Composition and method for producing same

Abstract

The present invention provides a composition as a novel material derived from algae, and a method for producing the same.　The composition contains a plasticizer and an alkali-treated product of algae bodies and / or residue derived from algae bodies, and has a water content of 30 mass% or less.

Description

Composition and method for producing the same

[0001] The present invention relates to a composition and a method for producing the same.

[0002] Algae such as microalgae have higher productivity than existing oil plants, and research into their application as a means of producing oils for the production of edible oils, transportation fuels, raw materials for chemical products, foods, food additives, etc. is being actively conducted both domestically and internationally (see, for example, Patent Document 1).

[0003] Japanese Patent Application Laid-Open No. 2015-231363

[0004] As mentioned above, various uses for the oil extracted from algae are being investigated. On the other hand, the residue after oil extraction has been considered for use as livestock feed, fertilizer, and as an energy source for waste-to-energy generation, but these uses have not yet been fully explored.

[0005] The present invention has been made in view of the above, and aims to provide a composition as a novel material derived from algae, and a method for producing the same.

[0006] As a result of intensive research to solve the above-mentioned problems, the inventors discovered that the above-mentioned problems can be solved by using an alkali-treated product of algal bodies and / or residue derived from algal bodies, and a plasticizer, and thus completed the present invention.

[0007] [1] A composition comprising an alkali-treated product of algae bodies and / or residue derived from algae bodies, and a plasticizer, wherein the water content is 30 mass% or less.

[0008] [2] The composition according to [1], wherein the plasticizer has at least one group selected from the group consisting of a carbonyl group, a carboxy group, a hydroxyl group, an amino group, and an amide group in the molecule.

[0009] [3] The composition according to [2], wherein the total number of carbonyl groups, carboxy groups, hydroxyl groups, amino groups, and amide groups in the plasticizer molecule is 2 or more.

[0010] [4] The composition according to any one of [1] to [3], wherein the content of the plasticizer is 1 part by mass or more and 1,000 parts by mass or less per 100 parts by mass (dry mass) of the alkali-treated product.

[0011] [5] The composition according to any one of [1] to [4], further treated with formalin.

[0012] [6] The composition according to any one of [1] to [5], further comprising a polymer additive.

[0013] [7] A method for producing the composition according to any one of [1] to [6], comprising: a step (A) of preparing a mixed solution of an alkali-treated product of algal cells and / or a residue derived from algal cells, and a plasticizer; and a step (B) of drying the mixed solution.

[0014] [8] The method for producing a composition according to [7], wherein the treatment temperature of the alkali treatment in the alkali-treated product is 40°C or higher and 140°C or lower.

[0015] [9] The method for producing the composition according to [7], further comprising: a step (C) of treating the composition obtained in the step (B) with formalin; and a step (D) of heat-treating the composition treated with formalin.

[0016] According to the present invention, it is possible to provide a composition as a novel material derived from algae, and a method for producing the same.

[0017] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments.

[0018] [Composition] The composition contains an alkali-treated product of algal cells and / or residue derived from algal cells, and a plasticizer, and has a water content of 30 mass % or less.

[0019] The present inventors investigated various treatments for algae-derived residues in order to utilize them. As a result, they found that by treating algae-derived residues with alkali, proteins and carbohydrates in the residues were dissolved, resulting in a homogenized alkali-treated solution. However, the alkali-treated product obtained by drying this residue was too brittle to be molded, making it difficult to use for various applications.

[0020] Further investigations revealed that mixing an alkali-treated residue derived from algae cells with a plasticizer resulted in a resin-like composition with good strength. Such a composition can be used, for example, as a substitute for fossil-derived resins (such as conventional synthetic resins). Furthermore, it was also found that a moldable resin-like composition can be obtained when algae cells are used instead of or together with algae cells.

[0021] Although the mechanism by which such an effect is achieved is not entirely clear, the inventors presume that it is due to the following mechanism. Proteins are composed of various amino acids and contain free carboxyl groups and amino groups. It is presumed that resin-like properties are exhibited by the reaction or interaction of these functional groups with the functional groups of the plasticizer. Examples of functional groups of plasticizers include hydroxyl groups, amino groups, and carboxyl groups. For example, resin-like properties can be exhibited by the reaction of carboxyl groups in the protein with hydroxyl groups or amino groups in the plasticizer, and the reaction of amino groups in the protein with carboxyl groups in the plasticizer.

[0022] [Alkali-treated product] The composition of the present invention contains an alkali-treated product of algal cells and / or residue derived from algal cells.

