CN102653606A - Rubber composition for tire, manufacturing method thereof and pneumatic tire using the rubber composition for tire - Google Patents
Rubber composition for tire, manufacturing method thereof and pneumatic tire using the rubber composition for tire Download PDFInfo
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- CN102653606A CN102653606A CN201110462610XA CN201110462610A CN102653606A CN 102653606 A CN102653606 A CN 102653606A CN 201110462610X A CN201110462610X A CN 201110462610XA CN 201110462610 A CN201110462610 A CN 201110462610A CN 102653606 A CN102653606 A CN 102653606A
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
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Abstract
The invention provides a method for manufacturing a rubber composition for a tire, and the method comprises: a kneading step, wherein a closed kneading machine is used to knead a rubber material and a silane coupling agent together, the rubber material is obtained by mixture of 100 mass parts of raw material rubber for the tire and 5-150 mass parts of silicon dioxide; and a holding step, wherein at the lower part of the closed kneading machine, under high temperature, a rubber block obtained by kneading is kept for a predetermined time, therefore, heat required for reaction of silicon dioxide and the silane coupling agent is provided for the rubber block, wherein in the 100 mass parts of raw material rubber for the tire, 5-100 mass parts of styrene butadiene rubber with the molecular weight distribution Mw/Mn being below 2.3 and end modification, and/or 10-60 mass parts of tin modified polybutadiene rubber by lithium initiator polymerization, the in modified polybutadiene rubber is provided with 50-3000 ppm of tin atom content ratio, 5-50 mass% of ethylene combination amount, and less-than 2.0 of molecular weight distribution Mw/Mn.
Description
Technical field
The present invention relates to rubber composition for tire (hereinafter; Sometimes abbreviate " rubber combination " as), its method of manufacture and the pneumatic tyre that uses above-mentioned rubber composition for tire; In said rubber combination; Silicon-dioxide and silane coupling agent fully react, and said rubber combination can improve the fuel consumption performance when being used for pneumatic tyre.
Background technology
In recent years, people's strong request pneumatic tyre satisfies the reduction fuel consumption simultaneously and improves wet earth-catching property.In order to satisfy this requirement, silicon-dioxide sneaked into as toughener be used for the for example rubber combination of tyre surface etc. of extrusion moulding article.
Yet, only use silicon-dioxide can not obtain enough enhanced.Therefore, traditionally, in kneading step, the silane coupling agent that will have alkoxyl group is sneaked into silicon-dioxide, and makes silicon-dioxide and silane coupling agent reaction, improves enhanced thus.Yet, in traditional kneading step, be difficult to make the sufficient reacting of silicon-dioxide and silane coupling agent to carry out.
As the method for this problem of reply, consider the rubber kneading is carried out the long time with the required heat of the reaction that silicon-dioxide and silane coupling agent are provided sufficiently.Yet,,, have the possibility that can not produce that productivity descends and rubber gelsization causes owing to mediate for a long time adopting should the kneading method time.
Then,, traditionally, exist in supposition under the prerequisite of unreacted silane coupling agent, use the excessive silane coupling agent of sneaking into that surpasses aequum to mediate usually in order to obtain to use the sufficient enhanced of silicon-dioxide.
Yet, using should the kneading method time, new problem has appearred.Or rather, in the extrusion step of after this kneading step, carrying out, be heated through the rubber combination of mediating, so, thereby residual unreacted silane coupling agent reacts and produces alcohol such as ethanol etc., in the extrusion moulding article, produces bubble thus.
In addition, descend and the rubber gelsization of kneading step and the kneading method that silane coupling agent is fully reacted, also proposed following method as being used for suppressing productivity.In the method, heating chamber is set, and under 40 to 100 ℃ temperature, the heating rubber combination thinks that it provides heat (such as patent documentation 1) in this heating chamber such as baking oven.
Yet, in the method, need the additional apparatus investment, and do not recognize that the sufficient amount of heat supply can be used for reducing fully the unreacted rate of silane coupling agent.Do not recognize the fuel consumption performance that has fully improved the tire that uses this rubber combination manufacturing yet.
The prior art document
Patent documentation
Patent documentation 1:JP-A 2007-246929
Summary of the invention
The problem that the present invention is to be solved
Consider the problems referred to above; The pneumatic tyre that the object of the present invention is to provide a kind of rubber composition for tire, its method of manufacture and use above-mentioned rubber composition for tire; This rubber combination does not need new facility investment; Can not cause that productivity reduces, and has reduced the unreacted rate of silane coupling agent fully, and when being used for pneumatic tyre, can improve the fuel consumption performance.
Be used for solution to the problems described above
In order to address the above problem; The present invention provides a kind of method that is used to make rubber composition for tire; This method is characterized in that through silicon-dioxide and silane coupling agent are sneaked into tire with making rubber composition for tire in the crude rubber said method comprises:
Kneading step; Wherein use airtight kneader that elastomeric material and silane coupling agent is kneaded together; This elastomeric material uses crude rubber and uses the silicon-dioxide acquisition of crude rubber as the 5-150 mass parts with respect to the above-mentioned tire of 100 mass parts through the tire that mixes 100 mass parts, and
Follow above-mentioned kneading step maintenance step afterwards closely; Wherein locate in the bottom of above-mentioned airtight kneader; Under high-temperature atmosphere, will keep the scheduled time through the block rubber that mediate to obtain, for providing silicon-dioxide and silane coupling agent, above-mentioned block rubber reacts required heat (hereinafter thus; Method with this type maintenance step is called as " temperature keeps the kneading method " and the step of similar this maintenance step is called as " temperature keeps mediating "), and
The above-mentioned tire of 100 mass parts with crude rubber in, the molecular weight distribution mw/mn that comprises the 5-100 mass parts is the styrene-butadiene rubber(SBR) of the end modification below 2.3, and/or
The 10-60 mass parts with lithium initiator polymeric tin modification polybutadiene rubber, this tin modification polybutadiene rubber has the tin atom content ratio of 50-3000ppm, the ethene binding capacity of 5-50 quality %, and 2.0 below molecular weight distribution mw/mn.
