JP2015028165A - Vulcanization accelerator, rubber composition, and tire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vulcanization accelerator synthesized from biomass including a plant resource, a rubber composition having the vulcanization accelerator blended therein, and a tire made using the rubber composition.SOLUTION: The vulcanization accelerator is a vulcanization accelerator synthesized from biomass including a plant resource. The value of δ13C of the vulcanization accelerator is -30 per mil to -27.0 per mil, or -22 per mil or more.

Description

  The present invention relates to a vulcanization accelerator synthesized from biological resources including plant resources, a rubber composition containing the vulcanization accelerator, and a tire using the rubber composition.

In recent years, methods for refining fuel oil from bio-derived renewable resources (so-called biomass) including plant resources have been proposed due to increasing demands for reducing fossil resource consumption and greenhouse gas emissions. (See Patent Document 1). Such a fuel oil is called a biofuel, and since it does not increase the total amount of carbon dioxide emission, it is expected in the future as a substitute for a fuel oil derived from fossil resources.
Many compounds derived from fossil resources have been used not only in the field of fuel oil, but also in fields such as household appliances, household goods, and automobiles, but in the same way as fuel oil, in order to reduce dependence on fossil resources, There is a need for a method of making compounds from biomass as an alternative to compounds whose resources are starting materials. As an example, also in the field of automobiles, a method for producing a compound as a tire material from biomass is required.

JP 2009-046661 A

  An object of the present invention is to provide a vulcanization accelerator synthesized from biological resources including plant resources, a rubber composition containing the vulcanization accelerator, and a tire using the rubber composition.

The present invention
[1] A vulcanization accelerator synthesized from biological resources including plant resources, and the value of δ13C of the vulcanization accelerator is −30 ‰ to −27.0 ‰, or −22 ‰ or more. Vulcanization accelerator,
[2] The vulcanization accelerator according to [1], wherein the value of δ13C is −28.5 ‰ to −27.5 ‰.
[3] The vulcanization accelerator according to [1] or [2], wherein the vulcanization accelerator is synthesized using biomethane obtained from biological resources including plant resources as a starting material,
[4] The vulcanization accelerator according to any one of [1] to [3], wherein the vulcanization accelerator is synthesized using biobenzene obtained from a biological resource including a plant resource as a starting material,
[5] The vulcanization accelerator according to any one of the above [1] to [4], wherein the vulcanization accelerator is a thiazole compound and a sulfenamide compound,
[6] Any of the above [1] to [5], wherein the vulcanization accelerator is 2-mercaptobenzothiazole, dibenzothiazyl disulfide, or N-cyclohexyl-2-benzothiazolylsulfenamide. Vulcanization accelerator according to
[7] A rubber composition containing the vulcanization accelerator according to any one of [1] to [6] above,
[8] A tire containing the rubber composition according to [7] above,
I will provide a.

  According to the present invention, a vulcanization accelerator synthesized from biological resources including plant resources, a rubber composition containing the vulcanization accelerator, and a tire using the rubber composition are provided. it can.

It is explanatory drawing explaining the method to synthesize | combine a vulcanization accelerator from the biological origin resources containing a plant resource.

Hereinafter, the vulcanization accelerator according to the embodiment of the present invention will be described in detail.
[Vulcanization accelerator]
The vulcanization accelerator according to the embodiment of the present invention is a vulcanization accelerator synthesized from biological resources including plant resources, and the value of δ13C of the vulcanization accelerator is −30 ‰ to −27.0. ‰ or -22 ‰ or more. Here, the value of δ13C of the vulcanization accelerator is measured by a stable isotope ratio measuring device.

