JP2018203915A - Method for producing polyurethane using saccharification residue - Google Patents

Abstract

To provide a polyurethane that is highly stable against ultraviolet rays.SOLUTION: A method for producing polyurethane includes the steps of (1) saccharifying lignocellulose, (2) solid-liquid separating a saccharified liquid obtained by the step (1) into a solid content and a liquid content, (3) causing a reaction to occur between the solid content separated by the step (2), polyol, and isocyanate.SELECTED DRAWING: None

Description

  The present invention relates to a polyurethane and a method for producing the same.

  Polyurethane obtained by reacting a polyol and an isocyanate compound is widely used for impact absorbing materials, soundproofing materials, automotive parts, fibers and the like.

  On the other hand, lignin is an aromatic polymer that is abundant in nature, and its use as a renewable resource has been studied in various places. However, its use is still not progressing.

  For example, in Patent Document 1, attempts have been made to use steam-explosive lignin as a polyol, which is a raw material of polyurethane described above, but in order to use it as a raw material of a polyol, it is necessary to extract using an organic solvent. Therefore, in the method described in Patent Document 1, it is described that lignin treated by the steam explosion method is used. More specifically, in Patent Document 1, steam explosion is performed by putting a raw material into a pressure-resistant container for a steam explosion apparatus, injecting 1 to 4 MPa of steam, leaving it for 1 to 15 minutes, and then immediately releasing the pressure. Has been done. However, such a steam explosion requires a dedicated device.

  In addition, polyurethane is often used in places where it is irradiated with ultraviolet rays in applications such as automobile parts and fibers, so that it is desired to improve the stability against ultraviolet rays.

JP2013-170245

  The problem to be solved by the present invention is to provide a polyurethane having high stability to ultraviolet rays.

Under such circumstances, the present inventors have intensively studied, and as a result, (1) a step of saccharifying lignocellulose, (2) solid-liquid separation of the saccharified solution obtained in the above step (1) into a solid component and a liquid component. It was found that the above-mentioned problems can be solved by producing polyurethane by a method comprising the step of reacting the solid content, polyol and isocyanate separated in the step (2), and the step of reacting the solid content. The present invention is based on such novel findings. Accordingly, the present invention provides the following sections:
Item 1. (1) saccharifying lignocellulose,
(2) A step of solid-liquid separation of the saccharified solution obtained in the step (1) into a solid content and a liquid content,
(3) A method for producing polyurethane, comprising a step of reacting the solid content, polyol, and isocyanate separated in the step (2).

  Item 2. Item 2. The method according to Item 1, wherein a fermentation step using a fermentation microorganism is performed in parallel with the step (1).

  Item 3. Item 3. The method according to Item 1 or 2, wherein in the step (3), 0.17 to 100 parts by mass of a polyol is blended with respect to 10 parts by mass of the solid content.

  Item 4. Item 4. The method for producing polyurethane according to any one of Items 1 to 3, wherein the solid content in the obtained polyurethane is 1 to 50% by mass with respect to the entire polyurethane raw material.

  Item 5. Item 5. The method for producing a polyurethane according to any one of Items 1 to 4, wherein silicone is further added in the step (3).

  Item 6. Item 6. The method for producing a polyurethane according to any one of Items 1 to 5, including at least one pretreatment step selected from the group consisting of chemical treatment and mechanical treatment before the step (1).

  Item 7. Item 7. The method for producing a polyurethane according to any one of Items 1 to 6, wherein the lignocellulose is derived from a hardwood material.

  Item 8. The polyurethane which contains 1-50 mass% of solid content derived from lignocellulose saccharified liquid or saccharified fermentation liquid with respect to the whole raw material.

  According to the present invention, it is possible to provide a polyurethane having high stability against ultraviolet rays. Moreover, according to this invention, lignin obtained as a by-product in bioethanol production | generation can be used as a polyol component in the case of urethane synthesis | combination, without using dedicated apparatuses, such as a steam explosion apparatus.

The present invention includes (1) a step of saccharifying lignocellulose,
(2) A step of solid-liquid separation of the saccharified solution obtained in the step (1) into a solid content and a liquid content,
(3) Provided is a method for producing polyurethane, which comprises a step of reacting the solid content, polyol and isocyanate separated in the step (2).