Further, the above-mentioned method that is used to make rubber composition for tire can have following characteristic: the styrene-butadiene rubber(SBR) of above-mentioned end modification is for having introduced the styrene-butadiene rubber(SBR) of amino end modification in its end.
Further, the above-mentioned method that is used to make rubber composition for tire can have the characteristic that is controlled by total mixing heat Q, and this always mixes heat Q is by the heat Q that kneading produced in the above-mentioned kneading step
1With by the heat Q that maintenance provided in the above-mentioned maintenance step
2Summation.
Here,
Q＝∑Q
1+∑Q
2，
Q
1＝EXP[(-20/(1.987/0.001)×{1/(T
1+273.16)-1/414.86}]×t
1，
Q
2＝EXP[(-20/(1.987/0.001)×{1/(T
2+273.16)-1/414.86}]×t
2，
0.5≤t
2≤6.0，
141.7≤T
2≤165.0，
t
1: the kneading time (minute),
t
2: the hold-time of locating in the bottom of airtight kneader (minute),
T
1: the rubber temperature of kneading (℃),
T
2: the rubber temperature when keeping at the place, bottom of airtight kneader (℃).
Further, the above-mentioned method that is used to make rubber composition for tire can have following characteristic:
Above-mentioned total mixing heat Q satisfies following formula:
8≤Q≤30。
Except the method for manufacture of rubber combination, the present invention also provides the rubber combination that uses the above-mentioned method that is used to make rubber combination to make.
Further, pneumatic tires according to the present invention has the tyre surface that uses above-mentioned rubber composition for tire to make.
The invention effect
In the present invention, after the elastomeric material that obtains through mixed silica and silane coupling agent is mediated, extruded rubber piece immediately not.On the contrary, the maintenance step is provided, wherein, under high-temperature atmosphere, block rubber has been kept preset time, for block rubber silicon-dioxide and the required heat of silane coupling agent reaction are provided thus at the place, bottom of airtight kneader.Through this structure, silane coupling agent and silicon-dioxide fully react, so can suppress the generation of following problem: produce bubble such as the alcohol that in extrusion step, produces because of unreacted silane coupling agent and in the extrusion moulding article.
In keeping step, only locate, under high-temperature atmosphere, keep block rubber, so do not need the additional apparatus investment in the bottom of airtight kneader.Further, do not carry out the long time, do not reduce and rubber gelsization so productivity can not take place owing to need rubber not mediated.In addition, owing to can during the hold-time, carry out the operation that is used to mediate elastomeric material subsequently, do not descend so can not cause productivity.
Further; Because the unreacted rate of silane coupling agent can be based on being controlled by kneading condition (rubber temperature of kneading time, kneading) and the definite total mixing heat of conservation condition (rubber temperature when hold-time, maintenance), so can easily control the manufacturing of rubber combination.
In the present invention, because the tyre rubber raw material comprises the styrene-butadiene rubber(SBR) of specific end modification and/or specific tin modification polybutadiene rubber, so can obtain wear resistance, earth-catching property and rolling resistance by further improved rubber combination.
Comprise the tyre surface of the rubber combination of manufacturing thus through use, can obtain to provide the pneumatic tyre than low fuel consumption.
Description of drawings
Fig. 1 for the unreacted rate that shows the rubber combination among the embodiment and wear resistance with always mix the synoptic diagram that concerns between the heat.
The synoptic diagram of Fig. 2 for concerning between unreacted rate (y) that shows the rubber combination among the embodiment and the natural logarithm of always mixing heat (x).
Embodiment
A. ultimate principle of the present invention
At first, ultimate principle of the present invention is described.
In traditional kneading step, after mediating, immediately the block rubber that obtains is discharged from airtight kneader and delivered on the forcing machine, then with the sheet form moulding.In aforesaid traditional kneading step, be difficult to make the sufficient reacting of silicon-dioxide and silane coupling agent to be accomplished.
The known heat that in kneading step, offers rubber combination (mixes heat Q
M) have following relation with the unreacted rate (y%) of silane coupling agent:
Y=-A ln (Q
M)+B (A, B are constant).
Following formula shows, in order to reduce the unreacted rate of silane coupling agent, should improve and mix heat Q
M
Because this reason, the idea that has proposed to mediate is for a long time mixed heat Q as improving
MMethod.Yet, owing to aforesaid problem occurs such as productivity decline, rubber gelsization etc., so think that this method is not suitable method.
The inventor considers; Replacement is mediated block rubber for a long time; Through on the forcing machine or roller at place, the bottom of airtight kneader, under high-temperature atmosphere, will mediate block rubber maintenance (delay) the suitable time of then from airtight kneader, discharging; Come further to provide heat, mix heat Q thereby can improve
MSo the contriver tests, the result finds, through adopting this method, can reduce the unreacted rate of silane coupling agent fully, does not need the additional apparatus investment simultaneously and can not cause the generation such as problems such as productivity decline, rubber gelsization.
Constant A in the following formula and B can be through changing some kneadings and maintenance (delay) condition and measuring the mixing heat Q under the change condition
MConfirm with the unreacted rate of silane coupling agent in the rubber combination.Though these numerical value rely on each and fill a prescription and change; But have been found that; Under normal conditions, the amount of the silicon-dioxide in sneaking into tyre surface is when promptly being the 5-150 mass parts based on the amount of the silicon-dioxide of the crude rubber of 100 mass parts; The rangeability of above-mentioned constant A and B is less, so A and B can be considered to constant.Under this prerequisite, the unreacted rate of silane coupling agent and the total mixing heat that in mediating and keeping, obtains can be considered to be approximately constant.
The result is; Have been found that; Can easily and rightly control the unreacted rate of silane coupling agent based on kneading condition (kneading time, mediate temperature) and conservation condition (hold-time, maintenance temperature), so can confirm to bring into play fully the method for the kneading elastomeric material of silicon-dioxide mixed performance quantitatively.
Specifically, as result of experiment, constant A in the following formula and B are respectively 0.0696 and 0.2488.And the unreacted rate through the demonstration silane coupling agent drawn based on above-mentioned numerical value with mix the figure that concerns between the heat, can confirm essential heat corresponding to the expection unreacted rate of silane coupling agent.
