing agent, vulcanization accelerator) and kneading them. The maximum temperature of the rubber composition in the last kneading stage is preferably from 60 to 140° C., more preferably from 80 to 120° C., even more preferably from 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, even more preferably from 0.5 minutes to 5 minutes.
As the synthetic diene rubber of the rubber component (A) for use in the present invention, usable here are styrene-butadiene copolymer rubber (SBR), polybutadiene rubber (BR), polyisoprene rubber (IR), butyl rubber (IIR), ethylene-propylene-diene tercopolymer rubber (EPDM), acrylonitrile-butadiene copolymer rubber, chloroprene rubber, etc. One or more different types of natural rubbers and synthetic diene rubbers may be used here either singly or as combined.
Preferably, a portion (A′) of the rubber component (A) in the present invention is at least one selected from solution-polymerized diene rubbers, and the residual portion (A″) of the rubber component (A) is at least one selected from natural rubbers and emulsion-polymerized diene rubbers. This is because the emulsion-polymerized diene rubber generally contains the organic acid compound (E) derived from an emulsifying agent, for example, a fatty acid or a resin acid, and therefore, adding a solution-polymerized diene rubber not containing a fatty acid or a resin acid as a portion (A′) of the rubber component (A) in the first stage of kneading betters the dispersibility of the inorganic filler (B) such as silica or the like, thereby more effectively enhancing the effect of improving the coupling function activity of the silane coupling agent (C) by incorporation of the vulcanization accelerator (D) and further enhancing the low-heat-generation property.
Here, the solution-polymerized diene rubber means a diene (co)polymer rubber obtained through solution polymerization of a conjugated diene compound, and includes, for example, a solution-polymerized styrene-butadiene copolymer rubber (hereinafter this may be referred to as “solution-polymerized SBR), a solution-polymerized polybutadiene rubber, a solution-polymerized styrene-butadiene-isoprene copolymer rubber, a solution-polymerized styrene-isoprene copolymer rubber, synthetic polyisoprene rubber, etc.
The silane coupling agent (C) used in the method for producing a rubber composition of the present invention is preferably one or more compounds selected from the group consisting of the compounds represented by the following general formulae (I) and (II).
Using the silane coupling agent (C) of the type, the rubber composition according to the method of the present invention is excellent in workability thereof in rubber processing and can give pneumatic tires having better abrasion resistance.
General formulae (I) and (II) are sequentially described below.
[Chem. 1]
(R1O)3-p(R2)pSi—R3—Sa—R3—Si(OR1)3-r(R2)r (I)
In the formula, plural R1's may be the same or different and are each a hydrogen atom, 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; plural R2's may be the same or different and are each a linear, cyclic, or branched alkyl group, having 1 to 8 carbon atoms; plural R3's may be the same or different and are each a linear or branched alkylene group, having 1 to 8 carbon atoms. a is 2 to 6 as an average value; and p and r may be the same or different and are each 0 to 3 as an average value. However, p and r are not 3 at the same time.
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, and bis(2-monoethoxydimethylsilylethyl) disulfide.
[Chem. 2]
(R4O)3-s(R5)sSi—R6—Sk—R7—Sk—R6—Si(OR4)3-t(R5)t (II)
In the formula, plural R4's may be the same or different and are each a hydrogen atom, 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; plural R5's may be the same or different and are each a linear, cyclic, or branched alkyl group, having 1 to 8 carbon atoms; plural R6's may be the same or different and are each a linear or branched alkylene group, having 1 to 8 carbon atoms. R7 is a divalent group of any of general formulae,
(—S—R8—S—),(—R9—Sm1—R10—),and(—R11—Sm2—R12—Sm3—R13—)
(R8 to R13 are each a divalent hydrocarbon group, a divalent aromatic group or a divalent organic group containing a heteroatom other than sulfur and oxygen, each having 1 to 20 carbon atoms; and m1, m2, and m3 are each 1 or more but less than 4 as an average value); plural k's may be the same or different and are each 1 to 6 as an average value; s and t are each 0 to 3 as an average value. However, s and t are not 3 at the same time.
Specific examples of the silane coupling agent (C) represented by the above-mentioned general formula (II) 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
(CH3CH2O)3Si—(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—S3—(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(OCH2CH3)3,etc.
