Marine biodegradability polymer compound, method for producing same, and marine biodegradability resin composition

Abstract

The present invention provides a marine biodegradability polymer compound which contains, as essential units, the following structural units: structural unit A derived from a marine biodegradability coupling agent (A), and structural unit B derived from a marine biodegradability coupling agent (B); the marine organism degradable linker (A) is a compound which contains two or more organic anions having a molecular weight of 100-10000, has a structure in which the organic anions are bonded to each other via ionic bonds generated by metal cations having a valence of 2 or more in the main chain, and contains two or more reactive groups X in the molecule; and a structural unit (B1) derived from a compound (B1) having, in the molecule, two or more reactive groups (Y) that react with the reactive group (X). Or a structural unit B2 which is a ring-opening polymerizable ring compound (B2) that generates a reactive group Y that reacts with the reactive group X in the molecule by opening the ring, the structural unit B2 being derived from a structural unit C in the case where the structural unit B1 is included, and the structural unit B2 being derived from a structural unit B2 that is a ring-opening polymerizable ring compound that generates a reactive group Y that reacts with the reactive group X in the molecule. And a reactive group X derived from a compound (C) other than the marine biodegradability linker, the compound (C) other than the marine biodegradability linker containing two or more reactive groups X in the molecule.

Description

Technical Field

[0001] The present invention relates to a marine biodegradable polymer compound, a method for producing the same, and a marine biodegradable resin composition. Background Art

[0002] In recent years, environmental pollution (marine pollution) caused by microplastics and adverse effects on ecosystems have become problems, and various studies for reducing the environmental load have been initiated. Among them, the development and popularization of biodegradable resins have received attention.

[0003] Regarding general biodegradable resins, although they exhibit high biodegradability in environments where a large number of microorganisms responsible for degradation exist, such as in soil and sludge, they have the disadvantage of being difficult to degrade in an environment with an extremely low concentration of microorganisms such as in the ocean (Non-Patent Document 1). In addition, for resins such as polycaprolactone (PCL) and polyhydroxyalkanoic acid (PHA) for which biodegradability in the ocean has been reported, it is known that their degradation rates vary greatly depending on the type of seawater. In this regard, it has been reported that various factors such as the presence or absence of degrading bacteria, the number of bacteria, salt concentration, pH, water temperature, dissolved oxygen concentration, and dissolved organic carbon content in seawater have an impact (Non-Patent Document 2).

[0004] In addition, as biodegradable resins, starch-based resins have also been put into practical use and are on the market. However, if they are made of a single starch raw material, their physical properties are very poor, and thus they are almost all mixed compositions with polyester-based resins that are difficult to biodegrade in the ocean, such as poly(butylene adipate-co-terephthalate) (PBAT) and polylactic acid (PLA). Therefore, even starch-based resins tend to have significantly reduced biodegradability in the ocean.

[0005] Under such circumstances, there is a demand for the development of materials that can be reliably degraded in any type of seawater while maintaining physical properties, materials that can promote the degradation of resins that are difficult to biodegrade in seawater, and materials that can reduce the environmental load.

[0006] Prior Art Documents

[0007] Non-Patent Documents

[0008] Non-Patent Document 1: Hideyoshi Takada, "Current Situation, International Trends, and Countermeasures of Microplastic Pollution", Journal of the Japan Society of Waste Resources Recycling, Vol. 29, No. 4, pp. 261-269, 2018

[0009] Non-Patent Document 2: Zhang Rongjing et al., "Degradation of Biodegradable Plastics in Seawater", Fisheries Engineering, Vol. 40, No. 2, pp. 143-149, 2003 Summary of the Invention

[0010] Problems to be Solved by the Invention

[0011] The present invention has been completed in view of the above actual situation, and an object thereof is to provide: a marine biodegradable polymer compound that promotes the degradation of resin in the ocean and promotes biodegradation, a method for producing the same, and a marine biodegradable resin composition containing the polymer compound.