Providing through calculating must heat and do not reduce the difference between the heat that is given under the kneading condition of productivity, confirms to keep the heat that provides in the step, and can confirm necessity hold-time by the maintenance temperature that on forcing machine, roller etc., keeps.Therefore, can keep (delays) definite hold-time, the rubber combination that the unreacted rate of silane coupling agent wherein of easily obtaining fully reduces through the block rubber after will mediating under the above-mentioned maintenance temperature.
B. the manufacturing of the rubber combination among the present invention
Next the manufacturing to the rubber combination among the present invention describes.
1. manufacturing installation and method of manufacture
As being used to make manufacturing installation, can use airtight kneader traditionally, for example Banbury mixer, kneader etc. according to rubber combination of the present invention.So do not need the additional apparatus investment.
As method of manufacture,, can adopt prior manufacturing method basically except the place, bottom that is included in airtight kneader keeps mediating the maintenance step of the block rubber that obtains.Based on show according to the unreacted rate of the silane coupling agent of aforesaid method with mixes the figure that concerns between the heat, kneading temperature and kneading time and maintenance temperature and hold-time can be set in the scope that does not reduce productivity suitably.
In this situation, the heat Q that offers rubber combination is through the heat Q that kneading produced in the kneading step
1With the heat Q that is provided through the maintenance block rubber that keeps in the step
2Summation (always mixing heat).
Consider suitable rubber temperature and suitable hold-time when keeping at airtight kneader bottom place, above-mentioned total mixing heat can be represented through following formula.
Q＝∑Q
1+∑Q
2，
Q
1＝EXP[(-20/(1.987/0.001)×{1/(T
1+273.16)-1/414.86}]×t
1，
Q
2＝EXP[(-20/(1.987/0.001)×{1/(T
2+273.16)-1/414.86}]×t
2，
0.5≤t
2≤6.0，
141.7≤T
2≤165.0，
t
1: the kneading time (minute),
t
2: the hold-time of locating in the bottom of airtight kneader (minute),
T
1: the rubber temperature of kneading (℃),
T
2: the rubber temperature when keeping at the place, bottom of airtight kneader (℃).
In following formula ,-20/ (1.987/0.001) corresponding in the Arrhenius equation as follows (Arrhenius equation) (E/R), and 414.86 corresponding to T
2The T of 141.7 ℃ of lower limit temperatures:
k＝A·exp(-E/RT)。
Here,
A: with the incoherent constant of temperature (frequency factor),
E: activation energy,
R: gas law constant,
T: T (K).
Keep temperature T
2Be more than 141.7 ℃, because when it is lower than 141.7 ℃, silicon-dioxide and silane coupling agent be fully reaction not, so can not bring into play the performance of silicon-dioxide fully.Keep temperature T
2Be below 165.0 ℃, because when it is higher than 165.0 ℃, thereby the sulphur atom that comprises in the silane coupling agent causes crosslinking reaction to carry out causing gelation.
Consider reactivity and processibility, hold-time t
2Be set at 0.5-6.0 minute.
Through setting suitable kneading temperature, kneading time based on following formula, keeping temperature and hold-time, can when the unreacted rate of controlling silane coupling agent is lower, make rubber combination.
When known unreacted rate when silane coupling agent surpassed 10%, the significant problem of appearance and step and correlation of attributes such as the pure bubble of generation in extrusion step, caused the porousness (vesicular) etc. in the tire thus.Therefore, preferably will always mix heat and be arranged so that the unreacted rate of silane coupling agent is no more than 10%.
As result of experiment, be 8 corresponding to total mixing heat Q of the unreacted rate of the silane coupling agent below 10%.Therefore, preferably will mediate condition and conservation condition and be arranged so that total mixing heat Q is more than 8.
When the unreacted rate of silane coupling agent is 5% when following, can improve the wear resistance of tire.As result of experiment, be 18 corresponding to total mixing heat Q of the unreacted rate of the silane coupling agent below 5%.Therefore, be arranged so that through mediating condition and conservation condition total mixing heat Q is more than 18, can make preferred rubber combination.
When total mixing heat Q was 30, the unreacted rate of silane coupling agent was lower than 1%, even and apply the heat above 30, can not expect further to reduce the unreacted rate of silane coupling agent, but reduced productivity unfriendly.Therefore, preferably will mediate condition and conservation condition is set at and makes total heat Q that mixes be no more than 30.
At sulfurating stage not, will keep the rubber combination after the step to extrude according to the shape of tyre surface, then through usual method on the tire molding machine with this rubber combination with other tyre element moulding, thereby be processed into not vulcanized tyre.Afterwards, can in vulcanizer, heat, pressurize this not vulcanized tyre have the outstanding fuel consumption performance and the pneumatic tyre of wet earth-catching property with manufacturing.
2. elastomeric material
As the elastomeric material that is used for according to rubber combination of the present invention, crude rubber, silicon-dioxide and silane coupling agent are by explanation successively.In addition, hereinafter also will be explained the carbon black as reinforcing filler.
(1) crude rubber
Two kinds of modified rubbers as follows are added in traditional crude rubber to obtain crude rubber to be used suitably.That is to say; Mentioned molecular weight distribution mw/mn (weight-average molecular weight/number-average molecular weight) be the styrene-butadiene rubber(SBR) (SBR of end modification) of the end modification below 2.3 with lithium initiator polymeric tin modification polybutadiene rubber (modification BR), wherein this tin modification polybutadiene rubber has ethene binding capacity and the 2.0 following molecular weight distribution mw/mns of tin atom content ratio, the 5-50 quality % of 50-3000ppm.
As the SBR of end modification, the preferred SBR that wherein is introduced at place, polymkeric substance end with the functional group of silicon-dioxide chemically bonded.Through improving the adhesivity with silicon-dioxide like this.
Functional group to be introduced comprises amino, hydroxyl, epoxy group(ing), alkyl silyl, alkoxysilyl, carboxyl, lactam group etc.Wherein, amino, epoxy group(ing), alkyl silyl and alkoxysilyl are preferred, because be outstanding and can improve fuel efficiency fully with the adhesivity of silicon-dioxide.Amino is preferred especially.
