JP2015042711A - Cap tread rubber composition for passenger car tire, cap tread rubber for passenger car tire, and pneumatic tire for passenger car - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cap tread rubber composition for a passenger car tire, which can give a cap tread rubber for a passenger car tire and a pneumatic tire for a passenger car having high mileage property and wet grip performance (particularly, wet grip performance) equivalent to those of a cap tread rubber for a passenger car tire and of a pneumatic tire for a passenger car using a conventional synthetic rubber, while responding to demands for recycling-oriented society.SOLUTION: The cap tread rubber composition for a passenger car tire contains a biomass-derived rubber which is obtained by polymerizing an aromatic vinyl and dienes and has pMC (percent Modern Carbon) of 1% or more measured in accordance with ASTMD6866-10.

Description

The present invention relates to a cap tread rubber composition for passenger car tires, a cap tread rubber for passenger car tires using the same, and a pneumatic tire for passenger cars.

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, it is desired to move away from fossil fuels as in the energy field, 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 of low fuel consumption, wet grip performance, and processability (particularly wet grip performance) as compared to synthetic rubber such as styrene butadiene rubber (SBR).

JP 2003-63206 A

The present invention solves the above-mentioned problems and responds to the demands of a recycling-oriented society, while reducing the fuel consumption and wet grip performance equivalent to conventional tread rubber for passenger car tires and pneumatic tires for passenger cars (especially using a synthetic rubber). An object of the present invention is to provide a cap tread rubber composition for passenger car tires and a passenger car tire tread rubber composition that can provide a pneumatic tire for passenger cars.

The present invention is a cap tread rubber composition for passenger car tires comprising a biomass-derived rubber obtained by polymerizing aromatic vinyl and dienes and having a pMC (percent modern carbon) measured according to ASTM D6866-10 of 1% or more. Related to things.

The biomass-derived rubber preferably has a glass transition temperature (Tg) of −60 ° C. or higher.

The dienes are preferably biomass-derived butadiene.

The aromatic vinyl is preferably biomass-derived styrene.

The dienes are preferably biomass-derived butadiene and the aromatic vinyl is biomass-derived styrene.

The butadiene is 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.

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 butadiene is preferably produced directly from biomass by at least one selected from the group consisting of microorganisms, plants, animals, and tissue cultures thereof.

It is preferable that the butadiene is converted from at least one selected from the group consisting of saccharides, 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 butadiene-producing microorganism, plant, animal, and tissue culture thereof are selected from the group consisting of a gene encoding HMG-CoA reductase, a gene encoding diphosphomevalonate decarboxylase, and a gene encoding amino acid decarboxylase. It is preferable that at least one gene introduced and / or modified.

The styrene is preferably produced directly from biomass by at least one selected from the group consisting of microorganisms, plants, animals, and tissue cultures thereof.

It is preferable that the styrene is converted from a cinnamic acid derived from biomass.

It is preferable that the plant is a plant belonging to at least one family selected from the group consisting of witch hazel, Egonaceae, oleander, solanaceae, carrot, and camellia.

The microorganism is at least one selected from the group consisting of Fusarium, Penicillium, Pichia, Candida, Debaryomyces, Tolropsis, Saccharomyces, Bacillus, Escherichia, Streptomyces, and Pseudomonas A microorganism belonging to the genus is preferable.

The microorganism is preferably a microorganism that has not been genetically modified.

The microorganism and / or plant is preferably one that has been engineered to highly express phenylalanine ammonia lyase.

The microorganism and / or plant is preferably one that has been engineered to highly express cinnamic acid decarboxylase (phenylacrylic acid decarboxylase).

The microorganism and / or plant is preferably one that has been engineered to highly express phenolic acid decarboxylase.

It is preferable that the styrene is obtained by metabolism of plants from cinnamic acid derived from biomass.

It is preferable that the styrene is obtained by fermentation of microorganisms from cinnamic acid derived from biomass.

The styrene is preferably obtained from a cinnamic acid derived from biomass by a catalytic reaction.

The butadiene is preferably a mixture of a plurality of biomass-derived butadienes having different origins.

The styrene is preferably a mixture of a plurality of biomass-derived styrenes having different origins.

The biomass-derived rubber preferably has a pMC of 100% or more.

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 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 present invention is also a cap tread rubber composition for passenger car tires containing a styrene butadiene rubber, wherein the styrene butadiene rubber is obtained by a reaction starting from biomass or a series of reactions as at least a part of raw butadiene and raw styrene. The present invention relates to a cap tread rubber composition for passenger car tires which is obtained by polymerization using a rubber.

The present invention also relates to a cap tread rubber for passenger car tires produced using the rubber composition.

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

According to the present invention, a cap tread for a passenger car tire comprising a biomass-derived rubber obtained by polymerizing aromatic vinyl and dienes and having a pMC (percent modern carbon) measured in accordance with ASTM D6866-10 of 1% or more. Since it is a rubber composition, while satisfying the demands of a recycling society, good fuel economy, wet grip performance, and workability (particularly wet grip performance) equivalent to the case of using a conventional synthetic rubber can be obtained. Accordingly, by using the rubber composition for a cap tread rubber for passenger car tires and a pneumatic tire for passenger cars, while responding to the demands of the recycling society, a cap tread rubber for passenger car tires using conventional synthetic rubber, air for passenger cars Cap tread rubber for passenger car tires and pneumatic tires for passenger cars having low fuel consumption and wet grip performance (especially wet grip performance) equivalent to those of entering tires can be provided.

It is a schematic diagram which shows simply the apparatus used for manufacture of butadiene. It is a figure which shows the produced plasmid typically. It is a figure which shows the result of an Example and a comparative example.

The cap tread rubber composition for passenger car tires of the present invention (hereinafter, also simply referred to as tire rubber composition or rubber composition) is obtained by polymerizing aromatic vinyl and dienes, and conforms to ASTM D6866-10. The biomass-derived rubber having a pMC (percent modern carbon) measured by 1% or more is included.

In the present invention, a biomass-derived rubber obtained by polymerizing aromatic vinyl and dienes and having a pMC (percent modern carbon) measured in accordance with ASTM D6866-10 of 1% or more is used as the rubber component.

pMC is the ratio of the ¹⁴ C concentration of the sample to the ¹⁴ C 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 tire rubber composition.

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.

In the present invention, by using a biomass-derived rubber obtained by polymerizing aromatic vinyl and dienes and having a pMC of a specific value or more in a tire rubber composition, the conventional synthesis is achieved while meeting the demands of the recycling society. Cap tread rubber for passenger car tires using rubber, cap tread rubber for passenger car tires having the same fuel economy and wet grip performance (particularly wet grip performance) as pneumatic tires for passenger cars, and pneumatic tires for passenger cars The problem that cannot be solved by the conventional technology can be solved. In the present invention, biomass is also referred to as biomass resources.

