JP6317497B2 - Tread rubber composition and pneumatic tire - Google Patents

Description

The present invention relates to a rubber composition for a tread and a pneumatic tire using the same.

Currently marketed tires are made up of raw materials comprising more than half of the total weight of petroleum resources. For example, general radial tires for passenger cars contain about 20% synthetic rubber, about 20% carbon black, and other aroma oils and synthetic fibers, and more than 50% of the total tire weight. It contains raw materials consisting of oil resources.

However, in recent years, environmental issues have become more important, regulations on CO ₂ emissions have been tightened, and oil feedstocks are finite and the supply volume has been decreasing year by year. As expected, there are limits to the use of raw materials made from petroleum resources.

Therefore, in recent years, there has been an increasing demand for the establishment of a recycling-oriented society, and in the materials field, as with the energy field, it is desired to move away from fossil fuels, and the use of biomass is drawing attention.

For example, in Patent Document 1, natural rubber is used instead of synthetic rubber, inorganic filler or biofiller is used instead of carbon black, vegetable oil or fat is used instead of petroleum oil, natural fiber is used instead of synthetic fiber, etc. A tire technology is disclosed that is prepared for the reduction of the future supply of oil that is kind to the earth by constituting 75% by weight or more of the total weight with raw materials made of non-oil resources.

However, natural rubber has problems such as low fuel consumption, performance on snow and ice, and wear resistance compared to synthetic rubber such as polybutadiene rubber.

JP 2003-63206 A

The present invention solves the above-mentioned problems and provides a pneumatic tire having low fuel consumption, performance on snow and ice, and wear resistance equivalent to those of conventional pneumatic tires using synthetic rubber while meeting the demands of a recycling society. An object of the present invention is to provide a rubber composition for a tread that can be used.

The present invention is obtained by polymerizing monomer components derived from biomass, and has a pMC (percent modern carbon) of 1% or more and a glass transition temperature (Tg) of −120 to −60 ° C. measured according to ASTM D6866-10. The present invention relates to a rubber composition for a tread that contains a certain biomass-derived rubber, and wherein the monomer component is at least one selected from the group consisting of butadiene, myrcene, ocimene, and cosmene.

The biomass-derived rubber is preferably a diene rubber.

Of the monomer components constituting the biomass-derived rubber, 50 mol% or more is preferably butadiene.

The biomass-derived rubber is a diene obtained by catalytic reaction from at least one biomass-derived component selected from the group consisting of biomass-derived alkyl alcohols, allyl alcohols, alkenes, aldehydes, and unsaturated carboxylic acids. It is preferable to polymerize.

The alkyl alcohol is preferably at least one selected from the group consisting of ethanol, butanol, and butanediol.

The butanol is selected from the group consisting of a gene related to the mevalonate pathway, a gene related to the MEP / DOXP pathway, a gene encoding butyryl CoA dehydrogenase, a gene encoding butyraldehyde dehydrogenase, and a gene encoding butanol dehydrogenase It is preferably produced by at least one selected from the group consisting of microorganisms, plants, animals, and tissue cultures into which at least one gene has been introduced.

The allyl alcohol is preferably crotyl alcohol and / or 3-buten-2-ol.

The alkenes are preferably butene and / or ethylene.

The ethylene is preferably converted from biomass by fermentation using at least one selected from the group consisting of microorganisms, plants, animals, and tissue cultures thereof.

It is preferable that the above-mentioned microorganisms, plants, animals, and tissue cultures that produce ethylene have been introduced and / or modified with a gene encoding ACC synthase.

The aldehyde is preferably acetaldehyde.

The unsaturated carboxylic acids are preferably tiglic acid and / or angelic acid.

The biomass-derived rubber is preferably obtained by polymerizing monomer components directly produced from biomass by at least one selected from the group consisting of microorganisms, plants, animals, and tissue cultures thereof.

It is preferable that the monomer component is butadiene, and the butadiene is converted from at least one selected from the group consisting of sugars, hemiterpenes, and amino acids.

The amino acid is preferably at least one selected from the group consisting of valine, leucine, isoleucine, and arginine.

The hemiterpene and / or the enzyme that converts an amino acid into butadiene is preferably at least one selected from the group consisting of HMG-CoA reductase, diphosphomevalonate decarboxylase, and amino acid decarboxylase.

The monomer component is butadiene, and microorganisms, plants, animals, and tissue cultures that produce the butadiene encode a gene encoding HMG-CoA reductase, a gene encoding diphosphomevalonate decarboxylase, and an amino acid decarboxylase. It is preferable that at least one gene selected from the group consisting of genes to be introduced is introduced and / or modified.

It is preferable that the biomass-derived rubber is a polybutadiene rubber obtained by enzymatic reaction of biomass-derived butadiene.

The enzyme involved in the enzyme reaction is preferably a long-chain prenyl chain extender.

The biomass-derived rubber is preferably a polybutadiene rubber produced by at least one tissue culture selected from the group consisting of microorganisms, plants, and animals.

The saccharide content in 100% by mass of the biomass is preferably 20% by mass or more.

It is preferable that the total content of amino acids and proteins in 100% by mass of the biomass is 10% by mass or more.

The total content of fatty acids and fatty acid esters in 100% by mass of the biomass is preferably 10% by mass or more.

The biomass-derived rubber is preferably obtained by polymerizing a plurality of monomer components having different origins as the biomass-derived monomer component.

The biomass-derived rubber is preferably obtained by polymerizing a monomer component derived from biomass and a monomer component derived from petroleum resources.

The biomass-derived rubber is a biomass-derived monomer component, or a biomass-derived monomer component and a petroleum resource, in a ratio appropriately selected according to the supply status of biomass resources, the supply status of petroleum resources, and / or market requirements. It is preferably obtained by polymerizing a monomer component derived therefrom.

The present invention also relates to a rubber composition for a tread containing a polybutadiene rubber, wherein the polybutadiene rubber is polymerized using at least a part of the raw material butadiene as a starting material or a series of reactions obtained from biomass. It is related with the rubber composition for treads obtained.

The present invention also provides a biomass-derived monomer component, or a biomass-derived monomer component and a petroleum resource-derived, in an appropriately selected ratio according to the supply status of biomass resources, the supply status of petroleum resources, and / or market requirements. Derived from biomass having a pMC (percent modern carbon) measured according to ASTM D6866-10 of 1% or more and a glass transition temperature (Tg) of −120 to −60 ° C. The present invention relates to a method for producing rubber.

The present invention also relates to a pneumatic tire having a tread produced using the rubber composition.

According to the present invention, pMC (percent Modern Carbon) obtained by polymerizing monomer components derived from biomass and measured according to ASTM D6866-10 is 1% or more, and the glass transition temperature (Tg) is −120 to −60. Since it is a rubber composition for a tread that includes a biomass-derived rubber at a temperature of at least one selected from the group consisting of butadiene, myrcene, ocimene, and cosmene, it meets the demands of a recycling society. However, good fuel efficiency, performance on snow and ice, and wear resistance equivalent to those obtained when conventional synthetic rubber is used can be obtained. Therefore, by using the rubber composition in a pneumatic tire, while meeting the demands of the recycling society, it has low fuel consumption, snow and ice performance, and wear resistance equivalent to those of conventional pneumatic tires using synthetic rubber. A pneumatic tire can be provided.

It is a schematic diagram which shows simply the apparatus used for manufacture of butadiene.

The rubber composition for a tread of the present invention is obtained by polymerizing a monomer component derived from biomass, and has a pMC (percent modern carbon) measured according to ASTM D6866-10 of 1% or more and a glass transition temperature (Tg) of − Including biomass-derived rubber at 120 to -60 ° C, the monomer component is at least one selected from the group consisting of butadiene, myrcene, ocimene, and cosmene.