[0023] The alkali-treated product refers to an alkali-treated product of algae cells and / or residues derived from algae cells, such as by contact with an alkaline solution. The alkali-treated product includes any component obtained by subjecting algae cells and / or residues derived from algae cells to an alkali treatment. Note that components obtained by subjecting algae cells and / or residues derived from algae cells to an alkali treatment include, for example, components derived from algae cells and / or residues derived from algae cells, and components derived from an alkaline solution.

[0024] The alkali-treated product may contain either an alkali-insoluble component that is insoluble in an alkali solution (such as an aqueous sodium hydroxide solution) or an alkali-soluble component that is soluble in an alkali solution, or both. From the viewpoint of facilitating the production of a material with good physical properties, it is preferable that the alkali-treated product contain both an alkali-insoluble component and an alkali-soluble component.

[0025] The alkali-treated product may be in the form of a solution, for example. In such a form, alkali-insoluble components can usually be confirmed as a precipitate, and alkali-soluble components can usually be confirmed as a supernatant.

[0026] The alkali in the alkali-treated product is not particularly limited, and examples thereof include ammonia, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal oxides, alkaline earth metal oxides, alkali metal carbonates, alkaline earth metal carbonates, quaternary ammonium hydroxide, etc. One type of alkali may be used, or two or more types may be used in combination.

[0027] Examples of alkali metal hydroxides include sodium hydroxide, potassium hydroxide, and lithium hydroxide; examples of alkaline earth metal hydroxides include magnesium hydroxide and calcium hydroxide; examples of alkali metal oxides include sodium oxide and potassium oxide; examples of alkaline earth metal oxides include magnesium oxide and calcium oxide; examples of alkali metal carbonates include sodium carbonate, potassium carbonate, and lithium carbonate; and examples of alkaline earth metal carbonates include magnesium carbonate and calcium carbonate.

[0028] The alkali is preferably an alkali metal hydroxide, more preferably sodium hydroxide.

[0029] The content of the alkali-treated product is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, based on the dry mass of the composition of the present invention. Furthermore, the content is preferably 90% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less. Within the above range, a moldable resin-like composition is likely to be obtained.

[0030] (Algal Cells) In this specification, algae refers to organisms that perform oxygenic photosynthesis, excluding mosses, ferns, and spermatophytes. As will be described later, Labyrinthulae do not perform photosynthesis, but are classified as algae in this specification due to their phylogenetic closeness. One type of algae may be used, or two or more types may be used in combination.

[0031] The algae is not particularly limited, and examples thereof include microalgae. In this specification, microalgae refer to algae with a microscopic structure that are organisms that perform oxygenic photosynthesis, excluding mosses, ferns, and spermatophytes that primarily live on land, and excluding multicellular marine algae (Biodiversity Series (3) Diversity and Lineage of Algae: edited by Hikaru Chihara, Shokabo Publishing (1999)). Microalgae also include those that form colonies of multiple cells. In this specification, the microscopic structure specifically refers to cells with a diameter of 1 to 100 μm. The cell size is the major axis diameter of the cell as observed using an optical microscope.

[0032] Well-known examples of such microalgae include those belonging to the phyla Chlorophyta, Heterokontophyta, and Cyanobacteria.

[0033] Examples of microalgae belonging to the division Chlorophyceae include algae belonging to classes such as Chlorophyceae, Trebouxiophyceae, Prasinophyceae, Ulvophyceae, and Charophyceae.

[0034] Examples of algae belonging to the Chlorophyceae class include algae of the genus Neochloris such as Neochloris oleoabundans, algae of the genus Nanochloris such as Nannochloris sp., algae of the genus Chlamydomonas such as Chlamydomonas reinhardtii, algae of the genus Scenedesmus such as Rock Shell, and algae of the genus Desmodesmus.

[0035] Examples of algae belonging to the Treboxiophyceae include algae of the genus Chlorella, such as Chlorella kessleri, and algae of the genus Parachlorella.

[0036] Examples of algae belonging to the Heterokontophyta include algae belonging to classes such as Chrysophyceae, Dictyochophyceae, Pelagophyceae, Rhaphidophyceae, Bacillariophyceae, Phaeophyceae, Xanthophyceae, and Eustigmatophyceae.

[0037] Examples of algae belonging to the Bacillariophyceae include algae of the genus Phaeodactylum.

[0038] Examples of algae belonging to the class Euphorbiae include algae of the genus Nannochloropsis.

[0039] Examples of algae belonging to the Cyanobacteria phylum include algae belonging to the Cyanophyceae class, such as algae of the genus Arthrospira, including Spirulina.

[0040] Labyrinthulae, which are unicellular fungus-like protists, are also classified as microalgae. Specific examples of Labyrinthulae include the genera Aurantiochytrium, Schizochytrium, Thraustochytrium, and Ulkenia. Labyrinthulae do not photosynthesize and are cultured under heterotrophic conditions, but are classified as microalgae in this specification.

