JP2007135401A - Method for decomposing resin having urethane bond and/or urea bond - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a means for efficiently decomposing a resin having a urethane bond and/or urea bond by utilizing a biological means. <P>SOLUTION: This culturing supernatant of microorganisms belonging to the genus Alternaria, having a capacity of cutting the urethane bond and/or urea bond, the microorganisms having the capacity of cutting the urea bond and the method for decomposing the resin by utilizing them are provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention mainly relates to a method for decomposing a resin having a urethane bond and / or a urea bond using biological means. Furthermore, the present invention relates to a method for separating the resin and the substrate using the method, and a method for efficiently recycling the resin.

  As resins having urethane bonds and / or urea bonds, polyurethane, polyurea and polyurethane urea are well known.

  Since these resins are difficult to be spoiled or deteriorated, they are used in a wide range of applications such as home appliances, furniture, and building materials according to their characteristics.

  However, with the increase in the amount of use, environmental problems have arisen due to the disposal of products and composite materials that use them. Therefore, there is a strong demand for an efficient decomposition method or recovery method.

  Conventionally, material recycling or chemical recycling has been mainly used as a resin decomposition method or recovery method (see Non-Patent Documents 1 and 2).

  Material recycling is a method of collecting and reusing waste as raw material for products. However, the reuse of the composite material of the resin and the base material takes time for separation of the resin and the base material, and there is a possibility that the recovery becomes insufficient.

  Chemical recycling is a method in which a resin is decomposed into monomers and oligomers by a chemical reaction and reused as a raw material. However, it is necessary to perform the treatment at a high temperature, and a complicated process is required for the treatment of the catalyst and the by-product, which is insufficient in efficiency.

  On the other hand, a method using a microorganism has been attracting attention. A method using microorganisms can be processed at room temperature, is efficient, has low energy, and has a low environmental impact.

  Until now, as a decomposition method using a microorganism of a resin having a urethane bond and / or a urea bond, a method of decomposing an ester bond of a polyol part has been reported.

However, ether-type resins having no ester bond are difficult to be decomposed by microorganisms (see Non-Patent Documents 3 to 18, etc.), and as a known technique that enables the decomposition of ether-type polyurethane by microorganisms, Patent Document 1 discloses. Only the disclosed method could be mentioned.
Kentaro Shima, CMC Co., Ltd., Plastic Recycling Technology, 2000, 7-27. Kentaro Shima, CMC Co., Ltd., Polyurethane Applied Technology, 1999, 229-239. Huang, SJ, C. Macri, M. Roby, C. Benedict, and JA Cameron. 1981. Biodegradation of polyurethanes derived from polycaprolactonediols. Am. Chem. Soc. Symp. Ser. 172: 471-487. Seal, KJ, and LHG Morton. 1986. Chemical Materials. In Biotechnology 8, ed. HJ Rehm, and G. Reed. VCH Verlagsgesellschaft, Weinheim, Germany. 584-605. Morton, LHG, and SB Surman. 1994. Biofilms in biodeterioration-a review. Int. Biodeterior. Biodegrad. 32: 203-221. Nakajima-Kambe, T., F. Onuma, N. Kimpara, and T. Nakahara. 1995. Isolation and characterization of bacterium which uses polyester polyurethane as a sole carbon and nitrogen source. FEMS. Microbiol. Lett. 129: 39-42 . Akutsu, Y., T. Nakajima-Kambe, N. Nomura, and T, Nakahara. 1998. Purification and properties of polyester polyurethane degradation enzyme from Comamonas acidvorans TB-35. Appl. Environ. Microbiol. 64: 62-67. Crabbe, JR, JR Campbell, L. Thompson, SL Walz, and WW Schultz. 1994. Biodegradation of colloidal ester-based polyurethane by soil fungi. Int. Biodeterior. Biodegrad. 33: 103-113. Jansen, B., F. Schumacher-Perdreau, G. Peteers, and G. Pulverer. 1991. Evidence for degradation of synthetic polyurethanes by Staphylococcus epidermidis. Zentralbl. Bakteriol. 276: 36-45. Ossefort, ZT, and FB Testroet. 1966. Hydrolytic stability of urethane elastomers. Rubber Chemistry and Technology. 39: 1308-1327. Darby, RT, and AM Kaplan. 1968. Fungal susceptibility of polyurethanes. Applied microbiology. 16: 900-905. Potts, JE, RA Clendinning, and WB Ackart.1973.The effect of chemical structure on the biodegradability of plastics.In Degradability of polymers and Plastics.Institute of Electrical Engineers and the Plastics Institute.London. 12 / 1-12 / 9. Filip, Z. 1978. Decomposition of polyurethanes in a garbage landfill leakage water and by soil micro-organisms.European Journal of Applied Microbiology and Biotechnology. 5: 225-231. Martens, R. and KH Domsch. 1981.Microbial degradation of polyurethane foams and isocyanate based polyureas in different media.Water, Air and Soil Pollution. 15: 503-509. Pathirana, RA and KJ Seal. 1985. Studies on polyurethane deteriorating fungi. Part3: Physico-mechanical and weight changes during fungal deterioration.International Biodeterioration. 21: 123-125. Seal, KJ, and M. Pantke.1986.An interlaboratory investigation into the biodeterioration testing of plastics, with special reference to polyurethanes.Part1: Petri dish test.Material und Organismen.21: 151-164. Claus Jurgen Simon. 2005. Plastics Business Data and Charts. Plastics Europe Deutschland Arbeisausschuss Statistik und Marktforschung Working Group Statistics and Market Research. CAMPBELL C J. 1996. The Status of World Oil Depletion at the end of 1995. Energy Explor Exploit. 14: 63-81. JP 2005-46009 A

  The present invention relates to a method for efficiently decomposing a resin having a urethane bond and / or a urea bond using biological means, a method for separating the resin and the substrate using the method, The main object is to provide a method for effectively reusing the resin.