<Lignocellulose raw material>
As a lignocellulosic raw material used as a raw material in the method of the present invention, as a woody system, chips or bark of papermaking trees, forest land residual materials, thinned wood, etc., sprouts generated from stumps of woody plants, sawmills, etc. Sawdust or sawdust that is generated, pruned branches and leaves of street trees, construction waste, etc. Examples include wastes (for example, EFB: Empty Fruit Bunch), herbaceous energy crops Eliansus, Miscanthus, and Napiergrass.
Further, as biomass, food waste such as paper derived from wood, waste paper, pulp, pulp sludge, sludge, sewage sludge, and the like can be used as raw materials. These biomasses can be used alone or in combination. The biomass can be used as a dry solid, a solid containing water, or a slurry.

  Examples of the woody lignocellulosic material include Eucalyptus, Salix, Poplar, Populus, Acacia, and Cryptomeria plants. Eucalyptus plants, Acacia plants, and Willow plants are preferable because they can be easily collected in large quantities as raw materials. Among the lignocellulosic raw materials derived from woody plants, forest land remnants (including bark and leaves) and bark are preferable. For example, bark of tree species such as Eucalyptus genus or Acacia genus commonly used for papermaking raw materials can be obtained in large quantities stably from lumber mills and chip factories for papermaking raw materials. Preferably used. Lignocellulose may be derived from a hardwood material, a softwood material, or a mixture thereof, but in the present invention, it is derived from a hardwood material from the viewpoint of efficiency. Those are preferred.

In the method of the present invention, before the step (1) (saccharification step), at least one pretreatment step selected from the group consisting of chemical treatment and mechanical treatment may be performed. Chemical treatment and mechanical treatment can be performed, for example, by the following methods:
<Mechanical processing>
In the present invention, the lignocellulose raw material can be subjected to mechanical treatment. Examples of the mechanical treatment include any mechanical means such as cutting, cutting, crushing, and grinding, and making lignocellulose easy to be saccharified in the next chemical treatment step. Although it does not specifically limit about the mechanical apparatus to be used, For example, a cutting device, a uniaxial crusher, a biaxial crusher, a hammer crusher, a refiner, a kneader, a ball mill etc. can be used.

  As a pre-process or post-process of the mechanical treatment, a foreign matter removing step by washing or the like for removing foreign matters (foreign matters other than lignocellulose such as stone, dust, metal, plastic) can be introduced.

  Examples of the method for washing the raw material include a method of removing water from the foreign material mixed with the raw material by spraying water on the raw material, or a method of removing the foreign material by immersing the raw material in water and sedimenting the foreign material. Moreover, the method of isolate | separating a foreign material from a raw material using apparatuses, such as a metal trap, is mentioned.

  If foreign materials are included in the raw materials, there is a possibility of causing damage to equipment parts used in mechanical processing such as refiner discs (plates), and causing problems in the manufacturing process such as clogging of piping. Therefore, it is desirable to introduce a foreign substance removing step.

<Chemical treatment>
In the present invention, a chemical treatment may be performed on the lignocellulose raw material. The chemical used in the chemical treatment is selected from one or more alkaline chemicals selected from sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate and sodium hydrogen carbonate, or sodium sulfite and the above alkaline chemicals A pretreatment including a chemical treatment of immersing in a solution containing one or more alkaline chemicals. Further, chemical treatment with an oxidizing agent such as ozone or chlorine dioxide is also possible.

  The chemical treatment is preferably performed as a post-treatment of the pretreatment in combination with the mechanical treatment.

  The amount of chemicals used in the chemical treatment can be arbitrarily adjusted according to the situation, but lignocellulose can be used to reduce the cost of chemicals and to prevent the yield from decreasing due to cellulose dissolution and over-decomposition. It is desirable that it is 50 parts by mass or less with respect to 100 parts by mass of the absolutely dry material. The immersion time and the treatment temperature of the chemical in the chemical treatment can be arbitrarily set depending on the raw materials and chemicals to be used, but a treatment time of 20 to 90 minutes and a treatment temperature of 80 to 200 ° C. are preferable. By tightening the processing conditions, elution or excessive decomposition of cellulose in the raw material may occur, so that the processing time is preferably 70 minutes or less and the processing temperature is preferably 180 ° C. or less.