The silane coupling agent (C) represented by the above-mentioned general formula (II) may be obtained, for example, according to the production method described in JP-A 2006-167919.
The silane coupling agent (C) involved in the present invention is especially preferably a compound represented by the general formula (I) among the compounds represented by the above general formulae (I) and (II). This is so because the vulcanization accelerator (D) easily activates the polysulfide bond portion which reacts with the rubber component (A).
In the present invention, the silane coupling agent (C) may be used singly or in a combination of two or more.
The amount of the silane coupling agent (C) blended in the rubber composition of the present invention is preferably such that the ratio by mass {silane coupling agent (E)/inorganic filler (B)} is from (1/100) to (20/100). This is because when the ratio is (1/100) or more, then the effect of improving the low heat-generating property of the rubber composition can be exhibited more effectively, and when (20/100) or less, then the cost of the rubber composition is reduced and the economic efficiency betters. Furthermore, the ratio by mass is more preferably from (3/100) to (20/100), particularly preferably from (4/100) to (10/100).
The guanidines, sulfenamides, thiazoles, thiurams, dithiocarbamates, thioureas, and xanthates are cited as the vulcanization accelerator (D) used in the method for producing a rubber composition of the present invention.
The guanidines in the present invention include 1,3-diphenylguanidine, 1,3-di-o-tolylguanidine, 1-o-tolylbiguanide, di-o-tolylguanidine salt of dicatechol borate, 1,3-di-o-cumenylguanidine, 1,3-di-o-biphenylguanidine, 1,3-di-o-cumenyl-2-propionylguanidine, and the like. Among these, 1,3-diphenylguanidine, 1,3-di-o-tolylguanidine, and 1-o-tolylbiguanide are preferable because these are highly reactive, and 1,3-diphenylguanidine is particularly preferable because this is more highly reactive.
The sulfenamides in the present invention include N-cyclohexyl-2-benzothiazolylsulfenamide, N, N-dicyclohexyl-2-benzothiazolylsulfenamnide, N-tert-butyl-2-benzothiazolylsulfenamnide, N-oxydiethylene-2-benzothiazolylsulfenamnide, N-methyl-2-benzothiazolylsulfenamnide, N-ethyl-2-benzothiazolylsulfenamnide, N-propyl-2-benzothiazolylsulfenamnide, N-butyl-2-benzothiazolylsulfenamnide, N-pentyl-2-benzothiazolylsulfenamnide, N-hexyl-2-benzothiazolylsulfenamnide, N-pentyl-2-benzothiazolylsulfenamnide, N-octyl-2-benzothiazolylsulfenamnide, N-2-ethylhexyl-2-benzothiazolylsulfenamnide, N-decyl-2-benzothiazolylsulfenamnide, N-dodecyl-2-benzothiazolylsulfenamnide, N-stearyl-2-benzothiazolylsulfenamnide, N,N-dimnethyl-2-benzothiazolylsulfenamnide, N,N-diethyl-2-benzothiazolylsulfenamnide, N,N-dipropyl-2-benzothiazolylsulfenamnide, N,N-dibutyl-2-benzothiazolylsulfenamnide, N,N-dipentyl-2-benzothiazolylsulfenamnide, N,N-dihexyl-2-benzothiazolylsulfenamnide, N,N-dipentyl-2-benzothiazolylsulfenamnide, N,N-dioctyl-2-benzothiazolylsulfenamnide, N,N-di-2-ethylhexylbenzothiazolylsulfenamnide, N-decyl-2-benzothiazolylsulfenamnide, N,N-didodecyl-2-benzothiazolylsulfenamide, N,N-distearyl-2-benzothiazolylsulfenamide, and the like. Among these, N-cyclohexyl-2-benzothiazolylsulfenamide and N-tert-butyl-2-benzothiazolylsulfenamide are preferable because they are highly reactive.
The thiazoles in 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-mercaptonaphtho[1,2-d]thiazole, 2-mercapto-5-methoxybenzothiazole, 6-amino-2-mercaptobenzothiazole, and the like. Among these, 2-mercaptobenzothiazole and di-2-benzothiazolyl disulfide are preferred as having high reactivity.
The thiurams in 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 monoisulfide, tetranonylthiuram monosulfide, tetradecylthiuram monosulfide, tetra dodecylthiuram monosulfide, tetrastearylthiuram monosulfide, tetrabenzylthiuram monosulfide, dipentamethylenethiuram tetrasulfide, and the like. Among these, tetrakis(2-ethylhexyl)thiuram disulfide and tetrabenzylthiuram disulfide are preferable because these are highly reactive.