[0012] Means for Solving the Problem

[0013] The inventors of the present invention repeatedly conducted in-depth studies to solve the above problems. As a result, it was found that: by subjecting the following marine biodegradable polymer compound to ion exchange with monovalent cations such as sodium and potassium in seawater, the molecules of the polymer compound are cleaved to promote marine degradation; the marine biodegradable polymer compound is a marine biodegradable polymer compound containing the following structural units as essential units: a structural unit A derived from a marine biodegradable linker (A), the marine biodegradable linker (A) having a structure in the main chain containing two or more organic anions with a molecular weight of 100 to 10,000 and bonded by an ionic bond formed by a divalent or higher metal cation, and containing two or more reactive groups X in the molecule; and a structural unit B1 derived from a compound (B1), the compound (B1) having two or more reactive groups Y in the molecule that react with the above reactive group X; or a structural unit B2 derived from a cyclic compound (B2), the cyclic compound (B2) being a cyclic compound capable of ring-opening polymerization, and by ring-opening, a reactive group Y that reacts with the above reactive group X is generated in the molecule. In the case of containing the structural unit B1, it further contains a structural unit C derived from a compound (C) other than the above marine biodegradable linker, the compound (C) other than the marine biodegradable linker containing two or more reactive groups X in the molecule. The marine biodegradable linker (A) is used as a linker, and in the polymer compound using the marine biodegradable linker (A) as a raw material, a cleavage site triggered by an ionic bond is introduced into the main chain, thereby imparting marine biodegradability.

[0014] Furthermore, it was found that: by using the above marine biodegradable polymer compound in combination with a resin, particularly a biodegradable resin, this material is first degraded once in seawater, resulting in (1) the effect of forming pores in the resin material, increasing the specific surface area of the resin, and promoting the proliferation of microorganisms responsible for degradation; (2) the effect of promoting secondary degradation, i.e., biodegradation by microorganisms, by undergoing primary degradation. As a result, the biodegradation of the resin material in the ocean can be promoted, and the present invention has been completed.

[0015] That is, the present invention provides the following marine biodegradable polymer compound, a method for producing the same, and a marine biodegradable resin composition.

[0016] 1. A marine biodegradable polymer compound, which is a marine biodegradable polymer compound containing the following as essential units:

[0017] Structural unit A, which is derived from a marine biodegradable linker (A), and the marine biodegradable linker (A) is a compound containing two or more organic anions with molecular weights of 100 to 10,000, having a structure in which the organic anions are bonded by ionic bonds generated by divalent or higher metal cations in the main chain, and containing two or more reactive groups X in the molecule; and

[0018] Structural unit B1, which is derived from a compound (B1), and the compound (B1) has two or more reactive groups Y in the molecule that react with the above reactive group X; or structural unit B2, which is derived from a cyclic compound (B2), and the cyclic compound (B2) is a cyclic compound capable of ring-opening polymerization, and by ring-opening, a reactive group Y that reacts with the above reactive group X is generated in the molecule,

[0019] wherein, when containing structural unit B1, it further contains:

[0020] Structural unit C, which is derived from a compound (C) other than the above marine biodegradable linker, and the compound (C) other than the marine biodegradable linker contains two or more reactive groups X in the molecule.

[0021] 2. The marine biodegradable polymer compound according to 1, wherein the above organic anion is selected from the group consisting of carboxylate anions (-COO - ), sulfonate anions (-SO3 - ), sulfate anions (-O-SO3 - ), and phosphate anions (-P(=O)(OH)-O - ) at least one.

[0022] 3. The marine biodegradable polymer compound according to 1 or 2, wherein the above organic anion has a repeating unit containing at least one bond selected from the group consisting of ether bonds, ester bonds, amide bonds, and carbonate bonds.

[0023] 4. The marine biodegradable polymer compound according to any one of 1 to 3, wherein the above divalent or higher metal cation is calcium ion, beryllium ion, magnesium ion, strontium ion, barium ion, zinc ion, aluminum ion, iron ion, copper ion, platinum ion, gold ion, titanium ion, nickel ion, cobalt ion, manganese ion, zirconium ion, ruthenium ion, rhodium ion, palladium ion, scandium ion, gallium ion, indium ion, or radium ion.

