JP5973324B2 - Tire member and manufacturing method thereof - Google Patents

Description

  The present invention relates to a tire member manufacturing method including a step of blending a rubber composition with a thiosulfuric acid compound containing an amino group, and a tire member obtained by the manufacturing method.

  As a method for improving the wear resistance performance of rubber, there is a method of increasing the amount of filler such as carbon black, which is generally attempted because it is easy. However, when the amount of filler is increased, the wear resistance performance is improved, but on the other hand, the workability decreases due to the increase in viscosity. When the viscosity is significantly increased, for example, a mastication process may be added to reduce the viscosity. However, when the process is added, the productivity decreases. Therefore, a method for improving the wear resistance performance without reducing productivity is required.

  On the other hand, it is known that by adding a thiosulfuric acid compound containing an amino group to a vulcanized rubber composition, it is possible to improve the heat resistance and viscoelasticity of the rubber. For example, Patent Documents 1 and 2 disclose that the heat resistance of a tire is improved by using S- (3-aminopropyl) thiosulfuric acid or the like. These documents 1 and 2 do not describe the wear resistance performance.

  The rubber obtained by the conventional process using the thiosulfuric acid compound is found to have a slightly improved wear resistance compared to the thiosulfuric acid compound-free rubber, but the degree is still insufficient. is there. Patent Document 1 describes that an anti-aging agent is added together with sulfur and a vulcanization accelerator, but in this case, there is a problem that fatigue resistance is lowered.

JP 2012-12458 A JP 2012-107232 A

  The present invention has been made in view of the above, and includes a step of blending the thiosulfuric acid compound containing the amino group, and a tire member that greatly improves the wear resistance without lowering productivity and fatigue resistance. An object of the present invention is to provide a manufacturing method and a tire member thereof.

  The method for producing a tire member of the present invention is obtained by the step (A) of mixing at least a rubber component, carbon black and / or an inorganic filler, and a thiosulfuric acid compound containing an amino group, and the step (A). In order to solve the above-mentioned problem, in the process (A), a rubber is produced by a method for producing a tire member comprising the step (B) of mixing the obtained mixture, a sulfur component, and a vulcanization accelerator. The components, carbon black and / or inorganic filler, and thiosulfuric acid compound containing an amino group are first mixed, and an antioxidant is added to the mixture and mixed.

  In the production method of the present invention, after the temperature of the mixture of the rubber component, the carbon black and / or inorganic filler, and the thiosulfuric acid compound containing an amino group reaches 140 ° C., the antiaging agent is added. And further mixing is preferable.

  More preferably, after mixing the rubber component, carbon black and / or inorganic filler, and a thiosulfuric acid compound containing an amino group while maintaining the temperature at 140 ° C. or higher for 1 minute or longer, the above aging prevention The agent is added and further mixed.

Moreover, as the thiosulfuric acid compound containing the amino group, one or more of thiosulfuric acid compounds represented by any of the following formulas (1) to (3) and salts thereof can be used. .

In Formula (1), n shows the integer of 2-9.

In the formula (2), R represents an alkanediyl group having 3 to 12 carbon atoms, and n represents an integer of 2 to 5.

  In the formula (3), R represents an alkanediyl group having 1 to 6 carbon atoms, and n represents an integer of 1 to 2.

  The production method of the present invention can be used to produce a tread member or a sidewall member of a tire.

The tire manufacturing method of the present invention is a method of manufacturing a tire member by the tire member manufacturing method of the present invention, and manufacturing a tire using the tire member .

  According to the present invention, as described above, the rubber component, the thiosulfuric acid compound containing an amino group, the carbon black and / or the inorganic filler are mixed first, and then the antiaging agent is added and mixed. As a result, a tire member with improved wear resistance can be obtained without lowering productivity and fatigue resistance.

  By shifting the timing of addition and mixing of the thiosulfate compound and the anti-aging agent in this way, the radicals generated from the rubber act efficiently on S- (3-aminopropyl) thiosulfate without being inhibited by the anti-aging agent. It is considered that the wear resistance performance is further improved. Moreover, it is thought that the bad influence to the rubber by an antiaging agent is also prevented.