For making the SBR of end modification; Preferably introduce functional group at the place, end of the SBR that obtains through solution polymerization; This is because the control of MWD is easier to, and can remove the lower-molecular-weight component as the factor that reduces fuel efficiency, further; Because living polymerization is prone to introduce functional group at the place, end.
The degree of modification of the functional group of the SBR of end modification is preferably 30-80 quality %, more preferably 50-70 quality %.When degree of modification is lower than 30 quality % since with the less binding capacity of silicon-dioxide, possibly fully not improve fuel efficiency.On the contrary, when degree of modification surpassed 80 quality %, existence became strong with the interaction of silicon-dioxide, thereby reduced the trend of the processibility of rubber kneading.
Styrene content among the SBR of end modification is preferably 10-45 quality %, more preferably 15-40 quality %.When styrene content is lower than 10 quality %, there is the trend that earth-catching property reduces, wear resistance reduces under the drying conditions.On the contrary, when styrene content surpasses 45 quality %, there is fuel efficiency (rolling resistance performance) downward trend.
Ethene binding capacity among the SBR of end modification is preferably 25-70 quality %, more preferably 30-60 quality %, further preferred 30-50 quality %.When the ethene binding capacity was lower than 25 quality %, the balance between earth-catching property and the fuel efficiency was tending towards deterioration.On the contrary, when the ethene binding capacity surpasses 70 quality %, the trend that exists wear resistance to reduce.In addition, curing time is tending towards increasing.Can measure this ethene binding capacity (1, the amount of 2-bonded butadiene unit) through the INFRARED SPECTRUM analytical procedure.
The MWD of the SBR of end modification (Mw/Mn) is preferably below 2.3, more preferably 1-2.2.When its MWD surpassed 2.3, the amount of lower-molecular-weight component increased, so fuel consumption efficiency is tending towards reducing.
Based on (GPC-8000 of Tosoh manufactured is serial through GPC (GPC); Detector: differential refractometer, pillar: the measured value that the TSKGEL SUPERMULTIPORE HZ-M of Tosoh manufactured) is scaled polystyrene standard obtains above-mentioned molecular weight distribution mw/mn.
The amount that is contained in the SBR of the end modification in the crude rubber of 100 quality % is preferably 5-100 quality %, and more preferably 10-90 quality % further is preferably 20-80 quality %, is preferably 30-70 quality % especially.When the amount of the SBR of end modification is lower than 5 quality %, there is the trend that it sneaks into effect that fully do not obtain.On the contrary, when the amount of the SBR of end modification surpasses 90 quality %, be tending towards reducing as the wear resistance of tyre performance.
Yet, in above-mentioned situation, when the SBR of independent use end modification, owing to be not that all end modification groups all react with silicon-dioxide or carbon, so the effect of the SBR of end modification can not perform at utmost.
On the contrary, when the SBR of end modification is not sneaked into, for example, use following unmodified SBR separately,, can not obtain further improved fuel consumption even use said temperature to keep the kneading method.In the present invention, the SBR that uses above-mentioned method of manufacture and the end modification with specific Mw/Mn through combination is as crude rubber, and the dispersiveness of silicon-dioxide improves, thereby can further improve the fuel consumption performance.In addition, also can improve the balance between rolling resistance and the earth-catching property, thereby can realize these performances simultaneously.
The amount that is contained in the modification BR in the crude rubber of 100 quality % is preferably 10-60 quality %, and more preferably 15-50 quality % further is preferably 20-45 quality %, is preferably 25-40 quality % especially.When the amount of modification BR is lower than 10 quality %, can not fully obtains it and sneak into effect.On the contrary, when the amount of modification BR surpasses 60 quality %, be tending towards deterioration as the destructive characteristics (destruction property) of tyre performance.
In the present invention; Except the SBR and modification BR of the modification of above-mentioned end; As crude rubber; Can use elastoprene for example tree elastomer (NR), polybutadiene rubber (BR), butyl rubber (butyl rubber, IIR), halogenated butyl rubber (X-IIR), unmodified styrene-butadiene rubber(SBR) (unmodified SBR) etc.Wherein, preferred unmodified SBR because its be high-compatibility and cheaply.
Unmodified SBR is not special to be limited, and can use to be generally used in the tire industry those, such as SBR of emulsion polymerization (E-SBR), solution polymerization styrene-butadiene rubber (S-SBR) etc.
Styrene content among the unmodified SBR is preferably 10-50 quality %, more preferably 15-45 quality %.When its styrene content was lower than 10 quality %, earth-catching property was tending towards descending.On the contrary, when its styrene content surpassed 50 quality %, wear resistance was tending towards descending.Styrene content among the SBR of end modification and the unmodified SBR is measured through HI-NMR and is calculated.
In the rubber components of 100 quality %, the content of unmodified SBR is preferably 30-90 quality %, more preferably 40-80 quality %, further preferred 50-70 quality %.When the content of unmodified SBR was lower than 30 quality %, processibility was tending towards descending.On the contrary, when the content of unmodified SBR surpasses 90 quality %, exist silicon-dioxide to be difficult for the trend of the balance variation between dispersion and earth-catching property and the wear resistance.
In the rubber components of 100 quality %, the SBR of end modification and the total content of unmodified SBR are preferably more than the 75 quality %, more preferably more than the 85 quality %, and further more than the preferred 95 quality %, 100 quality % most preferably.When its total content was lower than 75 quality %, wear resistance was tending towards deterioration.
(2) silicon-dioxide
Sneaking into silicon-dioxide is used to improve the enhanced of rubber combination and further improves its rolling resistance performance.Silicon-dioxide including, but not limited to: use silicon-dioxide that wet method makes, use silicon-dioxide that dry method makes etc.Silicon-dioxide can use separately or two or more silicon-dioxide uses capable of being combined.
Nitrogen adsorption specific surface area (N when silicon-dioxide
2SA) too hour, can not obtain competent enhanced.Yet, as the nitrogen adsorption specific surface area (N of silicon-dioxide
2When SA) too big, the dispersiveness of silicon-dioxide reduces, and hysteresis loss increases, and the rolling resistance degradation.Preferred its N
2The scope of SA is 170-250m
2/ g, more preferably 200-230m
2/ g.The N of above-mentioned silicon-dioxide
2The SA value is the value of measuring through the BET method according to ASTM D3037-81.