  As a result of intensive studies aimed at solving the above problems, the present inventor has found that the culture supernatant of a specific microorganism has the ability to cleave urethane bonds and urea bonds, and the specific microorganism. Was found to have the ability to cleave the urea bond, and further earnest studies were made to complete the present invention.

  That is, the present invention relates to the following technology.

  Item 1: A culture supernatant of a microorganism belonging to the genus Alternaria, which has the ability to cleave urethane bonds and / or urea bonds.

  Examples of specific embodiments include culture supernatants of microorganisms capable of cleaving urethane bonds, culture supernatants of microorganisms capable of cleaving urea bonds, microorganisms capable of cleaving urethane bonds and urea bonds Of culture supernatant.

  Item 2: The culture supernatant according to Item 1, wherein the microorganism is Alternaria alternate (Fr.) Kissler PURDK2 strain (FERM P-19445).

  In other words, it is a culture supernatant of an Alternaria alternate (Fr.) Kaisler PURDK2 strain (FERM P-19445) having the ability to cleave urethane bonds and / or urea bonds.

  Item 3: A composition for decomposing a resin having a urethane bond and / or a urea bond, comprising the culture supernatant according to Item 1 or 2 as an active ingredient.

  Examples of preferred embodiments include a polyurethane decomposing composition, a polyurea decomposing composition, and a polyurethane urea decomposing composition.

  Item 4: Having a urethane bond and / or a urea bond, including a step of bringing the culture supernatant according to Item 1 or 2 or the composition according to Item 3 into contact with a resin having a urethane bond and / or a urea bond Decomposition method of resin.

  Item 5: The culture supernatant according to Item 1 or 2 or the composition according to Item 3 is brought into contact with a resin portion of a composite material including a resin having a urethane bond and / or urea bond and a base material. A method for separating the resin and the substrate, including a step.

  Item 6: (1) a step of bringing the resin having urethane bond and / or urea bond into contact with the culture supernatant according to Item 1 or 2 or the composition according to Item 3 to decompose the resin; and (2) A method for recycling a resin having a urethane bond and / or a urea bond, which includes a step of recovering the decomposition product obtained in the step (1).

  Item 7: The method according to any one of Items 4 to 6, wherein the resin having a urethane bond and / or a urea bond is an ether type resin.

  Preferably, the method according to any one of Items 4 to 6, wherein the resin having a urethane bond and / or a urea bond is an ether type polyurethane, an ether type polyurea, or an ether type polytan urea.

  Item 8: A method for decomposing a resin having a urea bond, comprising the step of contacting a resin having a urea bond with a microorganism belonging to the genus Altanaria and having a capability of cleaving the urea bond.

  Item 9: The degradation method according to Item 8, wherein the microorganism is Alternaria alternate (Fr.) Kissler PURDK2 strain (FERM P-19445).

  In other words, a resin having a urea bond, comprising a step of contacting a resin having a urea bond with an Alternaria alternate (Fr.) Kissler PURDK2 strain (FERM P-19445) having an ability to cleave the urea bond. Disassembly method.

  Item 10: The decomposition method according to Item 8 or 9, wherein the resin having a urea bond is an ether type resin.

  The method according to Item 8 or 9, wherein the resin having a urea bond is an ether type polyurea or an ether type polyurethane urea.

  Furthermore, the present invention includes the following matters.

  Item 11: A method for separating the resin and the substrate, comprising the step of bringing the microorganism according to Item 8 or 9 into contact with a resin portion of a composite material including a resin having a urea bond and the substrate.

  Item 12: (1) A step of bringing the microorganism according to Item 8 or 9 into contact with a resin having a urea bond, and a step of decomposing the resin, and (2) recovering a decomposition product obtained in step (1) A method for recycling a resin having a urea bond, which includes a step.

  Item 13: An enzyme having a urethane bond and / or urea bond cleavage activity.

  Item 14: The enzyme according to Item 13, which is derived from a microorganism belonging to the genus Alternaria.

  Item 15: The enzyme according to Item 13 or 14, which is derived from Alternaria alternate (Fr.) Kissler PURDK2 strain (FERM P-19445).

  Item 16: A composition for decomposing a resin having a urethane bond and / or a urea bond, comprising the enzyme according to any one of Items 13 to 15 as an active ingredient.

  Item 17: Having a urethane bond and / or a urea bond, including a step of bringing the enzyme according to any one of Items 13 to 15 or the composition according to Item 16 into contact with a resin having a urethane bond and / or a urea bond. Decomposition method of resin.

  Item 18: The enzyme according to any one of Items 13 to 15 or the composition according to Item 16 is contacted with a resin portion of a composite material including a resin having a urethane bond and / or a urea bond and a substrate. The method of separating the said resin and a base material including the process to make.

  Item 19: (1) a step of bringing the resin according to any one of Items 13 to 15 or the composition according to Item 16 into contact with a resin having a urethane bond and / or a urea bond, and decomposing the resin; and (2) A method for recycling a resin having a urethane bond and / or a urea bond, including a step of recovering the decomposition product obtained in the step (1).

  Item 20: The method according to any one of Items 17 to 19, wherein the resin having a urethane bond and / or a urea bond is an ether type resin.

Hereinafter, the present invention will be described in more detail.
I. Resin having urethane bond and / or urea bond
I-1. Bond In this specification, the urethane bond refers to a structure represented by the following formula 1.

  In this specification, the breaking of a urethane bond refers to breaking of a nitrogen-carbon bond in a urethane bond.

  Moreover, in this specification, a urea bond means the structure shown by following formula 2.

  In the present specification, cleavage of a urea bond refers to cleavage of a nitrogen-carbon bond in a urea bond.

I-2. Resin In the present specification, a resin having a urethane bond and / or a urea bond has a reaction product of a polyisocyanate compound and a compound having active hydrogen as a basic skeleton. Active hydrogen compounds include polyol compounds, polyamine compounds and water.