  Hereinafter, embodiments for carrying out the present invention will be described in detail.

  The method for producing a tire member of the present invention includes at least the above-described step (A) and step (B), and in step (A), at least a rubber component, carbon black and / or an inorganic filler, and an amino group are contained. After mixing with the contained thiosulfate compound, the anti-aging agent is mixed.

  Examples of the rubber component that can be used in the present invention include various natural rubbers (NR), various polyisoprene rubbers (IR), various styrene butadiene rubbers (SBR), various polybutadiene rubbers (BR) and the like. May be used, or two or more of them may be used in combination. Preferably, natural rubber and various polybutadiene rubbers are used. In addition, as these rubbers, modified diene rubbers into which amino groups, alkoxysilane groups, hydroxy groups, epoxy groups, carboxyl groups, cyano groups, halogens and the like have been introduced can be used as necessary.

  Further, as carbon black, those usually used in the tire rubber field can be used without any particular limitation.

  Examples of the inorganic filler include silica, talc, clay, aluminum hydroxide, titanium oxide and the like that are usually used in the field of rubber for tires, and usually silica is preferably used. The inorganic filler referred to in the present invention does not contain carbon black.

  The blending amount of the carbon black and the inorganic filler is not particularly limited, and is appropriately adjusted depending on the use of the tire member. However, when only carbon black is used, usually 30 to 100 parts by mass of the rubber component. The range of 80 parts by mass is preferable, and when silica is blended, the range of 10 to 120 parts by mass is usually preferable per 100 parts by mass of the rubber component. Moreover, when mix | blending a silica, it is preferable to mix | blend 5-50 mass parts of carbon black per 100 mass parts of rubber components.

  When silica is used as the inorganic filler, it is preferable to use a silane coupling agent in combination. The kind of silane coupling agent is not particularly limited, and those generally used in rubber compositions for tires can be used. Examples thereof include sulfide silane and mercaptosilane. The content of the silane coupling agent is preferably 5 to 15% by mass with respect to silica.

  As the thiosulfuric acid compound containing an amino group used in the present invention, a thiosulfuric acid compound represented by any one of the above formulas (1) to (3) or a salt thereof can be preferably used. 1 type (s) or 2 or more types can be used. Examples of the salt include alkali metal salts such as lithium salt, sodium salt, potassium salt and cesium salt; transition metal salts such as cobalt salt and copper salt; typical metal salts such as zinc salt; substitution of ammonium salt, trimethylammonium salt and the like Examples thereof include unsubstituted ammonium salts. In these, metal salts, such as lithium, sodium, potassium, cesium, cobalt, copper, or zinc, are preferable, and lithium salt, sodium salt, or potassium salt is especially preferable. In the present invention, when a thiosulfuric acid compound and a salt thereof are used as a mixture thereof, such a mixture can be obtained by, for example, a method of mixing a thiosulfuric acid compound and a salt thereof, or a part of a thiosulfuric acid compound using a metal alkali. What was obtained by the method of chlorinating, the method of neutralizing a part of metal salt of a thiosulfuric acid compound using a proton acid, etc. can be used. In the following, “one or more of thiosulfuric acid compounds represented by any one of formulas (1) to (3) or salts thereof” is referred to as “thiosulfuric acid compounds and / or salts thereof”. Sometimes abbreviated.

  Preferred examples of the compound represented by the formula (1) include S- (3-aminopropyl) thiosulfuric acid, S- (3-aminobutyl) thiosulfuric acid, S- (3-aminopentyl) thiosulfuric acid, S- (3-aminohexyl) thiosulfuric acid.

  The compound represented by the formula (1) can be produced by any known method. For example, a salt of S- (3-aminopropyl) thiosulfuric acid is obtained by reacting 3-halopropylamine with sodium thiosulfate. Or a method of reacting potassium phthalimide with 1,3-dihalopropane, reacting the obtained compound with sodium thiosulfate, and then hydrolyzing the obtained compound. it can. S- (3-aminopropyl) thiosulfuric acid can be produced by neutralizing a salt of S- (3-aminopropyl) thiosulfuric acid with a protonic acid. The S- (3-aminopropyl) thiosulfuric acid and / or its salt thus produced can be isolated by operations such as concentration and crystallization, and the isolated S- (3-aminopropyl) The thiosulfuric acid and / or salt thereof usually contains about 0.1% to 5% of water.