[0041] As the microalgae, microalgae belonging to the Chlorophyceae, Treboxiophyceae, Bacillariophyceae, Cyanobacteria, and Labyrinthulophyceae are preferred, and microalgae belonging to the Treboxiophyceae are more preferred.

[0042] It is presumed that the proportions of high molecular components such as proteins, carbohydrates, and alginanes vary depending on the type of algae, and this changes the mechanical properties of the composition.

[0043] The content of algal bodies of the algae is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, based on the dry mass of the composition. Furthermore, the content is preferably 90% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less. Within the above range, a moldable resin-like composition is easily obtained.

[0044] (Residue derived from algae bodies) The residue derived from algae bodies refers to the portion remaining after all or part of the oil and the like has been extracted from the algae bodies. The extraction method is not particularly limited, and known methods for extracting oil and the like from algae bodies can be applied, such as a method of physically squeezing or compressing the algae bodies to squeeze the oil out of the algae bodies, or a method of immersing the algae bodies in an extraction solvent such as an organic solvent to chemically elute the oil.

[0045] The protein content in the residue derived from algae bodies is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more. Furthermore, the protein content is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less. Within the above range, a moldable resin-like composition is easily obtained.

[0046] The carbohydrate content in the residue derived from algae bodies is preferably 5% by mass or more, more preferably 10% by mass or more. Furthermore, the carbohydrate content is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. Within the above range, a moldable resin-like composition is easily obtained.

[0047] The content of the residue derived from algae bodies is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, based on the dry mass of the composition. Furthermore, the content is preferably 90% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less. Within the above range, a moldable resin-like composition is easily obtained.

[0048] The total content of algal cells and residues derived from algal cells is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, based on the dry mass of the composition. Furthermore, the content is preferably 90% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less. Within the above range, a moldable resin-like composition is easily obtained.

[0049] (Plasticizer) The plasticizer is a substance added to improve the processability of the composition. While not particularly limited, plasticizers having at least one group selected from the group consisting of carbonyl, carboxy, hydroxyl, amino, and amide groups in the molecule are preferred. Carboxy groups are more preferred because they undergo a condensation reaction with free amino groups in proteins to form covalent bonds, thereby improving the physical properties of the composition. Furthermore, plasticizers having a total of two or more carbonyl, carboxy, hydroxyl, amino, and amide groups in the molecule are preferred. Plasticizers with such functional groups tend to have a high affinity for proteins and carbohydrates contained in algae bodies and algae-derived residues, making it easier to obtain a moldable resin-like composition. The upper limit of the total is not particularly limited, but is, for example, 10 or less.

[0050] The number of carbon atoms of the plasticizer is not particularly limited, but may be, for example, 1 to 20, 2 to 15, or 4 to 12. The molecular weight of the plasticizer is not particularly limited, but may be, for example, 300 or less, 40 to 280, or 40 to 260.

[0051] Examples of the plasticizer having at least one group selected from the group consisting of a carbonyl group, a carboxy group, a hydroxyl group, an amino group, and an amide group in the molecule include polyols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, glycerin, trimethylolethane, trimethylolpropane, hexanetriol, and sorbitol; pyruvic acid, oxaloacetic acid, α-ketoglutaric acid, acetoacetic acid, and acetoacetate. Examples of suitable plasticizers include keto acids such as benzotricarboxylic acid and levulinic acid; dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, and itaconic acid; hydroxycarboxylic acids such as glycolic acid, lactic acid, hydroxyacrylic acid, glyceric acid, malic acid, tartaric acid, citric acid, and gluconic acid; amines such as ethylenediamine, propanediamine, butanediamine, pentanediamine, and hexanediamine; lactones such as butyrolactone, valerolactone, and caprolactone; lactams such as butyrolactam, valerolactam, and caprolactam; and monocarboxylic acids such as formic acid, acetic acid, propionic acid, and acrylic acid. When the exemplified compounds are polymerizable, a polymer of the compound may be used as the plasticizer, such as poly(meth)acrylic acid. These plasticizers may be used alone or in combination of two or more. Among these, polyols, keto acids, dicarboxylic acids, hydroxycarboxylic acids, amines, lactones, lactams, and poly(meth)acrylic acids are preferred, and levulinic acid, glutaric acid, sorbitol, gluconic acid, triethylene glycol, tetraethylene glycol, itaconic acid, pimelic acid, hexamethylenediamine, ε-caprolactone, ε-caprolactam, citric acid, succinic acid, acetic acid, and poly(meth)acrylic acid are more preferred, from the viewpoint of better achieving the effects of the present invention. These may be used alone or in combination of two or more.