The glass transition temperature (Tg) of the biomass-derived rubber is preferably −60 ° C. or higher. Despite the pMC being above a specific value, Tg is within this range, so that good low fuel consumption, wet, which could not be achieved with the natural rubber that is 100% biomass-derived rubber that has been used conventionally, Grip performance and workability (especially wet grip performance) are obtained, and while meeting the demands of the recycling society, low fuel consumption equivalent to conventional tread rubber for passenger car tires and pneumatic tires for passenger cars using synthetic rubber A cap tread rubber for passenger car tires having a wet grip performance (particularly wet grip performance) and a pneumatic tire for passenger cars can be provided. The Tg is preferably −55 ° C. or higher. When Tg is less than −60 ° C., wet grip performance tends to decrease. The Tg is preferably 0 ° C. or lower, more preferably −10 ° C. or lower, and further preferably −20 ° C. or lower. When Tg exceeds 0 ° C., the low temperature characteristics tend to deteriorate.
In addition, in this invention, Tg of rubber | gum (biomass origin rubber | gum) can be measured by the method as described in an Example.

The Mw (weight average molecular weight) of the biomass-derived rubber is preferably 0.1 × 10 ^{4 to} 100 × 10 ⁴ , more preferably 10 × 10 ⁴ to 80 × 10, because the effects of the present invention can be suitably obtained. ⁴ .
Similarly, Mw (weight average molecular weight) / Mn (number average molecular weight) of the biomass-derived rubber is preferably 0.1 to 10, more preferably 0.5 to 5.
In addition, Mw and Mn of the biomass-derived rubber can be measured by the method described in Examples.

The aromatic vinyl content (preferably styrene content) of the biomass-derived rubber is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more. If the aromatic vinyl content is less than 5% by mass, the grip performance may be significantly reduced. The aromatic vinyl content is preferably 60% by mass or less, more preferably 50% by mass or less, and still more preferably 40% by mass or less. When the aromatic vinyl content exceeds 60% by mass, the exothermic property is remarkably increased and the fuel efficiency tends to be deteriorated.
In the present invention, the aromatic vinyl content (preferably styrene content) of the biomass-derived rubber is calculated by H ¹ -NMR measurement.

Biomass-derived rubber is a rubber obtained by polymerizing aromatic vinyl and dienes. In the present invention, the rubber obtained by polymerizing aromatic vinyl and dienes is not limited to rubber obtained by polymerizing aromatic vinyl and dienes according to conventional methods, but also microorganisms, plants, animals, and tissues thereof. Also included are rubbers having aromatic vinyl and dienes as skeletal components obtained by a reaction with a culture (hereinafter also referred to as microorganisms) or an enzymatic reaction.

Moreover, the biomass-derived rubber may be a rubber obtained by polymerizing aromatic vinyl and dienes as monomer components so as to satisfy the above pMC. Specifically, the biomass-derived rubber satisfies the above pMC. In this case, at least one of aromatic vinyl and diene needs to be derived from biomass (a monomer component derived from biomass), but as described above, the higher the pMC, the better it can meet the demands of the recycling society. For this reason, it is preferable that both aromatic vinyl and dienes are biomass-derived monomer components.

In addition, a biomass-derived monomer component and a petroleum resource-derived monomer component may be used in combination as long as the pMC is satisfied. That is, biomass-derived dienes may be used in combination with dienes other than biomass-derived dienes (dienes derived from petroleum resources). Similarly, biomass-derived aromatic vinyl may be used in combination with aromatic vinyl other than biomass-derived aromatic vinyl (aromatic vinyl derived from petroleum resources).

Examples of the aromatic vinyl (aromatic vinyl monomer) include styrene, vinyl naphthalene, divinyl naphthalene, and the like. Among these, styrene (especially styrene derived from biomass) is preferable from the viewpoint of physical properties (particularly, good grip performance) of the obtained polymer and availability for industrial implementation. Styrene may have a substituent.

The diene (diene monomer) is preferably a conjugated diene monomer, such as butadiene (particularly 1,3-butadiene), isoprene, 1,3-pentadiene (piperine), 2,3-dimethyl-1,3- Examples thereof include butadiene and 1,3-hexadiene. Of these, butadiene (particularly, biomass-derived butadiene (1,3-butadiene)) is preferred from the viewpoint of the physical properties of the resulting polymer and the availability for industrial implementation.

In addition, the biomass-derived rubber includes structural units derived from other monomer components (monoterpene (myrcene, etc.) copolymerizable monomer components) other than aromatic vinyl and dienes as long as the above pMC is satisfied. You may go out.

The use ratio of the dienes and aromatic vinyl is preferably 50/50 to 90/10, more preferably 55/45 to 85/15, as the mass ratio of dienes / aromatic vinyl. If the ratio is less than 50/50, the polymer rubber may become insoluble in the hydrocarbon solvent, and uniform polymerization may not be possible. On the other hand, if the ratio exceeds 90/10, the strength of the polymer rubber may be reduced. May decrease.

As described above, biomass-derived butadiene is used as a biomass-derived rubber because it has good fuel efficiency, wet grip performance, and processability (particularly wet grip performance) while meeting the demands of a recycling society. Styrene butadiene rubber (biomass styrene butadiene rubber (BSBR)) obtained by polymerizing styrene is preferable.

As BSBR, as long as the above pMC is satisfied, monomer components other than butadiene and styrene (dienes other than butadiene (isoprene and the like), aromatic vinyls other than styrene (vinyl naphthalene and the like), monoterpene ( A structural unit derived from a copolymerizable monomer component) such as myrcene) may be included. The total amount of butadiene and styrene may not be derived from biomass. That is, biomass-derived butadiene may be used in combination with butadiene other than biomass-derived butadiene (butadiene derived from petroleum resources). Similarly, styrene derived from biomass may be used in combination with styrene other than biomass-derived styrene (styrene derived from petroleum resources).

The ratio of the biomass-derived monomer component in 100 mol% of the monomer component constituting the biomass-derived rubber is not particularly limited as long as it satisfies the above-mentioned pMC, but as described above, the higher the pMC, the more suitable for the demands of the recycling society. Is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, particularly preferably 90 mol% or more, most preferably 95 mol% or more, and 100 mol%. Also good.

Next, before explaining the method of preparing biomass-derived rubber from biomass, biomass in the present invention will be explained first.

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, glutamine, and phenylalanine. It is done. Of these, valine, leucine, isoleucine, arginine, and phenylalanine 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.

Next, a method for preparing biomass-derived rubber from biomass will be described. As described above, the biomass-derived rubber is preferably a styrene-butadiene rubber (biomass styrene-butadiene rubber (BSBR)) obtained by polymerizing butadiene derived from biomass and styrene. As, the case where the biomass-derived rubber is BSBR will be specifically described. As described above, in the present invention, BSBR includes not only BSBR obtained by polymerizing butadiene derived from biomass and styrene according to a conventional method, but also BSBR obtained by a reaction by a microorganism or an enzymatic reaction.

First, a method for preparing butadiene from biomass resources will be described, but the method for preparing butadiene is not limited to the method described below.

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 1.3.1.42) 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 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 that performs the butanediol fermentation is not particularly limited as long as it is a microorganism that can perform butanediol fermentation. For example, the genus Escherichia, the genus Zymomonas, the genus Candida, the Saccharomyces (Saccharomyces) ) Genus, Pichia genus, Streptomyces genus, Bacillus genus, Lactobacillus genus, Corynebacterium genus, Clostridium genus, blipsiella genus, ble. 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 (for example, Japanese Translation of PCT International Publication No. 2011-526489).