  Next, examples of the compound represented by the formula (2) include S-3- (piperidin-1-yl) propylthiosulfuric acid, S-4- (piperidin-1-yl) butylthiosulfuric acid, S-5- (piperidine). -1-yl) pentylthiosulfuric acid, S-6- (piperidin-1-yl) hexylthiosulfuric acid, S-7- (piperidin-1-yl) heptylthiosulfuric acid, S-8- (piperidin-1-yl) octylthiosulfuric acid, S-10- (piperidin-1-yl) decylthiosulfuric acid, S-12- (piperidin-1-yl) dodecylthiosulfuric acid, S-3- (pyrrolidin-1-yl) propylthiosulfuric acid, S-4- (pyrrolidine-1 -Yl) butylthiosulfuric acid, S-5- (pyrrolidin-1-yl) pentylthiosulfuric acid, S-6- (pyrrolidin-1-yl) hexylthiosulfuric acid, S-7- (pyrrolidin-1- Le) heptylthio sulfate, S-8- (pyrrolidin-1-yl) octylthio sulfate, S-10- (pyrrolidin-1-yl) decylthio sulfuric acid, S-12-(pyrrolidin-1-yl) dodecylthio sulfate. Among them, S-3- (piperidin-1-yl) propylthiosulfate, S-3- (piperidin-1-yl) propylthiosulfate sodium, S-6- (piperidin-1-yl) hexylthiosulfate or S-6- ( Piperidin-1-yl) hexyl thiosulfate sodium is preferred, and S-3- (piperidin-1-yl) propyl thiosulfate sodium is particularly preferred.

The compound represented by the formula (2) can be produced, for example, by the method represented by the following formula.

In the formula, R and n are the same as in formula (2), and X ₁ and X ₂ each independently represent a chlorine atom, a bromine atom or an iodine atom.

  According to such a production method, a sodium salt is usually obtained, but a desired compound can be produced by cation exchange if necessary. The obtained compound usually contains about 0.1 to 5% by mass of water.

  Next, examples of the compound represented by the formula (3) include S- (4-aminophenyl) methylthiosulfuric acid, S- [2- (4-aminophenyl) ethyl] thiosulfuric acid, S- [3- ( 4-aminophenyl) propyl] thiosulfuric acid, S- [4- (4-aminophenyl) butyl] thiosulfuric acid, S- [5- (4-aminophenyl) pentyl] thiosulfuric acid, S- [6- (4- Aminophenyl) hexyl] thiosulfuric acid, S-2- (3-aminophenyl) methylthiosulfuric acid, S- [2- (3-aminophenyl) ethyl] thiosulfuric acid, S- [3- (3-aminophenyl) propyl] Thiosulfuric acid, S- [4- (3-aminophenyl) butyl] thiosulfuric acid, S- [5- (3-aminophenyl) pentyl] thiosulfuric acid, S- [6- (3-aminophenyl) hexyl] thiosulfuric acid , S- (2-aminopheny ) Methylthiosulfuric acid, S- [2- (2-aminophenyl) ethyl] thiosulfuric acid, S- [3- (2-aminophenyl) propyl] thiosulfuric acid, S- [4- (2-aminophenyl) butyl] thio Sulfuric acid, S- [5- (2-aminophenyl) pentyl] thiosulfuric acid, S- [6- (2-aminophenyl) hexyl] thiosulfuric acid, S- (3,5-diaminophenyl) methylthiosulfuric acid, S- ( 3,4-Diaminophenyl) methylthiosulfuric acid, S- [2- (3,5-diaminophenyl) ethyl] thiosulfuric acid, S- [2- (3,4-diaminophenyl) ethyl] thiosulfuric acid and the like. Among them, S- [2- (4-aminophenyl) ethyl] thiosulfuric acid and sodium S- [2- (4-aminophenyl) ethyl] thiosulfate are preferable, and S- [2- (4-aminophenyl) ethyl] Sodium thiosulfate is particularly preferred.