The dithiocarbamates in 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, and the like. Among these, zinc dibenzyldithiocarbamate, zinc N-ethyl-N-phenyldithiocarbamate, zinc dimethyldithiocarbamate, and copper dimethyldithiocarbamate are preferable because these are highly reactive.
The thioureas in the present invention include N,N′-diphenylthiourea, trimethylthiourea, N,N′-diethylthiourea, N,N′-dimethylthiourea, 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, and the like. Among these, N,N′-diethylthiourea, trimethylthiourea, N,N′-diphenylthiourea, and N,N′-dimethylthiourea are preferable because these are highly reactive.
The xanthates in the present invention include zinc methyl xanthate, zinc ethyl xanthate, zinc propyl xanthate, zinc isopropyl xanthate, zinc butyl xanthate, zinc pentyl xanthate, zinc hexyl xanthate, zinc heptyl xanthate, zinc octyl xanthate, zinc 2-ethylhexyl xanthate, zinc decyl xanthate, zinc dodecyl xanthate, potassium methyl xanthate, potassium ethyl xanthate, potassium propyl xanthate, potassium isopropyl xanthate, potassium butyl xanthate, potassium pentyl xanthate, potassium hexyl xanthate, potassium heptyl xanthate, potassium octyl xanthate, potassium 2-ethylhexyl xanthate, potassium decyl xanthate, potassium dodecyl xanthate, sodium methyl xanthate, sodium ethyl xanthate, sodium propyl xanthate, sodium isopropyl xanthate, sodium butyl xanthate, sodium pentyl xanthate, sodium hexyl xanthate, sodium heptyl xanthate, sodium octyl xanthate, sodium 2-ethylhexyl xanthate, sodium decyl xanthate, sodium dodecyl xanthate, and the like. Among these, zinc isopropyl xanthate is preferable because it is highly reactive.
In the first stage of kneading in the present invention, preferably, the number of molecules (number of moles) of the vulcanization accelerator (D) is from 0.1 to 1.0 time the number of molecules (number of moles) of the silane coupling agent (C). When it is 0.1 times or more, then the silane coupling agent (C) can be activated sufficiently, and when 1.0 time or less, then it would not have any significant influence on the vulcanization speed. More preferably, the number of molecules (number of moles) of the vulcanization accelerator (D) is from 0.3 to 1.0 time the number of molecules (number of moles) of the silane coupling agent (C).
Additionally, the vulcanization accelerator (D) is used also as an accelerator in sulfur vulcanization and may be blended in an adequate amount in the last stage of kneading, if desired.
Further, one preferred method of adding the vulcanization accelerator (D) in the first stage of kneading comprises adding the vulcanization accelerator (D) after kneading the rubber component (A), all or a portion of the inorganic filler (B) and all or a portion of the silane coupling agent (C), followed by kneading them. This is because, according to the method, the reaction between the silane coupling agent (C) and the rubber component (A) can be made to proceed sufficiently after the reaction between the silane coupling agent (C) and silica has proceeded sufficiently.
As the inorganic filler (B) for use in the rubber composition production method of the present invention, usable are silica and an inorganic compound represented by the following general formula (III):
dM1.xSiOy*zH2O (III)
In the general formula (III), M1 represents at least one selected from, a metal selected from aluminum, magnesium, titanium, calcium and zirconium, and oxides or hydroxides of those metals, their hydrates, or carbonates of the metals; d, x, y and z each indicate an integer of from 1 to 5, an integer of from 0 to 10, an integer of from 2 to 5, and an integer of from 0 to 10, respectively.
In the general formula (III), when x and z are both 0, then the inorganic compound is at least one metal selected from aluminum, magnesium, titanium, calcium and zirconium, or a metal oxide or metal hydroxide thereof.
