JP2007000109A - New microorganism wu-yso9 strain, and method for biodegrading rubber - Google Patents

New microorganism wu-yso9 strain, and method for biodegrading rubber Download PDF

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JP2007000109A
JP2007000109A JP2005186470A JP2005186470A JP2007000109A JP 2007000109 A JP2007000109 A JP 2007000109A JP 2005186470 A JP2005186470 A JP 2005186470A JP 2005186470 A JP2005186470 A JP 2005186470A JP 2007000109 A JP2007000109 A JP 2007000109A
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rubber
strain
polyisoprene
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carbon black
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JP2007000109A5 (en
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Kuniki Kino
邦器 木野
Yuichi Ishino
裕一 石野
Kotaro Kirimura
光太郎 桐村
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Bridgestone Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/105—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with enzymes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

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Abstract

<P>PROBLEM TO BE SOLVED: To provide a new kind of microorganisms capable of degrading polyisoprene-based rubber, especially the rubber containing carbon black. <P>SOLUTION: The WU-YSO9 strain (FERM P-20314) belonging to the genus Ochrobactrum, a new cicroorganism. Because this strain has the activity of degrading polyisoprene-based rubbers, a new method for biodegrading rubber compositions is also provided. Furthermore, owing to the method, biodegradation of carbon black-containing rubber products can be achieved. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、ポリイソプレン系ゴムを分解する作用を有する、オクロバクトルム属の菌株ＷＵ−ＹＳ０９株（ＦＥＲＭ Ｐ−２０３１４）に関する。更に本発明は、ポリイソプレン系ゴムを含有するゴム組成物を、オクロバクトルム属の菌株ＷＵ−ＹＳ０９株（ＦＥＲＭ Ｐ−２０３１４）で微生物分解する方法に関する。   The present invention relates to a strain WU-YS09 (FERM P-20314) belonging to the genus Okrobactrum, which has an action of decomposing polyisoprene rubber. Furthermore, the present invention relates to a method for microbial degradation of a rubber composition containing a polyisoprene rubber with a strain WU-YS09 (FERM P-20314) belonging to the genus Okrobactrum.

廃タイヤは一般のプラスチック製品と比較しても回収率は高く、特にセメント工場を中心として燃料として再利用されている。しかしながら近年環境問題の高まりとともに、廃タイヤを燃料として燃やすのではなく、コンポストのように低温で分解する省エネルギー型の方法や分解した材料を再利用するマテリアルリサイクルの方法の開発が求められている。   Waste tires have a higher recovery rate than ordinary plastic products, and are reused as fuel, especially in cement factories. However, with the recent increase in environmental problems, there is a need to develop energy-saving methods that decompose at low temperatures, such as compost, and material recycling methods that reuse decomposed materials, instead of burning waste tires as fuel.

ゴム製品を分解する方法として、微生物による分解処理が考えられる。微生物分解は低温での処理なので、エネルギー消費は最も少ない処理法といえる。また、ゴム製品を微生物分解した後、分解物を再利用することも考えられる。例えば、分解されたモノマーやオリゴマーを再利用することや、粉ゴムの表面を微生物分解し、再度未加硫ゴムに混練り加硫することにより、新たな製品に利用することも考えられる。   As a method for decomposing a rubber product, a decomposing process using microorganisms can be considered. Microbial degradation is a low-temperature treatment, so energy consumption is the least treatment method. It is also conceivable to recycle the decomposition product after microbial decomposition of the rubber product. For example, it is conceivable to reuse the decomposed monomer or oligomer, or to microbially decompose the surface of the powdered rubber and knead it again with the unvulcanized rubber and vulcanize it for a new product.

ゴムの微生物分解については、従来様々な微生物がスクリーニングされ、検討されている。そのような微生物分解については、特開平９−１９４６２４号公報、特開平１１−６０７９３号公報等で報告されている。なおノカルディア属の放線菌は天然ゴムなどのポリイソプレン系ゴムを分解することが知られているが、通常のノカルディア属の菌ではカーボンブラックなどを配合した硬質ゴムを分解することは困難である。これまでに、カーボンブラックを含有したゴム製品を分解できる菌の例は非常に少なく、未だに実用化された例はない。   Various microorganisms have been screened and studied for microbial degradation of rubber. Such microbial degradation has been reported in JP-A-9-194624, JP-A-11-60793, and the like. Nocardia genus actinomycetes are known to degrade natural rubber and other polyisoprene-based rubbers, but normal Nocardia genus bacteria are difficult to degrade hard rubber compounded with carbon black. is there. To date, there are very few examples of bacteria capable of degrading rubber products containing carbon black, and no examples have yet been put to practical use.