The compound represented by the formula (3) can be produced, for example, by the method represented by the following formula.

  In the formula, R and n are the same as in the above formula (3), and X independently represents a chlorine atom, a bromine atom or an iodine atom.

  According to such a production method, a sodium salt is usually obtained, but a desired compound can be produced by cation exchange if necessary. The obtained compound usually contains about 0.1 to 5% by mass of water.

  The blending amount of the thiosulfuric acid compound and / or salt thereof in the step (A) of the production method of the present invention is preferably 0.2 parts by mass or more (ie 0.2 phr or more) with respect to 100 parts by mass of the rubber component. 2-5 mass parts is more preferable. If it is less than 0.2 parts by mass, there is a risk that the intended improvement in physical properties such as wear resistance, tear strength and fatigue resistance may be insufficient.

  Anti-aging agents that can be used in the present invention are not particularly limited, and conventionally used anti-aging agents such as amine-ketone type, aromatic secondary amine type, phenol type, and imidazole type can be used as appropriate. . These anti-aging agents may be used alone or in combination of two or more.

  Specific examples of amine-ketone type (quinoline type) include 2,2,4-trimethyl-1,2-dihydroquinoline polymer (TMDQ), 6-ethoxy-2,2,4-trimethyl-1,2- And dihydroquinoline (ETMDQ).

  Specific examples of the aromatic secondary amine system include N-phenyl-1-naphthylamine (PAN), N-phenyl-2-naphthylamine (PBN), octylated diphenylamine (ODPA), 4,4′-bis- ( α, α′-dimethylbenzyl) diphenylamine (CD), N, N′-di-2-naphthyl-p-phenylenediamine (DNPD), N, N′-diphenyl-p-phenylenediamine (DPPD), N-isopropyl -N-phenyl-p-phenylenediamine (IPPD), N-phenyl-N '-(1,3-dimethylbutyl) -p-phenylenediamine (6C or 6PPD) and the like.

  Specific examples of phenolic antioxidants include 2,6-di-t-butyl-4-methylphenol (DTBMP), styrenated phenol (SP), 2,2′-methylene-bis- (4-methyl- 6-t-butylphenol) (MBMBP), 2,6-di-t-butyl-4-methylphenol (BHT), 2,2′-methylene-bis- (4-ethyl-6-t-butylphenol) (MBETB) ), 4,4′-butylidene-bis- (3-methyl-6-tert-butylphenol) (BBMTBP), and the like (ELIOKEM) which is a butylated condensate of ρ-cresol and dicyclopentadiene. Wingstay-L), a reaction product of 4-methylphenol and dicyclopentadiene (Lowinox CPL manufactured by Chemtura) Such as hindered phenol-based anti-aging agents it may also be mentioned.

  Specific examples of the imidazole anti-aging agent include 2-mercaptobenzimidazole (MBI), zinc salt of 2-mercaptobenzimidazole (ZnMBI), nickel salt of dibutyldithiocarbamate (NiDBC) and the like.

  Among these, aromatic secondary amines are preferable from the viewpoint of high anti-aging effect, and among them, N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine is particularly preferable.

  The amount of the anti-aging agent is appropriately selected depending on the type and purpose of use, and is not particularly limited, but is usually preferably 1 to 15 parts by weight, and 1 to 8 parts by weight per 100 parts by weight of the rubber component. Is more preferable.

  In the step (A), in addition to the above carbon black and / or inorganic filler, amino group-containing thiosulfuric acid compound and anti-aging agent, it is usually used for the production of zinc oxide, stearic acid, oil and other tire rubber members. Other ingredients and additives can be blended. The timing of addition of these other components and additives is not particularly limited, and may be at the time of mixing carbon black and / or an inorganic filler and a thiosulfate compound, at the same time as the addition of the anti-aging agent, or otherwise. These compounding amounts are not limited, and are appropriately adjusted depending on the purpose of use of the tire member. Usually, the amount of zinc oxide used is within a range of 1 to 15 parts by mass per 100 parts by mass of the rubber component. It is preferable that it is within a range of 3 to 8 parts by mass. Moreover, it is preferable that the usage-amount of a stearic acid exists in the range of 0.5-10 mass parts per 100 mass parts of rubber components, and it is more preferable that it exists in the range of 1-5 mass parts.