When the mixed volume of silicon-dioxide too hour, can not obtain competent enhanced.Yet, when the mixed volume of silicon-dioxide is too big, the dispersed reduction, hysteresis loss increases, and the rolling resistance degradation.With respect to the crude rubber of 100 mass parts, the scope of the mixed volume of preferred silicon-dioxide is the 5-150 mass parts, more preferably 10-80 mass parts, further preferred 30-60 mass parts
(3) silane coupling agent
As silane coupling agent, can mention two (3-triethoxysilylpropyltetrasulfide) tetrasulfide, two (3-triethoxysilylpropyltetrasulfide) trisulphide, two (3-triethoxysilylpropyltetrasulfide) disulphide etc.Wherein, two (3-triethoxysilylpropyltetrasulfide) tetrasulfide is preferred, and this is because it has the big effect that improves enhanced.These silane coupling agents can use separately or two or more combinations is used.
When the mixed volume of silane coupling agent too hour, the viscosity of unvulcanized rubber increases, so the processibility deterioration.Yet, when the mixed volume of silane coupling agent is too big, can not obtain to meet the effect that cost increases.With respect to the silicon-dioxide of 100 mass parts, the scope of the mixed volume of preferred silane coupling agent is the 1-20 mass parts, more preferably the 2-15 mass parts.
(4) carbon black
In rubber combination of the present invention, preferably sneak into carbon black as filler.Through sneaking into carbon black, can improve enhanced and can further improve wear resistance.As carbon black, can use GPF, FEF, HAF, ISAF, SAF etc., but carbon black is not limited thereto.These carbon blacks can use separately or two or more combinations is used.
As sooty N
2SA too hour can not obtain competent enhanced.Yet, as sooty N
2When SA is too big, the dispersed reduction and the rolling resistance degradation.Preferred N
2The scope of SA value is 50-200m
2/ g, more preferably 100-150m
2/ g.Above-mentioned sooty N
2The SA value is the value of measuring according to JIS K6217 A.
But the sooty mixed volume too hour, can not obtain competent enhanced.Yet, when the sooty mixed volume is too big, the dispersed reduction, and rolling resistance degradation.With respect to the crude rubber of 100 mass parts, the scope of preferred sooty mixed volume is the 10-100 mass parts, more preferably 20-80 mass parts, further preferred 30-60 mass parts.
(5) other Synergist S-421 95
In rubber combination of the present invention, except above-mentioned elastomeric material, can optionally sneak into additive suitably such as oil, tackiness agent, inhibitor, antiozonidate, inhibitor, vulcanizing agent, vulcanization accelerator, vulcanization accelerator additive etc.
Be applicable to the tire of passenger car, commercial car and two wheeler by the rubber combination of above-mentioned elastomeric material acquisition.
Embodiment
Next, based on embodiment the present invention is further at length explained.
1. elastomeric material
In following embodiment, use the elastomeric material shown in the table 1-4.Below the elastomeric material shown in the his-and-hers watches 1-4 is described.
In table 3, embodiment 1-3 is that the SBR of end modification and the embodiment of temperature control kneading condition have been used in combination.Embodiment 4-6 is that combination has used modification BR and temperature to keep the embodiment of kneading condition.Embodiment 7-9 is that the SBR of end modification and the embodiment of modification BR and temperature maintenance kneading condition have been used in combination.
(1) crude rubber
SBR:SBR1502 (unmodified, styrene content: 23.5 quality %), the JSR manufactured.
(solution polymerization, end group: amino, degree of modification: 51 quality %, styrene content: 39 quality %, the ethene binding capacity: 31 quality %, Mw/Mn:2.1), Asahi Kasei Corporation makes the SBR of end modification (1): E10.
The SBR of end modification (2): wherein Mw/Mn becomes the SBR (1) of 3 end modification.
Modification BR (1): BR1250 (tin modification polybutadiene rubber (modification BR), use the polymerization of lithium, the ethene binding capacity as initiator: 10-13 quality %, Mw/Mn:1.5, the tin atom content ratio: 250ppm), the ZEON manufactured.
Modification BR (2): wherein Mw/Mn becomes 2.5 modification BR (1).
(2) fiting chemical article
Silicon-dioxide: DEGUSSA manufactured, Ultrasil VN3 (N
2SA:175m
2/ g).
Carbon black: Cabot Japan manufactured, Show Black N220 (N
2SA:111m
2/ g).
Silane coupling agent: DEGUSSA manufactured, Si69{ two (3-triethoxysilylpropyltetrasulfide) tetrasulfide }
Oil: Japan Energy manufactured, JOMO Process X140.
Wax: the emerging chemical industry of imperial palace Co., Ltd. makes, Sunnoc N.
Inhibitor: the emerging chemical industry of imperial palace Co., Ltd. makes, Noclac 6C{N-(1, the 3-dimethylbutyl)-N '-phenyl-Ursol D }.
Triple Pressed Stearic Acid: Japan Oil Co makes, Tsubaki.
Zinc oxide: Mitsu Mining & Smelting Co., Ltd makes, AENKA No.1.
Sulphur: crane sees that chemical industry Co., Ltd. makes powdery sulphur.
Vulcanization accelerator: the emerging chemical industry of imperial palace Co., Ltd. makes, Nocceler NS (the N-tertiary butyl-2-[4-morpholinodithio sulfinyl amine).
2. rubber cooperates the manufacturing of article
(1) first kneading step (being included in the maintenance step that provides after the kneading)
(a) kneading step
Put in the Banbury mixer crude rubber and chemical shown in " first mediates " in " title complex " among the table 1-4 and kneading, make that mediating temperature reached 140 ℃ in 3 minutes.Then, mediate according to kneading temperature and kneading time shown in " the 1st mediates " in " kneading temperature and time " among the table 1-4.
(b) keep step
After kneading, the block rubber that obtains is discharged in the bottom of Banbury mixer, keep according to the hold-time after temperature and the kneading after the kneading shown in " first mediates " in " kneading temperature and time " among the table 1-4 subsequently.