  The resin containing a urethane bond and / or a urea bond may be obtained by adding other raw materials as long as it is obtained using a polyisocyanate compound and a compound having active hydrogen as a main raw material. Examples of other raw materials include a crosslinking agent, a chain extender, and an active hydrogen-containing compound other than those described above.

  The method for producing a resin having a urethane bond and / or a urea bond is not particularly limited, and the resin may be produced after a suitable prepolymer is synthesized. For example, it may be obtained by synthesizing a prepolymer of both terminal isocyanates from a polymer diol and a diisocyanate, and then connecting the prepolymer with a diamine compound to increase the molecular weight.

  Moreover, the ratio of the amount of the polyisocyanate compound as a raw material to the polyol compound and / or the polyamine compound is not particularly limited. For example, the ratio between the number of moles of isocyanate groups and the sum of the number of moles of hydroxyl groups and amino groups may be 1, may be greater or less than 1, and the reactive groups remain at the ends. Resin may be used.

  In the present specification, when a resin having a urethane bond and / or a urea bond is referred to, (i) a resin having a urethane bond, (ii) a resin having a urea bond, and (iii) a resin having a urethane bond and a urea bond. Is included.

  The resin having a urethane bond is a generic name for resins obtained by reacting a polyisocyanate compound and a polyol compound as main raw materials, and includes, for example, polyurethane and polyurethane urea.

  The resin having a urea bond is a general term for resins obtained by reacting a polyisocyanate compound and a polyamine compound as main raw materials, and includes, for example, polyurea and polyurethane urea.

  The resin having a urethane bond and a urea bond is a general term for resins obtained by reacting a polyisocyanate compound, a polyol compound, a polyamine compound, and water as main raw materials, and includes, for example, polyurethane urea. The ratio of urethane bond and urea bond in the resin is not particularly limited.

  The resin may be a thermoplastic resin or a thermosetting resin. Moreover, an elastomer may be sufficient. The resin may be a non-foamed material or a foamed product (foam). The resin may be linear or branched, and may be cross-linked.

  In an example of the embodiment of the present invention, the resin having a urethane bond and / or a urea bond is an ether type resin.

  The ether type resin means a resin in which a polyaddition product of a polyether, in other words, a polyol compound and / or a polyamine compound as a raw material is a polyether.

  Examples of the ether type resin having a urethane bond and / or a urea bond include ether type polyurethane, ether type polyurea, and ether type polyurethane urea.

II. Cleavage of urethane bonds and / or urea bonds using culture supernatant of microorganisms
II-1. Culture supernatant According to the present invention, there is provided a culture supernatant of a microorganism belonging to the genus Alternaria, which has the ability to cleave urethane bonds and / or urea bonds.

  As the microorganism belonging to the genus Alternaria, the Alternaria alternate (Fr.) Kissler PURDK2 strain is preferably used. The PURDK2 strain is deposited at the Patent Organism Depositary, National Institute of Advanced Industrial Science and Technology under the deposit number FERM P-19445 (deposit date July 24, 2003).

  The culture supernatant is obtained by culturing a microorganism belonging to the genus Alternaria, and contains an extracellular secretion or an enzyme of the microorganism. Preferably, an enzyme having a cleavage activity of urethane bond and / or urea bond is included.

  For example, a microorganism belonging to the genus Alternaria is cultured in a medium containing carbohydrates for an appropriate period of time and grown, and then the culture solution is centrifuged to separate the cell part and collect the supernatant. Can be obtained. More specifically, the cells are grown on a medium containing a carbohydrate, for example, LB + glucose medium (polypeptone 10 g / L, yeast extract 5 g / L, NaCl 5 g / L, and glucose 10 g / L) (PURDK2 strain) When growing in LB glucose medium for 24 hours), the culture can be separated and obtained by centrifuging the culture solution at 4 ° C. and 7,000 g for 10 minutes.

  Alternatively, the microorganism can be obtained as a supernatant by suspending it in a liquid containing a culture medium, and then allowing it to grow at a suitable temperature.

  Moreover, the enzyme which has a cutting activity of a urethane bond and / or a urea bond can be obtained by isolating from the culture supernatant of the said microorganisms according to a conventional method.

II-2. Composition According to the present invention, a composition for decomposing a resin having a urethane bond and / or a urea bond is provided. The composition contains the culture supernatant as an active ingredient. Alternatively, it may contain an enzyme obtained from the culture supernatant.

  The composition of the present invention has a function of cleaving urethane bonds and / or urea bonds by the culture supernatant, and is suitably used for decomposing resins having urethane bonds and / or urea bonds.

  The composition of the present invention may consist of the culture supernatant itself, or may contain other components such as additives as an active ingredient. Furthermore, as long as it is within the range where the effect of this invention is show | played, another decomposition | disassembly adjuvant and a decomposition enzyme can also be mix | blended.

  The blending amount of such other components can be appropriately selected and adjusted as long as the effects of the present invention are not impaired.

  The method for producing the composition is not particularly limited, and the composition can be obtained by mixing the above culture supernatant with other components such as additives as necessary and appropriately preparing them according to known methods.

  The form of the composition is also not particularly limited, and can be arbitrarily prepared according to the type of product to be applied, usage mode, and the like. For example, it can be prepared in a suspension state.

II-3. Method for Decomposing Resin According to the present invention, there is provided a method for decomposing a resin having a urethane bond and / or a urea bond using a culture supernatant.

  An example of the embodiment is a method for decomposing a polyurethane, which comprises a step of contacting the culture supernatant of a microorganism belonging to the genus Altanaria that has the ability to cleave urethane bonds with polyurethane.

  Another example is a method for degrading polyurea, which comprises contacting polyurea with a culture supernatant of a microorganism belonging to the genus Altanaria that has the ability to cleave urea bonds.