As a method for converting the alkene to butadiene, for example, a method of converting butene into alumina, zeolite, or the like with butadiene, ethylene is partially converted into acetaldehyde with an oxidation catalyst such as palladium chloride or palladium acetate, alumina, Examples thereof include a method of obtaining butadiene by dehydration reaction with residual ethylene using a dehydration catalyst such as zeolite.

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 such as palladium, zeolite, and alumina. And the like.

Butadiene is obtained from biomass resources by the method described above.

Next, although the method of preparing styrene from biomass resources is demonstrated, the method of preparing styrene is not limited to the method demonstrated below.

Various methods can be used as a method for preparing styrene from biomass resources, and the method is not particularly limited. For example, biologically obtaining styrene directly from biomass resources by at least one selected from the group consisting of microorganisms, plants, animals, and tissue cultures thereof (particularly microorganisms, plants, and tissue cultures thereof). Treatment method; Method of obtaining styrene by subjecting biomass resource to the chemical treatment method; Method of obtaining styrene by subjecting biomass resource to the physical treatment method; Converting biomass resource to styrene by in vitro enzymatic reaction or the like Method; A method of combining these methods and the like can be mentioned. Of these, biological treatment methods are preferred. In this production method, a saccharide used as a carbon source in a culture medium is mainly used as a biomass resource.
The microorganisms, plants, and animals that convert biomass resources into styrene may or may not be genetically manipulated.

A direct conversion method (biological treatment method) from biomass resources to styrene using microorganisms and the like is not particularly limited, but is performed using an in vivo route for biosynthesis of styrene from phenylalanine via cinnamic acid. It is possible.

Phenylalanine is a substance that is biosynthesized by the shikimic acid pathway of most microorganisms and plants, and an in vivo pathway for biosynthesis of styrene from this phenylalanine via cinnamic acid is known. Therefore, at least selected from the group consisting of microorganisms, plants, animals, and tissue cultures thereof (particularly microorganisms, plants, and tissue cultures thereof) using these in vivo pathways possessed by microorganisms and the like. With one species, styrene can be obtained directly from biomass resources.

Microorganisms, plants, animals, and tissue cultures thereof (particularly microorganisms, plants, and tissue cultures thereof) may be phenylalanine ammonia lyase, cinnamic acid decarboxylase (phenyl acrylate decarboxylase), and / or phenolic acid de It is preferable from the viewpoint of efficiently producing styrene that it has been engineered to highly express carboxylase (particularly ferulic acid decarboxylase).

Similarly, microorganisms, plants, animals, and tissue cultures thereof (especially microorganisms, plants, and tissue cultures thereof) are used in the biosynthesis pathway of styrene because styrene can be produced efficiently. It is preferably modified so as to promote (overproduction) the production of phenylalanine considered to be a substrate.

Specifically, microorganisms, plants, animals, and tissue cultures thereof (particularly microorganisms, plants, and tissue cultures thereof) highly express enzymes involved in the shikimate pathway and / or feedback inhibitory enzymes. It is preferable that the operation is as follows.

More specifically, microorganisms, plants, animals, and tissue cultures thereof (especially microorganisms, plants, and tissue cultures thereof) are highly expressed enzymes involved in the shikimate pathway. It is preferable that feedback inhibition by L-phenylalanine is released in an enzyme involved in the L-phenylalanine biosynthetic pathway and / or that an enzyme released from feedback inhibition is highly expressed.

The enzyme involved in the shikimate pathway is not particularly limited, and examples thereof include allogenate dehydratase, prefenate aminotransferase, prefenate dehydratase, chorismate mutase and the like.

For the reason that styrene can be efficiently produced, phenylalanine and / or cinnamic acid (preferably phenylalanine and / or cinnamic acid derived from biomass) is added to a medium for culturing microorganisms (including soil for growing plants). It is preferable. By adding these compounds located upstream of the in vivo pathway for biosynthesis of styrene, styrene can be efficiently produced. The phenylalanine and cinnamic acid to be added can be prepared by culturing microorganisms or the like.

The microorganisms that can directly convert biomass resources into styrene are not particularly limited, but include Fusarium, Penicillium, Pichia, Candida, Debaryomyces, Toluropsis, Saccharomyces, Bacillus, Escherichia, Streptomyces, Examples include microorganisms belonging to the genus Pseudomonas. 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.

The microorganism belonging to the genus Fusarium is not particularly limited. oxysporum, F.M. roseum, F. et al. aquaductucum, F.A. fujikuroi, F.M. solani, F.M. graminearum, F.M. asiaticum, F.A. Culmorum and the like are preferable from the viewpoint of styrene conversion efficiency. Oxysporum is more preferred.

The microorganism belonging to the genus Penicillium is not particularly limited. citrinum, P.C. oxalicum, P.M. glabrum, P.M. chrysogenum, P.M. digitatum, P.A. camemberti, P.M. islandicum, P.I. verrucosum, P.M. cyclopium, P.M. commune, P.M. citro-vide, P.I. rugulosum, P.M. italicum, P.M. expansum, P.M. marneffei, P.M. griseofluvum, P.M. galaucum, P.M. roqueforti, P.M. CAMBERBERTI, P.M. Natatum, P.A. gladioli and the like are preferable from the viewpoint of styrene conversion efficiency. citrinum, P.C. oxalicum, P.M. CAMBERBERTI is more preferable. Citrinum is more preferred.

The microorganism belonging to the genus Pichia is not particularly limited, but Pichia carsonii, Pichia anomala, Pichia pastoris, Pichia farinosa, Pichia membranifaciens, and Pichia gusta are more preferable because of the efficiency of i.

The microorganism belonging to the genus Candida is not particularly limited. famata, C.I. etellsii, C.I. versatilis, C.I. stelata is preferred from the viewpoint of styrene conversion efficiency, and C.I. famata is more preferred.

The microorganism belonging to the genus Debaryomyces is not particularly limited, but Debaryomyces hansenii is preferable from the viewpoint of styrene conversion efficiency.

The microorganism belonging to the genus Torlopsis is not particularly limited.

The microorganism belonging to the genus Saccharomyces is not particularly limited. cerevisiae, S. et al. Bayanus, S.B. boulardi and the like are preferable from the viewpoint of styrene conversion efficiency.

The microorganism belonging to the genus Bacillus is not particularly limited. subtilis, B.M. thuringiensis, B.I. coagulans, B.M. licheniformis, B.I. megaterium and the like are preferable from the viewpoint of styrene conversion efficiency. Subtilis is more preferred.

The microorganism belonging to the genus Escherichia is not particularly limited. albertii, E .; blattae, E .; E. coli, E.I. fergusonii, E .; hermannii, E .; vulneris and the like are preferable from the viewpoint of styrene conversion efficiency. E. coli is more preferable.

The microorganism belonging to the genus Streptomyces is not particularly limited. griseus, S .; Kanamyceticus, S. peucetius, S .; galilaeus, S .; parvulus, S. et al. antibioticus, S .; lividans, S .; maritimus and the like are preferable from the viewpoint of styrene conversion efficiency.