  As the chemical treatment, 10 to 50% by mass of sodium sulfite and 0.1 to 5% by mass of alkali as a pH adjuster can be added to the lignocellulose raw material (dry weight). When sodium sulfite is added alone to the lignocellulose in the above-mentioned addition amount and heat-treated, an organic acid such as acetic acid is generated during hydrolysis, so that the pH is lowered and the hydrolyzed solution becomes acidic. When hydrolysis is continued under acidic conditions, the problem arises that xylose produced by hydrolysis is converted to furfural. Since furfural is an inhibitor of ethanol fermentation, it is desirable not to produce it as much as possible. Moreover, since the yield of xylose which is a fermentation substrate falls, ethanol production efficiency falls as a result. In the present invention, by adding sodium sulfite and an alkali as a pH adjuster to the lignocellulose raw material in the above-described amount and heat-treating, the pH during hydrolysis is maintained from neutral to weakly alkaline. Production and reduction in xylose yield can be suppressed. Moreover, since the pH of the aqueous solution containing lignocellulose after heat treatment (after hydrolysis) is 4.0 to 7.0 (neutral to weakly alkaline), the waste liquid or hydrolyzate after the hydrolysis treatment is neutralized. There is a merit that the amount of chemicals used for the reduction can be reduced.

  Examples of the alkali used as the pH adjuster include sodium hydroxide, potassium hydroxide, sodium carbonate and the like, but are not particularly limited to these chemicals.

  The heat treatment temperature in the case where the heat treatment is performed by adding 10 to 50% by weight of sodium sulfite and 0.1 to 5% by weight of alkali as a pH adjuster with respect to the lignocellulose raw material (dry weight) is 80 -200 degreeC is preferable and 120-180 degreeC is more preferable. Moreover, although heat processing time can be performed in 10 to 300 minutes, 30 to 120 minutes are preferable. By tightening the processing conditions, elution or excessive decomposition of cellulose in the raw material may occur, so that the processing temperature is preferably 180 ° C. or lower and the processing time is 120 minutes or shorter.

(Grinding treatment)
In the method of the present invention, a step of grinding and grinding the lignocellulose raw material obtained by the mechanical treatment and / or chemical treatment may be further performed. Specifically, it is preferable to grind the lignocellulose raw material in a refiner disk (plate) clearance in the range of 0.1 to 2.0 mm, and to grind in the range of 0.1 to 1.0 mm. Further preferred. As a refiner to be used, a single disk refiner, a double disk refiner, or the like can be used, and any refiner that can set the clearance of the opposing disk within a range of 0.1 to 2.0 mm can be used without particular limitation. it can. By making the clearance of the disk within the above range, the yield of sugar obtained by saccharification or parallel saccharification and fermentation increases, the yield of hydrolyzate (solid content) after grinding with a refiner, and the refiner's It is preferable in that electricity consumption required for operation can be suppressed.

  The material of the refiner disk (plate), the disk mold, the disk surface blade mold, the direction of the blade with respect to the disk surface, etc. should be used without any limitation as long as the material and shape are effective. Can do.

  The lignocellulosic raw material that has been subjected to the above grinding treatment is subjected to solid-liquid separation into an aqueous solution and a solid content, and the solid content is used as a raw material for saccharification or concurrent saccharification and fermentation. As a method for solid-liquid separation, for example, an apparatus that can be separated into an aqueous solution and a solid content using a screw press or the like and can be used without limitation as long as it can be separated into an aqueous solution and a solid content.

  It is preferable to perform sterilization treatment before saccharification or parallel saccharification fermentation using the raw material after the solid separation. By performing sterilization treatment, it is preferable to consume sugar due to various bacteria mixed in the lignocellulosic biomass raw material and to reduce the yield reduction of the product due to the saccharification by the enzyme.

  The sterilization treatment may be a method in which the raw material is exposed to a pH at which bacteria are difficult to grow, such as acid or alkali, but may be a method in which the raw material is treated at a high temperature, or a combination of both. About the raw material after an acid and an alkali treatment, it is preferable to use as a raw material, after adjusting to neutrality vicinity or pH suitable for a saccharification and / or saccharification fermentation process. In addition, even when pasteurized at a high temperature, it is preferably used as a raw material after the temperature is lowered to room temperature or a temperature suitable for the saccharification and fermentation process. Thus, by feeding out the raw material after adjusting the temperature and pH, it is possible to prevent the enzyme from being exposed to the outside of the preferred pH and the preferred temperature and being deactivated.

  The lignocellulose raw material subjected to the pretreatment is supplied to the saccharification step or the primary concurrent saccharification and fermentation step.