In the present invention, silica is preferred as the inorganic filler (B) from the viewpoint of satisfying both low rolling property and abrasion resistance. As silica, any commercially-available one is usable here; and above all, preferred is precipitated silica, fumed silica or colloidal silica, and particularly preferred is precipitated silica. Preferably, the BET specific surface area (as measured according to ISO 5794/1) of silica for use herein is from 40 to 350 m2/g. Silica of which the BET specific surface area falls within the range is advantageous in that it satisfies both rubber-reinforcing capability and dispersibility in rubber component. From this viewpoint, silica having a BET specific surface area in a range of 80 to 350 m2/g is more preferable, especially preferable being silica having a BET specific surface area in a range of 120 to 350 m2/g. As such silica, there may be used commercial products such as trade name “Nipsil AQ” (BET specific surface area=205 m2/g) and trade name “Nipsil KQ” produced by Tosoh Silica Corporation, and “Ultrasil VN3” (BET specific surface area=175 m2/g) produced by Degussa AG, and the like.
As the inorganic compound represented by the general formula (III), usable here are alumina (Al2O3) such as γ-alumina, α-alumina, etc.; alumina monohydrate (Al2O3.H2O) such as boehmite, diaspore, etc.; aluminum hydroxide [Al(OH)3] such as gibbsite, bayerite, etc.; aluminum carbonate [Al2(CO3)2], magnesium hydroxide [Mg(OH)2], magnesium oxide (MgO), magnesium carbonate (MgCO3), talc (3MgO.4SiO2.H2O), attapulgite (5MgO.8SiO2.9H2O), titanium white (TiO2), titanium black (TiO2n-1), calcium oxide (CaO), calcium hydroxide [Ca(OH)2], aluminum magnesium oxide (MgO.Al2O3), clay (Al2O3.2SiO2), kaolin (Al2O3.2SiO2.2H2O), pyrophyllite (Al2O3.4SiO2.H2O), bentonite (Al2O3.4SiO2.2H2O), aluminum silicate (Al2SiO5, Al4.3SiO4.5H2O, etc.), magnesium silicate (Mg2SiO4, MgSiO3, etc.), calcium silicate (Ca2SiO4, etc.), aluminum calcium silicate (Al2O3.CaO.2SiO2, etc.), magnesium calcium silicate (CaMgSiO4), calcium carbonate (CaCO3), zirconium oxide (ZrO2), zirconium hydroxide [ZrO(OH)2.nH2O], zirconium carbonate [Zr(CO3)2]; as well as crystalline aluminosilicate salts containing a charge-correcting hydrogen, alkali metal or alkaline earth metal such as various types of zeolite. Also, it is preferable when M3 in the general formula (5) is at least one selected from an aluminum metal, an oxide or a hydroxide of aluminum or a hydrate thereof, or a carbonate of aluminum. Among these, aluminum hydroxide is especially preferable.
One or more different types of the inorganic compounds of the general formula (III) may be used here either singly or as combined. The mean particle size of the inorganic compound is preferably within a range of from 0.01 to 10 μm from the viewpoint of the balance of kneading workability, abrasion resistance and wet grip performance, and more preferably within a range of from 0.05 to 5 μm.
As the inorganic filler (B) in the present invention, silica alone may be used, or silica as combined with at least one inorganic compound of the general formula (III) may be used.
If desired, the filler in the rubber composition in the present invention may contain carbon black in addition to the above-mentioned inorganic filler (B). Containing carbon black, the filler enjoys the effect of lowering the electric resistance of the rubber composition to thereby prevent static electrification thereof. Carbon black for use herein is not specifically defined. For example, preferred is use of high, middle or low-structure SAF, ISAF, IISAF, N339, HAF, FEF, GPF, SRF-grade carbon black; and more preferred is use of SAF, ISAF, IISAF, N339, HAF, FEF-grade carbon black. Preferably, the nitrogen adsorption specific surface area (N2SA, as measured according to JIS K 6217-2:2001) of such carbon black is from 30 to 250 m2/g. One alone or two or more different types of such carbon black may be used here either singly or as combined. In the present invention, the inorganic filler (B) does not include carbon black.
The inorganic filler (B) in the rubber composition in the present invention is used preferably in an amount of from 20 to 120 parts by mass relative to 100 parts by mass of the rubber component (A). When the amount is at least 20 parts by mass, then it is favorable from the viewpoint of securing wet performance; and when at most 120 parts by mass, then it is favorable from the viewpoint of reducing rolling resistance. Further, the amount is more preferably from 30 to 100 parts by mass.