The microorganism belonging to the genus Pseudomonas is not particularly limited. aeruginosa, P.A. syringae pv. Japan, P.A. melae, P.M. putida and the like are preferable from the viewpoint of styrene conversion efficiency. putida, P.A. putida IH-2000, P.I. putida S12 is more preferred. putida IH-2000, P.I. Putida S12 is more preferred.

As microorganisms capable of directly converting biomass resources into styrene, microorganisms belonging to the genus Penicillium and Escherichia are preferable. citrinum, transformed E. coli. E. coli is more preferable.

Plants that can directly convert biomass resources into styrene are not particularly limited, and examples include plants belonging to witch hazelaceae, ceraceae, oleander, solanaceae, carrot, and camellia. 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.

The plant (tree) belonging to the witch hazel family is not particularly limited, but from the viewpoint of styrene production efficiency, a plant (tree) belonging to the genus Fusu is preferable, and among them, Fuyu (Liquidambar formosana), Momibaiba styraciflua, Levantos More preferable is Trax (Liquidambabar orientalis), more preferred is Momijibahu and Levant Strax, and particularly preferred is Momijibafu.

Plants (trees) belonging to the family Egonaceae are not particularly limited, but plants (trees) belonging to the genus Egonaceae are preferable from the viewpoint of styrene production efficiency, and among them, Syrax officinalis, Syrax japonica, Anthracnaceae (Styrax benzoin Dryer) is more preferable, and egonoki is more preferable.

The plant belonging to the family Oleander is not particularly limited, but from the viewpoint of the efficiency of styrene production, plants belonging to the genus periwinkle, oleander, periwinkle, aria genus, and rubber genus are preferred, and plants belonging to the genus periwinkle (particularly, More preferred is periwinkle.

Plants belonging to the solanaceous family are not particularly limited, but plants belonging to the genus Tobacco are preferred from the viewpoint of the efficiency of styrene production. tabacum and N.C. rustica is more preferred.

Although it does not specifically limit as a plant which belongs to the carrot family, The plant which belongs to the carrot genus is preferable from a viewpoint of the efficiency of styrene production.

Although it does not specifically limit as a plant which belongs to the camellia family, The plant which belongs to the camellia genus, Sakaki genus, and the genus Mockkok is preferable from a viewpoint of the efficiency of styrene production.

As a plant capable of directly converting biomass resources into styrene, plants belonging to the family Hazelaceae, Egonaceae, Oleanderaceae are preferable, plants belonging to the genus Fusarium, Egonocera, and Catharanthus are more preferable, Japanese maple butter, Levant Strax, Egonoki, Periwinkle is more preferable, and Japanese periwinkle, egonoki and periwinkle are particularly preferable.

When the plant is a tree, the method for obtaining styrene from the tree is not particularly limited, but a method obtained by purifying a resin (sap) that exudes by scratching the trunk is preferable in terms of efficiency. It can also be obtained by pulverizing a tree bark, trunk, branch, root, leaf, etc., obtaining a volatile component by extraction with an appropriate solvent, heating, and / or ultrasonic irradiation, and then purifying it.

If the plant is not a tree, it is difficult to obtain styrene as a resin, but plant tissues (eg, stems, leaves, roots, flowers, etc.) are crushed and extracted with a suitable solvent, heated, and / or super After obtaining a volatile component by sonication or the like, styrene is obtained by purification.

It is also possible to obtain styrene by culturing the plant tissue and obtaining a volatile component from the cultured tissue by extraction with an appropriate solvent, heating, and / or ultrasonic irradiation.

The plant tissue to be cultured is not particularly limited, but callus derived from a plant tissue piece is preferable because styrene can be efficiently obtained. That is, it is preferable to induce callus from a plant tissue piece and to culture the induced callus.

The method for inducing callus is not particularly limited. For example, a plant growth hormone (for example, an auxin-type plant hormone (eg, dichlorophenoxyacetic acid) and / or a cytokinin-type plant hormone (eg, benzyladenine)) in a medium containing a plant is used. Examples thereof include a method for inducing callus by culturing tissue pieces (for example, buds, leaves, stems, etc.).

Other methods for preparing styrene from biomass resources include at least one selected from the group consisting of microorganisms, plants, animals, and tissue cultures thereof (particularly microorganisms, plants, and tissue cultures thereof). An intermediate (especially phenylalanine and / or cinnamic acid) capable of synthesizing styrene is obtained from biomass resources, and the above-mentioned biological treatment is performed on the obtained intermediate (particularly phenylalanine and / or cinnamic acid). A method of obtaining styrene by applying the above-mentioned chemical treatment method such as a catalytic reaction, the above-mentioned chemical treatment method, the above-mentioned physical treatment method, the above-mentioned in vitro enzyme reaction, a method combining these methods, or the like is also preferably used. Especially, the method of performing the said biological treatment method with respect to the obtained intermediate body (especially phenylalanine and / or cinnamic acid) is preferable.
Note that the microorganism, plant, or animal that converts the intermediate into styrene may or may not be genetically manipulated.

As a method for obtaining styrene by subjecting the obtained intermediate (particularly phenylalanine and / or cinnamic acid) to the above biological treatment method, for example, as described above, a culture medium for culturing the above microorganisms and the like Phenylalanine and / or cinnamic acid may be added to (including soil for cultivating plants), and the microorganisms and the like may be cultured in the medium. Thereby, styrene is biosynthesized from the added phenylalanine and / or cinnamic acid by the microorganisms and the like.

As a method for obtaining styrene by subjecting the obtained intermediate phenylalanine to the above-mentioned chemical treatment method such as catalytic reaction, for example, ammonia lyase such as phenylalanine ammonia lyase was allowed to act to convert it to cinnamic acid. Thereafter, a method of obtaining styrene by decarboxylation using a decarboxylase, a transition metal catalyst, zeolite, or the like, a method of obtaining styrene by direct treatment at a high temperature using zeolite, alumina, or the like can be mentioned.

Examples of a method for obtaining styrene by applying the above-mentioned chemical treatment method such as catalytic reaction to cinnamic acid, which is the obtained intermediate, include, for example, metal catalysts using transition metals and the like, zeolite, alumina and the like at high temperature. The method of obtaining styrene by a decarboxylation reaction by making it act by, etc. are mentioned.

Styrene is obtained from biomass resources by the method described above.

The method of polymerizing styrene butadiene rubber (biomass styrene butadiene rubber (BSBR)) from butadiene and styrene obtained from biomass resources by the above-mentioned method, etc. is a method known to those skilled in the art, butadiene derived from petroleum resources, styrene The method is similar to the method for polymerizing styrene-butadiene rubber from the above, 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) are used from the viewpoints of availability, performance of BSBR to be obtained, 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.

Styrene obtained from biomass resources is a plant (preferably a plant belonging to the witch hazel family, the ceraceae family, the oleander family, more preferably the genus Fusarium, the genus Echinaceae, or periwinkle from the viewpoint of availability, the performance of the obtained BSBR, etc. Styrene obtained by a plant belonging to the genus, more preferably euglena, Egonoki, or Catharanthus), a microorganism (preferably Penicillium, Escherichia, more preferably P. citrinum, transformed E. coli). The obtained styrene can be preferably used. Moreover, it is also suitable to use these styrene in combination.