δ13C represents the ratio of stable isotopes in the substance. δ13C is the ratio of ¹³ C to ¹² C in the target substance, and ¹³ C / ¹² C is compared to the isotope ratio in the standard sample (fossil of Cretaceous belemnite). This is an index indicating how much the deviation is, and this ratio is represented by ‰ (percentage). It means that the ratio of ¹³ C in a substance is so low that the value (negative value) of (delta) ^13C leaves | separates from zero.
Light isotopes are more diffusive and more reactive than heavy isotopes. For example, in the case of carbon atoms of carbon dioxide in the atmosphere taken into plants by photosynthesis, ¹² C is better than ¹³ C. It has been found that it is easily fixed in plants.
That is, the carbon atoms taken into the plant body have a relatively large amount of ¹² C and a smaller amount of ¹³ C than carbon atoms in the atmosphere. Therefore, the stable isotope ratio (δ13C) of carbon taken into the plant body is lower than the stable isotope ratio of carbon existing in the atmosphere.
This change in isotope ratio is called isotope fractionation and is represented by Δ13C (Δ13C is distinguished from δ13C).
Δ13C = (δ13C in the atmosphere) − (δ13C in the sample)
Therefore, the vulcanization accelerator-derived substance can be identified from the value of δ13C of the vulcanization accelerator.

  The value of δ13C of the vulcanization accelerator is preferably in the range of −21 ‰ to −12 ‰. Further, the value of δ13C of the vulcanization accelerator is more preferably in the range of −29.5 ‰ to −27.0 ‰. The value of δ13C of the vulcanization accelerator is more preferably in the range of −28.5 ‰ to −27.0 ‰.

Hereinafter, a vulcanization accelerator synthesized from biological resources including plant resources will be referred to as a bio-derived vulcanization accelerator. The bio-derived vulcanization accelerator is preferably a thiazole compound and a sulfenamide compound having a value of δ13C satisfying the above range. Furthermore, the bio-derived vulcanization accelerator is selected from 2-mercaptobenzothiazole, dibenzothiazyl disulfide, and N-cyclohexyl-2-benzothiazolylsulfenamide synthesized from biological resources including plant resources. At least one is preferred.
The content of the bio-derived vulcanization accelerator with respect to the total mass of the vulcanization accelerator is preferably 10 to 100% by mass.

[Method of synthesizing bio-derived vulcanization accelerator]
<Synthesis method>
The bio-derived vulcanization accelerator can be synthesized using methane obtained from biological resources including plant resources (hereinafter referred to as biomethane) as a starting material. The bio-derived vulcanization accelerator can be synthesized using benzene obtained from biological resources including plant resources (hereinafter referred to as biobenzene) as a starting material.
Hereinafter, a method for synthesizing a bio-derived vulcanization accelerator using biomethane and biobenzene as starting materials will be described with reference to FIG. FIG. 1 is an explanatory diagram for explaining a method of synthesizing a vulcanization accelerator from a biological resource including a plant resource.

(Biomass → Biomethane: Methane fermentation)
First, biomethane is synthesized from biomass by methane fermentation.
Examples of biological resources that can be used as raw materials for biobenzene include waste biomass such as food waste, food waste, livestock waste, sludge, and vegetation waste. It is known that biogas (methane gas / carbon dioxide = 60/40, including a trace amount of hydrogen sulfide) can be obtained by decomposing these organic substances by microorganisms. By purifying biogas, high-purity methane gas can be obtained.

(Biomethane → Biobenzene: Mo / ZSM-5 catalyst)
Next, biobenzene is synthesized from biomethane. A methane conversion rate of 6-12% was reported in a flow-through fixed bed reactor using a 6% Mo / ZSM-5 catalyst at 750 ° C., 3 atm (Patent No. 3755955, Patent No. 3755968, Patent No. 3745885 and Japanese Patent No. 3835765).

(Biobenzene → Mercaptobenzothiazole group vulcanization accelerator)
Vulcanization accelerators such as thiazole compounds and sulfenamide compounds from waste biomass according to the same route as the route for synthesizing vulcanization accelerators having an ordinary mercaptobenzothiazole group skeleton from benzene (from ordinary petroleum) Can be synthesized. Specifically, as shown in FIG. 1, M (MBT, 2-mercaptobenzothiazole), DM (MBTS (dibenzothiazyl disulfide)), CZ (CBS (N-cyclohexyl-2-benzothiazolylsulfenamide) At least one selected from)) can be synthesized.
For other vulcanization accelerators, bio-derived vulcanization accelerators can be synthesized by using known synthesis methods starting from biomethane synthesized from biomass and biobenzene synthesized from biomethane. .
Here, a part of the raw material used in the process of synthesizing the bio-derived vulcanization accelerator may be a fossil resource-derived resource or a biological resource including a plant resource. Further, the raw material may be a mixture of a fossil resource-derived raw material and a biological-derived raw material including a plant resource.