Also preferably, the filler in the rubber composition in the present invention is in an amount of from 20 to 150 parts by mass relative to 100 parts by mass of the rubber component (A). When the amount is at least 20 parts by mass, then it is favorable from the viewpoint of enhancing rubber composition reinforcing capability; and when at most 150 parts by mass, then it is favorable from the viewpoint of reducing rolling resistance.
Of the filler, the inorganic filler (B) accounts for, from the viewpoint of a balance between the wet performance and the rolling resistance, preferably 30 mass % or more, more preferably 40 mass % or more and particularly preferably 70 mass % or more.
In the first stage of kneading in the production method of the present invention, preferably, the number of molecules X of the organic acid compound (E) in the rubber composition is in the relationship represented by the following formula [A] relative to the number of molecules Y of the vulcanization accelerator (D) therein.
0≦X≦1.5×Y [A]
This is in order to further enhance the effect of improving the coupling function activity, obtained by blending of the vulcanization accelerator (D). This is in order to suitably suppress reduction of the effect of activity improvement, the reduction occurring when the number of molecules (number of moles) of the organic acid compound (E) is more than 1.5 times the number of molecules (number of moles) of the vulcanization accelerator (D). From this viewpoint, more preferably, the number of molecules (number of moles) of the organic acid compound (E) is not more than the number of molecules (number of moles) of the vulcanization accelerator (D).
In the production method of the present invention, the number of molecules (number of moles) of the organic acid compound (E) added to the rubber composition in the stage (Y) of kneading is preferably not more than the number of molecules (number of moles) of the vulcanization accelerator (D) added in the stage (Y), for the same reason as that for the above-mentioned formula (A).
The organic acid compound (E) blended in the rubber composition of the present invention includes organic acids such as saturated fatty acids, unsaturated fatty acids, resin acids such as rosin acids or modified rosin acids, and the like including stearic acid, palmitic acid, myristic acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, capric acid, pelargonic acid, caprylic acid, enanthic acid, caproic acid, oleic acid, vaccenic acid, linoleic acid, linolenic acid, nervonic acid, and the like; and metal salts or esters of the saturated fatty acids, the unsaturated fatty acids, and the resin acids.
In the present invention, 50 mol % or more of the organic acid compound (E) is preferably stearic acid because the compound has to sufficiently exhibit its function as a vulcanization accelerating aid.
Further, when an emulsion-polymerized styrene-butadiene copolymer is used as a portion or all of the rubber component (A), it is preferable, from the viewpoint of an emulsifier necessary to obtain the emulsion-polymerized styrene-butadiene copolymer, that 50 mol % or more of the organic acid compound (E) is accounted for by the rosin acids (including the modified rosin acids) and/or fatty acids which are contained in the emulsion-polymerized styrene-butadiene copolymer.
In the rubber composition production method of the present invention, various additives that are generally incorporated in a rubber composition, for example, a vulcanization activator such as zinc oxide 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.
As the kneading apparatus for the production method of the present invention, usable is any of a Banbury mixer, a roll, an intensive mixer, a twin screw extruder, etc.
The pneumatic tire of the present invention uses the rubber composition obtained according to the production method of the present invention, as at least one member of tread parts, base tread parts, sidewall parts, inner liners and side-reinforcing rubber parts. Especially preferred are pneumatic tires using the above-mentioned rubber composition as tread parts (cap tread parts and/or base tread parts) of those members.
The present invention is described in more detail with reference to the following Examples; however, the present invention is not limited at all by the following Examples.
The maximum temperature and the low-heat-generation property (tan δ index) of the rubber composition in each stage of kneading were evaluated according to the methods mentioned below.
A thermometer was inserted into the center part of the rubber composition just after discharged out from a Banbury mixer to measure the temperature. After three measurements, the arithmetic average of the found data was referred to as the maximum temperature.
Using a viscoelasticity measuring device (by Rheometric), tan δ 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. Taking the reciprocal of tan δ in each Comparative Example as 100, the data were expressed as index indication according to the following formula. The samples having a larger index value have a lower-heat-generation property and have a smaller hysteresis loss.