In the present invention, the rubber component is obtained by polymerizing at least one biomass-derived monomer component selected from the group consisting of butadiene, myrcene, ocimene, and cosmene (hereinafter, also simply referred to as a biomass-derived monomer component). Biomass-derived rubber having a pMC measured according to ASTM D6866-10 of 1% or more and a glass transition temperature (Tg) of −120 to −60 ° C. is used.

The pMC is a ratio of the 14C concentration of the sample to the 14C concentration of standard modern carbon, and in the present invention, this value is used as an index indicating the biomass ratio of the compound (rubber). The significance of this value is described below.

In 1 mole of carbon atoms (6.02 × 10 ²³ ) there are about 6.02 × 10 ^{11 14} C, which is about one trillionth of a normal carbon atom. ¹⁴ C is called a radioisotope and its half-life regularly decreases at 5730 years. It takes 26,000 years for all of these to collapse. Therefore, fossil fuels such as coal, oil, and natural gas, which are considered to have passed over 26,000 years after carbon dioxide in the atmosphere has been taken into plants and immobilized, are initially fixed. All of the ¹⁴ C elements that were also included in the are collapsed. Therefore, in the 21st century, fossil fuels such as coal, oil, and natural gas contain no ¹⁴ C element. Therefore, chemical substances produced using these fossil fuels as a raw material do not contain any ¹⁴ C element.

On the other hand, ¹⁴ C is a cosmic ray that undergoes a nuclear reaction in the atmosphere, is constantly generated, and balances with a decrease due to radiation decay. The amount of ¹⁴ C is constant in the earth's atmospheric environment. Therefore, the ¹⁴ C concentration of the biomass resource-derived substance circulating in the current environment has a value of about 1 × 10 ⁻¹² mol% with respect to the entire C atom as described above. Therefore, the ratio (biomass ratio) of natural resource-derived compounds (biomass resource-derived compounds) in a certain compound (rubber) can be calculated using the difference between these values.

This ¹⁴ C is generally measured as follows. Using accelerator mass spectrometry based on a tandem accelerator, ¹³ C concentration ( ¹³ C / ¹² C) and ¹⁴ C concentration ( ¹⁴ C / ¹² C) are measured. In the measurement, the ¹⁴ C concentration in the circulating carbon in the natural world as of 1950 is adopted as a standard standard reference that is a reference for the concentration of ¹⁴ C. As a specific standard substance, an oxalic acid standard provided by NIST (National Institute of Standards and Technology: National Institute of Standards and Technology) is used. The specific activity of carbon in this oxalic acid ( ¹⁴ C radioactivity intensity per gram of carbon) is fractionated for each carbon isotope, corrected to a constant value for ¹³ C, and attenuated from 1950 AD to the measurement date The corrected value is used as the standard ¹⁴ C concentration value (100%). The ratio of this value to the actually measured sample value is the pMC value used in the present invention.

Therefore, if rubber is made of a material derived from 100% biomass (natural system), it will show a value of about 110 pMC, although there are regional differences, etc. (currently it is not 100 under normal conditions) Often). On the other hand, when this ¹⁴ C concentration is measured for a chemical substance derived from fossil fuels such as petroleum, it indicates almost 0 pMC (for example, 0.3 pMC). This value corresponds to the biomass ratio of 0% mentioned above.

From the above, it is preferable in terms of environmental protection to use a rubber having a high pMC value, that is, a rubber having a high biomass ratio in the rubber composition for tread.

The pMC of the biomass-derived rubber measured according to ASTM D6866-10 (this value indicates the biomass ratio of the biomass-derived rubber) is 1% or more, preferably 10% or more, more preferably 50% or more, and further Preferably it is 100% or more, and the upper limit is not particularly limited. A higher pMC is preferable because it can meet the demands of the recycling society. Note that, as described above, a value exceeding 100% can be obtained due to the property of being calculated by the ratio to the standard substance.
In addition, in this invention, pMC of rubber | gum (biomass origin rubber | gum) is a value obtained by measuring based on ASTMD6866-10, and can be specifically measured by the method as described in an Example.
As described in the examples, in order to analyze the ¹⁴ C concentration of rubber, first, pretreatment of rubber is required. Specifically, the carbon contained in the rubber is oxidized and converted into carbon dioxide. Furthermore, it is necessary to separate the obtained carbon dioxide from water and nitrogen, reduce the carbon dioxide, and convert it into graphite, which is solid carbon. The obtained graphite is irradiated with a cation such as Cs ⁺ to generate negative ions of carbon, the carbon ion is accelerated using a tandem accelerator, and the charge is converted from negative ions to positive ions. Can separate the traveling trajectories of ¹² C ³⁺ , ¹³ C ³⁺ , and ¹⁴ C ³⁺ , and ¹⁴ C ³⁺ can be measured by an electrostatic analyzer.

The glass transition temperature (Tg) of the biomass-derived rubber is −120 to −60 ° C. When Tg is within this range, low fuel consumption, performance on snow and ice, and wear resistance that could not be achieved with natural rubber that is 100% biomass-derived rubber that has been conventionally used can be imparted to tires. . The Tg is preferably −80 ° C. or lower, more preferably −90 ° C. or lower, still more preferably −95 ° C. or lower, and particularly preferably −100 ° C. or lower. When Tg exceeds -60 ° C, the performance on snow and ice tends to deteriorate. The Tg is preferably −115 ° C. or higher. It is difficult to obtain a rubber having a Tg of less than -120 ° C, which may not be suitable for general use.
In addition, in this invention, Tg of rubber | gum (biomass origin rubber | gum) can be measured by the method as described in an Example.

In the present invention, a biomass-derived rubber obtained by polymerizing monomer components derived from biomass and having a pMC of a specific value or more and a specific glass transition temperature is used in a rubber composition for treads, thereby meeting the demands of a recycling society. While responding, the conventional technology of providing a pneumatic tire having low fuel consumption, snow and ice performance, and wear resistance equivalent to those of conventional pneumatic tires using synthetic rubber can be solved.

The biomass-derived rubber is preferably a myrcene polymer or a diene rubber, more preferably a diene rubber, and polybutadiene can be obtained because of good fuel economy, performance on snow and ice, and wear resistance. More preferably, it is rubber (biomass polybutadiene rubber (BBR)).
Here, the diene rubber can be copolymerized with other monomer components other than the diene monomer (aromatic diene monomer (styrene, etc.), monoterpene (myrcene, etc.), etc., as long as the above pMC and Tg are satisfied. A structural unit derived from such a monomer component).
In addition, as BBR, as long as the above pMC and Tg are satisfied, monomer components other than butadiene (diene monomers other than butadiene (isoprene and the like), aromatic diene monomers (styrene and the like), monoterpene (myrcene) Etc.) Constituent units derived from the copolymerizable monomer component) may be included.

The cis content of BBR is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more, because good wear resistance and bending fatigue resistance can be obtained.
The cis content of BBR can be measured by the method described in the examples.

Mw (weight average molecular weight) / Mn (number average molecular weight) of BBR is preferably 1 to 10, more preferably 1 to 5, because good wear resistance and flex fatigue resistance can be obtained.
In addition, Mw and Mn of BBR can be measured by the method described in Examples.

The biomass-derived rubber is a rubber obtained by polymerizing a monomer component derived from biomass.
In the present invention, the rubber obtained by polymerizing the monomer component derived from biomass includes not only rubber obtained by polymerizing the monomer component derived from biomass according to the conventional method, but also microorganisms, plants, animals, and tissue cultures thereof. In the following, rubber obtained by a reaction by an enzyme reaction (also referred to as a microorganism or the like) is also included.
In the present invention, biomass is also referred to as biomass resources.