  Another example is a method for decomposing polyurethane urea, which comprises a step of contacting polyurethane urea with a microorganism belonging to the genus Alternaria, which has the ability to cleave urethane bonds and urea bonds.

  As a microorganism belonging to the genus Alternaria (Alternaria), the Alternaria alternato (Fr.) Kaisler PURDK2 strain deposited at the Patent Organism Depositary of National Institute of Advanced Industrial Science and Technology under the accession number FERM P-19445 is preferably used. It is done.

  The method of bringing the culture supernatant into contact with the resin can be appropriately set within the range where the effects of the present invention are exhibited.

  For example, a culture supernatant prepared by separating a precipitate from a culture of microorganisms cultured in an appropriate liquid medium or a composition containing the same may be sprayed on the resin surface or injected into the resin.

  Alternatively, a liquid culture medium containing microorganisms may be sprayed on the resin surface or injected into the resin, and contacted with the resin with a culture supernatant obtained by growing at the sprayed or injected site.

  For example, after a microorganism is applied to the resin surface at an appropriate interval, a liquid medium (for example, LB + glucose medium) is further applied to the application site, and left at an optimum temperature for the growth of the microorganism. The resin can be decomposed (dissolved) by culturing the microorganism with the supernatant containing the secretion or enzyme produced by the microorganism to be grown.

  In addition, after injecting the microorganism into the resin, a liquid medium (for example, LB + glucose medium) is injected into the injection site, and the microorganism is cultured in the resin by leaving it at an optimum temperature for the growth of the microorganism. Then, the resin can be decomposed (dissolved) by the supernatant containing the secreted product or enzyme produced by the grown microorganisms.

  The decomposition conditions of the resin can be appropriately selected and set within the conditions in which the urethane bond and / or urea bond is broken. Preferably, the decomposition reaction can be promoted by setting the temperature to an appropriate temperature.

II-4. Reuse (recycle) method
(II-4a) Method for Separating Resin and Substrate According to the present invention, in a composite material comprising a resin having a urethane bond and / or urea bond and a substrate, using a culture supernatant of microorganisms A method for efficiently separating the resin and the substrate is provided. The separation method of the present invention includes a method in which a resin and / or a substrate is separated in a form that can be recovered and / or reused. The reusable form includes a case where the collected resin or the base material itself is recycled as it is, and a case where it can be reused (recycled) with a little modification.

  In this specification, the term “base material” refers to a part constituting household appliances or furniture manufactured using a material that is not decomposed by the culture supernatant (eg, steel, wood, hard plastic, etc.). Not limited.

  The composite material configured to include a resin having a urethane bond and / or urea bond and a base material includes, for example, a composite material including polyurethane, polyurea or polyurethane urea and a base material.

  The configuration of the composite material is not particularly limited as long as the effect of the present invention is achieved. For example, a composite material obtained by fixing, bonding or adhering the resin to a base material made of a material such as steel, wood, or hard plastic with a rivet, an adhesive, or the like is exemplified. Moreover, the composite material obtained by spraying or making it coat | cover on base materials, such as piping and a wall, is illustrated. Moreover, the composite material obtained by inject-molding this resin to base materials, such as a formwork, is illustrated.

  In the separation method of the present invention, (1) the microorganism is brought into contact with the composite material together with the growth medium, the microorganism is cultured at the contact location, and the resin is decomposed by the supernatant containing the secretion or enzyme produced by the cultured microorganism. Either a method and (2) a method in which a culture supernatant of a microorganism is prepared in advance, and the prepared culture supernatant is contacted with a composite material to decompose the resin can be applied.

  For example, polyurethane is used as a thermoplastic resin, urethane foam (foamed polyurethane), elastomer, etc., as a heat insulating material for home appliances, an elastic body for furniture, and the like. More specifically, the urethane foam is filled between the outer wall and the inner wall of the refrigerator as a heat insulating material. The base material constituting the outer wall or the inner wall is often made of hard plastic. Urethane foam is bonded (fixed) to one or both of the outer wall and the inner wall with a rivet or an adhesive to form a composite material. By assembling this composite material, a refrigerator in which urethane foam is filled between the outer wall and the inner wall is manufactured. When the refrigerator is discarded, a composite material in which the base material and the urethane foam are bonded together is generated by disassembling the refrigerator. By allowing the culture supernatant to cut the urethane bond to act on this composite material, the base material can be recovered in a substantially reusable state.

  As a method of decomposing (dissolving) urethane foam from a composite material formed by laminating a base material and urethane foam, the composite material is immersed in a liquid medium containing microorganisms or a culture supernatant produced by microorganisms, A method of leaving at an appropriate temperature, a method of spraying a liquid medium containing microorganisms on the urethane foam portion of the composite material, or a culture supernatant or a composition containing the culture supernatant of the present invention directly on polyurethane foam A method of applying is employed. By these methods, the urethane foam can be decomposed and the substrate can be recovered.

  Polyurea is excellent in water resistance and weather resistance, and is used as a coating film. Examples of the substrate constituting the article to be coated include hard plastic and concrete. By allowing the above culture supernatant having the ability to cleave urea bonds to act on a composite material in which polyurea is applied to such a substrate, the substrate can be recovered in a substantially reusable state. .

  As a method of decomposing and separating polyurea from a composite material comprising a base material and polyurea, a method of immersing the composite material in a liquid medium containing the microorganism and leaving it at an appropriate temperature, a polyurea of the composite material A method of spraying a liquid medium containing the microorganism on the part, a method of directly applying the microorganism on polyurea, or the like is employed. By these methods, polyurea is decomposed (dissolved), and the substrate is recovered.

  Polyurethane urea is excellent in removability, moldability, etc., and is used as a binder or elastic yarn. By decomposing polyurethane urea by applying the above-mentioned culture supernatant having the ability to cut urethane bonds and / or urea bonds to composite materials in which polyurethane urea is bonded, laminated and knitted to various substrates. The substrate can be recovered in a substantially reusable state. When recovering the base material, the polyurethane urea may be decomposed, or the decomposition product may be recovered and reused. Moreover, after crushing a decomposition product, you may add and shape | mold a binder.