Low heat generation index={(tan δ of vulcanized rubber composition of each Comparative Example)/(tan δ of corresponding vulcanized rubber composition tested)}×100
(CH3CH2O)3Si—(CH2)3—S—(CH2)6—S2.5—(CH2)6—S—(CH2)3—Si(OCH2CH3)3
(typical example C1 of silane coupling agent (II))
119 g (0.5 mol) of 3-mercaptopropyltriethoxysilane was put into a 2-liter separable flask equipped with a nitrogen-introducing duct, a thermometer, a Dimroth condenser and a dropping funnel, and with stirring, 151.2 g (0.45 mol) of an ethanol solution of sodium ethoxide having an effective ingredient concentration of 20% was added thereto. Subsequently, this was heated up to 80° C. and stirred for 3 hours. Afterwards, this was cooled and transferred into a dropping funnel.
Next, 69.75 g (0.45 mol) of 1,6-dichlorohexane was put into a separable flask similar to the above, heated up to 80° C., and the reaction product of 3-mercaptopropyltriethoxysilane and sodium ethoxide was slowly and dropwise added thereto. After the addition, this was stirred for 5 hours at 80° C. Subsequently, this was cooled, and salt was separated from the obtained solution through filtration, and ethanol and excessive 1,6-dichlorohexane were removed therefrom through reduced-pressure distillation. The solution obtained was distilled under reduced pressure to obtain 137.7 g of a colorless transparent liquid with a boiling point of 148 to 150° C./0.005 torr. As a result of IR analysis, 1H-NMR analysis and mass spectrometry analysis (MS analysis), the product was a compound represented by (CH3CH2O)3Si—(CH2)3S—(CH2)6—Cl. Through gas chromatography analysis (GC analysis), the purity of the compound was 97.5%.
Next, 80 g of ethanol, 5.46 g (0.07 mol) of anhydrous sodium sulfide and 3.36 g (0.105 mol) of sulfur were put into the same 0.5-liter separable flask as above, and heated up to 80° C. With stirring the solution, 49.91 g (0.14 mol) of the above (CH3CH2O)3Si—(CH2)3—S—(CH2)6—Cl was gradually and dropwise added thereto. After the addition, this was stirred for 10 hours at 80° C. After the stirring, this was cooled, the formed salt was taken out through filtration, and then the solvent ethanol was evaporated away under reduced pressure.
The obtained, red-brown transparent solution was analyzed through IR analysis, 1H-NMR analysis and supercritical fluid chromatography analysis, which confirmed that the product is a compound represented by an average compositional formula,
(CH3CH2O)3Si—(CH2)3—S—(CH2)6—S2.5—(CH2)6—S—(CH2)3—Si(OCH2CH3)3
In GPC analysis, the purity of the product was 85.2%.
According to the compounding recipes and the kneading methods shown in Table 1, the rubber composition was kneaded in a Banbury mixer under the control that the maximum temperature thereof in the first stage of kneading could be 150° C. in every case, and in the stage (Y) of the second stage of kneading, the components shown in Table 1 were added and kneaded, and in Examples 1, 2 and 4 to 11 and Comparative Examples 1, 2 and 4 to 11, the maximum temperature of the rubber composition was controlled to be 130° C. In Example 3 and Comparative Example 3, the stage (Y) of the second stage of kneading was omitted.
Next, in the last stage (Z) of kneading, the vulcanizing agent and others were added and kneaded under the control that the maximum temperature of the rubber composition in the last stage of kneading could be 110° C. in every case, thereby preparing 22 types of rubber compositions of Examples 1 to 11 and Comparative Example 11. The obtained 22 types of rubber compositions were evaluated for the low-heat-generation property (tan δ) thereof according to the method mentioned above. The results are shown in Table 1.
As obvious from Table 1, the rubber composition of Example 1 was better than the rubber composition of Comparative Example 1 and the rubber compositions of Examples 2 to 5 were better than the comparative rubber compositions of Comparative Examples 2 to 5, all in point of the low-heat-generation property (tan δ index).
According to the production method for a rubber composition of the present invention, it is possible to obtain a rubber composition excellent in low-heat-generation property with successfully inhibiting the coupling function activity of the silane coupling agent used from lowering and with further increasing the coupling activity thereof, and the production method is therefore favorably used as a production method for members such as tread parts, base tread parts, sidewall parts, inner liners, side-reinforcing rubber parts and others of various types of pneumatic tires for passenger cars, small-size trucks, minivans, pickup trucks and big-size vehicles (trucks, buses, construction vehicles, etc.) and others, especially for tread members of pneumatic radial tires.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2011-284438 | Dec 2011 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2012/083353 | 12/21/2012 | WO | 00 | 6/25/2014 |