[0024] 5. The marine biodegradable polymer compound according to any one of 1 to 4, wherein the equivalent average of metal ions with a valence of 2 or more in 1 molecule is 1 to 100 eq / 10 5 g.

[0025] 6. The marine biodegradable polymer compound according to any one of 1 to 5, wherein the melting temperature of the marine biodegradable linker (A) is 180 °C or lower.

[0026] 7. The marine biodegradable polymer compound according to any one of 1 to 6, wherein the average value of the number of metal cations contained in 1 molecule of the marine biodegradable linker (A) is greater than 1.

[0027] 8. The marine biodegradable polymer compound according to any one of 1 to 7, wherein the relative degree of degradation of cellulose of the marine biodegradable linker (A) is 40% or more.

[0028] 9. The marine biodegradable polymer compound according to any one of 1 to 8 above, wherein the reactive group X and the reactive group Y are each independently a hydroxyl group, an amino group, an isocyanate group, or a carboxyl group.

[0029] 10. The marine biodegradable polymer compound according to any one of 1 to 9, wherein the content ratio of the structural unit A to the structural unit C (A:C) is expressed as a molar ratio and is 0.1:99.9 to 90:10.

[0030] 11. The marine biodegradable polymer compound according to any one of 1 to 10, which is a polyester, a polyurethane, a polyamide, or a polyurea.

[0031] 12. The marine biodegradable polymer compound according to any one of 1 to 11, wherein any one or more of the marine biodegradable linker (A), the compound (B1), and the compound (C) is trifunctional or higher.

[0032] 13. The marine biodegradable polymer compound according to any one of 1 to 12, wherein the ends of the marine biodegradable polymer compound are blocked.

[0033] 14. An additive comprising the marine biodegradable polymer compound according to any one of 1 to 13.

[0034] 15. A marine biodegradable resin composition comprising the marine biodegradable polymer compound according to any one of 1 to 13.

[0035] 16. The marine biodegradable resin composition according to 15, which further comprises a biodegradable resin.

[0036] 17. The marine biodegradable resin composition according to claim 16, wherein the content of the above-mentioned marine biodegradable polymer compound is 1 to 99% by mass, and the content of the above-mentioned biodegradable resin is 1 to 99% by mass.

[0037] 18. A molded article obtained from the marine biodegradable resin composition according to any one of claims 15 to 17.

[0038] 19. A method for producing a marine biodegradable polymer compound, wherein a marine biodegradable linker (A), a compound (B1), and a compound (C) other than the marine biodegradable linker are polymerized. The marine biodegradable linker (A) is a compound containing two or more organic anions with a molecular weight of 100 to 10,000, having a structure in which the organic anions are bonded through ionic bonds generated by divalent or higher metal cations in the main chain, and containing two or more reactive groups X in the molecule. The compound (B1) has two or more reactive groups Y in the molecule that react with the above-mentioned reactive group X. The compound (C) other than the marine biodegradable linker contains two or more reactive groups X in the molecule; or a marine biodegradable linker (A) and a cyclic compound (B2) are polymerized. The marine biodegradable linker (A) is a compound containing two or more organic anions with a molecular weight of 100 to 10,000, having a structure in which the organic anions are bonded through ionic bonds generated by divalent or higher metal cations in the main chain, and containing two or more reactive groups X in the molecule. The cyclic compound (B2) is a cyclic compound capable of ring-opening polymerization, and by ring-opening, reactive groups Y that react with the above-mentioned reactive group X are generated in the molecule.

[0039] 20. The method for producing a marine biodegradable polymer compound according to claim 19, wherein the polymerization is polycondensation.

[0040] 21. The method for producing a marine biodegradable polymer compound according to claim 19 or 20, which includes a step of mixing the marine biodegradable linker (A), the compound (B1), and the compound (C) or the marine biodegradable linker (A) and the compound (B2) before polymerization.

[0041] 22. The method for producing a marine biodegradable polymer compound according to any one of claims 19 to 21, wherein the usage ratio of the marine biodegradable linker (A) to the compound (C) ((A):(C)), expressed as a molar ratio, is 0.1:99.9 to 90:10.