<Saccharification step [Step (1)]>
The method of the present invention includes a step of saccharifying lignocellulose as step (1). A saccharification process can be performed as follows, for example. A lignocellulosic raw material optionally subjected to a pretreatment suitable for an enzymatic saccharification reaction is mixed with an appropriate amount of water and an enzyme to form a raw material suspension, which is supplied to the saccharification step. Lignocellulose-based raw materials are saccharified (cellulose → glucose, hemicellulose → glucose, xylose) by enzymes (cellulase, hemicellulase).

<Concurrent saccharification and fermentation process>
Moreover, in this invention, it is preferable to perform the fermentation process using a fermentation microorganism in parallel with a saccharification process (1). Specifically, the lignocellulosic raw material is mixed with an appropriate amount of water and an enzyme to form a raw material suspension, and further mixed with microorganisms such as yeast and supplied to the parallel saccharification and fermentation step. The lignocellulosic raw material is saccharified by an enzyme, and the produced saccharide is fermented to ethanol by a fermentation microorganism (such as yeast).

  It is preferable that the suspension concentration of the lignocellulosic material used in the saccharification process or the concurrent saccharification and fermentation process is 1 to 30% by mass.

  Cellulolytic enzymes used in the saccharification step or the concurrent saccharification and fermentation are enzymes collectively called cellulases having cellobiohydrolase activity, endoglucanase activity, and betaglucosidase activity.

  Each cellulolytic enzyme may be added with an appropriate amount of an enzyme having the respective activity, but the commercially available cellulase preparation has the above-mentioned various cellulase activities and also has a hemicellulase activity. Since many products are available, a commercially available cellulase preparation may be used.

  Commercially available cellulase preparations include the genus Trichoderma, the genus Acremonium, the genus Aspergillus, the genus Phanerochaete, the genus Trametes, and the genus Humicola There are cellulase formulations derived from Commercially available products of such cellulase preparations are all trade names, for example, cellulosin T2 (manufactured by HIPI), mecerase (manufactured by Meiji Seika Co., Ltd.), Novozyme 188 (manufactured by Novozyme), multifect CX10L (manufactured by Genencor) ), GC220 (manufactured by Genencor).

  0.5-100 mass parts is preferable and, as for the usage-amount of the cellulase formulation with respect to 100 mass parts of raw material solid content, 1-50 mass parts is especially preferable.

  The pH of the reaction solution in the saccharification step or the concurrent saccharification and fermentation step is preferably maintained in the range of 3.5 to 10.0, more preferably in the range of 4.0 to 7.5.

  The temperature of the reaction solution in the saccharification step or the concurrent saccharification and fermentation step is not particularly limited as long as it is within the optimum temperature range of the enzyme, preferably 25 to 50 ° C, more preferably 30 to 40 ° C. The reaction is preferably continuous, but may be semi-batch or batch. The reaction time varies depending on the enzyme concentration, but in the case of a batch system, it is 10 to 240 hours, more preferably 15 to 160 hours. Also in the case of a continuous type, the average residence time is 10 to 150 hours, more preferably 15 to 100 hours.

  In the concurrent saccharification and fermentation process, fermented microorganisms that can ferment sugars (hexose sugar, pentose sugar) are used. Examples of fermenting microorganisms include Saccharomyces cerevisiae, Pichia stipitis, Candida shiientais, and Pachisolen sapiens. -Bacteria such as mobilis (Zymomonas mobilis). In addition, genetically modified microorganisms (yeast, bacteria, etc.) produced using genetic recombination techniques can also be used. As the genetically modified microorganism, a microorganism capable of simultaneously fermenting hexose and pentose can be used without particular limitation.

  Microorganisms may be immobilized. Immobilizing microorganisms can eliminate the step of separating and re-recovering microorganisms in the next step, so that at least the burden required for the recovery step can be reduced, and the loss of microorganisms can be reduced. . Moreover, the collection of microorganisms can be facilitated by selecting microorganisms having aggregating properties.

<Fermentation process>
Moreover, in this invention, you may perform the saccharification process and fermentation process of a process (1) with another reaction tank. In this case, the processing solution after the saccharification step is transferred to a fermentation step and fermented using a fermentation microorganism. Examples of fermenting microorganisms include Saccharomyces cerevisiae, Pichia stipitis, Candida shiientais, and Pachisolen sapiens. -Bacteria, such as mobilis (Zymomonas mobilis), etc. are mentioned. In addition, genetically modified microorganisms (yeast, bacteria, etc.) produced using genetic recombination techniques can also be used. As the genetically modified microorganism, a microorganism capable of simultaneously fermenting hexose and pentose can be used without particular limitation.