[Rubber composition]
The rubber composition according to the embodiment of the present invention is blended with the bio-derived vulcanization accelerator of the present invention. The rubber composition further contains a rubber component, an inorganic filler, carbon black, and other additives. The rubber composition only needs to use a bio-derived vulcanization accelerator, and components other than the vulcanization accelerator can be appropriately selected according to the purpose.

<Rubber component>
There is no restriction | limiting in particular in the rubber component which can be mix | blended with the rubber composition of this invention, According to the objective, it can select suitably.
Examples of the rubber component include butadiene polymer, natural rubber, epoxidized natural rubber, various butadiene rubbers, various styrene-butadiene copolymer rubbers, isoprene rubber, butyl rubber, bromide of a copolymer of isobutylene and p-methylstyrene, Halogenated butyl rubber, acrylonitrile butadiene rubber, chloroprene rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, isoprene -Butadiene copolymer rubber, chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, polysulfide rubber, silicone rubber, fluorine rubber, urethane rubber and the like. These may be used individually by 1 type and may use 2 or more types together.

<Rubber component derived from biomass>
The rubber component that can be blended in the rubber composition of the present invention is preferably a rubber component synthesized from biological resources including plant resources.
(Bio-butadiene rubber)
An example of a rubber component synthesized from biological resources including plant resources is biobutadiene rubber. Biobutadiene rubber is produced from a biobutadiene monomer obtained by synthesizing bioethanol synthesized from biological resources including plant resources using a starting material.
A bioethanol produced from biomass is brought into contact with a composite metal oxide containing at least magnesium and silicon as metal elements under heating to produce a mixture containing a biobutadiene monomer component. A biobutadiene monomer component is extracted from this mixture, and a butadiene polymer is produced using the extracted biobutadiene monomer component.

  The method for producing the butadiene polymer is not particularly limited, and any of solution polymerization method, gas phase polymerization method, and bulk polymerization method can be used. Among these, the solution polymerization method is preferable. Moreover, any of a batch type and a continuous type may be sufficient as the superposition | polymerization form. As a polymerization method, any of an anionic polymerization method using an organometallic compound as a polymerization initiator and a coordination polymerization method using a rare earth metal compound as a polymerization initiator can be used.

The butadiene polymer may be a copolymer synthesized from a biobutadiene monomer and a monomer copolymerizable with the biobutadiene monomer. Examples of monomers copolymerizable with the biobutadiene monomer include conjugated diene compounds and aromatic vinyl compounds. Examples of the conjugated diene compound include 1,3-pentadiene, 2,3-dimethylbutadiene, 2-phenyl-1,3-butadiene, 1,3-hexadiene and the like. In this embodiment, isoprene is excluded from the conjugated diene compound copolymerizable with the biobutadiene monomer.
Examples of the aromatic vinyl compound include styrene, p-methylstyrene, m-methylstyrene, p-tert-butylstyrene, α-methylstyrene, chloromethylstyrene, vinyltoluene and the like.
The monomer copolymerizable with the biobutadiene monomer may be either one synthesized from biological resources including plant resources or one derived from petrochemicals. Moreover, the normal butadiene monomer which is not derived from bioethanol may be contained in a predetermined amount.

<Reinforcing filler>
A reinforcing filler can be blended in the rubber composition as necessary. Examples of the reinforcing filler include carbon black and inorganic filler, and at least one selected from carbon black and inorganic filler is preferable.
There is no restriction | limiting in particular in an inorganic filler, According to the objective, it can select suitably. Examples of inorganic fillers include silica, aluminum hydroxide, clay, alumina, talc, mica, kaolin, glass balloon, glass beads, calcium carbonate, magnesium carbonate, magnesium hydroxide, calcium carbonate, magnesium oxide, titanium oxide, and titanium. Examples include potassium acid and barium sulfate. These may be used individually by 1 type and may use 2 or more types together. In addition, when using an inorganic filler, you may use a silane coupling agent suitably.
There is no restriction | limiting in particular in content of a reinforcing filler, According to the objective, it can select suitably. The reinforcing filler is preferably contained in an amount of 5 to 200 parts by mass with respect to 100 parts by mass of the rubber component.
The effect which reinforces a rubber composition as content of a reinforcing filler is 5 mass parts or more is acquired. A rubber component and a reinforcing filler can be mixed as it is 200 mass parts or less, and the performance as a rubber composition can be improved.