[0052] A part or all of the plasticizer in the composition may or may not be covalently bonded to the alkali-treated product, but it is preferable that it is covalently bonded.

[0053] The content of the plasticizer is preferably from 1 to 1,000 parts by mass, more preferably from 20 to 300 parts by mass, and even more preferably from 50 to 200 parts by mass, relative to 100 parts by mass (dry mass) of the alkali-treated product. Within the above range, a moldable resin-like composition is likely to be obtained.

[0054] The content of the plasticizer is preferably 1 part by mass to 1,000 parts by mass, more preferably 20 parts by mass to 300 parts by mass, and even more preferably 50 parts by mass to 200 parts by mass, relative to a total of 100 parts by mass (dry mass) of the algae bodies and residue derived from the algae bodies. Within the above range, a moldable resin-like composition is likely to be obtained.

[0055] When the composition contains an alkali-treated algal body and a plasticizer, the content of the plasticizer is preferably 1 part by mass to 1,000 parts by mass, more preferably 20 parts by mass to 300 parts by mass, and even more preferably 50 parts by mass to 200 parts by mass, per 100 parts by mass (dry mass) of the algal body. Within the above range, a moldable resin-like composition is easily obtained.

[0056] When the composition contains an alkali-treated residue derived from algae cells and a plasticizer, the content of the plasticizer is preferably 1 part by mass to 1,000 parts by mass, more preferably 20 parts by mass to 300 parts by mass, and even more preferably 50 parts by mass to 200 parts by mass, per 100 parts by mass (dry mass) of the residue derived from algae cells. Within the above range, a moldable resin-like composition is likely to be obtained.

[0057] In the present invention, the content of the plasticizer and the like in the composition is calculated from the amount added or measured by infrared absorption spectroscopy.

[0058] [Water] The water content in the composition is 30% by mass or less, preferably 10% by mass or less. The lower limit of the water content is not particularly limited, but is, for example, 0.1% by mass or more.

[0059] [Polymer additive] The composition of the present invention may contain a polymer additive. This tends to further improve the mechanical strength of the composition. The polymer additive may be a natural polymer or a synthetic polymer. These may be used alone or in combination of two or more.

[0060] Examples of natural polymers include, but are not limited to, polysaccharides, proteins, etc. Examples of polysaccharides include agar, pectin, pectic acid, pectinic acid, carrageenan, gellan gum, xanthan gum, locust bean gum, guar gum, tara gum, tamarind seed gum, psyllium seed gum, starch, curdlan, chitin, chitosan, pullulan, furcellaran, celluloses (nitrocellulose, methylcellulose, hydroxypropylmethylcellulose, sodium carboxymethylcellulose, microfibrous cellulose, fermented cellulose, etc.), hyaluronic acid, alginic acid or a salt thereof, mannans (konjac mannan, galactomannan, etc.), gum arabic, karaya gum, tragacanth gum, arabinogalactan, gum ghatti, glucosamine, and soybean polysaccharides. Among these, chitosan is preferred.

[0061] Examples of synthetic polymers include, but are not limited to, polylactic acid, polyglycolic acid, copolymers of polylactic acid and polyglycolic acid, polyepsilon caprolactone, polyhydroxybutyric acid, N-substituted acrylamide, N-substituted methacrylamide, N-vinyl acetamide, polyethylene oxide, polyethylene glycol, and polyvinyl alcohol.

[0062] The weight average molecular weight (Mw) of the polymer additive is preferably 500 or more, more preferably 1,000 or more, and even more preferably 5,000 or more. The upper limit of Mw is not particularly limited, but may be, for example, 1,000,000 or less, or 500,000 or less. In this specification, Mw of the polymer additive is the weight average molecular weight measured by gel permeation chromatography (GPC) in terms of standard polystyrene.

[0063] When the composition contains a polymer additive, the content of the polymer additive is preferably 1 part by mass or more and 1,000 parts by mass or less, more preferably 5 parts by mass or more and 200 parts by mass or less, and even more preferably 10 parts by mass or more and 100 parts by mass or less, relative to 100 parts by mass (dry mass) of the alkali-treated product. When the content is within the above range, the mechanical strength of the composition is likely to be improved.

[0064] When the composition contains a polymer additive, the content of the polymer additive is preferably 1 part by mass to 1,000 parts by mass, more preferably 5 parts by mass to 200 parts by mass, and even more preferably 10 parts by mass to 100 parts by mass, relative to a total of 100 parts by mass (dry mass) of the algae bodies and residue derived from the algae bodies. Within the above range, the mechanical strength of the composition is likely to be improved.