特開平９−１９４６２４号公報JP-A-9-194624 特開平１１−６０７９３号公報Japanese Patent Laid-Open No. 11-60793

そこで、ゴムの微生物分解に利用できる新規な微生物を得ること、特にカーボンブラックを含有したゴム製品を分解することができる微生物を得ることが本発明の課題である。   Accordingly, it is an object of the present invention to obtain a novel microorganism that can be used for microbial degradation of rubber, particularly to obtain a microorganism that can degrade a rubber product containing carbon black.

そこで、本発明者らが鋭意検討して天然ゴム分解菌の探索を行った結果、ゴム製品を分解できる微生物であるＷＵ−ＹＳ０９株を見いだした。ＷＵ−ＹＳ０９株によれば、従来困難であったカーボンブラックを含有するゴム製品を分解することが可能である。よって本発明により上記課題を解決することが可能となった。本発明の方法は、タイヤなどのゴム製品の廃棄及び再利用に有用である。   Then, as a result of the present inventors diligently searching and searching for natural rubber-degrading bacteria, the WU-YS09 strain, which is a microorganism capable of degrading rubber products, was found. According to the WU-YS09 strain, it is possible to decompose a rubber product containing carbon black, which has been difficult in the past. Therefore, the present invention can solve the above problems. The method of the present invention is useful for the disposal and reuse of rubber products such as tires.

本発明は次の（１）〜（７）からなる。
（１）ポリイソプレン系ゴムを分解する作用を有する、オクロバクトルム属の菌株ＷＵ−ＹＳ０９株（ＦＥＲＭ Ｐ−２０３１４）。
（２）ポリイソプレン系ゴムを含有するゴム組成物を、オクロバクトルム属の菌株ＷＵ−ＹＳ０９株（ＦＥＲＭ Ｐ−２０３１４）で微生物分解する方法。
（３）前記ゴム組成物のポリイソプレン系ゴム含有量が１０重量％以下であることを特徴とする（２）に記載の方法。
（４）前記ポリイソプレン系ゴムがシスポリイソプレンゴムである（２）に記載の方法。
（５）前記ゴム組成物がカーボンブラックを含有することを特徴とする（２）に記載の方法。
（６）前記ゴム組成物がゴム粉である（２）に記載の方法。
（７）前記ゴム組成物がゴム製品を破砕したゴム片である（２）に記載の方法。 The present invention comprises the following (1) to (7).
(1) A strain WU-YS09 strain (FERM P-20314) belonging to the genus Okrobactrum having an action of decomposing polyisoprene rubber.
(2) A method in which a rubber composition containing a polyisoprene rubber is microbially decomposed with a strain WU-YS09 (FERM P-20314) belonging to the genus Okrobactrum.
(3) The method according to (2), wherein the rubber composition has a polyisoprene rubber content of 10% by weight or less.
(4) The method according to (2), wherein the polyisoprene rubber is cis polyisoprene rubber.
(5) The method according to (2), wherein the rubber composition contains carbon black.
(6) The method according to (2), wherein the rubber composition is rubber powder.
(7) The method according to (2), wherein the rubber composition is a rubber piece obtained by crushing a rubber product.

本発明により、新規な微生物であるオクロバクトルム属の菌株ＷＵ−ＹＳ０９株（ＦＥＲＭ Ｐ−２０３１４）が与えられた。ＷＵ−ＹＳ０９株はポリイソプレン系ゴムを分解する活性を有する。よって本発明により、ポリイソプレン系ゴムを分解する新たな方法が与えられた。更に本発明により、カーボンブラックを含有するゴム製品の微生物分解が可能となった。   According to the present invention, the strain WU-YS09 (FERM P-20314) belonging to the genus Okrobactrum, which is a novel microorganism, was provided. WU-YS09 strain has an activity of decomposing polyisoprene rubber. Thus, the present invention provides a new method for decomposing polyisoprene rubber. Furthermore, the present invention has made it possible to microbially decompose rubber products containing carbon black.