The molecular weight, branching, and microstructure of the obtained BSBR can be arbitrarily selected by changing the polymerization conditions according to a known method in accordance with the desired tire performance.

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. Biomass-derived styrene can be obtained using various plants and microorganisms.

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. Specifically, a mixture of a plurality of biomass-derived butadienes having different origins is used as the biomass-derived butadiene, and / or a mixture of a plurality of biomass-derived styrenes having different origins is used as the biomass-derived styrene. It is preferable to do. 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 or styrene into BSBR 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 BSBR 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 to BSBR, a medium containing butadiene (preferably butadiene obtained from biomass resources), styrene (preferably styrene obtained from biomass resources), microorganisms, plants, animals, and these And a method of polymerizing BSBR by culturing at least one selected from the group consisting of the above-mentioned tissue culture bodies.

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, BSBR is a reaction starting from biomass (from biomass resources to butadiene and / or styrene) as at least part of raw material butadiene (butadiene as a monomer component) and raw material styrene (styrene as a monomer component). One obtained by a one-step reaction (a reaction that directly produces butadiene and / or styrene from biomass resources) or a series of reactions (a series of reactions that produce butadiene and / or styrene starting from biomass resources) is used. It was obtained by polymerization.

The content of the biomass-derived rubber (preferably BSBR) in 100% by mass of the rubber component is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 50% by mass or more. The upper limit of the content is not particularly limited, but is preferably 95% by mass or less, and more preferably 90% by mass or less. When the content of biomass-derived rubber (preferably BSBR) is within the above range, good fuel economy, wet grip performance, and workability (particularly wet grip performance) can be obtained while meeting the demands of the recycling society. .

In addition to biomass-derived rubber, rubber components that can be used in rubber compositions for tires include natural rubber (NR), epoxidized natural rubber (ENR), diene-based 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), etc.) Is mentioned. A rubber component may be used independently and may use 2 or more types together. Among them, the combination of biomass-derived rubber and NR allows us to obtain good fuel efficiency, wet grip performance, workability, wear resistance, and bending fatigue resistance while meeting the demands of the recycling society. , BR is preferable, and BR is more preferable. It is also preferable to use NR and BR together.

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 40% by mass or less, more preferably 30% by mass or less. When the NR content is within the above range, good fuel economy, wet grip performance, workability, wear resistance, and bending fatigue resistance can be obtained while meeting the demands of the recycling society.

The content of BR 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 40% by mass or less, more preferably 30% by mass or less. When the BR content is within the above range, good fuel economy, wet grip performance, workability, wear resistance, and bending fatigue 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 50 to 100 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 and the bending fatigue resistance 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, more preferably 15 parts by mass or more, still more preferably 25 parts by mass or more, and particularly preferably 45 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 90 parts by mass or less. When the silica content is within the above range, good fuel efficiency is obtained, and a good reinforcing effect (wear resistance, flex fatigue resistance) is also obtained.

Among the fillers, carbon black is preferably included from the viewpoint of improving the grip performance, 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 grip performance, abrasion 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 grip performance, 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 is deteriorated, and low fuel consumption, wear resistance, and bending fatigue resistance tend to be deteriorated.

The content of silica in 100% by mass of silica and carbon black is preferably 40% by mass or more, more preferably 60% by mass or more, still more preferably 80% by mass or more, and may be 100% by mass. . Thereby, the pMC of the rubber composition can be increased, and good fuel efficiency can be obtained.

In addition to the above components, the rubber composition for tires contains a compounding agent generally used in the production of a rubber composition, such as a silane coupling agent, oil, stearic acid, zinc oxide, wax, anti-aging agent, 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.

The cap tread rubber composition for passenger car tires of the present invention means a rubber composition used for a cap tread of a pneumatic tire for passenger cars. Here, the cap tread is a surface layer portion of a tread having a multilayer structure. For example, a tread having a two-layer structure [a surface layer (cap tread) and an inner surface layer (base tread)] is a surface layer.

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 cap tread rubber for passenger car tires of the present invention is produced by an ordinary method using the rubber composition. That is, if necessary, a rubber composition containing various additives is extruded in accordance with the shape of a cap tread for passenger car tires at an unvulcanized stage, molded, heated and pressurized in a vulcanizer, and then used for passenger cars. Cap tread rubber for tires can be manufactured.

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

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

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

(PMC of butadiene, styrene, styrene butadiene rubber)
The pMC of butadiene, styrene, and styrene butadiene rubber was measured according to ASTM D6866-10 by the following method.
A sample (butadiene, styrene, or styrene butadiene 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)). ¹⁴ C concentration and ¹³ C concentration were measured by the measuring device, 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.

(Styrene content of styrene-butadiene rubber)
The styrene content was measured using an AV400 NMR apparatus manufactured by BRUKER and data analysis software TOP SPIN2.1.

(Glass transition temperature (Tg) of styrene butadiene 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.

(Weight average molecular weight (Mw), molecular weight distribution (Mw / Mn) of styrene butadiene rubber)
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 there
acetobutylicum (ATCC824) was inoculated 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.
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 shown in 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%.

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

Production Example 5 (Production of styrene from trees belonging to the witch hazel family)
A part of the bark of Japanese barb (Liquidamba bar styracifura) was peeled off, and a total of 620 g of the exuded resin was immersed in toluene. After leaving for half a day, the toluene solution was filtered and distilled to obtain 2.4 g of a fraction at 130 to 160 ° C. The obtained fraction was separated and purified by HPLC to obtain 0.8 g of styrene. The pMC value indicating the biomass ratio of the obtained styrene (biomass-derived styrene) was 109%.
Further, 1 kg of peeled bark was treated in the same manner to obtain 0.8 g of styrene. The pMC value indicating the biomass ratio of the obtained styrene (biomass-derived styrene) was 109%.

Production Example 6 (Production of styrene from trees belonging to the family Aceraceae)
610 g of Syrax jamonica resin was treated in the same manner as in Production Example 5 to obtain 0.1 g of styrene. The pMC value indicating the biomass ratio of the obtained styrene (biomass-derived styrene) was 109%.

Production Example 7 (Production of styrene by plant tissue culture)
The periwinkle buds were cut out, immersed in a 70% ethanol solution and then about 0.5% sodium hypochlorite solution, and then washed with sterile water. Washed tissue pieces (buds) were placed on MS medium supplemented with 1.0 mg / l dichlorophenoxyacetic acid and 1.0 mg / l benzyladenine. This was cultured at 25 ° C. for 5 weeks to form callus.
Next, 50 mg of cinnamic acid derived from biomass, 1.0 mg was added to the Gamborg B5 liquid medium (Gamburg OL, Miller RA, Ojima K., Experimental Cell Research, 50, 151-158 (1968).). 10 g of the above callus was transplanted to 20 ml of a medium supplemented with / l dichlorophenoxyacetic acid, 1.0 mg / l benzyladenine and 3% sucrose. This was cultured for 12 days under shaking at a culture temperature of 25 ° C. and in the dark at a rotation speed of 100 rpm.
The cultured tissue was taken out, washed with water, dried, and then frozen and pulverized, extracted with hexane, and the extract was separated and purified by HPLC to obtain 6 mg of styrene. The pMC value indicating the biomass ratio of the obtained styrene (biomass-derived styrene) was 109%.
Moreover, the cinnamic acid derived from biomass was prepared by further purifying the cinnamic acid derived from an herb (Gomanohagusa) sold for aroma use by high performance liquid chromatography.