[0065] When the polymer additive and the plasticizer are contained in the same composition, a preferred combination thereof is one in which the polymer additive is chitosan and the plasticizer is a keto acid, a dicarboxylic acid, a hydroxycarboxylic acid, a monocarboxylic acid, or two or more of these.

[0066] [Formalin Treatment] The composition may be treated with formalin, which tends to improve the modulus of elasticity and the maximum point stress, making it easier to obtain a composition with high strength.

[0067] [Physical Properties] The elastic modulus of the composition is not particularly limited and may be appropriately selected depending on the application, but is preferably 0.1 MPa or more and 10,000 MPa or less, more preferably 1 MPa or more and 5,000 MPa or less. In this specification, the elastic modulus of the composition means a value measured by the method described in the Examples below.

[0068] The maximum point test force of the composition is not particularly limited and may be appropriately selected depending on the application, but is preferably 0.01 N or more and 100 N or less, more preferably 0.1 N or more and 10 N or less. In this specification, the maximum point test force of the composition means a value measured by the method described in the examples below.

[0069] The maximum point stress of the composition is not particularly limited and may be appropriately selected depending on the application, but is preferably 0.01 MPa or more and 100 MPa or less, more preferably 0.1 MPa or more and 30 MPa or less. In this specification, the maximum point stress of the composition means a value measured by the method described in the examples below.

[0070] The maximum stroke of the composition is not particularly limited and may be appropriately selected depending on the application, but is preferably 0.1% or more and 100% or less, more preferably 1% or more and 50% or less. In this specification, the maximum stroke of the composition means a value measured by the method described in the Examples below.

[0071] [Uses] The composition can be used, for example, in the same applications as fossil resource-derived resins (conventional synthetic resins, etc.). Specific uses include vehicle parts, electrical and electronic equipment parts, electric wires, building materials, agricultural, fishery, and gardening supplies, chemical industry supplies, civil engineering materials, industrial and commercial materials, furniture, stationery, daily necessities and miscellaneous goods, clothing, containers and packaging supplies, toys, leisure goods, and medical supplies. These uses can be appropriately selected depending on the physical properties of the composition, etc.

[0072] [Method for producing the composition] The method for producing the composition includes a step (A) of preparing a mixed solution of an alkali-treated product of algal cells and / or a residue derived from algal cells, and a plasticizer, and a step (B) of drying the mixed solution.

[0073] [Step (A)] In step (A), a mixed solution of an alkali-treated product of algal cells and / or a residue derived from algal cells and a plasticizer is prepared. When the composition contains a polymer additive, a mixed solution of the alkali-treated product, a plasticizer, and a polymer additive is prepared.

[0074] The preparation method is not particularly limited, and may involve alkali-treating algae cells and / or residue derived from algae cells and then mixing with a plasticizer, or mixing algae cells and / or residue derived from algae cells and then alkali-treating. It is particularly preferred to alkali-treat algae cells and / or residue derived from algae cells and then mixing with a plasticizer. The polymer additive may be mixed with the plasticizer, or may be mixed at a different time from the plasticizer. When a polymer is used as the plasticizer, the polymer itself may be mixed, or a monomer and, if necessary, a polymerization initiator may be mixed to polymerize the polymer. Examples of the polymerization initiator include conventionally known thermal polymerization initiators.

[0075] Examples of the alkali treatment include a method of contacting the algae with an alkaline solution and a method of adding an alkali to a solution containing algae bodies or residues derived from algae bodies.

[0076] Examples of the solvent in the alkaline solution include water, methanol, ethanol, ethylene glycol, dimethylformamide, and dimethyl sulfoxide.

[0077] The time for the alkali treatment is not particularly limited and is, for example, from 0.1 to 24 hours. The temperature for the alkali treatment is not particularly limited, but from the viewpoint of accelerating the alkali treatment, it is preferably from 40 to 140°C, more preferably from 50 to 140°C, and even more preferably from 60 to 120°C.

[0078] The amount of alkali used in the alkali treatment is preferably 0.01 parts by mass or more and 5 parts by mass or less per 100 parts by mass of the total of the algae bodies, the residue derived from the algae bodies, and the plasticizer.

[0079] After the alkali treatment, the alkali-soluble or alkali-insoluble components may be separated from the alkali-treated product by a separation step such as centrifugation or extraction. However, from the viewpoint of effectively utilizing the entire algal body of the algae, it is preferable not to separate them.

[0080] [Step (B)] In step (B), the mixed solution obtained in step (A) is dried.

[0081] The drying method is not particularly limited, and examples thereof include heat drying, reduced pressure drying, etc. The temperature in heat drying is not particularly limited, but is, for example, 50° C. or higher and 200° C. or lower. The time for heat drying is not particularly limited, but is, for example, 0.1 hours or higher and 48 hours or lower.