以下、発明の実施の形態を貝体的に説明する。
本発明は新規微生物であるオクロバクトルム属の菌株であるＷＵ−ＹＳ０９株である。また本発明はポリイソプレン系ゴムを含有するゴム製品を上記微生物で分解する方法である。天然ゴムなどのポリイソプレン系ゴムは放線菌の類で分解できることはよく知られているが、ポリイソプレンゴムを分解できる細菌の例は少ない。さらにカーボンブラックなどを配合した硬質ゴムを分解する放線菌の例は極めて少なく、そのような細菌の例はほとんどない。本発明で、発明者は多くの土壌から天然ゴム分解菌を鋭意スクリーニングした結果、タイヤなどのゴム製品に使用されるカーボン配合ゴムを分解できるＷＵ−ＹＳ０９株の細菌を見出した。 Hereinafter, embodiments of the invention will be described in a shell form.
This invention is WU-YS09 strain | stump | stock which is a strain of the genus Okrobactrum which is a novel microorganism. The present invention is also a method for decomposing a rubber product containing a polyisoprene-based rubber with the above microorganisms. It is well known that polyisoprene rubber such as natural rubber can be decomposed by actinomycetes, but there are few examples of bacteria capable of degrading polyisoprene rubber. Furthermore, there are very few examples of actinomycetes that decompose hard rubber compounded with carbon black and the like, and there are almost no examples of such bacteria. In the present invention, as a result of intensive screening of natural rubber-degrading bacteria from many soils, the inventor found WU-YS09 strain bacteria capable of degrading carbon-containing rubber used in rubber products such as tires.

ＷＵ−ＹＳ０９株は独立行政法人 産業技術総合研究所 特許生物寄託センターにＦＥＲＭ Ｐ−２０３１４株として２００４年１２月７日に寄託されている。本発明においてＷＵ−ＹＳ０９株は無機塩の液体培地中で粉ゴムを資化しながら増殖する。上記の無機塩としては窒素、リン、カリウム、カルシウム、マグネシウムなどを含むものが挙げられる。   WU-YS09 strain was deposited on December 7, 2004 as FERM P-20314 strain at the National Institute of Advanced Industrial Science and Technology (AIST). In the present invention, the WU-YS09 strain grows while assimilating powdered rubber in a liquid medium of an inorganic salt. As said inorganic salt, what contains nitrogen, phosphorus, potassium, calcium, magnesium etc. is mentioned.

本発明を適用する対象となるポリイソプレン系ゴムとしては、主鎖がシスポリイソプレン及びトランスポリイソプレンであるゴムまたはエラストマーを挙げることができる。本発明においてシスポリイソプレンであるゴムが最も好ましいが、イソプレンと他のモノマーとの共重合体を主鎖とするゴムまたはエラストマーにも本発明を適応することが可能である。具体的なシスポリイソプレンとしては、それに限定されるものではないが、天然ゴムやＮａｔｓｙｎなどの合成シスポリイソプレンが例示され、トランスポリイソプレンとしてはガッタパーチャなどの天然系ゴムが例示される。   Examples of the polyisoprene rubber to which the present invention is applied include rubbers or elastomers whose main chain is cis polyisoprene and trans polyisoprene. In the present invention, rubber which is cis polyisoprene is most preferable, but the present invention can also be applied to rubber or elastomer having a copolymer of isoprene and another monomer as a main chain. Specific examples of cis polyisoprene include, but are not limited to, natural rubber and synthetic cis polyisoprene such as Natsyn, and trans polyisoprene includes natural rubber such as gutta percha.

ゴム粉を構成するゴムエラストマー中のポリイソプレン系ゴムの含有量が１０重量％以上であれば本方法の適応が可能である。ゴムエラストマー中のポリイソプレンは５０重量％以上が好ましく、さらに好ましくは８０重量％以上であるが、その範囲に限定されるものではない。   If the content of the polyisoprene rubber in the rubber elastomer constituting the rubber powder is 10% by weight or more, the present method can be applied. The polyisoprene in the rubber elastomer is preferably 50% by weight or more, more preferably 80% by weight or more, but is not limited to this range.