[0042] 23. The method for producing a marine biodegradable polymer compound according to any one of 19 to 22, wherein the melting temperature of the marine biodegradable linking agent (A) is 180 °C or lower, and polymerization is carried out by melting the marine biodegradable linking agent (A), the compound (B1) and the compound (C) or the marine biodegradable linking agent (A) and the compound (B2).

[0043] 24. A compound comprising two or more organic anions having a molecular weight of 100 to 10,000, having a structure in which the organic anions are bonded through ionic bonds generated by divalent or higher metal cations in the main chain, and containing two or more amino groups, carboxyl groups, thiol groups, vinyl groups or isocyanate groups in the molecule.

[0044] Effects of the Invention

[0045] Regarding the marine biodegradable polymer compound of the present invention, since it has marine biodegradability, a composition or molded article containing the same promotes biodegradation in the ocean and is useful in countermeasures against marine pollution. By using the marine biodegradable polymer compound of the present invention, an environmentally friendly composition or molded article can be obtained. Detailed Description

[0046] [Marine Biodegradable Polymer Compound]

[0047] The marine biodegradable polymer compound of the present invention contains the following structural units as essential units: a structural unit A derived from a marine biodegradable linking agent (A) (hereinafter also referred to as the marine biodegradable linking agent (A)), the marine biodegradable linking agent (A) being a compound containing two or more organic anions having a molecular weight of 100 to 10,000, having a structure in which the organic anions are bonded through ionic bonds generated by divalent or higher metal cations in the main chain, and containing two or more reactive groups X in the molecule; and a structural unit B1 derived from a compound (B1) (hereinafter also referred to as the compound (B1)), the compound (B1) having two or more reactive groups Y in the molecule that react with the above reactive group X, or a structural unit B2 derived from a cyclic compound (B2) (hereinafter also referred to as the compound (B2)), the cyclic compound (B2) being a ring-opening polymerizable cyclic compound, and by ring-opening, reactive groups Y that react with the above reactive group X are generated in the molecule. However, in the case of containing the structural unit B1, a structural unit C is also contained, which is derived from a compound (C) other than the marine biodegradable linking agent (A) (hereinafter also referred to as the compound (C)), and the compound (C) other than the marine biodegradable linking agent (A) contains two or more reactive groups X in the molecule.

[0048] The marine biodegradable linker (A) is composed of the following compounds: including two or more organic anions with a molecular weight of 100 to 10,000, having a structure in which the organic anions are bonded by ionic bonds generated by divalent or higher metal cations in the main chain, and including two or more reactive groups X in the molecule.

[0049] Regarding the above-mentioned organic anions, from the viewpoints of biodegradability in seawater and mechanical properties, their molecular weight is 100 to 10,000. The lower limit of the molecular weight is preferably 400 or more, more preferably 500 or more, further preferably 600 or more, and most preferably 700 or more. On the other hand, the upper limit of the molecular weight is preferably 6,000 or less, more preferably 5,000 or less, further preferably 4,000 or less, and most preferably 3,000. If the molecular weight exceeds 10,000, biodegradation is difficult, and if it is less than 100, the proportion of ions in the resin increases, and a decrease in mechanical properties is feared, so it is not preferred. It should be noted that the molecular weight of the organic anion in the present invention means the number average molecular weight determined by the end group quantification method.

[0050] The above-mentioned organic anion preferably has a monovalent anionic substituent selected from a carboxylate anion (-COO - ), a sulfonate anion (-SO3 - ), a sulfate anion (-O-SO3 - ), and a phosphate anion (-P(=O)(OH)-O - ). As the above-mentioned organic anion, a carboxylate anion is particularly preferred.

[0051] The above-mentioned organic anion preferably has a repeating unit having at least one bond selected from an ether bond, an ester bond, an amide bond, and a carbonate bond. Specifically, the above-mentioned repeating unit preferably comes from a polyalkylene glycol, a polyester, a polycaprolactone, a polycarbonate, or a polyamide.