  The mixing of the rubber component, carbon black and / or inorganic filler, thiosulfuric acid compound and / or salt thereof, and the subsequent anti-aging agent in the step (A) is an operation generally referred to as “kneading”. For example, it can be performed using a known mixing device such as a Banbury mixer, which includes at least a stirring rotor, a jacket through which a heating and cooling medium flows, and a pressure ram. The heating / cooling medium is heated as necessary to reach a desired temperature, flows through the jacket, and heats or cools the mixture by heat transfer on the wall surface of the mixing container. As the heating / cooling medium, water is usually used. The pressurizing ram is moved up and down in the cylinder to adjust the pressure inside the mixer. It is preferable that the mixing device further includes a temperature sensor that detects the temperature of the mixture in the device and a control unit that controls the rotational speed of the rotor.

  The addition and mixing of the anti-aging agent is preferably performed after the temperature of the mixture of the rubber component, carbon black and / or inorganic filler, and the thiosulfuric acid compound containing an amino group reaches 140 ° C. It is more preferable to carry out after mixing while maintaining the temperature of the mixture at 140 ° C. or higher for 1 minute or longer. As for the temperature of the mixture at the time of adding the said anti-aging agent, 150 degreeC or more is more preferable, and 150-170 degreeC is especially preferable. The mixing time while maintaining the temperature at 140 ° C. or higher is more preferably 2 minutes or longer, and particularly preferably 2 to 6 minutes. The specific method of adjusting the temperature is not particularly limited, and can be performed by known means such as adjusting the temperature of the heating / cooling medium and controlling the rotational speed of the rotor. Control can be easily and reliably performed by automatically controlling by PID (Proportional Integral Differential) control.

  Although the temperature and mixing time of the mixture in the step (A) after adding the anti-aging agent are not particularly limited, it is usually 145 to 170 ° C, about 2 to 8 minutes, and 170 ° C or less. It is preferable to discharge.

  Next, the (B) process which mixes the mixture obtained by the said (A) process, a sulfur component, and a vulcanization accelerator is demonstrated.

  Examples of the sulfur component include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur. Usually, powdered sulfur is preferred, and insoluble sulfur is preferred when used for tire members having a large amount of sulfur such as belt members. In addition, the thiosulfuric acid compound represented by said formula (1)-(3) and its salt shall not be contained in the sulfur component as used in this specification. The amount of sulfur component used is preferably in the range of 0.3 to 5 parts by mass, more preferably in the range of 0.5 to 3 parts by mass, per 100 parts by mass of the rubber component.

  The vulcanization accelerator is not particularly limited, and examples thereof include thiazole vulcanization accelerators, sulfenamide vulcanization accelerators, and guanidine vulcanization accelerators.

  The ratio of the sulfur component to the vulcanization accelerator is not particularly limited, but is preferably in the range of sulfur component / vulcanization accelerator = 2/1 to 1/2 by mass ratio. In addition, the so-called EV vulcanization, in which the ratio of sulfur / vulcanization accelerator, which is a method for improving heat resistance in rubber components mainly composed of natural rubber, is 1 or less is used in applications where heat resistance improvement is particularly required. It is preferably used in the invention.

  Mixing of the kneaded product obtained in step (A), the sulfur component, and the vulcanization accelerator in step (B) is also an operation generally referred to as kneading. For example, kneading such as an open roll or a Banbury mixer. It can carry out according to a conventional method using an apparatus.

  The kneading time in this step (B) is usually preferably 1 to 10 minutes, more preferably 2 to 8 minutes. If the kneading time is 1 minute or more, the dispersibility of the sulfur component or the vulcanization accelerator in the rubber component tends to be improved, and if it is 10 minutes or less, the deterioration of the rubber component tends to be suppressed. In the point which improves the viscoelastic property of the vulcanized rubber finally obtained, it is preferable, respectively.