(2) second kneading steps (being included in the maintenance step that provides after the kneading)
(a) kneading step
Then, put in Banbury mixer and kneading with block rubber the chemical shown in " second mediates " in " title complex " among the table 1-4, make that mediating temperature reached 140 ℃ in 3 minutes.Then, mediate according to kneading temperature and kneading time shown in " second mediates " in " kneading temperature and time " among the table 1-4.
(b) keep step
After kneading, the block rubber that obtains is discharged in the bottom of Banbury mixer, keep according to the hold-time after temperature and the kneading after the kneading shown in " second mediates " in " kneading temperature and time " among the table 1-4 subsequently.
(3) final kneading step
Then, the chemical shown in " the final kneading " in " title complex " of table among the 1-4 put in the Banbury mixer and at 90 ℃ with block rubber mediated 3 minutes down, thereby obtain unvulcanized rubber combination.
(reference examples)
Use the elastomeric material shown in the table 1-4, under " the kneading temperature and time " shown in the table 1-4, mediate.
3. mix the calculating of heat, unreacted rate and productivity
(1) calculating of mixing heat
According to the heat Q that produces in computes first kneading step and each comfortable kneading step of second kneading step
1With through in keeping step, keeping the heat Q that block rubber provided
2
Q
1＝EXP[(-20/(1.987/0.001)×{1/(T
1+273.16)-1/414.86}]×t
1
Here,
t
1: the kneading time (minute),
T
1: the kneading temperature (℃),
Q
2＝EXP[(-20/(1.987/0.001)×{1/(T
2+273.16)-1/414.86}]×t
2，
t
2: the hold-time (minute),
T
2: the maintenance temperature (℃).
Q with above-mentioned acquisition
1And Q
2Obtain first kneading step and second kneading step mixing heat separately mutually.Then, with the mixing heat addition of first kneading step and second kneading step to obtain always to mix heat Q.The result is shown in table 1-4.
(2) calculating of the unreacted rate of silane coupling agent
For the unvulcanized rubber combination that obtains in each embodiment and the reference examples, the unreacted rate is according to following steps 1)-3) ratio of the peak area of the unreacted Si69 that obtains calculates.
1) from each unvulcanized rubber combination, extract unreacted Si69 with acetone, and through its peak area of liquid chromatography for measuring (a).
2), measure the peak area (b) of the Si69 before sneaking into according to identical mode.
3) ratio of the peak area of unreacted Si69 is peak area (a)/peak area (b).
The result is shown in table 1-4.
(3) calculating of productivity
With kneading time of reference examples 1 (comprise first mediate with second kneading in reach 140 ℃ 3 minutes) productivity be defined as 100, and confirm productivity according to following formula.Numerical value is big more, productivity high more (the kneading amount is big more).The result is shown in table 1-4.
Productivity=(the kneading time in kneading in the reference examples 1 time/each embodiment or the reference examples) * 100
The manufacturing of vulcanized rubber and test tire with and the assessment of performance
(1) manufacturing of vulcanized rubber and test tire
(a) manufacturing of vulcanized rubber
Under 170 ℃, with the unvulcanized rubber compsn press vulcanization that obtains in each embodiment and the reference examples 15 minutes to obtain vulcanized rubber.
(b) manufacturing of test tire
The unvulcanized rubber compsn that obtains in each embodiment and the reference examples is processed into tire tread form, and bonding with other tyre element, vulcanize 15 minutes down to make test tire (tire size: 195/65R15) at 170 ℃ then.
(2) assessment of performance
(a) wear resistance
Use the Lambourn wear testing machine, under the condition of the slip ratio of the applied load of room temperature, 1.0kgf and 30%, measure the Lambourn wear loss of each vulcanizate compositions.According to the Lambourn wear loss volume calculated loss that obtains.VOLUME LOSS in the reference examples 1 is defined as 100, and according to the computes wear index.Wear index=(VOLUME LOSS in the VOLUME LOSS in the reference examples 1/each embodiment or the reference examples) * 100
This numerical value is big more, wear resistance high more (VOLUME LOSS is more little).The result is shown in table 1-4.
(b) grab the ground index
Use each test tire, carry out driving test on the test track of dried asphalt road having.The stability of the manipulation control in the driving is assessed by test drive person, and with exponential representation, wherein the index in the reference examples 1 is set to 100.Numerical value is big more, and the earth-catching property on dry pavement (control stability) is high more.The result is shown in table 1-4.
(c) rolling resistance index
Use visco-elasticity spectrometer VES (manufacturing of Co., Ltd. of this makings of rock institute), the tan δ of each vulcanizate compositions of mensuration under the condition of the dynamic strain of 70 ℃ temperature, 10% initial strain and 2%.Tan δ in the reference examples 1 is defined as 100, and according to the computes rolling resistance index.
Rolling resistance index=(the tan δ in the tan δ in the reference examples 1/each embodiment or the reference examples) * 100
This numerical value is big more, rolling resistance performance good more (rolling resistance is more little).The result is shown in table 1-4.
Table 1
Table 2
Table 3
Table 4
1-4 can know according to table; Used the SBR and the modification BR of end modification therein and carried out temperature and kept among the embodiment of kneading with specific Mw/Mn; Wear resistance, earth-catching property and anti-coefficient of rolling resistance significantly improve, and these performances are improved with the well balanced mode through synergy.On the contrary, be described below, in reference examples, do not obtain these performances with the well balanced mode.
Shown in table 3 and 4, in embodiment 1-9, the unreacted rate of silane coupling agent reduces because of total increase that mixes heat.Compare with the unreacted rate (20%) of the silane coupling agent of in the rubber combination of except keeping step, making according to embodiment 1 respectively, being measured, the unreacted rate of the silane coupling agent among the embodiment obviously reduces.
1-4 can know according to table, and when the unreacted rate of silane coupling agent reduced, wear resistance, earth-catching property and coefficient of rolling resistance improved.
Next, Performance Evaluation result in the reference examples is described.In reference examples 2, though used the SBR of end modification, keep mediating, so and be unrealized with respect to the adequate performance improvement of reference examples 1 owing to carry out temperature.