  As a method of decomposing and separating polyurethane urea from a composite material comprising a base material and polyurethane urea, a method in which the composite material is immersed in a liquid medium containing the microorganism and left at an appropriate temperature, a composite material A method of spraying a liquid medium containing the microorganisms on the polyurethane urea part of the polyurethane urea or a method of directly applying the microorganisms onto the polyurethane urea is employed. By these methods, the polyurethane urea is decomposed (dissolved), and the substrate is recovered.

(II-4b) Recycling method of resin and / or base material The base material separated from the composite material by the above method (II-4a) may be reused as it is or after appropriate processing. it can.

  The decomposed resin can be reused as it is or after appropriate processing. For example, after the decomposed resin is pulverized as necessary, it can be used as a product by adding a binder and molding.

  When the resin is recovered at the same time as the recovery of the base material so that both the base material and the resin can be reused, for example, the culture supernatant of the microorganism of the present invention is applied to the adhesive portion between the base material and the resin. Either contact or inject a microorganism suspended in a liquid containing a growth medium, and leave (culture) at an appropriate temperature.

  By this method, the extracellular secretions or enzymes contained in the culture supernatant or the supernatant of the microorganism after culture react at the site where the base material and the resin are bonded, and the resin at the bonded portion is decomposed (dissolved). By doing, a base material and resin can be peeled easily.

  Further, after the microorganisms are applied linearly to the surface of the resin at appropriate intervals, or injected into the resin, a liquid medium (for example, LB + glucose medium) is further applied or injected into the application or injection site, By leaving it at the optimum temperature for the growth of the microorganism, the microorganism is cultured at a desired position on or in the resin, and the resin is decomposed (dissolved) by the secretion or enzyme of the microorganism contained in the culture supernatant. Thus, a resin having a desired size can be collected.

(II-4c) Utilization method of decomposition product of resin By the above method, the decomposition product obtained by decomposing the resin can be recovered and reused. For example, a low molecular compound produced by the decomposition of the resin can be appropriately purified and reused as a raw material for resins and other products.

  The compound produced by the decomposition may include a compound having an amino group at the terminal and a compound having a hydroxyl group at the terminal.

  As an embodiment, for example, the culture supernatant of the present invention is contacted with a resin having a urethane bond and / or a urea bond to be decomposed, and a compound produced by the decomposition is recovered and purified to obtain a urethane bond and / or a urea bond. And a method of using it as a raw material of a resin having

III. Cleavage of urea bonds using microorganisms
III-1. Method for Decomposing Resin Having Urea Bond According to the present invention, a method for decomposing a resin having a urea bond is provided by utilizing the ability of a microorganism to cleave a urea bond.

  Resins having a urea bond include polyurea and polyurethaneurea. For example, the polyurethane urea obtained by making a polyisocyanate compound, a polyol compound, a polyamine compound, and water react as a main raw material is contained.

  The resin having a urea bond may be an ether type resin, and examples thereof include ether type polyurea and ether type polyurethane urea.

  As an example of the embodiment of the decomposition method, there is a method for decomposing polyurea, which comprises contacting a polyurea with a microorganism belonging to the genus Alternaria and capable of cleaving a urea bond. In a specific embodiment, the polyurea is an ether type polyurea.

  Another example is a method for decomposing polyurethane urea, which includes a step of bringing polyurethane urea into contact with a microorganism belonging to the genus Altanaria and capable of cleaving a urea bond. In a specific embodiment, the polyurethaneurea is an ether type polyurethaneurea.

  Microorganisms belonging to the genus Altanaria are used as microorganisms having the ability to cleave urea bonds. Among these, the Alternaria alternato (Fr.) Kissler PURDK2 strain deposited at the National Institute of Advanced Industrial Science and Technology Patent Biological Deposit Center under the deposit number FERM P-19445 is preferably used.

  The method of bringing the microorganism into contact with the resin can be appropriately set within the range where the effects of the present invention are exhibited. For example, microorganisms cultured in an appropriate liquid medium may be sprayed on the surface of polyurea or polyurethaneurea, or injected into the interior of polyurea or polyurethaneurea.

  The decomposition conditions can be appropriately set within the range of conditions under which the urea bond is cleaved. In particular, heating to an appropriate temperature is preferable in that the reaction is accelerated.

III-2. Recycling method The method for decomposing a resin having a urea bond is a method for separating the resin and the base material from a composite material including the resin having a urea bond and the base material, and the resin is decomposed and recovered. And can be applied to a method of reuse. In the method of separating the resin and the substrate, the substrate can be recovered in a reusable form. The reusable form includes a case where the collected base material itself is recycled as it is, and a state where it can be reused (recycled) with a little modification.

  Examples of the composite material including a resin having a urea bond and a base material include a composite material including a polyurea or polyurethane urea and a base material.

  The separation method of the present invention can be carried out, for example, by bringing microorganisms into contact with the joint between the resin and the substrate in the composite material or by injecting them into the resin.

  For example, the substrate can be recovered in a substantially reusable state by allowing a microorganism having the ability to cleave urea bonds to act on a composite material comprising polyurea and the substrate.

  As a method for decomposing polyurea from a composite material comprising a base material and polyurea and separating it from the base material, a method of immersing the composite material in a liquid medium containing the microorganism and leaving it at an appropriate temperature, composite A method of spraying a liquid medium containing the microorganism on the polyurea portion of the material or a method of directly applying the microorganism on the polyurea is employed. By these methods, polyurea is decomposed (dissolved), and the substrate is recovered.