[0082] The method for producing the composition may further include a step (C) of treating the composition obtained in the step (B) with formalin, and a step (D) of heat-treating the composition treated with formalin.

[0083] [Step (C)] In step (C), the composition obtained in step (B) is treated with formalin.

[0084] The method of formalin treatment is not particularly limited, and examples thereof include a method in which the composition obtained in step (B) is immersed in formalin.

[0085] The concentration of formalin (aqueous formaldehyde solution) is preferably 0.1% by mass or more and 40% by mass or less, and the treatment time is preferably 0.1 hours or more and 24 hours or less.

[0086] [Step (D)] In step (D), the composition treated with formalin in step (C) is subjected to a heat treatment.

[0087] The heat treatment time is preferably 0.1 hours or more and 24 hours or less, and the heat treatment temperature is preferably 50°C or more and 200°C or less.

[0088] The present invention will be described in more detail below with reference to examples, but the scope of the present invention is not limited to these examples.

[0089] [Preparation of algal cell-derived residue] 5.0 g of dried powder of Chlorella algae cells and 30 mL of a mixed solvent of 75% by mass of chloroform and 25% by mass of methanol were added to a container, and the mixture was heat-treated at 60° C. for 15 hours. The solid content was then filtered. The solid content was dried to obtain 3.50 g (dry mass) of residue derived from Chlorella algae cells.

[0090] In the same manner as for Chlorella, 5.0 g of dried powder of each alga was used to obtain 3.7 g (dry mass) of residue derived from Parachlorella algae, 3.0 g (dry mass) of residue derived from Aurantiochytrium algae, 3.9 g (dry mass) of residue derived from Ikadzu algae, 3.0 g (dry mass) of residue derived from Nannochloropsis algae, and 3.9 g (dry mass) of residue derived from Phaeodactylum algae.

[0091] [Analysis of Residue Components] (Protein) The protein content in each residue was measured by converting the nitrogen content (coefficient: 6.25). The results are shown in Table 1.

[0092] (Carbohydrates) The carbohydrate content in each residue was measured by the orcinol-sulfuric acid method. The results are shown in Table 1.

[0093]

[0094] [Preparation of Composition] (Example 1) 1.0 g (dry mass) of residue derived from Chlorella algae, 25 mL of water, and 100 μL of 50% by mass aqueous sodium hydroxide solution were added to a container and heat-treated overnight (18 hours) at 60°C. Next, 1.0 g of levulinic acid was added to the container and heat-treated at 60°C for 2 hours. The heat-treated solution was transferred to a 76 mm diameter Petri dish (made of PTFE) and heat-treated overnight (18 hours) at 60°C, and further heat-treated overnight (18 hours) at 100°C to resinify, thereby obtaining the composition of Example 1.

[0095] Example 2 A composition of Example 2 was obtained in the same manner as in Example 1, except that the amount of levulinic acid added was changed to 0.8 g.

[0096] Example 3 A composition of Example 3 was obtained in the same manner as in Example 1, except that the amount of levulinic acid added was changed to 0.6 g.

[0097] Comparative Example 1: 1.0 g (dry mass) of residue derived from Chlorella algae, 25 mL of water, and 100 μL of 50% by mass aqueous sodium hydroxide solution were added to a container and heat-treated overnight (18 hours) at 60°C. The heat-treated solution was transferred to a 76 mm diameter Petri dish (made of PTFE) and heat-treated overnight (18 hours) at 60°C, and then further heat-treated overnight (18 hours) at 100°C to obtain a composition of Comparative Example 1. This composition was so brittle that it would break upon contact, making it impossible to measure mechanical properties such as elastic modulus.

[0098] Example 4 A composition of Example 4 was obtained in the same manner as in Example 1, except that 1.0 g of levulinic acid was changed to 1.0 g of glutaric acid.

[0099] Example 5 A composition of Example 5 was obtained in the same manner as in Example 1, except that 1.0 g of levulinic acid was changed to 1.0 g of sorbitol.

[0100] Example 6 A composition of Example 6 was obtained in the same manner as in Example 1, except that 1.0 g of levulinic acid was changed to 1.0 g of gluconic acid.

[0101] Example 7 A composition of Example 7 was obtained in the same manner as in Example 1, except that 1.0 g of levulinic acid was changed to 1.0 g of triethylene glycol.

[0102] (Example 8) A composition of Example 8 was obtained in the same manner as in Example 1, except that 1.0 g (dry mass) of the residue derived from the algae of Chlorella was changed to 1.0 g (dry mass) of the residue derived from the algae of Parachlorella.