In the present invention, biomass (biomass resource) means a biologically-neutral carbon-neutral organic resource. Specifically, it is stored by converting into a form such as starch or cellulose. It is a resource that excludes fossil resources, including products made by processing animal bodies, plants and animal bodies.

The biomass resource may be edible or non-edible, and is not particularly limited. From the viewpoint of effective use of resources without competing with food, it is preferable to use non-edible materials.

Specific examples of biomass resources include, for example, cellulosic crops (pulp, kenaf, straw, rice straw, waste paper, papermaking residue, etc.), wood, charcoal, compost, natural rubber, cotton, sugarcane, okara, fat (rapeseed oil, Cottonseed oil, soybean oil, coconut oil, castor oil, etc.), carbohydrate crops (corn, potatoes, wheat, rice, rice husk, rice bran, old rice, cassava, sago palm, etc.), bagasse, buckwheat, soybean, essential oil (pine root oil, orange) Oil, eucalyptus oil, etc.), pulp black liquor, garbage, vegetable oil residue, marine product residue, livestock excrement, food waste, algae, drainage sludge, and the like.

The biomass resources may be those obtained by processing them (that is, biomass-derived substances). Treatment methods include, for example, biological treatment methods using the action of microorganisms, plants, animals, and tissue cultures thereof; chemical treatment methods using acids, alkalis, catalysts, thermal energy, light energy, etc. Known methods such as physical treatment methods such as miniaturization, compression, microwave treatment, electromagnetic wave treatment and the like.

Moreover, as a biomass resource, what was extracted and refine | purified from the said biomass resource or the biomass resource which performed the said process (namely, biomass-derived substance) may be sufficient. For example, saccharides, proteins, amino acids, fatty acids, fatty acid esters and the like purified from biomass resources may be used.

The saccharide is not particularly limited as long as it is derived from biomass.For example, sucrose, glucose, trehalose, fructose, lactose, galactose, xylose, allose, talose, gulose, altrose, mannose, idose, arabinose, apiose, maltose, cellulose , Starch, chitin and the like.

The protein is not particularly limited as long as it is a compound derived from biomass and formed by linking amino acids (preferably L-amino acids), and includes oligopeptides such as dipeptides.

The amino acid is not particularly limited as long as it is an organic compound derived from biomass and having both an amino group and a carboxyl group, and examples thereof include valine, leucine, isoleucine, arginine, lysine, asparagine, and glutamine. Of these, valine, leucine, isoleucine and arginine are preferable. The amino acid may be L-type or D-type, but L-type is preferred because it is abundant in nature and easy to use as a biomass resource.

The fatty acid is not particularly limited as long as it is derived from biomass, and examples thereof include butyric acid, oleic acid, linoleic acid, palmitic acid, and stearic acid.

The fatty acid ester is not particularly limited as long as it is derived from biomass, and examples thereof include animal-derived fats, vegetable oils, biomass-derived oils and fats modified products, and the like.

As a biomass resource, various materials and impurities may be mixed, but the content of saccharide in 100% by mass of biomass is preferably 20% by mass or more for efficient conversion, and 30 More preferably, it is more preferably 50% by mass or more. In another embodiment, the total content of amino acids and proteins in 100% by mass of biomass is preferably 10% by mass or more, more preferably 20% by mass or more, and more preferably 30% by mass or more. Is more preferable. In yet another embodiment, the total content of fatty acids and fatty acid esters in 100% by mass of biomass is preferably 10% by mass or more for efficient conversion.

The monomer component derived from biomass is at least one selected from the group consisting of butadiene (1,3-butadiene), myrcene (β-myrcene), ocimene (β-oscymene), and cosmene. Moreover, in addition to these, hemiterpenes such as tiglic acid and angelic acid; sesquiterpenes; squalenes; diterpenes; carotenoids and the like may be used as monomer components derived from biomass. As the monomer component derived from biomass, butadiene (1,3-butadiene) is preferable because good fuel efficiency, performance on snow and ice, and abrasion resistance can be obtained.
Milsen can be extracted from laurels and verbena, osmen can be extracted from lavender and lima beans, and cosmen can be extracted from cosmos.

The proportion of butadiene in 100 mol% of the monomer component constituting the biomass-derived rubber is preferably 50 mol% or more, more preferably 70 mol% or more, because good fuel efficiency, performance on snow and ice, and wear resistance can be obtained. More preferably, it is 80 mol% or more, Especially preferably, it is 90 mol% or more, Most preferably, it is 95 mol% or more, and 100 mol% may be sufficient.

In the following, the case where the biomass-derived rubber is BBR obtained by polymerizing biomass-derived butadiene will be specifically described as a representative example. As described above, in the present invention, BBR obtained by polymerizing biomass-derived butadiene is obtained not only by BBR obtained by polymerizing biomass-derived butadiene according to a conventional method, but also by a reaction by a microorganism or an enzyme reaction. BBRs included are also included.

Various methods can be used as a method for preparing butadiene from biomass resources, and the method is not particularly limited. For example, a biological treatment method for directly obtaining butadiene from biomass resources by at least one selected from the group consisting of microorganisms, plants, animals, and tissue cultures thereof; applying the above chemical treatment method to biomass resources A method of obtaining butadiene by the above-mentioned method; a method of obtaining butadiene by applying the above physical treatment method to biomass resources; a method of converting biomass resources to butadiene by in vitro enzymatic reaction or the like; a method of combining these methods, and the like. Note that the microorganisms, plants, and animals that convert biomass resources into butadiene may or may not be genetically manipulated.

The direct conversion method from biomass resources to butadiene using microorganisms or the like is not particularly limited, but can be performed using an in vivo route for converting amino acids into alkyl alcohols and / or hemiterpenes.

As the amino acid, valine, leucine, isoleucine and arginine are preferable. Moreover, as hemiterpenes, tiglic acid and / or angelic acid are preferable.

As a preferable example, a gene encoding an enzyme having a decarboxylase activity and / or a gene encoding an enzyme having a reductase activity is introduced and / or modified into a microorganism, plant, animal, or tissue culture thereof. And a method of obtaining butadiene from amino acids and / or hemiterpenes.

Examples of the enzyme having decarboxylase activity include diphosphomevalonate decarboxylase (EC 4.1.1.13), various amino acid decarboxylases, and enzymes having reductase activity include HMG-CoA reductase, 12-oxo. Phytodienoic acid reductase (EC 1.3.3.1.42) etc. are mentioned.

As a preferable example of producing butadiene by fermentation by an in vivo reaction via an amino acid, various decarboxylase enzymes can be added to tiglic acid and / or angelic acid synthesized in vivo along the natural metabolic pathway of microorganisms and the like from isoleucine. The method of producing by making it act is mentioned. In addition, butadiene can be obtained by a decarboxylase reaction using various fatty acid derivatives produced during the metabolism of amino acids.

The amino acid necessary to obtain butadiene may be added directly to the medium, but as a preferred example, the amino acid was biosynthesized by biosynthesis by fermentation of plant pulverized material, livestock waste, etc. It is preferable to use amino acids. In this case, butadiene rubber is converted from saccharides and / or proteins.

Whereas general fermentation alcohol and alkene production methods mainly use saccharides as biomass resources, this production method can also effectively utilize biomass resources centered on amino acids and proteins. It is useful because of its large nature.