  The mixture obtained as described above is subjected to a heat treatment generally called vulcanization. The heat treatment is performed under normal pressure or under pressure, and the treatment temperature is usually about 120 ° C to 180 ° C.

  The tire member of the present invention obtained as described above is suitably used as a tread member such as a cap tread or a base tread of various tires or a sidewall member because the wear resistance, tear strength, fatigue resistance, etc. are improved in a balanced manner. be able to.

  Specifically, the mixture is extruded into a predetermined cross-sectional shape corresponding to a target tire member such as a tread member or a sidewall member, or a ribbon-like rubber strip is formed from the mixture and spiraled on a drum. The tire member is obtained by turning into a shape and forming a cross-sectional shape corresponding to the target tire member. The tire of the present invention is obtained by vulcanizing and molding such a tire member together with other tire members constituting the tire such as an inner liner, a carcass, a belt, a bead core, and a bead filler according to a conventional method.

  Examples of the present invention will be described below, but the present invention is not limited to these examples. The blending ratios shown below are based on mass (“parts by mass”, “mass%”, etc.) unless otherwise specified. Moreover, the manufacturing method of the thiosulfuric acid compound containing the amino group used in the following Examples and Comparative Examples is as follows.

[Production of S- (3-aminopropyl) thiosulfuric acid sodium salt]
The reaction vessel was purged with nitrogen, and 25 g (0.11 mol) of 3-bromopropylamine bromate, 28.42 g (0.11 mol) of sodium thiosulfate pentahydrate, 125 ml of methanol and 125 ml of water were placed in the reaction vessel. The resulting mixture was refluxed at 70 ° C. for 4.5 hours.

  The reaction mixture was allowed to cool and methanol was removed under reduced pressure. To the reaction mixture from which methanol had been removed, 4.56 g of sodium hydroxide was added and stirred at room temperature for 30 minutes. Thereafter, sodium bromide as a by-product was removed by hot filtration. The filtrate was concentrated under reduced pressure until crystals precipitated, and then allowed to stand. The crystals were collected by filtration and washed with ethanol and hexane, and the crystals obtained were dried under vacuum to obtain sodium salt of S- (3-aminopropyl) thiosulfuric acid.

[Manufacture of tire tread members]
In accordance with the blending A to E shown in Table 1 below, the components in the step (A) of the blending shown in the following Table 2 are introduced into the Banbury mixer by the following mixing method and mixed, and then (B) of each blending After adding and mixing the vulcanization accelerator and sulfur in the process, vulcanization was performed by heating at 150 ° C. for 30 minutes to obtain a tire tread member. The results are shown in Table 2.

[Manufacture of side wall members]
In accordance with the formulas F to H shown in Table 1 below, the components in the step (A) of the formula shown in the following Table 3 are introduced into the Banbury mixer by the following mixing method and mixed, and then (B) of each formula After adding and mixing the vulcanization accelerator and sulfur in the process, vulcanization was performed by heating at 150 ° C. for 30 minutes to obtain a sidewall member. The results are shown in Table 3.

Details of each formulation shown in Table 1 are as follows.
Natural rubber: RSS # 3
BR: BR150L manufactured by Ube Industries, Ltd.
Carbon Black A: Toast Carbon Co., Ltd. Seast 7HM (N234)
Carbon Black B: Toast Carbon Co., Ltd. Seast KH (N339)
Silica: NIPSEAL AQ manufactured by Tosoh Silica Industry Co., Ltd.
Silane coupling agent: Si75 manufactured by Evonik Degussa
Process oil: JOMO process P200 manufactured by Japan Energy Co., Ltd.
Zinc oxide: manufactured by Mitsui Mining & Smelting Co., Ltd. Zinc flower Stearic acid: manufactured by NOF Corporation Anti-aging agent: manufactured by Sumitomo Chemical Co., Ltd. Antigen 6C
Sulfur: Tsurumi Chemical Co., Ltd. Powdered sulfur Vulcanization accelerator: Sanshin Chemical Industry Co., Ltd. TBBS