In reference examples 3 and 4, use the SBR (Mw/Mn=3) of end modification.Yet the content of its molecular weight broad and lower-molecular-weight component increases, so, the balance deterioration of low fuel consumption and the competent improvement in performance that is unrealized.
In reference examples 5, though modification BR is used, do not keep mediating owing to carry out temperature, improve with respect to the adequate performance of reference examples 1 so be unrealized.
In reference examples 6 and 7, modification BR (Mw/Mn=2.5) is used.Yet the content of its molecular weight broad and lower-molecular-weight component increases, so the balance deterioration of low fuel consumption and the competent improvement in performance that is unrealized.
In reference examples 8,, do not obtain competent effect though temperature is enhanced with respect to reference examples 1.
In reference examples 9 and 10, through prolonging the reaction that the kneading time improves coupling agent, but the degradation of productivity is bigger.
As unreacted rate and the wear resistance shown in the rubber combination shown in the 1-4 are as shown in Figure 1 with the relation that it always mixes between the heat.In Fig. 1, the total heat that mixes of X-coordinate representative, left ordinate zou is represented the unreacted rate (%) of silane coupling agent, and right ordinate zou is represented wear resistance.
Be based on the unreacted rate result's who demonstrates outstanding productivity and silane coupling agent in the table 3 and 4 embodiment 1-9, the relation between the unreacted rate (y) that Fig. 2 shows rubber combination and the natural logarithm of always mixing heat (x).In Fig. 2, the total natural logarithm (Ln) of mixing heat of X-coordinate representative, and ordinate zou is represented the unreacted rate of silane coupling agent.
Can know that by Fig. 1 when total mixing heat is 8 when above, the unreacted rate of silane coupling agent can be controlled as below 10%.When the unreacted rate of silane coupling agent is 10% when following, the significant problem that can suppress aforesaid and step and correlation of attributes is such as producing pure bubble in extrusion step, thereby causes the porousness (vesicular) in the tire.
Should also be appreciated that when total mixing heat is 18 when above, the unreacted rate of silane coupling agent can be controlled as below 5%.When the unreacted rate of silane coupling agent is 5% when following, can improve the wear resistance of tire as stated.This also can find out from table 1-4.
Can know by Fig. 1, total when mixing heat Q was 30, the unreacted rate of silane coupling agent was about 1%, even and always mix heat and be increased to and surpass 30, can not expect the significant reduction of unreacted rate.
In Fig. 1, use according to four defibers of the title complex and the condition of kneading and represent always to mix the relation between heat and the wear resistance.That is; A is the lines based on the situation (reference examples 1,3,4,6-10) that only keeps mediating; B is the lines based on the situation (embodiment 4-6, and reference examples 5) that has made up modification BR and maintenance kneading, and c is based on having made up situation (the embodiment 1-3 of modification SBR with the maintenance kneading; And reference examples 2) lines, and d is the lines based on the situation (embodiment 7-9) that has made up modification SBR, modification BR and kept mediating.Can know by Fig. 1, use various technology, even, also can improve wear resistance always to mix heat be identical through combination.
Can know formula y=-A ln (Q by Fig. 2
MConstant A among the)+B and B can be determined.The inventor is verified, and in some embodiment except the foregoing description, even in preferable range, change the mixed volume of silane coupling agent suitably, A and B are also almost constant.
Describe the present invention based on above-mentioned embodiment, but the present invention is not limited to above-mentioned embodiment.Can carry out various changes to above-mentioned embodiment in protection scope of the present invention or in the equivalency range.
Claims (6)
1. method that is used to make rubber composition for tire, this method is characterized in that through silicon-dioxide and silane coupling agent are sneaked into tire with making rubber composition for tire in the crude rubber said method comprises:
Kneading step; Wherein use airtight kneader that elastomeric material and silane coupling agent is kneaded together; Said elastomeric material obtains with crude rubber with respect to the silicon-dioxide of the said tire of 100 mass parts with the 5-150 mass parts of crude rubber through the tire that mixes 100 mass parts, and
Maintenance step after said kneading step; Wherein locate in the bottom of said airtight kneader; Keep the scheduled time under high-temperature atmosphere through mediating the block rubber that obtains, thus for said block rubber provides silicon-dioxide and the required heat of silane coupling agent reaction, and
The said tire of 100 mass parts with crude rubber in, comprise
The molecular weight distribution mw/mn of 5-100 mass parts is the styrene-butadiene rubber(SBR) of the end modification below 2.3, and/or
The 10-60 mass parts with lithium initiator polymeric tin modification polybutadiene rubber, said tin modification polybutadiene rubber has the tin atom content ratio of 50-3000ppm, the ethene binding capacity of 5-50 quality % and 2.0 below molecular weight distribution mw/mn.
2. the method that is used to make rubber composition for tire as claimed in claim 1 is characterized in that, the styrene-butadiene rubber(SBR) of said end modification is the styrene-butadiene rubber(SBR) of having introduced amino end modification in its end.
3. according to claim 1 or claim 2 the method that is used to make rubber composition for tire is characterized in that, based on the manufacturing of total mixing heat Q control rubber combination, said total mixing heat Q is for by the heat Q that kneading produced in the said kneading step
1With by the heat Q that maintenance provided in the said maintenance step
2Summation, wherein,
Q＝∑Q
1+∑Q
2，
Q
1＝EXP[(-20/(1.987/0.001)×{1/(T
1+273.16)-1/414.86}]×t
1，
Q
2＝EXP[(-20/(1.987/0.001)×{1/(T
2+273.16)-1/414.86}]×t
2，
0.5≤t
2≤6.0，
141.7≤T
2≤165.0，
t
1: the kneading time, minute,
t
2: the hold-time of locating in the bottom of airtight kneader, minute,
T
1: the rubber temperature of kneading ℃, and
T
2: the rubber temperature that keeps at place, the bottom of airtight kneader ℃.
4. the method that is used to make rubber combination as claimed in claim 3 is characterized in that, said total mixing heat Q satisfies following formula: 8≤Q≤30.
5. a rubber combination uses like each described method manufacturing that is used to make rubber combination among the claim 1-5.