[0052] There is no particular limitation on the above-mentioned divalent or higher metal cations, and examples thereof include calcium ions, beryllium ions, magnesium ions, strontium ions, barium ions, zinc ions, aluminum ions, iron ions, copper ions, platinum ions, gold ions, titanium ions, nickel ions, cobalt ions, manganese ions, zirconium ions, ruthenium ions, rhodium ions, palladium ions, scandium ions, gallium ions, indium ions, radium ions, etc. Among these, calcium ions, beryllium ions, magnesium ions, strontium ions, barium ions, zinc ions, aluminum ions, etc. are preferred, and calcium ions, magnesium ions, aluminum ions, etc. are more preferred.

[0053] Regarding the marine biodegradable linker (A), the average number of metal cations contained in one molecule is 1 or more, and preferably greater than 1 from the viewpoint of obtaining a higher promotion effect of marine biodegradability. Regarding the upper limit of the number of the above metal cations, from the viewpoint of mechanical properties, it is preferably 10 or less, more preferably 3 or less. That is, the marine biodegradable linker (A) is preferably a compound having a structure in which two or more monovalent organic anions each having at least one reactive group X and one monovalent anionic substituent are bonded by one divalent or higher metal cation (hereinafter also referred to as compound (A1)), and a mixture of a compound having a structure in which two or more polyvalent organic anions each having a monovalent anionic substituent are bonded by a divalent or higher metal cation and the terminal thereof is blocked by a monovalent organic anion having at least one reactive group X and one monovalent anionic substituent via a divalent or higher metal cation (hereinafter also referred to as compound (A2)). In other words, compound (A2) contains, via a divalent or higher metal cation, one or more structural units composed of two or more polyvalent organic anions each having a monovalent anionic substituent, and the terminal thereof is blocked by the above monovalent organic anion via a divalent or higher metal cation. That is, compound (A1) has only one metal cation in one molecule, and compound (A2) has two or more metal cations in one molecule.

[0054] The marine biodegradable linker (A) preferably has a melting temperature of 180 °C or lower. Regarding the above melting temperature, considering processability, reactivity with other components, and physical properties of the obtained polymer compound, it is preferably 40 to 180 °C, more preferably 60 to 150 °C.

[0055] The marine biodegradable linker (A) preferably has a relative cellulose degradation degree of 40% or more. It should be noted that in the present invention, the relative cellulose degradation degree refers to the degradation degree relative to cellulose after being immersed in seawater for 60 days. The marine biodegradable linker (A) more preferably has a relative cellulose degradation degree of 50% or more, further preferably 60% or more, and most preferably 80% or more. It should be noted that the relative cellulose degradation degree can be measured by a marine biodegradation test method of BOD according to ASTM D6691 and modified therefrom.

[0056] The reactive group X is preferably a group selected from a hydroxyl group, an amino group, a carboxyl group, and an isocyanate group. From the viewpoints of reactivity and chemical stability, a hydroxyl group, an amino group, or a carboxyl group is more preferable, a hydroxyl group or an amino group is more preferable, and a hydroxyl group is most preferable. The marine biodegradable linker (A) preferably has a reactive group X at the end of the main chain.

[0057] Regarding the marine biodegradable linker (A), from the perspective of biodegradability, it is preferably bifunctional, and from the perspective of adjusting physical properties and biodegradability, compounds with trifunctionality or higher can be used.

[0058] Regarding the marine biodegradable linker (A), from the perspective of promoting biodegradability, it is preferably free of a ring structure. However, from the perspective of adjusting physical properties and biodegradability, a ring structure can be introduced.

[0059] The number average molecular weight of the marine biodegradable linker (A) is preferably 500 to 10,000, more preferably 1,000 to 8,000, and even more preferably 1,500 to 6,000 when considering processability and mechanical physical properties. If the number average molecular weight is within the above range, it is preferred from the perspectives of reactivity and controlling the overall biodegradation rate. It should be noted that the number average molecular weight is the polystyrene conversion measurement value using gel permeation chromatography (GPC).

[0060] The marine biodegradable linker (A) can be synthesized by introducing the above-mentioned monovalent anionic substituent into a compound having two or more reactive groups X and ionically bonding it using a salt compound (polyvalent metal salt) having a divalent or higher metal cation.