  In addition, the base material is substantially reusable by decomposing the polyurethane urea by causing a microorganism having an ability to cleave the urea bond to act on the composite material including the polyurethane urea and the base material. Can be recovered. Can be recovered. As a method of decomposing and separating polyurethane urea from a composite material comprising a base material and polyurethane urea, a method in which the composite material is immersed in a liquid medium containing the microorganism and left at an appropriate temperature, a composite material A method of spraying a liquid medium containing the microorganisms on the polyurethane urea part of the polyurethane urea or a method of directly applying the microorganisms onto the polyurethane urea is employed. By these methods, the polyurethane urea is decomposed and the substrate is recovered.

  Further, the base material separated from the composite material by the above method can be reused as it is or after appropriate processing.

  The decomposed resin can be reused as it is or after appropriate processing. For example, after the decomposed resin is pulverized as necessary, it can be used as a product by adding a binder and molding.

  When the resin is recovered at the same time as the recovery of the base material so that both the base material and the resin can be reused, for example, the microorganism of the present invention is brought into contact with the bonded portion between the base material and the resin, or Inject microorganisms and leave (culture) at an appropriate temperature.

  By this method, the base material and the resin can be easily peeled by the microorganisms decomposing (dissolving) the resin at the bonding site between the base material and the resin.

  In addition, the microorganisms are applied to the surface of the resin in a linear manner at an appropriate interval, or injected into the resin, so that the resin is decomposed (dissolved) at a desired position on or in the resin to obtain a desired size. This resin can be recovered.

  In addition, the decomposition product obtained by decomposing a resin having a urea bond can be recovered and reused by the above method. For example, a low molecular compound produced by the decomposition of the resin can be appropriately purified and reused as a raw material for resins and other products.

  The compound produced by the decomposition includes a compound having an amino group at the terminal, a compound having a hydroxyl group at the terminal, and the like.

  As an embodiment, for example, there is a method in which a resin having a urea bond is decomposed by bringing the microorganism into contact therewith, and a compound produced by the decomposition is recovered and purified and used as a raw material for the resin having a urea bond.

  According to the present invention, a culture supernatant having the ability to cleave urethane bonds and / or urea bonds is provided. Furthermore, a composition for decomposing a resin having a urethane bond and / or a urea bond using the culture supernatant as an active ingredient is provided. The culture supernatant can efficiently decompose a resin having a urethane bond and / or a urea bond. In addition, handling becomes easier and convenience is improved as compared with the case of using microorganisms.

  In addition, according to the present invention, a microorganism having an ability to cleave urea bonds is provided. This makes it possible to efficiently decompose the resin having a urea bond.

  According to the present invention, a method for efficiently decomposing a resin having a urethane bond and / or a urea bond is provided by utilizing these biological means.

  In particular, according to the present invention, there is provided a method for efficiently decomposing not only ester type resins but also ether type polyurethanes, polyureas and polyurethane ureas by cleaving the urethane bonds and / or urea bonds of the resins. Is done.

In addition, according to the present invention, a method for easily recovering a base material from household appliances, furniture, automobiles, building materials, or the like using a resin such as polyurethane, polyurea, or polyurethane urea as a material using the above decomposition method. Is provided. Furthermore, the method of collect | recovering those resins or its decomposition product with a base material and recycling effectively is provided.
The method of the present invention has excellent decomposition efficiency, can be carried out under mild conditions, has low energy, and has a low environmental impact.

  The present invention having such features greatly contributes to effective use of resources and reduction of environmental load.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not restrict | limited to these Examples.

  In the following examples, Alternaria alternate (Fr.) Kaysler PURDK2 strain (FERM P), which has been deposited at the Patent Organism Depositary, National Institute of Advanced Industrial Science and Technology as a microorganism belonging to the genus Altanaria. -19445) was used.

Example 1: Decomposition of urethane bond by PURDK2 strain
In order to analyze the cleavage of the urethane bond by the PURDK2 strain, the decomposition mode was analyzed using the model compound Diphenylmethane-4,4′-diethylcarbamate (E-MDI) (see FIG. 1) of the resin having a urethane bond as a substrate.

1.1 Method
Diphenylmethane-4,4'-diethylcarbamate (E-MDI) LB + glucose medium supplemented with 0.01 g (polypeptone 10 g / L, yeast extract 5 g / L, NaCl 5 g / L, and glucose 10 g / L) 100 mL 24 hours ago 10% of the cultured PURDK2 strain was inoculated and cultured at 30 ° C. and 100 rpm for 0, 12, 24, and 36 hours. After culturing, 30 mL of a chloroform / methanol (3: 1) solution was added and stirred sufficiently. Centrifugation was performed at 4,000 g for 30 minutes, and the resulting chloroform layer was recovered. Further, the collected chloroform layer was centrifuged at 10,000 g for 10 minutes, and then 1 μL of the obtained chloroform layer was analyzed by gas chromatography (GC). In addition, the obtained degradation product was identified by GC / MS. In addition, the analysis was carried out in the same manner using the uninoculated strain as a control.

1.2 Analysis results
Four peaks were detected by GC analysis of E-MDI, of which peak III was E-MDI and peaks I, II, and IV were unreacted (see FIG. 2).

  When the E-MDI degradation product by the PURDK2 strain was analyzed by GC, the E-MDI decreased by 45% in 24 hours of culture. This suggested that the PURDK2 strain degrades E-MDI. In addition, a new peak thought to be an intermediate metabolite was detected (see Fig. 3).

  The structure of the compound indicated by peak EP1 detected in the degradation product (intermediate metabolite) in PURDK2 strain culture for 24 hours was identified by GC / MS analysis (see FIG. 4).

  As a result, EP1 was identified as diphenylmethane-4-amin-4'-ethylcarbamate (Fig. 5).

  EP1 is considered to be a compound obtained by cleaving the urethane bond of E-MDI (see FIG. 6). From this, it became clear that the PURDK2 strain cleaves the urethane bond of E-MDI.