Production Example 8 (Production of styrene by a microorganism whose gene has not been modified)
24 g of potato dextrol medium powder (manufactured by Sigma Aldrich) was dissolved in 1000 mL of purified water, and autoclaved at 121 ° C. for 20 minutes. Before use, chloramphenicol was added to a final concentration of 100 mg / L.
Penicillium citrinum (ATCC 9849) was inoculated into the medium, and statically cultured at 25 ° C. for 2 weeks under sealed conditions. Then, after adding hexane to a culture container and shaking, the production | generation of styrene was confirmed by isolate | separating a hexane layer and analyzing by GC / MS. The pMC value indicating the biomass ratio of the obtained styrene (biomass-derived styrene) was 109%.

Production Example 9 (Styrene production by genetically modified Escherichia coli)
<Preparation of encP gene (gene encoding phenylalanine ammonia lyase) fragment and construction of encP expression plasmid>
Streptomyces maritimus encP gene (1572 bp from start codon to stop codon (GenBank accession number: AF254925 nucleotide number 16269-17840)) was prepared as an artificial gene, and the DNA inserted into the SmaI site of the cloning vector pUC19 plasmid was inserted into PCR. A mold was used. PCR was performed using an upstream primer (SEQ ID NO: 1) containing an NdeI site on the 5 ′ end side and a downstream primer (SEQ ID NO: 2) containing a BamHI site on the 5 ′ end side, and the reaction solution was subjected to QIAprep PCR Purification Kit ( The DNA fragment E of the encP gene (NdeI-encP-BamHI: 1592 bp) containing novel restriction enzyme sites at both ends was obtained.
By a general recombinant DNA procedure, DNA fragment E treated with NdeI restriction enzyme and BamHI restriction enzyme was ligated to the NdeI-BamHI site of pET11a vector (Novagen) and transformed into E. coli DH-5α competent cell. The LB agar medium containing 50 μg / mL of ampicillin was inoculated and cultured at 37 ° C. overnight. The E. coli colonies formed on the agar medium were cultured with shaking in 5 mL of LB liquid medium containing 50 μg / mL of ampicillin at 37 ° C. overnight, and a plasmid was extracted from the resulting E. coli using QIAprep Spin Miniprep Kit (Qiagen). A plasmid in which the DNA sequence of GenBank accession number AF254925 was confirmed to be inserted into the target site of the pET11a vector by DNA sequence analysis was designated as encP expression plasmid pET11-encP (plasmid shown in FIG. 2 (a)).

<Isolation of FDC1 gene (gene encoding ferulic acid decarboxylase)>
Genomic DNA was purified from the budding yeast Saccharomyces cerevisiae using Yeast Geno-DNA-Template (Geno Technology, Inc), and used as a template for the first PCR. PCR was performed using the upstream primer (SEQ ID NO: 3) and the downstream primer (SEQ ID NO: 4), the reaction solution was purified with QIAprep PCR purification Kit (Qiagen), and the resulting DNA was used as a template for the second PCR. It was. A second PCR was performed using an upstream primer (SEQ ID NO: 5) containing a BspHI site on the 5 ′ end side and a downstream primer (SEQ ID NO: 6) containing a HindIII site on the 5 ′ end side, and the reaction solution was subjected to QIAprep PCR Purification with purification kit (Qiagen) gave a DNA fragment F of the FDC1 gene (BspHI-FDC1-HindIII: 1525 bp) with new restriction enzyme sites added to both ends.

<Isolation of PAD1 gene (gene encoding cinnamic acid decarboxylase)
Using the Saccharomyces cerevisiae genome described above as a template, PCR was performed using an upstream primer (SEQ ID NO: 7) and a downstream primer (SEQ ID NO: 8), and the reaction solution was purified by PCR purification Kit (Qiagen). DNA was used as a template for the second PCR. A second PCR was performed using an upstream primer (SEQ ID NO: 9) containing an NdeI site on the 5 ′ end side and a downstream primer (SEQ ID NO: 10) containing an XhoI site on the 5 ′ end side, and the reaction solution was subjected to QIAprep PCR. Purification with purification kit (Qiagen) gave a DNA fragment P (NdeI-PAD1-XhoI: 746 bp) of the PAD1 gene with new restriction enzyme sites added to both ends.

<Construction of FDC1 / PAD1 co-expression plasmid>
The FDC1 gene DNA fragment F was inserted into the multiple cloning site-1 (MCS-1) of pRSFDuet-1 (Novagen), and the PAD1 gene DNA fragment P was inserted into the multiple cloning site-2 (MCS-2) by the following procedure.
By a general recombinant DNA procedure, DNA fragment F treated with BspHI restriction enzyme and HindIII restriction enzyme was inserted into NcoI site and HindIII site in multiple cloning site-1 of pRSFDuet-1 vector (Novagen). PRSF-FDC1 was constructed in the same procedure as that for pET11-encP except that the ampicillin in the agar medium and liquid medium was changed to kanamycin.
Similarly, the DNA fragment P treated with the NdeI restriction enzyme and the XhoI restriction enzyme was incorporated into the NdeI site and the XhoI site of pRSF-FDC1 (derived from MCS-2 of the original vector pRSFDuet-1). pRSF-FDC1-PAD1 (plasmid shown in FIG. 2 (b)) was used.

<Production of transformant>
pET11-encP and pRSF-FDC1-PAD1 were simultaneously transformed into E. coli BL21 (DE3) competent cells, seeded on LB agar medium containing 35 μg / mL ampicillin and 20 μg / mL kanamycin, and cultured at 30 ° C. overnight. Formation of E. coli colonies was confirmed on the agar medium.

<Production of styrene by the transformant>
E. coli colonies transformed with pET11-encP and pRSF-FDC1-PAD1 are inoculated into 1 mL of LB liquid medium containing 35 μg / mL of ampicillin and 20 μg / mL of kanamycin, and cultured with shaking overnight at 30 ° C. did. A 50 mL LB liquid medium containing 35 μg / mL ampicillin and 20 μg / mL kanamycin in a 300 mL Meyer flask was inoculated with 100 μL of the preculture solution and cultured with shaking at 30 ° C. for 15 hours. While measuring the absorbance (A600) of the culture solution at a wavelength of 600 nm every 30 minutes, the culture was further continued under the same conditions. When A600 reached 0.8, 1M isopropyl-β- was used to induce protein expression. 25 μL of thiogalactopyranoside (IPTG) (final concentration 0.5 mM) was added, and further cultured for 8 hours.