As another method for preparing butadiene from biomass resources, an intermediate capable of synthesizing butadiene from biomass resources is obtained by at least one selected from the group consisting of microorganisms, plants, animals, and tissue cultures thereof. Then, the obtained intermediate is subjected to the above chemical treatment method such as catalytic reaction, the above physical treatment method, the above in vitro enzymatic reaction, a method combining these methods, and the like to give butadiene (diene such as butadiene). ) Is also preferably used.

Examples of intermediates capable of synthesizing butadiene include alkyl alcohols, allyl alcohols, alkenes, aldehydes, and unsaturated carboxylic acids.

The alkyl alcohol is not particularly limited as long as it is derived from biomass, and ethanol, butanol, and butanediol are preferable, and butanol and butanediol are more preferable. In addition, butanol may be 1-butanol, 2-butanol, or a mixture thereof.

Known methods for producing ethanol from biomass resources using ethanol (eg, ethanol derived from biomass resources is also referred to as bioethanol) or butanol (butanol derived from biomass resources is also referred to as biobutanol) by fermentation are known methods. There are various known methods for obtaining bioethanol from biomass resources (for example, sugarcane and glucose) by ethanol fermentation with yeast, and biomass from biomass resources (for example, glucose) by acetone / butanol fermentation (ABE fermentation) by fermenting fungi. A method for obtaining butanol is common. In the case of ABE fermentation, since a mixed solvent such as butanol and acetone is obtained, biobutanol can be obtained by distillation. Furthermore, butanol can also be obtained from bioethanol by a catalytic reaction or via acetaldehyde.

The microorganism that performs ABE fermentation is not particularly limited as long as it is a microorganism that can perform ABE fermentation. For example, Escherichia genus, Zymomonas genus, Candida genus, Saccharomyces genus, Pichia genus, Streptomyces genus, Bacillus genus, Lactobacillus genus, Corynebacterium genus, Clostridium genus, Saccharomyces (Saccharomyces genus) Is mentioned. These strains can be used in any form, such as wild strains, mutant strains, and recombinant strains derived by genetic engineering techniques such as cell fusion or genetic manipulation. Among them, microorganisms belonging to the genus Clostridium are preferable, and Clostridium acetobutylicum, Clostridium beijerinckii, Clostridium saccharobutyricum, and Clostridium saccharoperperylacetonicum are more preferable.

One preferred example of a method for producing biobutanol includes, for example, a gene associated with the mevalonate pathway, a gene associated with the MEP / DOXP pathway, a gene encoding butyryl CoA dehydrogenase, a gene encoding butyraldehyde dehydrogenase, and Butanol is obtained by fermentation with at least one selected from the group consisting of microorganisms, plants, animals, and tissue cultures into which at least one gene selected from the group consisting of genes encoding butanol dehydrogenase has been introduced. The method to obtain is mentioned (for example, Japanese translations of PCT publication No. 2010-508017).

Ethanol and butanol produced by fermentation from biomass resources are also commercially distributed as bioethanol and biobutanol (for example, Biobutanol manufactured by DuPont).

In addition, butanediol is produced directly by various fermentation as a raw material for bioplastic (for example, Syu MJ, Appl Microbiological Biotechnol 55: 10-18 (2001), Qin et al., Chinese J Chem Eng 14 (1): 132- 136 (2006), Japanese translations of PCT publication No. 2011-522563, JP-A-62-285779, JP-A-2010-115116, etc.) and can be easily used as bio-derived butanediol. Further, butanediol may be produced by converting succinic acid, fumaric acid, furfural and the like derived from biomass.

The microorganism for performing butanediol fermentation is not particularly limited as long as it is a microorganism capable of performing butanediol fermentation. For example, Escherichia, Zymomonas, Candida, Saccharomyces ) Genus, Pichia genus, Streptomyces genus, Bacillus genus, Lactobacillus genus, Corynebacterium genus, Clostridium genus, clepsis ell Examples include microorganisms belonging to the genus Saccharomyces. These strains can be used in any form, such as wild strains, mutant strains, and recombinant strains derived by genetic engineering techniques such as cell fusion or genetic manipulation. Among them, the genus Bacillus, Clostridium, preferably a microorganism belonging to the Kuripushiera genus Clostridium autoethanogenum (Clostridium autoethanogenum), Bacillus polymyxa, Bacillus subtilis, Bacillus pumilus, Bacillus macerans, Bacillus licheniformis, Bacillus megaterium, Klebsiella pneumoniae is more preferable .

From the alkyl alcohol, the biological treatment method such as fermentation, the chemical treatment method such as catalytic reaction, the physical treatment method, the in vitro enzyme reaction, the method combining these methods, etc. Can be converted to butadiene.

As a direct conversion method from alkyl alcohols to butadiene, for example, there is a method of converting ethanol and / or butanol to butadiene using a dehydration and dehydrogenation catalyst such as hydroxyapatite, Ta / SiO ₂ , alumina, zeolite and the like. Are known.

The allyl alcohol is not particularly limited as long as it is derived from biomass, and crotyl alcohol and 3-buten-2-ol are preferable because of easy conversion to butadiene.

Crotyl alcohol and 3-buten-2-ol may be obtained directly from biomass resources by fermentation of microorganisms or the like, or may be obtained by reducing biomass-derived crotonic acid and its derivatives. It is also possible to obtain crotyl alcohol using biomass-derived butanediol as a catalyst for zeolite, alumina, cerium oxide or the like (for example, JP-A No. 2004-306011).

Examples of the method for converting allyl alcohol to butadiene include a method for converting crotyl alcohol to butadiene by dehydrating with a catalytic reduction catalyst such as generally known zeolite and alumina.

Alkenes are not particularly limited as long as they are derived from biomass, and ethylene and butene (also called butylene) are preferable, and ethylene is more preferable.

Biomass-derived ethylene and butene can be produced by, for example, bioethanol using a dehydration catalyst such as alumina or zeolite or ethylene by high-temperature treatment, or biobutanol using a dehydration catalyst such as alumina or zeolite or high-temperature treatment. The method of conversion etc. are mentioned.

The alkenes (ethylene, butene) can also be obtained directly from biomass resources by fermentation using at least one selected from the group consisting of microorganisms, plants, animals, and tissue cultures thereof. .

Microorganisms, plants, animals, and tissue cultures that carry out the above-mentioned ethylene fermentation have a production efficiency such that a gene encoding an enzyme having ACC synthase (ethylene synthase) activity is introduced and / or modified. Although it is preferable at a point, it is not this limitation.

Microorganisms, plants, animals, and tissue cultures that perform the above-mentioned butene fermentation have introduced and / or modified a gene encoding an enzyme having diphosphomevalonate decarboxylase (EC 4.1.1.13) activity. However, the present invention is not limited to this.

Examples of the method for converting the alkenes to butadiene include a method in which butene is converted into butadiene with alumina, zeolite, etc., ethylene is partially converted into acetaldehyde with an oxidation catalyst such as palladium chloride, and then dehydration reaction with residual ethylene. The method of obtaining butadiene by doing is mentioned.

The aldehyde is not particularly limited as long as it is derived from biomass, and acetaldehyde is preferable.

Acetaldehyde may be obtained directly from biomass resources by fermentation of microorganisms or the like, or may be obtained by converting biomass-derived ethylene into acetaldehyde using an oxidation catalyst such as palladium chloride.

Examples of the method for converting aldehydes to butadiene include a method of dehydrating with ethylene.

The unsaturated carboxylic acids are not particularly limited as long as they are derived from biomass, and tiglic acid and angelic acid are preferable.

Tiglinic acid and angelic acid may be obtained directly from biomass resources by fermentation of microorganisms or the like. Specifically, tiglic acid and angelic acid can be synthesized in vivo from isoleucine by a natural metabolic pathway possessed by microorganisms. Moreover, you may refine | purify from a lotus oil etc.