[0103] (Example 9) A composition of Example 9 was obtained in the same manner as in Example 1, except that 1.0 g (dry mass) of the residue derived from Chlorella algae was changed to 1.0 g (dry mass) of the residue derived from Aurantiochytrium algae.

[0104] (Example 10) The composition of Example 10 was obtained in the same manner as in Example 1, except that 1.0 g (dry mass) of residue derived from Chlorella algae was changed to 1.0 g (dry mass) of residue derived from Ikadama algae.

[0105] (Example 11) A composition of Example 11 was obtained in the same manner as in Example 1, except that the amount of the residue derived from Chlorella algae was changed to 2.5 g (dry weight), the amount of the 50% by mass sodium hydroxide aqueous solution was changed to 250 μL, and the amount of levulinic acid was changed to 2.5 g.

[0106] Example 12 The composition of Example 11 was immersed in a 37% by mass aqueous formaldehyde solution at room temperature overnight (18 hours), and then heat-treated at 100°C overnight (18 hours) to obtain a composition of Example 12.

[0107] Example 13: 1.0 g (dry mass) of dried powder of Chlorella algae, 25 mL of water, and 100 μL of 50% by mass sodium hydroxide aqueous solution were added to a container and heat-treated overnight (18 hours) at 60°C. Next, 1.0 g of levulinic acid was added to the container and heat-treated at 60°C for 2 hours. The heat-treated solution was transferred to a 76 mm diameter Petri dish (made of PTFE) and heat-treated overnight (18 hours) at 60°C, and further heat-treated at 100°C for 18 hours to resinify, thereby obtaining the composition of Example 13.

[0108] Example 14 A composition of Example 14 was obtained in the same manner as in Example 13, except that the amount of levulinic acid was changed to 0.6 g.

[0109] Example 15 A composition of Example 15 was obtained in the same manner as in Example 14, except that the treatment temperature after the addition of the 50% by mass aqueous sodium hydroxide solution was set to 100°C.

[0110] Example 16 A composition of Example 16 was obtained in the same manner as in Example 15, except that itaconic acid was used as the plasticizer.

[0111] Example 17 A composition of Example 17 was obtained in the same manner as in Example 15, except that glutaric acid was used as the plasticizer.

[0112] Example 18 A composition of Example 18 was obtained in the same manner as in Example 15, except that pimelic acid was used as the plasticizer.

[0113] Example 19 A composition of Example 19 was obtained in the same manner as in Example 15, except that gluconic acid was used as the plasticizer.

[0114] Example 20 A composition of Example 20 was obtained in the same manner as in Example 15, except that tetraethylene glycol was used as the plasticizer.

[0115] Example 21 A composition of Example 21 was obtained in the same manner as in Example 15, except that hexamethylenediamine was used as the plasticizer.

[0116] Example 22 A composition of Example 22 was obtained in the same manner as in Example 15, except that epsilon-caprolactone was used as the plasticizer.

[0117] Example 23 A composition of Example 23 was obtained in the same manner as in Example 15, except that epsilon-caprolactam was used as the plasticizer.

[0118] Example 24 A composition of Example 24 was obtained in the same manner as in Example 15, except that spirulina was used as the algae and glutaric acid was used as the plasticizer.

[0119] Example 25 A composition of Example 25 was obtained in the same manner as in Example 15, except that Phaeodactylum was used as the algae and glutaric acid was used as the plasticizer.

[0120] Example 26: 1.0 g (dry mass) of residue derived from Chlorella algae, 25 mL of water, 100 μL of 50% by mass aqueous sodium hydroxide solution, and 1.0 g of levulinic acid were added to a container and heat-treated overnight (18 hours) at 60° C. The heat-treated solution was transferred to a 76 mm diameter Petri dish (made of PTFE) and heat-treated overnight (18 hours) at 60° C., and further heat-treated overnight (18 hours) at 100° C. to resinify the solution, thereby obtaining the composition of Example 26.

[0121] (Example 27) A composition of Example 27 was obtained in the same manner as in Example 17, except that 0.4 g of chitosan (Chitosan 10 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., the same applies to chitosan hereinafter) was added as a polymer additive to the container together with 0.6 g of glutaric acid.

[0122] Example 28 A composition of Example 28 was obtained in the same manner as in Example 17, except that 0.2 g of chitosan was added as a polymer additive to the container together with 0.6 g of glutaric acid.

[0123] Example 29 A composition of Example 29 was obtained in the same manner as in Example 17, except that citric acid was used as the plasticizer and 0.4 g of chitosan was added as a polymer additive to the container together with 0.6 g of citric acid.