Example 2 Degradation of urethane bonds by PURDK2 strain culture supernatant
In order to confirm whether E-MDI is degraded by the culture supernatant of PURDK2 strain, degradation analysis was performed using E-MDI.

2.1 Method 3% PURDK2 preculture was inoculated into 100 mL of LB + glucose medium supplemented with 5 pieces of ether type polyurethaneurea (1 cm ³ ), and cultured at 30 ° C. and 100 rpm for 24 hours. The obtained culture broth was centrifuged at 4 ° C. and 7,000 g for 10 minutes to separate the supernatant and the bacterial cells. This was repeated twice.

  0.01 g of E-MDI was added to a 20 mM phosphate buffer solution (pH 7.0), and 1 mL, 5 mL, and 10 mL of the culture supernatant were added thereto to make a total volume of 100 mL. After mixing, the mixture was shaken at 30 ° C. and 100 rpm for 1 hour. After shaking, chloroform / methanol extraction was performed, and 1 μL of the resulting chloroform layer was analyzed by GC. Moreover, the obtained decomposition product was identified by GC / MS. The culture supernatant was heated in boiling water for 10 minutes, and 10 mL of the supernatant in which the enzyme was inactivated was similarly analyzed.

2.2 Analysis results
FIG. 7 shows the GC analysis results of E-MDI degradation using the PURDK2 strain culture supernatant.

  In the system to which 10 mL of culture supernatant was added, E-MDI decreased by 98% in 1 hour of reaction, and a new peak that was considered as an intermediate metabolite was detected (see FIG. 7.D). In addition, the system with 5 mL (1/2) and 1 mL (1/10) of the added supernatant showed 51.4% and 8.9% E-MDI degradation rates, respectively (see Figures 7.B and C). ).

  Furthermore, in order to confirm whether the degradation of E-MDI by the culture supernatant was due to the enzyme, an analysis was performed on a system in which the enzyme was inactivated by heating the culture supernatant (see FIG. 7E). Since there was almost no difference between the peak area and the system in which no addition was made (see FIG. 7.A), it was confirmed that E-MDI was not decomposed. From this, it was confirmed that the PURDK2 strain culture supernatant contains a protein (enzyme) that degrades E-MDI.

  Subsequently, the structure of the compound indicated by the peak EP2 detected by analysis of the degradation product (intermediate metabolite) from the culture supernatant of the PURDK2 strain was identified by GC / MS analysis (see FIG. 8).

  As a result, EP2 was identified as diphenylmethane-4-amin-4'-ethylcarbamate (see Fig. 9).

  EP2 is considered to be a compound obtained by cleaving the urethane bond of E-MDI (see FIG. 10). From this, it was clarified that the culture supernatant cleaves the urethane bond of E-MDI, and it was considered that the PURDK2 strain produces an enzyme that cleaves the urethane bond of E-MDI outside the cells.

3． Degradation of urea binding by PURDK2 strain
In order to analyze whether the PURDK2 strain cleaves the urea bond, the decomposition mode was analyzed using the model compound Diphenylmethane-4,4′-dibuthylurea (D-MDI) (see FIG. 11) of the resin having a urea bond as a substrate.

3.1 Method
10% of PURDK2 strain preculture was inoculated into 100 mL of LB + glucose medium supplemented with 0.01 g of D-MDI, and cultured at 30 ° C. and 100 rpm for 0, 12, 24, and 36 hours. After culture, chloroform / methanol extraction was performed and GC analysis was performed. Moreover, the obtained decomposition product was identified by GC / MS. The analysis was performed in the same manner using a non-inoculated system as a control.

3.2 Analysis results
Two peaks were detected by GC analysis of D-MDI, peak I was D-MDI, and peak II was unreacted (see FIG. 12).

  Analysis of the D-MDI degradation product by the PURDK2 strain by GC revealed that D-MDI decreased by 27% in 24 hours of culture, suggesting that the PURDK2 strain degrades D-MDI. In addition, a new peak thought to be an intermediate metabolite was detected (see FIG. 13).

  The structure of the compound indicated by the peak DP1 detected in the degradation product (intermediate metabolite) in the PURDK2 strain cultured for 24 hours was identified by GC / MS analysis (see FIG. 14).

  As a result, DP1 was identified as dibutylamin (see FIG. 15).

  DP1 is considered to be a compound obtained by cleaving the urea bond of D-MDI (see FIG. 16). This indicates that the PURDK2 strain cleaves the urea bond of D-MDI.

Four. Degradation of urea binding by PURDK2 culture supernatant
In order to confirm whether the resin having urea bonds was decomposed by the culture supernatant of the PURDK2 strain, analysis was performed using D-MDI.

4.1 Method 3% of PURDK2 strain preculture was inoculated into 100 mL of LB + glucose medium supplemented with 5 pieces of ether type polyurethaneurea (1 cm ³ ), and cultured at 30 ° C. and 100 rpm for 24 hours. The obtained culture broth was centrifuged at 4 ° C. and 7,000 g for 10 minutes to separate the supernatant and the bacterial cells. This was repeated twice. Add 0.01 g of Diphenylmethane-4,4'-dibuthylurea (D-MDI) to a 20 mM phosphate buffer solution (pH 7.0), and add 1 mL, 5 mL, and 10 mL of the culture supernatant, respectively, to a total volume of 100 mL. did. After mixing, the mixture was shaken at 30 ° C. and 100 rpm for 1 hour. After shaking, chloroform / methanol extraction was performed, and 1 μL of the resulting chloroform layer was analyzed by GC. Moreover, the obtained decomposition product was identified by GC / MS. The culture supernatant was heated in boiling water for 10 minutes, and 10 mL of the supernatant in which the enzyme was inactivated was similarly analyzed.

4.2 Results and discussion
FIG. 17 shows the GC analysis results of D-MDI degradation using the PURDK2 strain culture supernatant.