Examples of the method for converting the unsaturated carboxylic acid to butadiene include a method for converting tiglic acid and angelic acid by acting various decarboxylases, a metal catalyst, zeolite, alumina and the like. Methods and the like.

The method of polymerizing polybutadiene rubber (biomass polybutadiene rubber (BBR)) from butadiene obtained from biomass resources by the above-described method is a method known to those skilled in the art, and polymerizes polybutadiene rubber from butadiene derived from petroleum resources. It is the same as the method and is not particularly limited.

As butadiene obtained from biomass resources, butadiene derived from alkyl alcohols (preferably ethanol, butanol (more preferably butanol)) and alkenes (preferably ethylene) from the viewpoints of availability, performance of the obtained BBR, and the like. ) And butadiene derived from unsaturated carboxylic acids (preferably tiglic acid) can be suitably used. It is also suitable to use these butadienes in combination.

The molecular weight, branching and microstructure of the obtained BBR can be arbitrarily selected by changing the polymerization conditions according to a known method in accordance with the desired tire performance. In addition, monomer components other than butadiene (monoene monomers other than butadiene (such as isoprene), aromatic diene monomers (such as styrene), monomer components capable of copolymerization such as monoterpene (such as myrcene)) and any ratio ( However, it is also possible to carry out copolymerization at a ratio satisfying the above pMC and Tg). Further, butadiene obtained from biomass resources may be used in combination with butadiene other than butadiene obtained from biomass resources (butadiene derived from petroleum resources).

On the other hand, there are currently some biomass complex plans centered on bioethanol, bioethylene, etc., but bioethanol and bioethylene are mainly produced using saccharides and / or celluloses as biomass resources. However, other biomass resources such as proteins, lipids, and amino acids cannot be effectively used. Furthermore, sugars can lead to competition with food, and over-exploitation of cellulose can lead to deforestation, which may not necessarily be environmentally friendly.

Therefore, depending on the demands for the overall environment, such as the supply status of various biomass resources, the supply status of petroleum resources, and market demands (eg, competitive trends with demand for biomass resources as food), Use multiple biomass-derived monomer components as monomer components, use a combination of biomass-derived monomer components and petroleum-derived monomer components, and adjust the usage ratio of these monomer components to the optimal ratio. It is preferable to use them. This makes it possible to effectively utilize a wide range of biomass resources such as sugars, proteins, and lipids without relying on a single type of biomass resource, stabilizing the supply of biomass-derived rubber, and improving the environment according to the situation during production. Consideration can be made. For example, butadiene derived from biomass can be obtained using bioethanol, biobutanol, terpenes, and other various substrates described above.

In addition, when using two or more monomer components derived from biomass, it is preferable to use the monomer component derived from different biomass, ie, the monomer component obtained from different biomass resources. Thereby, a some biomass resource can be used effectively and it can respond according to the request to the above-mentioned comprehensive environment suitably.

Another preferred example of converting butadiene obtained from biomass resources into BBR is a method utilizing an enzyme reaction. Several enzymes (long-chain prenyl chain extenders) contained in rubber latex are known to have an effect of promoting the polymerization reaction of dienes, and polymerization can be performed in vivo or in vitro using these enzymes. Can do.

It does not specifically limit as a long chain prenyl chain extension enzyme, A well-known thing can be used.

As a method for directly obtaining BBR from biomass resources, for example, by culturing (tissue culture) at least one selected from the group consisting of microorganisms, plants, animals, and tissue cultures having diene polymerization ability. , A method for directly converting biomass resources into BBR, a medium supplemented with butadiene (preferably butadiene obtained from biomass resources), and at least one selected from the group consisting of microorganisms, plants, animals, and tissue cultures thereof. Examples include a method of polymerizing BBR by culturing seeds.

Preferred examples of the microorganisms having the above-mentioned diene polymerization ability include plants such as para rubber tree, Indian rubber tree, dandelion, fig, noge, smelt guayule, guayule, sabzilla, eucommia, and tissue cultures thereof.

In the case of culturing microorganisms and the like, since sugars such as glucose are usually used as a carbon source, all compounds produced by microorganisms and the like correspond to biomass resource-derived substances.

As described above, BBR is a reaction starting from biomass (a one-stage reaction from biomass resources to butadiene (a reaction that directly generates butadiene from biomass resources) as at least part of the raw material butadiene (butadiene as a monomer component). ) Or a series of reactions (a series of reactions in which butadiene is produced using a biomass resource as a starting material) and obtained by polymerization.

The content of the biomass-derived rubber (preferably BBR) in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 20% by mass or more. The upper limit of the content is not particularly limited, but is preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 50% by mass or less. When the content of the biomass-derived rubber (preferably BBR) is within the above range, good fuel efficiency, performance on snow and ice, wear resistance, and bending fatigue resistance can be obtained.

As rubber components that can be used other than biomass-derived rubber, natural rubber (NR), epoxidized natural rubber (ENR), diene synthetic rubber (isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), Styrene isoprene butadiene rubber (SIBR), chloroprene rubber (CR), acrylonitrile butadiene rubber (NBR), ethylene propylene diene rubber (EPDM), butyl rubber (IIR), halogenated butyl rubber (X-IIR) and the like. A rubber component may be used independently and may use 2 or more types together. Among these, NR is preferable because it can be used in combination with biomass-derived rubber to achieve good fuel efficiency, performance on snow and ice, wear resistance, and bending fatigue resistance while meeting the demands of a recycling society. SBR is also preferable because good snow and ice performance and abrasion resistance can be obtained.

The NR is not particularly limited, and for example, those commonly used in the tire industry such as SIR20, RSS # 3, TSR20, and the like can be used.

The content of NR in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 10% by mass or more. The content is preferably 50% by mass or less, more preferably 30% by mass or less. When the content of NR is within the above range, good performance on snow and ice, low fuel consumption, wear resistance, and bending fatigue resistance can be obtained while meeting the demands of the recycling society.

The SBR is not particularly limited, and those generally used in the tire industry such as emulsion polymerization styrene butadiene rubber (E-SBR) and solution polymerization styrene butadiene rubber (S-SBR) can be used.

The content of SBR in 100% by mass of the rubber component is preferably 30% by mass or more, more preferably 40% by mass or more. Moreover, this content becomes like this. Preferably it is 70 mass% or less, More preferably, it is 60 mass% or less. When the SBR content is within the above range, good performance on snow and ice, low fuel consumption, and wear resistance can be obtained while meeting the demands of the recycling society.

The rubber composition of the present invention preferably contains a filler. Any filler can be used without limitation as long as it is commonly used in tires. Examples of the filler include silica, carbon black, aluminum hydroxide, clay, calcium carbonate, montmorillonite, cellulose, glass balloon, and various short fibers. As the filler, silica, carbon black, and aluminum hydroxide are preferable in terms of tire physical properties. These may be used alone or in combination of two or more.

The amount of the filler is preferably 10 to 200 parts by weight, more preferably 20 to 180 parts by weight, still more preferably 30 to 150 parts by weight, and particularly preferably 40 to 80 parts by weight with respect to 100 parts by weight of rubber. It is. When the amount is less than 10 parts by mass, the strength of the rubber composition becomes insufficient, and the wear resistance, bending fatigue resistance, and performance on snow and ice tend to decrease. On the other hand, when it exceeds 200 parts by mass, the filler is not sufficiently dispersed in the rubber, and the rubber properties (low fuel consumption, wear resistance, and bending fatigue resistance) tend to be lowered.

Among the fillers, silica is preferably contained from the viewpoint of improving the fuel efficiency of the tire.