[0124] Example 30 A composition of Example 30 was obtained in the same manner as in Example 17, except that succinic acid was used as the plasticizer and 0.4 g of chitosan was added as a polymer additive to the container together with 0.6 g of succinic acid.

[0125] Example 31 A composition of Example 31 was obtained in the same manner as in Example 17, except that acetic acid was used as the plasticizer and 0.4 g of chitosan was added as a polymer additive to the container together with 0.6 g of acetic acid.

[0126] (Example 32) A composition of Example 32 was obtained in the same manner as in Example 17, except that 0.6 g of polyacrylic acid (Polyacrylic acid 5000, Mw: 5000, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; the same applies to the following polyacrylic acids) was added to the container instead of 0.6 g of glutaric acid.

[0127] Example 33 A composition of Example 33 was obtained in the same manner as in Example 17, except that 0.6 g of acrylic acid and 0.03 g of VA-044 (2,2′-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride) were added to the vessel instead of 0.6 g of glutaric acid.

[0128] Example 34 A composition of Example 34 was obtained in the same manner as in Example 25, except that 0.2 g of chitosan was added as a polymer additive to the container together with 0.6 g of glutaric acid.

[0129] Example 35 A composition of Example 35 was obtained in the same manner as in Example 25, except that 0.6 g of polyacrylic acid was added to the vessel instead of 0.6 g of glutaric acid.

[0130] Example 36 A composition of Example 36 was obtained in the same manner as in Example 25, except that 0.6 g of acrylic acid and 0.03 g of VA-044 (2,2′-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride) were added to the vessel instead of 0.6 g of glutaric acid.

[0131] [Elastic Modulus] Using a small benchtop testing machine EZ-LX (manufactured by Shimadzu Corporation), a test piece processed into a No. 7 dumbbell shape was pulled at a rate of 10 mm / min to measure the elastic modulus of each composition. The results are shown in Tables 2 to 9.

[0132] [Maximum point test force] Using a small benchtop testing machine EZ-LX (manufactured by Shimadzu Corporation), a test piece processed into a No. 7 dumbbell shape was pulled at a rate of 10 mm / min to measure the maximum point test force of each composition. The results are shown in Tables 2 to 9.

[0133] [Maximum stress] Using a small benchtop testing machine EZ-LX (manufactured by Shimadzu Corporation), a No. 7 dumbbell-shaped test piece was pulled at a rate of 10 mm / min to measure the maximum stress of each composition. The results are shown in Tables 2 to 9.

[0134] [Maximum stroke] Using a small benchtop testing machine EZ-LX (manufactured by Shimadzu Corporation), a No. 7 dumbbell-shaped test piece was pulled at a rate of 10 mm / min to measure the maximum stroke of each composition. The results are shown in Tables 2 to 9.

[0135] [Water Content] The water content of each composition was measured using a halogen moisture meter HX-204 (manufactured by Mettler). The results are shown in Tables 2 to 9.

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144] Unlike Comparative Example 1, Examples 1 to 36 produced moldable resin-like compositions. Furthermore, by varying the amount and type of plasticizer, the type of algae, formalin treatment, and the addition of polymer additives, compositions with a wide range of mechanical properties were obtained. For reference, the mechanical properties of conventional synthetic resins are shown in Table 10.

[0145]

Claims

1. A composition comprising an alkali-treated product of algae bodies and / or residue derived from algae bodies, and a plasticizer, the composition having a water content of 30 mass% or less.

2. The composition according to claim 1, wherein the plasticizer has at least one group selected from the group consisting of a carbonyl group, a carboxyl group, a hydroxyl group, an amino group, and an amide group in the molecule.

3. The composition according to claim 2, wherein the total number of carbonyl groups, carboxy groups, hydroxyl groups, amino groups and amide groups in the plasticizer molecule is 2 or more.

4. The composition according to claim 1, wherein the content of the plasticizer is 1 part by mass or more and 1,000 parts by mass or less per 100 parts by mass (dry mass) of the alkali-treated product.

5. The composition of claim 1, further treated with formalin.

6. The composition of claim 1 further comprising a polymeric additive.

7. A method for producing a composition according to any one of claims 1 to 6, comprising: a step (A) of preparing a mixed solution of an alkali-treated product of algae bodies and / or a residue derived from algae bodies, and a plasticizer; and a step (B) of drying the mixed solution.

8. The method for producing a composition according to claim 7, wherein the treatment temperature of the alkali treatment in the alkali-treated product is 40°C or higher and 140°C or lower.

9. A method for producing the composition according to claim 7, further comprising the steps of: (C) treating the composition obtained in step (B) with formalin; and (D) heat-treating the composition treated with formalin.

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