Details of the mixing methods [1] to [3] shown in Tables 2 and 3 are as follows.
Mixing method [1]: After the rubber component was added, all the components in step (A) of each formulation shown in Table 1 were added together, mixed, and discharged at 160 ° C.
Mixing method [2]: After charging the rubber component, all components other than the anti-aging agent in step (A) of each formulation shown in Table 1 were added together, mixed, and discharged at 160 ° C. (An anti-aging agent was mixed with sulfur and an accelerator in the step (B).)
Mixing method [3]: After adding the rubber component, S- (3-aminopropyl) thiosulfuric acid and carbon black and / or inorganic filler of each formulation shown in Table 1 are added, and the mixture is used using PID control. The mixture was mixed for 1 minute while maintaining the temperature at 140 ° C., then all the remaining components in step (A) were added, mixed for 2 minutes, and discharged at 160 ° C.

The details of the evaluation methods of wear resistance, bending fatigue resistance and viscosity (workability) are as follows.
Abrasion resistance performance: Based on JIS K6264, the slip rate was 30%, the applied load was 40 N, and the amount of falling sand was 20 g / min. The results are shown as an index with the value of Comparative Example 1 as 100. Larger values indicate better wear resistance.

  Bending fatigue resistance: A bending crack growth test was conducted in accordance with JIS K6260 (Demach bending crack test). The measurement was performed under the condition of a temperature of 23 ° C., and the number of times until the crack growth reached 2 mm was obtained. An index with Comparative Example 1 as 100 is shown. The larger the value, the better the fatigue resistance.

Workability (viscosity): Based on JIS K6300, ML (1 + 4) was determined under the conditions of a preheating time of 1 minute, a rotor operating time of 4 minutes, and a measurement temperature of 100 ° C. It shows with. A smaller value indicates better workability.

  From the results shown in Tables 2 and 3, it can be seen that in the production methods of the examples of the present invention, wear resistance is improved without any deterioration in fatigue resistance and workability. On the other hand, in Comparative Examples 3 and 7 in which an anti-aging agent was added simultaneously with carbon black and / or an inorganic filler, a thiosulfate compound, etc., the degree of improvement in wear resistance performance was low, and the anti-aging agent was added in step (B) In Comparative Examples 4 and 8 added in Step 1, it is recognized that the fatigue resistance is lowered.

  The tire member obtained by the manufacturing method of the tire member of the invention can be used for various tires such as radial tires for passenger cars and heavy load tires such as trucks and buses.

Claims (6)

At least a rubber component, carbon black and / or an inorganic filler, and a thiosulfuric acid compound containing an amino group are mixed (A), the mixture obtained by the step (A), a sulfur component, A method for producing a tire member comprising a step (B) of mixing a sulfur accelerator,
In the step (A), a rubber component, carbon black and / or an inorganic filler, and a thiosulfuric acid compound containing an amino group are first mixed, and an anti-aging agent is added to the mixture and further mixed. A method for manufacturing a tire member, which is characterized.   After the temperature of the mixture of the rubber component, carbon black and / or inorganic filler, and thiosulfuric acid compound containing an amino group reaches 140 ° C., the anti-aging agent is added and further mixed. The method for manufacturing a tire member according to claim 1.   After mixing the rubber component, carbon black and / or inorganic filler, and thiosulfuric acid compound containing amino group while maintaining the temperature at 140 ° C. or higher for 1 minute or longer, add the anti-aging agent. The method for manufacturing a tire member according to claim 2, further mixing. The thiosulfuric acid compound containing an amino group is one or more of thiosulfuric acid compounds represented by any of the following formulas (1) to (3) and salts thereof: The manufacturing method of the tire member of any one of Claims 1-3.

In Formula (1), n shows the integer of 2-9.

In the formula (2), R represents an alkanediyl group having 3 to 12 carbon atoms, and n represents an integer of 2 to 5.

In the formula (3), R represents an alkanediyl group having 1 to 6 carbon atoms, and n represents an integer of 1 to 2.   A tire tread member or a sidewall member is manufactured, The tire member manufacturing method according to any one of claims 1 to 4 characterized by things. The tire manufacturing method which manufactures a tire member by the manufacturing method of the tire member of any one of Claims 1-5, and manufactures a tire using this tire member.