  In the system to which 10 mL of culture supernatant was added, D-MDI decreased by 54.5% in 1 hour of reaction, and a new peak that was considered as an intermediate metabolite was detected (FIG. 17.D). In addition, the systems with added supernatant volume of 5 mL (1/2) and 1 mL (1/10) showed D-MDI degradation rates of 25.1% and 7.3%, respectively (Figures 17.B and C). .

  Furthermore, in order to confirm whether the degradation of D-MDI by the culture supernatant was due to the enzyme, an analysis was performed on a system in which the enzyme was inactivated by heating the culture supernatant (FIG. 17E). Since there was almost no difference in the peak area from the system without addition (FIG. 17.A), it was confirmed that D-MDI was not decomposed. From this, it was confirmed that the PURDK2 strain culture supernatant contains a protein (enzyme) that degrades D-MDI.

  Next, the structure of the compound indicated by the peak DP2 detected by analysis of the degradation product (intermediate metabolite) from the culture supernatant of the PURDK2 strain was identified by GC / MS analysis (see FIG. 18).

  As a result, DP2 was identified as dibutylamin (FIG. 19).

  DP2 is considered to be a compound obtained by cleaving the urea bond of D-MDI (see FIG. 20). This revealed that the culture supernatant of the PURDK2 strain cleaves the urea bond of D-MDI.

1 is a drawing showing the structure of a model compound Diphenylmethane-4,4′-diethylcarbamate (E-MDI) of a resin having a urethane bond. □ indicates the urethane bond of the compound. It is drawing which shows the GC analysis result of E-MDI. It is a figure which shows the result of having investigated E-MDI degradation product in culture | cultivation 24 hours by PURDK2 strain | stump | stock by GC. A shows the case of uninoculated bacteria. B shows the GC analysis result of the degradation product after 24 hours culture of PURDK2 strain. It is drawing which shows the mass spectrum of EP1. It is a figure which shows the structure identified about EP1. It is the figure which illustrated the result of having analyzed the cutting site of E-MDI by PURDK2 strain. ↓ indicates the urethane bond cleavage site by the PURDK2 strain. It is the figure which showed the GC analysis result of E-MDI decomposition | disassembly by the culture supernatant of PURDK2 strain. When A was added with no supernatant, B was added with 1 mL of culture supernatant, C was added with 5 mL of culture supernatant, D was added with 10 mL of culture supernatant, and E was inactivated. The result when 10 mL of culture supernatant is added is shown. It is drawing which shows the mass spectrum of EP2. It is a figure which shows the structure identified about EP2. It is drawing which showed the result of having analyzed the cutting | disconnection site | part of E-MDI by the culture supernatant of PURDK2 strain | stump | stock. ↓ indicates the urethane bond cleavage site in the culture supernatant of the PURDK2 strain. 1 is a drawing showing the structure of a model compound diphenylmethane-4,4′-dibuthylurea (D-MDI) of a resin having a urea bond. □ indicates the urea bond of the compound. It is drawing which shows the GC analysis result of D-MDI. The result of having investigated D-MDI degradation in culture | cultivation 24 hours by PURDK2 strain | stump | stock by GC is shown. A shows the case of uninoculated bacteria. B shows the GC analysis result of the degradation product after 24 hours culture of PURDK2 strain. It is a figure which shows the mass spectrum of the D-MDI degradation product by PURDK2 strain. 2 is a drawing showing the molecular structure of DP1. It is the figure which illustrated the result of having analyzed the cutting site of D-MDI by PURDK2 strain. ↓ indicates the urea bond cleavage site by the PURDK2 strain. It is the figure which showed the GC analysis result of D-MDI decomposition | disassembly by the culture supernatant of PURDK2 strain. When A is added without supernatant, B is added with 1 mL of culture supernatant, C is added with 5 mL of culture supernatant, D is added with 10 mL of culture supernatant, and E is inactivated. The results when 10 mL of the cultured supernatant was added are shown. It is a figure which shows the mass spectrum of the D-MDI degradation product by the PURDK2 strain culture supernatant. It is drawing which shows the molecular structure of DP2. It is drawing which showed the result of having analyzed the cutting | disconnection site | part of D-MDI by the culture supernatant of PURDK2 strain | stump | stock. ↓ indicates the urea bond cleavage site in the culture supernatant of the PURDK2 strain.

Claims (10)

A culture supernatant of a microorganism belonging to the genus Alternaria, which has the ability to cleave urethane bonds and / or urea bonds. The culture supernatant according to claim 1, wherein the microorganism is Alternaria alternate (Fr.) Kissler PURDK2 strain (FERM P-19445). A composition for decomposing a resin having a urethane bond and / or a urea bond, comprising the culture supernatant according to claim 1 as an active ingredient. Decomposition of a resin having a urethane bond and / or a urea bond, comprising the step of bringing the culture supernatant according to claim 1 or the composition according to claim 3 into contact with a resin having a urethane bond and / or a urea bond. Method. A step of bringing the culture supernatant according to claim 1 or the composition according to claim 3 into contact with a resin portion of a composite material comprising a resin having a urethane bond and / or a urea bond and a base material. A method for separating the resin and the substrate. (1) contacting the resin having a urethane bond and / or urea bond with the culture supernatant according to claim 1 or the composition according to claim 3 to decompose the resin; and (2 ) A method for recycling a resin having a urethane bond and / or a urea bond, including a step of recovering the decomposition product obtained in the step (1). The method according to any one of claims 4 to 6, wherein the resin having a urethane bond and / or a urea bond is an ether type resin. A method for decomposing a resin having a urea bond, comprising a step of bringing a resin having a urea bond into contact with a microorganism belonging to the genus Alternaria and capable of cleaving the urea bond. The degradation method according to claim 8, wherein the microorganism is Alternaria alternate (Fr.) Kissler PURDK2 strain (FERM P-19445). The decomposition method according to claim 8 or 9, wherein the resin having a urea bond is an ether type resin.

Images