<Other additives>
Other additives include conventional vulcanization accelerators other than bio-derived vulcanization accelerators. As conventional vulcanization accelerators, compounds such as guanidine, aldehyde-amine, aldehyde-ammonia, thiazole, sulfenamide, thiourea, thiuram, dithiocarbamate, and xanthate can be used.
If necessary, reinforcing agents, softeners, fillers, vulcanization aids, colorants, flame retardants, lubricants, foaming agents, plasticizers, processing aids, antioxidants, anti-aging agents, anti-scorch agents Well-known substances such as ultraviolet ray inhibitors, antistatic agents, anti-coloring agents, and other compounding agents can be used depending on the intended use. Other additives may also be synthesized from biological resources including plant resources.

[Crosslinked rubber composition]
The rubber composition of the present invention may contain a crosslinking agent in addition to the vulcanization accelerator, rubber component, inorganic filler, carbon black, and other additives of the present invention. A rubber composition containing a cross-linking agent can form a cross-linked cross-linked rubber composition.

<Crosslinking agent>
There is no restriction | limiting in particular in the crosslinking agent which can be used for preparation of a crosslinked rubber composition, According to the objective, it can select suitably. For example, sulfur crosslinking agent, organic peroxide crosslinking agent, inorganic crosslinking agent, polyamine crosslinking agent, resin crosslinking agent, sulfur compound crosslinking agent, oxime-nitrosamine crosslinking agent sulfur and the like can be mentioned. Among these, in the case of a rubber composition for tires, it is preferable to use a sulfur-based crosslinking agent.
There is no restriction | limiting in particular in content of a crosslinking agent, According to the objective, it can select suitably. The crosslinking agent is preferably contained in an amount of 0.1 to 20 parts by mass with respect to 100 parts by mass of the rubber component.
If content of a crosslinking agent is 0.1 mass part or more, it can bridge | crosslink so that a predetermined effect may be acquired. If it is 20 mass parts or less, it can prevent that a bridge | crosslinking advances during kneading | mixing, and will not impair the physical property of a vulcanizate.

[tire]
The tire of the present invention includes the rubber composition or the crosslinked rubber composition of the present invention. In the tire of the present invention, components other than the rubber composition or the crosslinked rubber composition can be appropriately selected depending on the purpose.
Examples of the application site of the rubber composition or crosslinked rubber composition of the present invention in a tire include treads, base treads, sidewalls, side reinforcing rubbers, and bead fillers. The application site is not limited to these.
The tire of the present invention can be manufactured using a conventional method. For example, on a tire molding drum, members usually used for manufacturing a tire such as a carcass layer, a belt layer, and a tread layer made of unvulcanized rubber are sequentially laminated, and the drum is removed to obtain a green tire. Next, the desired tire can be manufactured by heat vulcanizing the green tire according to a conventional method.

[Applications other than tires]
In addition to tire applications, the rubber composition of the present invention or the crosslinked rubber composition of the present invention may be used for anti-vibration rubber, seismic isolation rubber, belts (conveyor belts), rubber crawlers, various hoses, Moran and the like. it can.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
[Evaluation method]
<Measurement of δ13C>
The value of δ13C of the bio-derived vulcanization accelerator produced from biomethane was measured with a stable isotope ratio measuring device.
<Evaluation of vulcanization speed>
As for the vulcanization rate, the value of 155 ° C. and Tc (90) was measured by the method specified in JIS K6300-2: 2001. For the measurement, “Charast meter W type” manufactured by Nichigo Corporation was used, and it was expressed as an index with the vulcanized rubber of the comparative example as 100.
<Evaluation of 300% elongation tensile stress>
The 300% elongation tensile stress was determined in accordance with JIS K 6251. The 300% elongation tensile stress was expressed as an index with the vulcanized rubber of the comparative example as 100.