  Microorganisms may be immobilized. By immobilizing microorganisms, the process of separating and re-recovering microorganisms in the next process can be omitted, so that at least the burden required for the recovery process can be reduced and the loss of microorganisms can be reduced. is there. Moreover, the collection of microorganisms can be facilitated by selecting microorganisms having aggregating properties.

<Solid-liquid separation step [Step (2)]>
The method of the present invention includes, as step (2), a step of solid-liquid separation of the saccharified solution obtained in the above step (1) into a solid content and a liquid content. Specifically, the saccharified solution or saccharified fermentation solution obtained in the above step (1) can be transferred to a solid-liquid separator and separated into a liquid component (filtrate) and a solid component (residue). As an apparatus for performing solid-liquid separation, a screw press, a screen, a filter press, a belt press, a rotary press, or the like can be used. As the screen, a vibrating screen to which a vibrating device is added can be used. The mesh size used in the solid-liquid separation is preferably 1.25 to 600 mesh, more preferably 60 to 600 mesh.
The collected solid content (residue) is used for the urethane synthesis reaction described later. The liquid component separated in the solid-liquid separation step can be used as a raw material for bioethanol. In the present specification, the solid content separated from the liquid component by the solid-liquid separation from the lignocellulose saccharified solution or saccharified fermentation solution may be referred to as a residue.

<Urethane synthesis reaction [Step (3)]>
The method of the present invention includes, as step (3), a step of reacting the solid content separated in the above step (2), a polyol, and an isocyanate.

  The polyol is not particularly limited, and any known urethane raw material can be used as appropriate, and examples thereof include polyether polyol and polyester polyol. Examples of polyether polyols include polyols obtained by polymerizing alkanolamines such as ethanolamine and diethanolamine and alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide; these alkylene oxides, ethylene glycol, and propylene Aliphatic polyhydric alcohols such as glycol, tetramethylene glycol, glycerin, trimethylolpropane, pentaerythritol, aromatic amine compounds such as toluenediamine, diphenylmethane-4,4-diamine, alkanolamines such as ethanolamine and diethanolamine And polyols obtained by reacting.

  Specific examples of the polyester polyol include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, glycerin, trimethylolpropane, and the like, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, Examples thereof include condensation polymers with carboxylic acids such as dimer acid and oligomeric acid. These polyols can be used individually by 1 type or in combination of 2 or more types.

  Although it does not specifically limit as a mass average molecular weight of a polyol, For example, 2500-50000 are preferable and 5000-25000 are more preferable.

  Isocyanate is not particularly limited, and known urethane raw materials can be used as appropriate, and examples thereof include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and modified products thereof. .

  Examples of the aliphatic polyisocyanate include hexamethylene diisocyanate, trimethylene diisocyanate, pentamethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, and trimethylhexamethylene diisocyanate.

  Examples of the alicyclic polyisocyanate include cyclopentane diisocyanate, cyclohexane diisocyanate, methylene bis (cyclohexyl isocyanate), bis (isocyanate methyl) cyclohexane, trimethyl cyclohexyl isocyanate, and the like.

  Examples of aromatic polyisocyanates include phenylene diisocyanate, diphenyl diisocyanate, toluylene diisocyanate, triisocyanate toluene, triisocyanate benzene, diphenyl ether diisocyanate, naphthylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, triphenylmethane triisocyanate, diisocyanate dimethylbenzene. , Diisocyanate diethylbenzene, tetramethylxylylene diisocyanate and the like.

  Examples of the modified body include biuret bodies, adduct bodies, and isocyanurate bodies of these isocyanates. These isocyanates can be used individually by 1 type or in combination of 2 or more types.

  Although the blending ratio of the solid content (residue) in this step is not particularly limited, for example, it is usually 0.1 to 20 parts by mass, preferably 0.25 to 10 parts by mass, more preferably 10 parts by mass of isocyanate. Can be blended in the range of 0.5 to 5 parts by mass.

  The blending ratio of the polyol in this step is not particularly limited. For example, it is usually 0.25 to 30 parts by weight, preferably 0.5 to 15 parts by weight, more preferably 1 to 10 parts by weight of isocyanate. It can mix | blend in 7.5 mass parts.