The nitrogen adsorption specific surface area (N ₂ SA) of silica by the BET method is preferably 50 m ² / g or more, and more preferably 100 m ² / g or more. If it is less than 50 m ² / g, the rubber strength tends to decrease, and the wear resistance and bending fatigue resistance tend to decrease. Further, the N ₂ SA is preferably 250 m ² / g or less, and more preferably 200 m ² / g or less. If it exceeds 250 m ² / g, processability tends to deteriorate, and fuel economy, wear resistance, and bending fatigue resistance tend to deteriorate.
The _N 2 SA of silica is a value determined by the BET method in accordance with ASTM D3037-93.

The content of silica is preferably 5 parts by mass or more and more preferably 15 parts by mass or more with respect to 100 parts by mass of the rubber component. The content of the silica is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, still more preferably 100 parts by mass or less, and particularly preferably 50 parts by mass or less. When the silica content is within the above range, good fuel efficiency can be obtained, good reinforcing effect (wear resistance, flex fatigue resistance), and performance on snow and ice can be obtained.

Among the fillers, carbon black is preferably included from the viewpoint of improving the wear resistance and bending fatigue resistance of the tire.

The nitrogen adsorption specific surface area (N ₂ SA) of carbon black is preferably 50 m ² / g or more, and more preferably 90 m ² / g or more. If it is less than 50 m ² / g, sufficient reinforcing properties cannot be obtained, and sufficient wear resistance and bending fatigue resistance may not be obtained. The _N 2 SA is preferably 180 m ² / g or less, more preferably 130m ² / g. If it exceeds 180 m ² / g, it becomes difficult to disperse, and the fuel economy, wear resistance, and bending fatigue resistance tend to deteriorate.
Incidentally, _N 2 SA of carbon black, JIS K 6217-2: determined by 2001.

The content of carbon black is preferably 5 parts by mass or more, more preferably 15 parts by mass or more with respect to 100 parts by mass of the rubber component. If it is less than 5 parts by mass, sufficient wear resistance and bending fatigue resistance may not be obtained. The content is preferably 100 parts by mass or less, more preferably 70 parts by mass or less, and still more preferably 50 parts by mass or less. When the amount exceeds 100 parts by mass, dispersibility deteriorates, and there is a tendency that fuel efficiency, wear resistance, bending fatigue resistance, and performance on snow and ice are deteriorated.

In addition to the above components, the rubber composition for treads contains compounding agents generally used in the production of rubber compositions, such as silane coupling agents, oils, stearic acid, zinc oxide, waxes, anti-aging agents, vulcanization An agent, a vulcanization accelerator and the like can be appropriately blended.

As a method for producing the rubber composition of the present invention, known methods can be used. For example, the above components are kneaded using a rubber kneader such as an open roll, a Banbury mixer, a closed kneader, and then added. It can be manufactured by a method of sulfurating.

In addition, the supply status of biomass resources, the supply status of petroleum resources (eg, monomer components derived from petroleum resources), and / or market demands (eg, demand for biomass resources as food when producing rubber compositions) (Competitive trends)) In accordance with demands for the overall environment, such as biomass-derived monomer components, petroleum resource-derived monomer components, the ratio of the monomer components derived from biomass is appropriately selected, and the biomass-derived monomer component, or By polymerizing the monomer component derived from biomass and the monomer component derived from petroleum resources and polymerizing the biomass-derived rubber, it is possible to produce a biomass-derived rubber having the same performance as when a conventional synthetic rubber is used.

The pneumatic tire of the present invention is produced by a usual method using the rubber composition. That is, if necessary, a rubber composition containing various additives is extruded in accordance with the shape of a tread or the like at an unvulcanized stage, molded by a normal method on a tire molding machine, After bonding together with the tire member to form an unvulcanized tire, the tire can be manufactured by heating and pressing in a vulcanizer.

The pneumatic tire of the present invention is suitably used as a passenger car tire, truck / bus tire, motorcycle tire, competition tire, and the like.

The present invention will be specifically described based on examples, but the present invention is not limited to these examples.

The butadiene and polybutadiene rubber obtained in the following production examples were evaluated by the following methods.

(Butadiene, polybutadiene rubber pMC)
The pMC of butadiene and polybutadiene rubber was measured according to ASTM D6866-10 by the following method.
A sample (butadiene or polybutadiene rubber) was burned to generate carbon dioxide (CO ₂ ), and the carbon dioxide was purified by a vacuum line. Next, the purified carbon dioxide was reduced with hydrogen using iron as a catalyst to produce graphite (C). Then, the obtained graphite was packed into a cathode having an inner diameter of 1 mm with a hand press, fitted into a wheel, and mounted on a measuring device ( ¹⁴ C-AMS dedicated device based on a tandem accelerator (manufactured by NEC)). The measurement apparatus measured ¹⁴ C concentration and ¹³ C concentration, and pMC (%) indicating a biomass ratio was calculated using oxalic acid provided from the National Bureau of Standards (NIST) as a standard sample. It should be noted that correction using the ¹³ C concentration value was performed when calculating the pMC.

(Cis content of polybutadiene rubber)
The cis content was measured using an AV400 NMR apparatus manufactured by BRUKER and data analysis software TOP SPIN2.1.

(Glass transition temperature (Tg) of polybutadiene rubber)
According to JIS-K7121, the glass transition temperature (Tg) was measured on the conditions of the temperature increase rate of 10 degree-C / min using the automatic differential scanning calorimeter (DSC-60A) by Shimadzu Corporation.

(Molecular weight distribution of polybutadiene rubber (Mw / Mn))
The weight average molecular weight (Mw) and number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) method under the following conditions (1) to (8). And the molecular weight distribution (Mw / Mn) of the polymer was calculated | required from measured Mw and Mn.
(1) Apparatus: HLC-8020 manufactured by Tosoh Corporation
(2) Separation column: Tosoh GMH-XL (two in series)
(3) Measurement temperature: 40 ° C
(4) Carrier: Tetrahydrofuran (5) Flow rate: 0.6 mL / min (6) Injection volume: 5 μL
(7) Detector: Differential refraction (8) Molecular weight standard: Standard polystyrene

Production Example 1 (Production of butadiene from butanol)
<Manufacture of biobutanol>
A 300 ml fermentor (DASGIP) was filled with 250 ml of synthetic medium (containing sugars) as described in Soni et al (Soniet al, 1987, Appl. Microbiol. Biotechnol. 27: 1-5) and sparged with nitrogen for 30 minutes. . Clostridium acetobutyricum (ATCC824) was inoculated there under anaerobic conditions. The culture temperature was kept constant at 35 ° C., and the pH was adjusted to 5.5 using NH 4 OH solution. During the culture, anaerobic conditions were maintained and the shaking speed was maintained at 300 rpm. After culturing for 5 days, the culture solution was distilled and separated by an ion exchange resin method which has been conventionally known to obtain biobutanol (1-butanol).

<Production of butadiene from biobutanol>
Biomass-derived butadiene was synthesized using biobutanol (1-butanol) obtained by <production of biobutanol> as a raw material, using the apparatus shown in FIG.

An alcohol introduction tube (raw material introduction tube) 21, a heating device (electric furnace) 22 for vaporizing the introduced alcohol, a dehydration reaction column 23 for dehydrating the alcohol, and a product obtained by the dehydration reaction A cooling device 24 for cooling to remove water from the purified alkene mixture, a heating device 25 for vaporizing the alkene, a second-stage reaction column 26 for further dehydrogenating the alkene to synthesize butadiene, and production The apparatus (refer FIG. 1) provided with the cooling device 27 for collect | recovering the obtained reaction product was used. The dehydration reaction column 23 was packed with 10 g of aluminum oxide (101095100 manufactured by Merck) as a catalyst.