<Measurement of styrene production in the culture medium>
The culture solution was centrifuged, hexane was added to the supernatant, and the mixture was vigorously stirred. After centrifugation, the hexane layer was separated and analyzed by GC / MS to confirm the production of styrene. The production amount of styrene was 140 mg / L. The pMC value indicating the biomass ratio of the obtained styrene (biomass-derived styrene) was 109%.

Production Example 10 (Production of Biomass Styrene Butadiene Rubber (BSBR))
As biomass-derived butadiene, the biomass-derived styrene obtained in Production Examples 5-9 is used as the biomass-derived styrene, which is a mixture of the biomass-derived butadiene (1,3-butadiene) obtained in Production Examples 1-4. The mixture was used as a monomer component to synthesize BSBR (corresponding to the biomass-derived rubber of the present invention).
The chemicals used are as follows.
Cyclohexane: Anhydrous cyclohexanebutadiene manufactured by Kanto Chemical Co., Ltd .: Mixture of biomass-derived butadiene obtained in Production Examples 1-4 Styrene: Mixture of biomass-derived styrene obtained in Production Examples 5-9 TMEDA: Kanto Chemical Co., Ltd. Tetramethylethylenediamine butyllithium solution manufactured by: 1.6M-n-butyllithium / hexane solution manufactured by Kanto Chemical Co., Ltd. BHT solution: BHT manufactured by Kanto Chemical Co., Ltd. (2,6-tert-butyl-p-cresol) ) A solution prepared by dissolving 0.1 g in 100 ml of isopropanol manufactured by Kanto Chemical Co., Ltd. <Synthesis of BSBR>
The reaction kettle (500 ml pressure-resistant stainless steel container) was purged with nitrogen, and while maintaining the nitrogen atmosphere, 180 ml of cyclohexane, 20 ml (222 mmol) of butadiene, 3.5 ml (30 mmol) of styrene, and 0.3 ml (2 mmol) of TMEDA were added and stirred. Started.
Next, the temperature inside the container was raised to 40 ° C., 0.06 ml of a butyl lithium solution was added, and polymerization was started. After stirring for 3 hours, 0.1 ml of BHT solution was added to the polymer solution and stirred for 5 minutes, and then the polymer solution was taken out. The polymer solution was poured into 300 ml ethanol with stirring to solidify the polymer. The obtained polymer was air-dried and then dried under reduced pressure for 24 hours to obtain biomass styrene butadiene rubber (BSBR). The yield was 95%. As a result of the analysis, Mw of the obtained BSBR was 40.2 × 10 ⁴ , Mw / Mn was 1.07, pMC indicating biomass ratio was 108%, Tg was −25 ° C., and styrene content was 22.3 mass%. there were.

Below, various chemical | medical agents used by the Example and the comparative example are demonstrated.
NR: RSS # 3 (Tg: -75 ° C)
SBR: NS116 manufactured by Nippon Zeon Co., Ltd. (Tg: −25 ° C., styrene content: 21% by mass, Mw is 68.7 × 10 ⁴ , Mw / Mn is 1.12)
BSBR: Biomass styrene butadiene rubber obtained by Production Example 10 (corresponding to biomass-derived rubber of the present invention)
BR: BR1220 manufactured by Nippon Zeon Co., Ltd.
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 diameter: 15 nm, N ₂ SA: 175 m ² / g)
Silane coupling agent: Si75 (bis (3-triethoxysilylpropyl) disulfide) 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 Hua 1 manufactured by Mitsui Mining & Smelting Co., Ltd.
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)
Using a Banbury mixer, the compounding amount shown in Step 1 of Table 1 was added and kneaded at about 150 ° C. for 5 minutes. Thereafter, to the mixture obtained in Step 1, sulfur and a vulcanization accelerator in the blending amounts shown in Step 2 are added, and kneaded for 3 minutes at about 80 ° C. using an open roll. A vulcanized rubber composition was obtained. The obtained unvulcanized rubber composition was molded into a cap tread shape, bonded to another tire member, and vulcanized at 170 ° C. for 15 minutes to produce a pneumatic tire for passenger cars. The rubber test piece was evaluated by cutting out rubber from the cap tread portion of the tire.

The resulting unvulcanized rubber composition, vulcanized rubber composition, and passenger car pneumatic tire were evaluated as follows. The results are shown in Table 1.

(1) Using a rolling resistance index viscoelastic spectrometer VES (manufactured by Iwamoto Seisakusho Co., Ltd.), each compounding (vulcanized rubber composition) under the conditions of a temperature of 70 ° C., an initial strain of 10%, and a dynamic strain of 2%. The tan δ was measured, and the tan δ of Comparative Example 1 was set to 100. 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

(2) WET performance index Using a pneumatic tire for passenger cars, run the vehicle on a wet asphalt road test course, and evaluate the grip performance (grip feeling, brake performance, traction performance) at this time. It was. 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. The larger the index, the better the WET performance (wet grip performance).

(3) Processability Index Regarding the obtained unvulcanized rubber composition, according to JIS K 6300-1, “Unvulcanized rubber—physical properties—Part 1: Determination of viscosity and scorch time by Mooney viscometer” The Mooney viscosity (ML) of the unvulcanized rubber composition at the time when 4 minutes passed by rotating a small rotor under a temperature condition of 130 ° C. heated by preheating for 1 minute using a Mooney viscosity tester. _{1 + 4/130 ° C.} ). The measurement result was set to 100 as the result of Comparative Example 1, and the Mooney viscosity of each formulation was indicated by an index according to the following formula. The larger the index, the lower the Mooney viscosity and the better the workability.
(Processability index) = (Mooney viscosity of Comparative Example 1) / (Mooney viscosity of each formulation) × 100

From Table 1, since Comparative Example 2 employs BR 20% by mass and SBR 80% by mass as the rubber component, good fuel economy, wet grip performance, and processability are obtained, but the entire rubber component The pMC is low and it cannot fully meet the demands of the recycling society. On the other hand, in Comparative Examples 3 and 4, since NR100% by mass, NR80% by mass, or BR20% by mass is adopted as the rubber component, the pMC of the entire rubber component is increased, and the demand of the recycling society is met. Although it was possible, the wet grip performance was greatly reduced. On the other hand, in Example 1, since 20 mass% of BR and 80 mass% of BSBR are adopted as the rubber component, the pMC of the entire rubber component is increased, which can meet the demands of the recycling society and is good. Low fuel consumption, wet grip performance, and workability (particularly wet grip performance) were also obtained. Also in other examples, the pMC was high, which could meet the demands of the recycling society, and good fuel economy, wet grip performance, and workability were obtained. In FIG. 3, the relationship between the pMC of the example and the comparative example and the evaluation results of low fuel consumption, wet grip performance, and processability is plotted. As is clear from this figure, in the example in which BSBR is blended, It is clear that pMC is high, can meet the demands of the recycling society, and can also achieve good fuel economy, wet grip performance, and processability.