  The blending ratio of the solid content (residue) and the polyol in this step is not particularly limited. For example, the polyol is usually 0.17 to 100 parts by mass, preferably 0 with respect to 10 parts by mass of the solid content (residue). .25 to 80 parts by mass, more preferably 0.5 to 40 parts by mass, and still more preferably 1 to 20 parts by mass.

  In this step, a catalyst for promoting the reaction may be added. The reaction catalyst is not particularly limited, and a known catalyst for urethane reaction can be appropriately used. For example, tin catalysts such as dibutyltin dilaurate and tin octylate, triethylenediamine, bis (2-dimethyl) (Aminoethyl) ether, N, N-dimethylhexylamine, amine catalyst such as N, N, N ′, N′-tetramethylhexamethylenediamine, hydroxylamine catalyst, imidazole catalyst, quaternary ammonium salt catalyst, Examples thereof include potassium-based catalysts such as potassium acetate and potassium octylate, and lead-based catalysts such as lead octylate. These catalysts can be used individually by 1 type or in combination of 2 or more types. Although the compounding ratio of a catalyst is not specifically limited, For example, it is 0.01-10 mass parts normally with respect to 10 mass parts of isocyanate, Preferably, it is 0.05-5 mass parts, More preferably, it is 0.1-2. It can mix | blend in 5 mass parts.

  In this step, it is preferable to add silicone. Although the blending ratio of silicone is not particularly limited, for example, it is usually 0.1 to 10 parts by weight, preferably 0.25 to 5 parts by weight, more preferably 0.5 to 2. It can mix | blend in 5 mass parts.

  In the urethane reaction, in addition to the above, various components known to be blended with polyurethane, for example, foam stabilizers, foaming agents, crosslinking agents, flame retardants, fillers, colorants, stabilizers, release agents Etc. may be blended.

  Step (3) can be performed by mixing each of the above components and optionally water or the like. In the present invention, the above components may be mixed at one time, or some components may be mixed first, and the resulting mixture and the remaining components may be mixed. For example, a method in which the solid content separated in the above step (2) and a polyol are first mixed to obtain a polyol solution, and then the polyol solution is mixed with an isocyanate or the like is preferable. By this step, the polyol and the polyol component contained in the solid content react with the isocyanate to form polyurethane. Although content of the said solid content in the polyurethane obtained by the method of this invention is not specifically limited, For example, it is 1-50 mass% normally with respect to the whole raw material of a polyurethane, Preferably, it is 1.5-40 mass. %, More preferably 2 to 30% by mass.

  Although reaction time is not specifically limited, For example, 1 minute-60 minutes, Preferably it is 2 minutes-30 minutes, More preferably, it can set suitably in 4 minutes-15 minutes. The reaction temperature is not particularly limited, but can be appropriately set within a range of, for example, 20 to 150 ° C, preferably 30 to 100 ° C, and more preferably 40 to 80 ° C. The pressure is not particularly limited, and the reaction may be performed without adjusting the pressure, or may be performed under pressure or under reduced pressure.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