The catalyst for the second stage dehydrogenation reaction was prepared as follows. Chromium nitrate (5.8 g) was dissolved in ion-exchanged water, and 6 g of SSZ-35 type zeolite (silica / alumina ratio: 40) was added and impregnated therein. Then, it was dried in an oven at 100 ° C. to obtain a precursor. This precursor was put in a ceramic container, and calcined at 700 ° C. for 3 hours in the presence of air to obtain a chromium-supported zeolite catalyst containing 10% by mass of chromium.
Then, the second stage reaction column 26 was charged with 10 g of the chromium-supported zeolite catalyst.

Nitrogen gas was supplied to the dehydration reaction column 23 from a gas introduction tube (not shown). The supply rate of nitrogen gas was 1 / hr in terms of LHSV. After heating the dehydration reaction column 23 to a predetermined temperature by the heating device 22, a predetermined amount of biobutanol was supplied from the alcohol introduction tube 21. The reaction conditions were: reaction temperature: 500 ° C., reaction pressure: normal pressure, and a molar ratio of biobutanol to nitrogen (biobutanol / nitrogen): 50/50. The reaction time was 2 hours. The product was collected in a cooling device (product trap) 24 connected to the column 23 for dehydration reaction, and water was separated.

The second stage reaction column 26 was heated to 500 ° C. The cooling device (product trap) 27 was cooled to −20 ° C. Through a cooling device (product trap) 24, a preheated mixed gas (butene mixture / nitrogen / air obtained in the first stage dehydration reaction 1: 1: 1) was introduced at a feed rate of 1 / hr in terms of LHSV. The resulting reaction mixture was separated and purified by the method described in JP-A-60-115532 to obtain biomass-derived butadiene in a yield of 8%. The pMC value indicating the biomass ratio of the obtained butadiene (biomass-derived butadiene) was 105%.

Production Example 2 (Production of butadiene from bioethanol)
A known method for converting ethanol to butadiene using the apparatus of FIG. 1 (Kirshenbaum, I. (1978). Butadiene. In M. Grayson (Ed.), Encyclopedia of Chemical Technology, 3rd ed. pp. 313-337.New York: John Wiley & Sons.) Biomass-derived butadiene was synthesized using commercially available bioethanol. The value of pMC indicating the biomass ratio of the obtained butadiene (biomass-derived butadiene) was 108%.

Production Example 3 (Production of butadiene from bioethylene)
A catalyst prepared by dissolving 0.5 mmol / L of palladium acetate in 0.3 mol / L Na ₃ H ₃ PMo ₉ V ₃ O ₄₀ was introduced into the second stage reaction column 26 of the apparatus of FIG. Replaced. Biomass-derived ethylene (prototype, product from corn-derived bioethanol) was introduced there. The apparatus was reacted for 1 hour while circulating the catalyst solution through the circulation line 28 under the conditions of 150 ° C. and 0.5 MpaG. After removing the catalyst solution through the drain of the cooling device 27, an alumina catalyst in which bioethanol was immersed (alumina KHA-46 manufactured by Sumitomo Chemical Co., Ltd.) was added and reacted at 400 ° C. for 5 hours. The formation of butadiene was confirmed by analyzing the reaction mixture by GC / MS. The pMC value indicating the biomass ratio of the obtained butadiene (biomass-derived butadiene) was 109%.

Production Example 4 (Production of butadiene from tiglic acid)
500 mg of tiglic acid (intermediate amino acid intermediate) 500 mg, 30 mg of tetrakistriphenylphosphine palladium (0) and 10 mg of triethylboron separated and purified from haze oil were placed in an argon-filled autoclave and reacted at 200 ° C. for 1 hour. The product was analyzed by GC / MS to confirm the formation of butadiene. The value of pMC indicating the biomass ratio of the obtained butadiene (biomass-derived butadiene) was 108%.

When the biomass-derived butadiene obtained in Production Examples 1 to 4 was measured using an AV400 NMR apparatus (data analysis software TOP SPIN 2.1) manufactured by BRUKER, these butadienes were 1,3-butadiene. confirmed.

Production Example 5 (Manufacture of biomass polybutadiene rubber (BBR))
BBR (corresponding to the biomass-derived rubber of the present invention) was synthesized using a mixture of the biomass-derived butadiene (1,3-butadiene) obtained in Production Examples 1 to 4 as a monomer component.
<Catalyst adjustment>
A solution of neodymium octoate (0.09 mmol) in cyclohexane, toluene solution of methylalumoxane (2.7 mmol), diisobutylaluminum hydride (4.7 mmol) and cyclohexane solution of silicon tetrachloride (0.09 mmol) 5 times that of neodymium Reaction aging was carried out with an amount of 1,3-butadiene (biomass-derived butadiene) at 50 ° C. for 30 minutes.
<Synthesis of BBR>
A nitrogen-substituted autoclave having an internal volume of 5 liters was charged with 2.4 kg of cyclohexane and 300 g of 1,3-butadiene (biomass-derived butadiene) under nitrogen. A preliminarily prepared catalyst was charged into these and polymerization was performed at 50 ° C. for 30 minutes.
After completion of the polymerization, 0.3 g of 2,4-di-t-butyl-p-cresol was added as a methanol solution, desolvated, and dried to obtain 250 g of biomass polybutadiene rubber (BBR). PMC which shows the biomass ratio of obtained BBR was 105%, Tg was -110 degreeC, cis content was 99.0 mass%, and Mw / Mn was 2.1.

Below, various chemical | medical agents used by the Example and the comparative example are demonstrated.
NR: RSS # 3 (Tg: -75 ° C)
SBR: SBR1502 manufactured by JSR Corporation (styrene content: 23.5% by mass)
BR: Nipol BR1220 manufactured by Nippon Zeon Co., Ltd.
BBR: Biomass polybutadiene rubber obtained in Production Example 5 (corresponding to biomass-derived rubber of the present invention)
Carbon black: Seast N220 manufactured by Mitsubishi Chemical Corporation (N ₂ SA: 114 m ² / g)
Silica: Ultrasil VN3 manufactured by Evonik Degussa (average primary particle size: 15 nm, N ₂ SA: 175 m ² / g)
Silane coupling agent: Si75 manufactured by Evonik Degussa
Oil: Process X-140 manufactured by Japan Energy Co., Ltd.
Wax: Sunnock N manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
Zinc oxide: Zinc Hana No. 1 manufactured by Mitsui Mining & Smelting Co., Ltd. Stearic acid: Stearic acid “Kashiwa” manufactured by NOF Corporation
Anti-aging agent: Antigen 6C (N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine) manufactured by Sumitomo Chemical Co., Ltd.
Sulfur: Powder sulfur vulcanization accelerator manufactured by Karuizawa Sulfur Co., Ltd. (1): Noxeller CZ (N-cyclohexyl-2-benzothiazolylsulfenamide) manufactured by Ouchi Shinsei Chemical Co., Ltd.
Vulcanization accelerator (2): Noxeller D (N, N'-diphenylguanidine) manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.

(Examples and Comparative Examples)
In accordance with the formulation shown in Table 1, chemicals other than sulfur and a vulcanization accelerator were kneaded using a 1.7 L Banbury mixer. Next, using an open roll, sulfur and a vulcanization accelerator were added to the kneaded product and kneaded to obtain an unvulcanized rubber composition. Next, the obtained unvulcanized rubber composition was press vulcanized with a 2 mm thick mold at 170 ° C. for 15 minutes to obtain a vulcanized rubber composition (vulcanized rubber sheet).
Further, after the obtained unvulcanized rubber composition was formed into a tread shape, it was bonded to another tire member to form an unvulcanized tire, which was tested by press vulcanization at 170 ° C. for 12 minutes. Tires (tire size: 195 / 65R15) were manufactured.