本発明で対象となるゴム製品はカーボンブラックを含有することができる。カーボンブラックの含有量は通常の廃タイヤから採取された粉ゴムであれば３０〜７０ｐｈｒであるが、その範囲内に限定されるものではなく、カーボンブラックの含有量が３０ｐｈｒ以下及び７０ｐｈｒ以上でも本発明の方法は適応可能である。   The rubber product targeted by the present invention can contain carbon black. The carbon black content is 30 to 70 phr if it is a powder rubber collected from a normal waste tire, but is not limited to that range, and even if the carbon black content is 30 phr or less and 70 phr or more, The inventive method is adaptable.

本発明で分解の対象となるゴムは、イソプレン系ゴムであれば、ゴム工業で通常使用されているシランカップリング剤、硫黄、加硫剤、加硫促進剤、加硫促進助剤、酸化防止剤、オゾン劣化防止剤、老化防止剤、プロセス油、亜鉛華（ＺｎＯ）、ステアリン酸、過酸化物等の通常の配合剤が配合されたものでよい。ただし、ゴム配合剤の中にＷＵ−ＹＳ０９株の増殖を阻害する配合剤が配合されている場合は、粉ゴムを溶剤抽出し、これを除去する必要がある。   If the rubber to be decomposed in the present invention is an isoprene-based rubber, a silane coupling agent, sulfur, vulcanizing agent, vulcanization accelerator, vulcanization accelerating agent, antioxidant that are usually used in the rubber industry Ordinary compounding agents such as an agent, an ozone deterioration preventing agent, an antiaging agent, a process oil, zinc white (ZnO), stearic acid, and peroxide may be blended. However, when a compounding agent that inhibits the growth of the WU-YS09 strain is blended in the rubber compounding agent, it is necessary to solvent-extract the powdered rubber and remove it.

本発明ではさらに微粉砕したゴム粉であれば微生物の分解効率がさらに向上する。ここにおけるゴム粉が、ゴム製品をロール粉砕法などの常温で機械的に破砕する方法や液体窒素などにより冷凍してから破砕する冷凍破砕法や、超高圧水を用いる水撃粉砕法で微粉砕したゴム粉であれば、微生物の分解効率がさらに向上する。   In the present invention, if the rubber powder is further finely pulverized, the decomposition efficiency of microorganisms is further improved. The rubber powder here is finely pulverized by a method of mechanically crushing rubber products at room temperature such as a roll crushing method, a freezing crushing method of freezing and crushing with liquid nitrogen, or a water hammer crushing method using ultra-high pressure water If the rubber powder is used, the decomposition efficiency of microorganisms is further improved.

また、粉ゴムを完全に分解するのではなく、粉ゴムの表面を微生物分解し、再度未加硫ゴムに混練り加硫することにより、新たな製品に利用することも可能である。ここ用いる粉ゴムは、廃タイヤ・チューブを破砕して得られる粉末ゴムに限らず、タイヤ製造時に発生する未加硫スクラップ物、タイヤ加硫時に発生するスピュー片などを粉砕したものでもよい。また、ゴム粉でなく、ゴム製品を破砕したゴム片でも本発明による微生物分解は可能である。以下実施例で本発明を具体的に説明するが、本発明はこれらの実施例により限定されるものではない。   Further, instead of completely decomposing the powdered rubber, the surface of the powdered rubber can be microbially decomposed and kneaded with the unvulcanized rubber again and vulcanized to be used for a new product. The powder rubber used here is not limited to powder rubber obtained by crushing waste tires and tubes, but may be one obtained by pulverizing unvulcanized scrap generated during tire production, spew pieces generated during tire vulcanization, and the like. In addition, microbial degradation according to the present invention is possible even with a rubber piece obtained by crushing a rubber product instead of rubber powder. EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