[Experimental Example 1]
[Preprocessing]
A material obtained by treating a lignocellulose raw material (eucalyptus globulus) with a plug screw (manufactured by Shinryo Kogyo Co., Ltd.) was used as a raw material. After adding 120 g of 97% sodium sulfite and 6.4 g of sodium hydroxide to 400 g (absolute dry weight) of the raw material, water was added to adjust the volume of the aqueous solution to 2.4 L. The raw material suspension was mixed and then heated at 170 ° C. for 2 hours. The raw material suspension after the heat treatment was ground using a refiner (manufactured by Kumagai Riki Kogyo Co., Ltd., KRK high concentration disk refiner) with the disc clearance set to 0.5 mm. This ground material suspension was solid-liquid separated into a solid (raw material 1) and a liquid by a screw press (manufactured by Togoku Industry Co., Ltd., SHX-200X1500L, mesh size 1.2 mm). A saccharification and fermentation test was carried out using the solid content after solid-liquid separation (raw material 1) as a raw material.
[Saccharification and fermentation test]
Yeast (Isachenchia orientalis) was inoculated into 50 ml of YPD medium and cultured overnight at 37 ° C. with shaking (preculture). In a 3L saccharification and fermentation vessel, 1L of liquid medium (glucose 10g / L, caustic liquor 20g / L, urea 4.4g / L), preculture solution 50ml, commercial cellulase (Accellerase TRIO, Genencor) 80g, raw material (raw material 1 ) Was added so that the final concentration was 10% by mass, and the final volume was made up to 2000 ml with distilled water. This mixed solution was subjected to saccharification and fermentation (main culture) at 37 ° C. for 48 hours, and the obtained saccharification and fermentation solution was subjected to solid-liquid separation by the following method.
[Solid-liquid separation]
The saccharified fermentation broth obtained above is centrifuged (7850 rpm, 20 minutes), and the resulting precipitate is dried at −50 ° C., 5 Pa, 48 hours with a freeze dryer (FZ-6, manufactured by Asahi Life Sciences), and the residue (Saccharification and fermentation residue) was obtained. It was 25 mass% when the cellulose content contained in a residue was measured by the phenol sulfuric acid method.
[Urethane reaction]
A polyol solution was obtained by mixing 0.5 g of the saccharification and fermentation residue obtained above and 1 g of polyol (polyethylene glycol 400) for 1 minute. To the resulting polyol solution, 10 g of isocyanate (methylenediphenyl 4,4-diisocyanate), 10 g of water, 1 g of silicone and a few drops of catalyst (dibutyltin dilaurate [IV]) were added and mixed for 1 minute to the entire raw material. As a result, a polyurethane having a residue content of 2.2% by mass was obtained.
[Evaluation]
<Measurement of weight loss rate>
A sample of polyurethane obtained in Experimental Example 1 having a thickness of 1 cm and a weight of 5 g was irradiated with ultraviolet rays for 1 hour, then stored in a thermostat at 80 ° C. for 12 weeks, and the change in weight was measured. The results are shown in Table 1.

[Experiment 2]
The urethane reaction was performed by the following method using the residue obtained in Experimental Example 1. Other than that, it tested by the method similar to Experimental example 1 all. The results are shown in Table 1.
[Urethane reaction]
A polyol solution was obtained by mixing 1 g of the saccharification and fermentation residue obtained above and 1 g of polyol (polyethylene glycol 400) for 1 minute. To the resulting polyol solution, 10 g of isocyanate (methylenediphenyl 4,4-diisocyanate), 10 g of water, 1 g of silicone and a few drops of catalyst (dibutyltin dilaurate [IV]) were added and mixed for 1 minute to the entire raw material. As a result, a polyurethane having a residue content of 4.3% by mass was obtained.

[Experiment 3]
The urethane reaction was performed by the following method using the residue obtained in Experimental Example 1. Other than that, it tested by the method similar to Experimental example 1 all. The results are shown in Table 1.
[Urethane reaction]
A polyol solution was obtained by mixing 4 g of the saccharification and fermentation residue obtained above and 1 g of a polyol (polyethylene glycol 400) for 1 minute. To the resulting polyol solution, 10 g of isocyanate (methylenediphenyl 4,4-diisocyanate), 10 g of water, 1 g of silicone and a few drops of catalyst (dibutyltin dilaurate [IV]) were added and mixed for 1 minute to the entire raw material. As a result, a polyurethane having a residue content of 15.4% by mass was obtained.

[Experimental Example 4]
The urethane reaction was performed by the following method using the residue obtained in Experimental Example 1. Other than that, it tested by the method similar to Experimental example 1 all. The results are shown in Table 1.
[Urethane reaction]
A polyol solution was obtained by mixing 5 g of the saccharification and fermentation residue obtained above and 0.5 g of polyol (polyethylene glycol 400) for 1 minute. To the resulting polyol solution, 10 g of isocyanate (methylenediphenyl 4,4-diisocyanate), 10 g of water, 1 g of silicone and a few drops of catalyst (dibutyltin dilaurate [IV]) were added and mixed for 1 minute to the entire raw material. As a result, a polyurethane having a residue content of 18.9% by mass was obtained.

[Experimental Example 5]
The urethane reaction was performed by the following method using the residue obtained in Experimental Example 1. Other than that, it tested by the method similar to Experimental example 1 all. The results are shown in Table 1.
[Urethane reaction]
A polyol solution was obtained by mixing 5 g of the saccharification and fermentation residue obtained above and 0.1 g of polyol (polyethylene glycol 400) for 1 minute. To the resulting polyol solution, 10 g of isocyanate (methylenediphenyl 4,4-diisocyanate), 10 g of water, 1 g of silicone and a few drops of catalyst (dibutyltin dilaurate [IV]) were added and mixed for 1 minute to the entire raw material. As a result, a polyurethane having a residue content of 19.2% by mass was obtained.