The obtained vulcanized rubber composition and test tire were evaluated as follows. The results are shown in Table 1.

(1) Low temperature hardness Measured at −10 ° C. with a type A hardness meter according to JIS K6253.
The results are shown as an index with Comparative Example 1 as 100. The smaller the index, the lower the hardness and the better the performance on snow and ice.

(2) Tg (glass transition temperature)
Using a viscoelastic spectrometer VES (manufactured by Iwamoto Seisakusho Co., Ltd.), the peak value of tan δ of each formulation was measured under the conditions of a temperature of −100 to 100 ° C. and a dynamic strain of 0.5%. It was.

(3) Using a fuel-efficient viscoelastic spectrometer VES (manufactured by Iwamoto Seisakusho Co., Ltd.), tan δ of each formulation was measured under conditions of a temperature of 70 ° C., an initial strain of 10%, and a dynamic strain of 2%. The tan δ of 1 was set to 100, and the index was expressed by the following calculation formula. The larger the index, the better the rolling resistance (low fuel consumption).
(Rolling resistance index) = (tan δ of Comparative Example 1) / (tan δ of each formulation) × 100

(4) The performance test tire on snow and ice was mounted on a domestic 2000cc FR vehicle, and the actual vehicle performance was evaluated under the following conditions (on ice and on snow). Specifically, the handling performance by feeling was evaluated for starting, accelerating and stopping using the vehicle. Feeling evaluation is based on Comparative Example 1 as 100, and the test driver judged that the performance was clearly improved was 120, and a good level that was never seen so far was 140. I put it on.
(On ice) (on snow)
Test place: Hokkaido Nayoro Test Course Hokkaido Nayoro Test Course Temperature: -1 to -6 ° C -2 to -10 ° C

(5) After wearing a wear resistance test tire on a domestic FF vehicle and running 8000 km, the groove depth of the tire tread is measured, and the travel distance when the tire groove depth is reduced by 1 mm is calculated by the following formula: Indexed by The higher the index, the better the wear resistance.
(Abrasion resistance index) = (travel distance when 1 mm groove depth of each compound is reduced) / (travel distance when tire groove of Comparative Example 1 is reduced by 1 mm) × 100

From Table 1, in Comparative Example 1, since NR 20% by mass, SBR 50% by mass, and BR 30% by mass are adopted as rubber components, good fuel efficiency, performance on snow and ice, and wear resistance are obtained. The pMC of the rubber component as a whole is low, and it cannot fully meet the demands of the recycling society. On the other hand, in Comparative Example 2, since NR50% by mass and SBR50% by mass are adopted as the rubber component, the pMC of the entire rubber component is increased, and although it can meet the demands of the recycling society, low fuel consumption, The performance on snow and ice and wear resistance were greatly reduced. On the other hand, in Example 1, since NR20% by mass, SBR50% by mass, and BBR30% by mass are adopted as the rubber component, the pMC of the entire rubber component is increased, and the demand for the recycling society can be met. In addition, good fuel economy, performance on snow and ice, and wear resistance were also obtained. By using biomass-derived rubber (BBR) by comparing Examples 1 and 2 and Comparative Examples 1 and 3, good fuel economy and performance on snow and ice equivalent to the case of using conventional synthetic rubber (BR) It was found that abrasion resistance was obtained.

21 Alcohol introduction pipe (raw material introduction pipe)
22 Heating device (electric furnace)
23 Dehydration reaction column 24 Cooling device 25 Heating device 26 Second stage reaction column 27 Cooling device 28 Circulation line

Claims (18)

A method for producing a rubber composition for a tread containing a polybutadiene rubber, wherein the polybutadiene rubber is polymerized using at least a part of butadiene as a monomer component obtained by a reaction starting from biomass or a series of reactions. all SANYO obtained by,
The polybutadiene rubber is catalyzed by at least one biomass-derived component selected from the group consisting of biomass-derived allyl alcohols, alkenes, aldehydes, and unsaturated carboxylic acids (excluding microbial in vivo reactions). A method for producing a rubber composition for a tread, which is obtained by polymerizing butadiene obtained by the above method. Method for producing the allyl alcohols, crotyl alcohol and / or 3-buten-2-ol in a claim 1 for tread rubber composition. Manufacturing method of the alkenes, butene and / or ethylene in a claim 1 for tread rubber composition. The rubber composition for a tread according to claim 3 , wherein the ethylene is converted from biomass by fermentation using at least one selected from the group consisting of microorganisms, plants, animals, and tissue cultures thereof. Manufacturing method. The method for producing a rubber composition for a tread according to claim 4, wherein the ethylene-producing microorganism, plant, animal, and tissue culture body thereof are introduced and / or modified with a gene encoding ACC synthase. . Method for producing the aldehydes, the tread rubber composition of claim 1 wherein the acetaldehyde. Method for producing the unsaturated carboxylic acids, the tread rubber composition according to claim 1, wherein a tiglic acid and / or angelic acid. The method for producing a rubber composition for a tread according to claim 1, wherein the polybutadiene rubber is obtained by converting butadiene derived from biomass into polybutadiene rubber by an enzymatic reaction. The method for producing a rubber composition for a tread according to claim 8, wherein the enzyme involved in the enzyme reaction is a long-chain prenyl chain-extending enzyme. The method for producing a rubber composition for a tread according to claim 1, wherein a content of saccharide in 100% by mass of the biomass is 20% by mass or more. The manufacturing method of the rubber composition for treads of Claim 1 whose total content of the amino acid and protein in the said biomass 100 mass% is 10 mass% or more. The manufacturing method of the rubber composition for treads of Claim 1 whose total content of the fatty acid and fatty-acid ester in 100 mass% of said biomass is 10 mass% or more. The method for producing a rubber composition for a tread according to any one of claims 1 to 12 , wherein the polybutadiene rubber is obtained by polymerizing a plurality of monomer components having different origins as biomass-derived monomer components. The method for producing a rubber composition for a tread according to any one of claims 1 to 13 , wherein the polybutadiene rubber is obtained by polymerizing a monomer component derived from biomass and a monomer component derived from petroleum resources. The polybutadiene rubber is a biomass-derived monomer component, or a biomass-derived monomer component and a petroleum resource-derived, at a ratio appropriately selected according to the supply status of biomass resources, the supply status of petroleum resources, and / or market requirements. The method for producing a rubber composition for a tread according to any one of claims 1 to 14 , which is obtained by polymerizing the monomer component. The rubber composition for a tread contains 15 to 100 parts by mass of carbon black having a nitrogen adsorption specific surface area of 90 to 180 m ² / g with respect to 100 parts by mass of a rubber component. A method for producing a rubber composition for a tread. A step of producing a tread rubber composition for a process according to any one of claims 1-16, the pneumatic tire manufacturing method comprising the step of preparing a tread of a rubber composition was prepared. Biomass-derived monomer component or biomass-derived monomer component and petroleum resource-derived monomer component at a ratio selected as appropriate according to the supply status of biomass resources, the supply status of petroleum resources, and / or market requirements characterized by polymerizing the monomer component derived from biomass, allyl alcohols from biomass, alkenes, aldehydes, and catalysis of at least one biomass-derived component selected from the group consisting of unsaturated carboxylic acids (However, the microbial in vivo reaction is excluded.) The butadiene obtained by according to ASTM D6866-10 has a pMC (percent modern carbon) of 1% or more and a glass transition temperature (Tg) of −120 to −60. A method for producing biomass-derived rubber at ℃.

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