6. pneumatic tyre, it has the tyre surface that uses rubber composition for tire as claimed in claim 5 to make.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011046568A JP5378435B2 (en) | 2011-03-03 | 2011-03-03 | Rubber composition for tire, method for producing the same, and pneumatic tire using the rubber composition for tire |
| JP2011-046568 | 2011-03-03 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102653606A true CN102653606A (en) | 2012-09-05 |
| CN102653606B CN102653606B (en) | 2016-01-20 |
Family
ID=46729348
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110462610.XA Expired - Fee Related CN102653606B (en) | 2011-03-03 | 2011-12-23 | Rubber composition for tire, its manufacture method and use the pneumatic tyre of this rubber composition for tire |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP5378435B2 (en) |
| CN (1) | CN102653606B (en) |
| BR (1) | BR102012003785A2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103665729A (en) * | 2012-09-18 | 2014-03-26 | 中国石油天然气股份有限公司 | Oil-extended styrene-butadiene rubber containing nano silicon dioxide on surface, composition and preparation method thereof |
| CN106661237A (en) * | 2014-07-15 | 2017-05-10 | 住友橡胶工业株式会社 | Method for producing rubber composition for tires, and pneumatic tire |
| CN106795334A (en) * | 2014-10-17 | 2017-05-31 | 日本瑞翁株式会社 | Rubber composition for tire |
| CN111032766A (en) * | 2017-09-01 | 2020-04-17 | 株式会社可乐丽 | Rubber composition for tire |
| CN113748027A (en) * | 2019-04-18 | 2021-12-03 | 米其林集团总公司 | Tire tread having improved rolling resistance and wear |
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| CN1974647A (en) * | 2005-12-01 | 2007-06-06 | 住友橡胶工业株式会社 | Rubber composition for tyre and tyre with tread using same |
| JP2007246929A (en) * | 2007-07-05 | 2007-09-27 | Sumitomo Rubber Ind Ltd | Method for producing rubber product |
| CN101735498A (en) * | 2008-11-05 | 2010-06-16 | 住友橡胶工业株式会社 | Rubber composition and tire |
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| JP4076631B2 (en) * | 1998-08-11 | 2008-04-16 | 住友ゴム工業株式会社 | Rubber composition |
| JP3950678B2 (en) * | 2001-11-22 | 2007-08-01 | 旭化成ケミカルズ株式会社 | Rubber composition |
| JP4346351B2 (en) * | 2003-05-28 | 2009-10-21 | 横浜ゴム株式会社 | Method and equipment for kneading rubber composition |
| JP4639981B2 (en) * | 2005-06-16 | 2011-02-23 | 横浜ゴム株式会社 | Kneading control method of silica compound rubber |
| JP4853038B2 (en) * | 2006-02-15 | 2012-01-11 | 横浜ゴム株式会社 | Kneading system for silica compounded rubber material |
| JP4975356B2 (en) * | 2006-04-17 | 2012-07-11 | 住友ゴム工業株式会社 | Rubber composition for tire tread |
| JP5232203B2 (en) * | 2010-08-24 | 2013-07-10 | 住友ゴム工業株式会社 | Rubber composition for tire, method for producing the same, and studless tire |
| JP5652158B2 (en) * | 2010-11-25 | 2015-01-14 | 横浜ゴム株式会社 | Method for producing rubber composition for tire tread |
| JP5276649B2 (en) * | 2010-12-06 | 2013-08-28 | 住友ゴム工業株式会社 | Method for producing rubber composition |
-
2011
- 2011-03-03 JP JP2011046568A patent/JP5378435B2/en not_active Expired - Fee Related
- 2011-12-23 CN CN201110462610.XA patent/CN102653606B/en not_active Expired - Fee Related
-
2012
- 2012-02-17 BR BRBR102012003785-8A patent/BR102012003785A2/en not_active Application Discontinuation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1974647A (en) * | 2005-12-01 | 2007-06-06 | 住友橡胶工业株式会社 | Rubber composition for tyre and tyre with tread using same |
| JP2007246929A (en) * | 2007-07-05 | 2007-09-27 | Sumitomo Rubber Ind Ltd | Method for producing rubber product |
| CN101735498A (en) * | 2008-11-05 | 2010-06-16 | 住友橡胶工业株式会社 | Rubber composition and tire |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103665729A (en) * | 2012-09-18 | 2014-03-26 | 中国石油天然气股份有限公司 | Oil-extended styrene-butadiene rubber containing nano silicon dioxide on surface, composition and preparation method thereof |
| CN103665729B (en) * | 2012-09-18 | 2016-05-11 | 中国石油天然气股份有限公司 | Oil-extended styrene buadiene rubber, composition and method of making the same that nano silicon is contained on a kind of surface |
| CN106661237A (en) * | 2014-07-15 | 2017-05-10 | 住友橡胶工业株式会社 | Method for producing rubber composition for tires, and pneumatic tire |
| CN106661237B (en) * | 2014-07-15 | 2019-02-15 | 住友橡胶工业株式会社 | Method of the manufacture for tire and the rubber composition of pneumatic tire |
| CN106795334A (en) * | 2014-10-17 | 2017-05-31 | 日本瑞翁株式会社 | Rubber composition for tire |
| CN106795334B (en) * | 2014-10-17 | 2019-06-18 | 日本瑞翁株式会社 | Rubber composition for tire |
| CN111032766A (en) * | 2017-09-01 | 2020-04-17 | 株式会社可乐丽 | Rubber composition for tire |
| CN111032766B (en) * | 2017-09-01 | 2022-03-01 | 株式会社可乐丽 | Rubber composition for tire |
| CN113748027A (en) * | 2019-04-18 | 2021-12-03 | 米其林集团总公司 | Tire tread having improved rolling resistance and wear |
| CN113748027B (en) * | 2019-04-18 | 2023-06-09 | 米其林集团总公司 | Tire tread with improved rolling resistance and wear |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5378435B2 (en) | 2013-12-25 |
| BR102012003785A2 (en) | 2014-01-14 |
| JP2012184289A (en) | 2012-09-27 |
| CN102653606B (en) | 2016-01-20 |
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