[Experimental Example 6]
Pretreatment was carried out in the same manner as in Experimental Example 1, and saccharification tests were carried out by the following method using the solid content (raw material 1) after solid-liquid separation as a raw material.
[Saccharification test]
In a 3 L saccharification container, 1 L of liquid medium (glucose 10 g / L, caustic liquor 20 g / L, urea 4.4 g / L), 80 g of commercially available cellulase (Accellerase TRIO, Genencor), and a final concentration of 10 raw materials The raw material was added so that it might become mass%, and the final volume was made up to 2000 ml with distilled water. This mixed solution was saccharified for 48 hours at 37 ° C., and the resulting saccharified solution was subjected to solid-liquid separation in the same manner as in Experimental Example 1 to obtain a residue (saccharification residue). It was 40 mass% when the cellulose content contained in a residue was measured by the phenol sulfuric acid method. Hereinafter, the urethane reaction was carried out by the following method using the residue obtained in the same manner as in Experimental Example 1. The results are shown in Table 1.
[Urethane reaction]
A polyol solution was obtained by mixing 1 g of the saccharification residue obtained above and 1 g of a polyol (polyethylene glycol 400) for 1 minute. To the resulting polyol solution, 10 g of isocyanate (methylenediphenyl 4,4-diisocyanate), 10 g of water, 1 g of silicone and a few drops of catalyst (dibutyltin dilaurate [IV]) were added and mixed for 1 minute to the entire raw material. As a result, a polyurethane having a residue content of 4.3% by mass was obtained.

[Experimental Example 7]
In the method of Experimental Example 6, all tests were performed under the same conditions as in Experimental Example 6 except that 4 g of saccharification residue and 1 g of polyol were mixed. The results are shown in Table 1.

[Experimental Example 8]
In the method of Experimental Example 6, all tests were performed under the same conditions as Experimental Example 6 except that 5 g of saccharification residue and 0.5 g of polyol were mixed. The results are shown in Table 1.

[Experimental Example 9]
In the method of Experimental Example 3, all tests were performed under the same conditions as in Experimental Example 3 except that silicone was not added by urethane reaction. The results are shown in Table 1.

[Experimental Example 10]
In the method of Experimental Example 7, all tests were performed under the same conditions as in Experimental Example 8 except that silicone was not added by urethane reaction. The results are shown in Table 1.

[Experimental Example 11]
In the method of Experimental Example 1, all tests were performed under the same conditions as in Experimental Example 1 except that no residue (saccharification and fermentation residue) was added by urethane reaction. The results are shown in Table 1.

  As shown in Table 1, the weight of the polyurethane produced in Experimental Examples 1 to 8 (polyurethane produced using a residue as a raw material) due to UV deterioration is greater than the polyurethane produced in Experimental Example 11 (a polyurethane produced from a raw material not containing a residue). The rate of decrease was low. From this result, it is possible to produce a polyurethane having a low weight reduction rate with respect to ultraviolet rays by using the residue after saccharification or saccharification and fermentation of lignocellulose as a raw material for polyurethane.

  According to the present invention, it is possible to provide a polyurethane having a low weight reduction rate due to ultraviolet rays.

Claims (8)

(1) saccharifying lignocellulose,
(2) A step of solid-liquid separation of the saccharified solution obtained in the step (1) into a solid content and a liquid content,
(3) A method for producing polyurethane, comprising a step of reacting the solid content, polyol, and isocyanate separated in the step (2). The method of Claim 1 which performs the fermentation process using a fermentation microorganism in parallel with the said process (1). The method according to claim 1 or 2, wherein in the step (3), 0.17 to 100 parts by mass of a polyol is blended with respect to 10 parts by mass of the solid content. Content of the said solid content in the obtained polyurethane is 1-50 mass% with respect to the whole raw material of a polyurethane, The manufacturing method of the polyurethane of any one of Claims 1-3 characterized by the above-mentioned. The method for producing a polyurethane according to any one of claims 1 to 4, wherein silicone is further added in the step (3). The method for producing a polyurethane according to any one of claims 1 to 5, comprising at least one pretreatment step selected from the group consisting of chemical treatment and mechanical treatment before the step (1). . The method for producing a polyurethane according to any one of claims 1 to 6, wherein the lignocellulose is derived from a hardwood material. The polyurethane which contains 1-50 mass% of solid content derived from lignocellulose saccharified liquid or saccharified fermentation liquid with respect to the whole raw material.