シリコーン栓付きのガラス容器に準備した表１の組成の培地に、アセトン抽出済みの１ｍｍ角のゴム片８ｇ／Ｌを入れ、９０℃でオートクレープ中で滅菌処理した。そのゴム片は、表２の組成で天然ゴムを配合したものである。これにラテックス手袋ゴムを唯一の炭素源として前培養したＷＵ−ＹＳ０９株の菌液を加え、３０℃において１４日間４０ｒｐｍで振とう培養した後、１２０ｒｐｍに切り替え、合計で５０日間培養した。その後、培養液にアセトンを加え、ゴム片をろ紙でろ過した。ろ過したゴム片を純水で数回洗浄し、十分に乾燥したことを確認後、ゴム片の重量減少を測定したところ、９．８８％の重量減少が計測された。よって、ＷＵ−ＹＳ０９株がカーボンブラックを配合したゴムでも分解できることが確認された。   A medium of the composition shown in Table 1 prepared in a glass container with a silicone stopper was charged with 8 g / L of a 1 mm square rubber piece already extracted with acetone, and sterilized at 90 ° C. in an autoclave. The rubber piece is a blend of natural rubber with the composition shown in Table 2. To this was added a bacterial solution of WU-YS09 strain pre-cultured using latex glove rubber as the sole carbon source, and after shaking culture at 40 rpm for 14 days at 30 ° C., switching to 120 rpm and culturing for a total of 50 days. Thereafter, acetone was added to the culture solution, and the rubber pieces were filtered with a filter paper. The filtered rubber piece was washed several times with pure water, and after confirming that it was sufficiently dried, the weight loss of the rubber piece was measured. As a result, a weight loss of 9.88% was measured. Therefore, it was confirmed that the WU-YS09 strain can be decomposed even with rubber containing carbon black.

Figure 2007000109
Figure 2007000109

Figure 2007000109
Figure 2007000109

本発明の新規の微生物であるオクロバクトルム属の菌株ＷＵ−ＹＳ０９株（ＦＥＲＭ Ｐ−２０３１４）はポリイソプレン系ゴムを分解する作用を有する。また該微生物により、これまでは困難であったカーボンブラックを含有するゴム製品の微生物分解が可能とである。よって本発明の微生物を用いた微生物分解方法は、タイヤなどのゴム製品の廃棄及び再利用に有用である。   The strain WU-YS09 (FERM P-20314) of the genus Okrobactrum, which is a novel microorganism of the present invention, has an action of degrading polyisoprene rubber. In addition, the microorganism enables the microbial degradation of rubber products containing carbon black, which has been difficult until now. Therefore, the microbial decomposition method using the microorganism of the present invention is useful for the disposal and reuse of rubber products such as tires.

Claims (7)

ポリイソプレン系ゴムを分解する作用を有する、オクロバクトルム属の菌株ＷＵ−ＹＳ０９株（ＦＥＲＭ Ｐ−２０３１４）。   A strain WU-YS09 (FERM P-20314) belonging to the genus Okrobactrum having an action of degrading polyisoprene rubber. ポリイソプレン系ゴムを含有するゴム組成物を、オクロバクトルム属の菌株ＷＵ−ＹＳ０９株（ＦＥＲＭ Ｐ−２０３１４）で微生物分解する方法。   A method in which a rubber composition containing a polyisoprene rubber is microbially decomposed with a strain WU-YS09 (FERM P-20314) belonging to the genus Okrobactrum. 前記ゴム組成物のポリイソプレン系ゴム含有量が１０重量％以下であることを特徴とする請求項１に記載の方法。   The method according to claim 1, wherein the rubber composition has a polyisoprene rubber content of 10% by weight or less. 前記ポリイソプレン系ゴムがシスポリイソプレンゴムである請求項２に記載の方法。   The method according to claim 2, wherein the polyisoprene-based rubber is cis polyisoprene rubber. 前記ゴム組成物がカーボンブラックを含有することを特徴とする請求項２に記載の方法。   The method of claim 2, wherein the rubber composition contains carbon black. 前記ゴム組成物がゴム粉である請求項２に記載の方法。   The method according to claim 2, wherein the rubber composition is rubber powder. 前記ゴム組成物がゴム製品を破砕したゴム片である請求項２に記載の方法。   The method according to claim 2, wherein the rubber composition is a rubber piece obtained by crushing a rubber product.
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JP2003009847A (en) * 2001-06-28 2003-01-14 Tokyo Gas Co Ltd Cyan compound-degrading microorganism

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WO2011039489A1 (en) * 2009-10-02 2011-04-07 Centre National De La Recherche Scientifique - Cnrs - Bacterial strains and variants thereof that can degrade polylactic acid, and uses of same
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CN102639690B (en) * 2009-10-02 2014-05-21 国家科学研究中心 Bacterial strains and variants thereof that can degrade polylactic acid, and uses of same

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