[Biobutadiene polymer]
As the butadiene polymer as the rubber component, a biobutadiene polymer obtained by polymerizing a biobutadiene monomer synthesized from a bio-derived renewable resource (biomass) including plant resources was used.
<Manufacture of biobutadiene polymer>
(Manufacture of catalyst)
A silica-magnesia composite oxide synthesized by a sol-gel method was used as a catalyst. The manufacturing method of this catalyst is as follows. First, Mg (OH) ₂ gel was synthesized by dropping 100 mL of a 14% aqueous ammonia solution into a solution of Mg (NO ₃ ) ₂ .6H ₂ O (64 g) dissolved in 100 mL of distilled water. On the other hand, Si (OH) ₄ gel was synthesized by dropping 12.5 mL of 1.38 M nitric acid and 50 mL of 14% aqueous ammonia into a solution of Si (OC ₂ H ₅ ) ₄ (55 mL) dissolved in 150 mL of ethanol. The obtained Mg (OH) ₂ gel was subjected to suction filtration after washing with distilled water, and the Si (OH) ₄ gel was subjected to suction filtration after washing with ethanol. These two kinds of gels were mixed, and the mixed gel was air-dried, then dried at 80 ° C., 500 ° C., and calcined in an N ₂ atmosphere to produce a silica-magnesia composite oxide catalyst.

(Production of biobutadiene monomer)
Bioethanol obtained by fermenting sugarcane, tapioca and corn starches with yeast was used as a starting material.
A biobutadiene monomer was produced by contacting the catalyst produced by the above method with the bioethanol.
As the reaction apparatus, a fixed bed gas flow type catalytic reaction apparatus was used. The manufactured silica-magnesia composite oxide catalyst was filled in a quartz reaction tube, and was subjected to heat treatment at 500 ° C. for 2 hours in a carrier gas atmosphere (N ₂ ; gas flow rate 66 mL / min) as a pretreatment.
After completion of the pretreatment, the temperature of the catalyst tube was lowered to the reaction temperature, and bioethanol gas diluted with N ₂ was introduced. The reaction temperature was 350 ° C. or 450 ° C.
The mixture containing the biobutadiene monomer was recovered by performing the following separation operation on the gas generated by the reaction. First, the product gas was bubbled into hexane, so that the target biobutadiene monomer was dissolved in the solvent. The recovered butadiene solution was purified by drying to further remove impurities such as ethanol, acetaldehyde, diethyl ether, ethoxyethylene, and ethyl acetate.

(Production of biobutadiene polymer)
A nitrogen-substituted 5 L autoclave was charged with a monomer solution in which 2.4 kg of cyclohexane and 300 g of a biobutadiene monomer produced based on the above production example of a biobutadiene monomer were dissolved in a nitrogen atmosphere. To the autoclave, as catalyst components, a cyclohexane solution of neodymium versatate (0.09 mmol), a toluene solution of methylaluminoxane (MAO, 3.6 mmol), diisobutylaluminum hydride (DIBAH, 5.5 mmol) and diethylaluminum chloride (0. (18 mmol) in toluene and 1,3-butadiene (4.5 mmol) were aged at 40 ° C. for 30 minutes, and a pre-prepared catalyst composition was charged, followed by polymerization at 60 ° C. for 60 minutes. 200 g of this polymer solution was extracted into a methanol solution containing 0.2 g of 2,4-di-tert-butyl-p-cresol, and after the polymerization was stopped, the solvent was removed by steam stripping and dried with a roll at 110 ° C. To obtain a biobutadiene polymer.

[Manufacture of bio-derived vulcanization accelerator]
<Production Example 1>
Biomass (methane gas / carbon dioxide = 60/40) was obtained from biomass such as food waste, food waste, livestock waste, sludge, and vegetation waste by decomposing these biomass with microorganisms. Next, the obtained biogas was purified to obtain high-purity methane gas.
Next, biobenzene was synthesized from biomethane using a 6% Mo / ZSM-5 catalyst at 750 ° C. and 3 atm using a flow-through fixed bed reactor. Next, according to a conventional method, biobenzene was reacted with concentrated nitric acid in the presence of concentrated sulfuric acid to synthesize nitrobenzene, and nitrobenzene was reduced with iron powder and nitric acid to synthesize aniline. DM (MBTS (dibenzothiazyl disulfide)) of vulcanization accelerator B was obtained from 2-mercaptobenzothiazole obtained by reacting the obtained aniline with carbon disulfide synthesized using petroleum as a starting material.