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

(Sequence table free text)
Sequence number 1: Upstream primer (encP-U-Nde)
SEQ ID NO: 2: Downstream primer (encP-L-Bam)
SEQ ID NO: 3: upstream primer (FDC1-gU)
SEQ ID NO: 4: Downstream primer (FDC1-gL)
SEQ ID NO: 5: upstream primer (FDC1-nU-BspHI)
Sequence number 6: Downstream side primer (FDC1-nL-Hind)
SEQ ID NO: 7: upstream primer (PAD1-gU)
SEQ ID NO: 8: Downstream primer (PAD1-gL)
SEQ ID NO: 9: upstream primer (PAD1-nU-Nde)
SEQ ID NO: 10: downstream primer (PAD1-nL-Xho)

Claims (40)

A cap tread rubber composition for passenger car tires comprising a biomass-derived rubber obtained by polymerizing aromatic vinyl and dienes and having a pMC (percent modern carbon) measured according to ASTM D6866-10 of 1% or more. The cap tread rubber composition for passenger car tires according to claim 1, wherein the biomass-derived rubber has a glass transition temperature (Tg) of -60 ° C or higher. The cap tread rubber composition for passenger car tires according to claim 1 or 2, wherein the dienes are biomass-derived butadiene. The cap tread rubber composition for a passenger car tire according to any one of claims 1 to 3, wherein the aromatic vinyl is biomass-derived styrene. The cap tread rubber composition for a passenger car tire according to claim 1 or 2, wherein the diene is butadiene derived from biomass and the aromatic vinyl is styrene derived from biomass. The butadiene is 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. The cap tread rubber composition for passenger car tires according to claim 3 or 5. The cap tread rubber composition for a passenger car tire according to claim 6, wherein the alkyl alcohol is 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 The tread for passenger car tires according to claim 7, wherein the tread is 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. Rubber composition. The cap tread rubber composition for a passenger car tire according to claim 6, wherein the allyl alcohol is crotyl alcohol and / or 3-buten-2-ol. The cap tread rubber composition for passenger car tires according to claim 6, wherein the alkenes are butene and / or ethylene. The cap tread for a passenger car tire according to claim 10, 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. Rubber composition. The cap tread rubber composition for passenger car tires according to claim 11, wherein the microorganisms, plants, animals, and tissue culture bodies that produce ethylene are introduced and / or modified with a gene encoding ACC synthase. . The cap tread rubber composition for passenger car tires according to claim 6, wherein the aldehyde is acetaldehyde. The cap tread rubber composition for a passenger car tire according to claim 6, wherein the unsaturated carboxylic acids are tiglic acid and / or angelic acid. The cap tread rubber for passenger car tires according to claim 3 or 5, wherein the butadiene is directly produced from biomass by at least one selected from the group consisting of microorganisms, plants, animals, and tissue cultures thereof. Composition. The cap tread rubber composition for passenger car tires according to claim 15, wherein the butadiene is converted from at least one selected from the group consisting of sugars, hemiterpenes, and amino acids. The cap tread rubber composition for a passenger car tire according to claim 16, wherein the amino acid is at least one selected from the group consisting of valine, leucine, isoleucine, and arginine. The cap for passenger car tire according to claim 16, wherein the enzyme that converts hemiterpenes and / or amino acids into butadiene is at least one selected from the group consisting of HMG-CoA reductase, diphosphomevalonate decarboxylase, and amino acid decarboxylase. Tread rubber composition. The butadiene-producing microorganism, plant, animal, and tissue culture thereof are selected from the group consisting of a gene encoding HMG-CoA reductase, a gene encoding diphosphomevalonate decarboxylase, and a gene encoding amino acid decarboxylase. The cap tread rubber composition for passenger car tires according to claim 15, wherein at least one gene introduced and / or modified. 6. The cap tread rubber for passenger car tires according to claim 4 or 5, wherein the styrene is produced directly from biomass by at least one selected from the group consisting of microorganisms, plants, animals, and tissue cultures thereof. Composition. The cap tread rubber composition for a passenger car tire according to claim 4 or 5, wherein the styrene is converted from a cinnamic acid derived from biomass. 21. The cap tread rubber for passenger car tires according to claim 20, wherein the plant belongs to at least one family selected from the group consisting of witch hazel, Echinaceae, oleander, solanaceae, carrot, and camellia. Composition. The microorganism is at least one selected from the group consisting of Fusarium, Penicillium, Pichia, Candida, Debaryomyces, Tolropsis, Saccharomyces, Bacillus, Escherichia, Streptomyces, and Pseudomonas The cap tread rubber composition for passenger car tires according to claim 20, which is a microorganism belonging to the genus. The cap tread rubber composition for a passenger car tire according to claim 20, wherein the microorganism is a microorganism not genetically modified. 21. The cap tread rubber composition for a passenger car tire according to claim 20, wherein the microorganism and / or plant is engineered to highly express phenylalanine ammonia lyase. 26. The cap tread rubber composition for passenger car tires according to claim 20 or 25, wherein the microorganism and / or plant is engineered so as to highly express cinnamic acid decarboxylase (phenylacrylic acid decarboxylase). 27. The cap tread rubber composition for passenger car tires according to any one of claims 20, 25, and 26, wherein the microorganism and / or the plant is engineered to highly express phenolic acid decarboxylase. The cap tread rubber composition for a passenger car tire according to claim 21, wherein the styrene is obtained from a cinnamic acid derived from biomass by plant metabolism. The cap tread rubber composition for a passenger car tire according to claim 21, wherein the styrene is obtained by fermentation of microorganisms from a cinnamic acid derived from biomass. The cap tread rubber composition for a passenger car tire according to claim 21, wherein the styrene is obtained by a catalytic reaction from cinnamic acid derived from biomass. The cap tread rubber composition for a passenger car tire according to claim 3 or 5, wherein the butadiene is a mixture of a plurality of biomass-derived butadienes having different origins. The cap tread rubber composition for a passenger car tire according to claim 4 or 5, wherein the styrene is a mixture of a plurality of biomass-derived styrenes having different origins. The cap tread rubber composition for a passenger car tire according to any one of claims 1 to 32, wherein the biomass-derived rubber has a pMC of 100% or more. The cap tread rubber composition for passenger car tires according to any one of claims 1 to 33, wherein the biomass-derived rubber is 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 an appropriately selected ratio according to the supply status of biomass resources, the supply status of petroleum resources, and / or market requirements. The cap tread rubber composition for a passenger car tire according to any one of claims 1 to 34, wherein the cap tread rubber composition is obtained by polymerizing a monomer component derived therefrom. The cap tread rubber composition for a passenger car tire according to any one of claims 3 to 5, wherein a saccharide content in 100% by mass of the biomass is 20% by mass or more. The cap tread rubber composition for passenger car tires according to any one of claims 3 to 5, wherein the total content of amino acids and proteins in 100% by mass of biomass is 10% by mass or more. A cap tread rubber composition for passenger car tires containing styrene butadiene rubber, wherein the styrene butadiene rubber is obtained by a reaction starting from biomass or a series of reactions as at least part of raw butadiene and raw styrene. A cap tread rubber composition for passenger car tires obtained by polymerization. A tread rubber for passenger car tires produced using the rubber composition according to any one of claims 1 to 38. A pneumatic tire for a passenger car having a cap tread produced using the rubber composition according to any one of claims 1 to 38.

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