<Production Example 2>
In Production Example 1, the obtained aniline was reacted with carbon disulfide synthesized using charcoal as a starting material, except that vulcanization accelerator C DM (MBTS (dibenzothia Zil disulfide)) was obtained. The method for producing carbon disulfide from charcoal is as follows.
(1) Charcoal is heated to bright red and charged into the reactor.
(2) The molten sulfur is introduced from the lower part of the reactor and heated to 850 to 950 ° C.
(3) The vaporized sulfur reacts with the upper charcoal to obtain crude carbon disulfide. The crude carbon disulfide is obtained as a gas from the top of the reactor. Crude carbon disulfide includes unreacted sulfur and hydrogen sulfide.
(4) The crude carbon disulfide is distilled so that the sulfur content is 5 / 100,000 or less.
(5) The reaction furnace includes a method using a cast iron retort (referred to as a retort method), a method using an electric furnace made of a refractory brick (electric arc type or resistor heating type), and the like. Further, a gas method in which methane gas and sulfur vapor are reacted may be used. The retort method was applied this time.

[Examples 1 and 3 and Comparative Example 1]
A rubber composition was prepared according to the formulation shown in Table 1, and vulcanized at 145 ° C for 33 minutes to obtain a vulcanized rubber. In Examples 1 and 3, the above-mentioned biobutadiene polymer was used as a rubber component, and in Comparative Example 1, a conventional butadiene rubber was used.
Vulcanization accelerators B and C are produced from biological resources including plant resources by the above production method.
The vulcanization accelerator A used in Comparative Example 1 is derived from petroleum resources and is a vulcanization accelerator DM (di-2-benzothiazolyl disulfide, manufactured by Ouchi Shinsei Chemical Co., Ltd., Noxeller DM). . For each vulcanized rubber obtained in Examples 1 and 3 and Comparative Example 1, the vulcanization rate and 300% elongation tensile stress were measured and evaluated. The results are shown in Table 2.

* 1: Nitrogen adsorption specific surface area: 42 m ² / g, manufactured by Tokai Carbon Co., Ltd., Seast F
* 2: Microcrystalline wax, manufactured by Nippon Seiwa Co., Ltd., Ozoace 0701
* 3: N- (1,3-dimethylbutyl) -N′-p-phenylenediamine, manufactured by Ouchi Shinsei Chemical Co., Ltd., NOCRACK 6C
* 4: Vulcanization accelerator DPG: Nouchira D manufactured by Ouchi Shinsei Chemical Co., Ltd.
* 5: Vulcanization accelerator CBS: Sunseller CM-G, manufactured by Sanshin Chemical Industry Co., Ltd.

From Table 2, the value of δ13C of the vulcanization accelerator B compounded in Example 1 is −29 ‰, and the value of δ13C of the vulcanization accelerator C compounded in Example 3 is −28 ‰. It was. Further, the value of δ13C of the vulcanization accelerator A blended in Comparative Example 1 was −23 ‰.
From Table 2, the vulcanization rate and 300% elongation tensile stress of the vulcanized rubber obtained by vulcanizing the rubber composition having the biobutadiene rubber of Example 1 and 3 and the bio-derived vulcanization accelerator are shown. The index is comparable to the index of vulcanization speed and 300% elongation tensile stress of vulcanized rubber obtained by vulcanizing a rubber composition having a petroleum-derived butadiene rubber and a vulcanization accelerator in Comparative Example 1. The value of was shown.
From this, the vulcanized rubber compounded with the vulcanization accelerator synthesized from biological resources including plant resources was formulated with the vulcanization accelerator derived from petroleum resources at vulcanization speed and 300% elongation tensile stress. It was found that it is not inferior to conventional vulcanized rubber.

[Examples 2 and 4 and Comparative Example 2]
Examples 2 and 4 and Comparative Example 2 were prepared by preparing a rubber composition according to the formulation shown in Table 3 (using styrene-butadiene copolymer rubber (SBR) as a rubber component) and vulcanizing at 145 ° C. for 33 minutes. A vulcanized rubber was obtained.
Of the vulcanization accelerator DPG, the vulcanization accelerator DM, and the vulcanization accelerator NS blended in Examples 2 and 4, the vulcanization accelerator DM is the vulcanization accelerator produced in the above Production Examples 1 and 2. Agents B and C. On the other hand, the vulcanization accelerator DPG (1,3-diphenylguanidine, manufactured by Ouchi Shinsei Chemical Co., Ltd., Noxeller D) blended in Comparative Example 2 and the vulcanization accelerator DM (di-2-benzothiazolyl disulfide, Ouchi Shinsei Chemical Co., Ltd., Noxeller DM) and vulcanization accelerator NS (Nt-butyl-2-benzothiazylsulfenamide) are derived from petroleum resources.
For each vulcanized rubber obtained in Examples 2 and 4 and Comparative Example 2, the vulcanization rate and 300% elongation tensile stress were measured and evaluated. The results are shown in Table 4.

* 6: JSR, # 1500
* 7: Nitrogen adsorption specific surface area: 93 m ² / g, Tokai Carbon Co., Ltd., Seast KH
* 8: Nippon Sil AQ, manufactured by Tosoh Silica Corporation
* 9: E75, made by Evonik Degussa, Si75
* 10: N- (1,3-dimethylbutyl) -N'-p-phenylenediamine * 11: Vulcanization accelerator DPG: Ouchi Shinsei Chemical Co., Ltd., Noxeller D
* 12: Vulcanization accelerator NS: Ouchi Shinsei Chemical Co., Ltd., Noxeller NS

From Table 4, the value of δ13C of vulcanization accelerator B compounded in Example 2 is −29 ‰, and the value of δ13C of vulcanization accelerator C compounded in Example 4 is −28 ‰. It was. Further, the value of δ13C of the vulcanization accelerator A blended in Comparative Example 2 was −23 ‰.
From Table 4, the vulcanization speed and 300% elongation tensile of the vulcanized rubber obtained by vulcanizing the rubber composition having the synthetic rubber derived from petroleum resources of Examples 2 and 4 and the bio-derived vulcanization accelerator. The index of stress is an index of the vulcanization speed and 300% elongation tensile stress of a vulcanized rubber obtained by vulcanizing a rubber composition having a synthetic rubber derived from petroleum resources of Comparative Example 2 and a conventional song collection accelerator. The value was comparable.
Thus, a vulcanized rubber compounded with a synthetic rubber and a vulcanization accelerator synthesized from biological resources including plant resources is vulcanized from petroleum resources at a vulcanization rate and 300% elongation tensile stress. It was found that there was no inferiority to conventional vulcanized rubber blended with an accelerator.

Claims (8)

A vulcanization accelerator synthesized from biological resources including plant resources,
A vulcanization accelerator having a value of δ13C of the vulcanization accelerator of −30 ‰ to −27.0 ‰, or −22 ‰ or more.   The vulcanization accelerator according to claim 1, wherein the value of δ13C is -28.5 ‰ to -27.5 ‰.   The vulcanization accelerator according to claim 1 or 2, wherein the vulcanization accelerator is synthesized using biomethane obtained from biological resources including plant resources as a starting material.   The vulcanization accelerator according to any one of claims 1 to 3, wherein the vulcanization accelerator is synthesized by using biobenzene obtained from a biological resource including a plant resource as a starting material.   The vulcanization accelerator according to any one of claims 1 to 4, wherein the vulcanization accelerator is a thiazole compound and a sulfenamide compound.   The vulcanization accelerator is at least one selected from 2-mercaptobenzothiazole, dibenzothiazyl disulfide, and N-cyclohexyl-2-benzothiazolylsulfenamide. The vulcanization accelerator according to any one of the above.   A rubber composition comprising the vulcanization accelerator according to any one of claims 1 to 6.   A tire comprising the rubber composition according to claim 7.

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