[0061] Examples of the compound having two or more reactive groups X include polyhydric alcohols, polyamines, polycarboxylic acids or their acid chlorides, polyisocyanates, etc.

[0062] Examples of the above polyhydric alcohols include compounds having two or more hydroxyl groups such as polyalkylene glycols, polycaprolactone polyols, polyester polyols, polyamide polyols, polyester polyamide polyols, polycarbonate polyols, etc. For example, polyethylene glycol, polypropylene glycol, Placcel 210B, 220N, 308 (manufactured by Daicel Corporation), bis(4-hydroxybutyl) polybutylene glycol succinate, bis(6-hydroxyhexyl) polybutylene glycol succinate, bis(4-hydroxybutyl) polybutylene glycol adipate, N,N'-bis(4-hydroxybutyl) poly(hexamethylene adipamide), bis(4-hydroxybutyl) polybutylene glycol terephthalate, Kuraray Polyol P-510, P-1010, P-2010, P-2050, P-520, C-590, F-1010 (manufactured by Kuraray Co., Ltd.), etc. These can be synthesized by known methods or commercially available products can be used.

[0063] Examples of the above polyamines include compounds having two or more amino groups such as polyalkylene glycol diamines, polycaprolactam polyamines, polyester polyamines, polyamide polyamines, polyester polyamide polyamines, and polycarbonate polyamines. For example, bis(2-aminoethyl) polyethylene glycol, bis(2-aminopropyl) polypropylene glycol, poly(hex-6-caprolactam)-1,2-acetamide, bis(4-aminobutyl) polybutylene glycol succinate, bis(6-aminohexyl) polybutylene glycol succinate, N,N'-bis(4-aminobutyl) poly(tetramethylene succinamide), N,N'-bis(6-aminohexyl) poly(hexamethylene succinamide), etc. These can be synthesized by known methods or commercially available products can be used.

[0064] Examples of the above polycarboxylic acids include compounds having two or more carboxyl groups such as polyalkylene glycol dicarboxylic acids, polycaprolactone polycarboxylic acids, polycaprolactam polycarboxylic acids, polyester polycarboxylic acids, polyamide polycarboxylic acids, polyester polyamide polycarboxylic acids, and polyacrylic acid. For example, polyethylene glycol disuccinate, polypropylene glycol disuccinate, poly(hex-6-caprolactone)-1,2-ether disuccinate, bis(4-succinoxybutyl) polybutylene glycol succinate, bis(4-adipoxybutyl) polybutylene glycol adipate, N,N'-bis(4-succinoxybutyl) poly(tetramethylene succinamide), N,N'-bis(6-succinylbutylhexyl) poly(hexamethylene succinamide), etc. In addition, products in which these polycarboxylic acids are introduced into acid chlorides, acid anhydrides, or esters can be used. These can be synthesized by known methods or commercially available products can be used.

[0065] Examples of the above polyisocyanates include compounds having two or more isocyanate groups such as polyalkylene diisocyanates, polycaprolactone polyisocyanates, polyalkylene polyol polyisocyanates, and polyalkylene polyamine polyisocyanates. For example, bis(2-isocyanatoethyl) polyethylene glycol, polypropylene glycol disuccinate, poly(hex-6-caprolactam)-1,2-acetamide diisocyanate, bis(4-isocyanatobutyl) polybutylene glycol succinate, bis(6-isocyanatohexyl) polybutylene glycol succinate, N,N'-bis(4-isocyanatobutyl) poly(tetramethylene succinamide), N,N'-bis(6-isocyanatohexyl) poly(hexamethylene succinamide), etc. These can be synthesized by known methods or commercially available products can be used.

[0066] As a method for introducing a monovalent anionic substituent into the compound having two or more reactive groups X above, when introducing, for example, -COO -In the case of, methods for subjecting the above compound having two or more reactive groups X and a dicarboxylic anhydride to an esterification reaction or an amidation reaction in the presence of a monovalent metal salt can be cited. Examples of the above dicarboxylic anhydride include phthalic anhydride, trimellitic anhydride (this compound has one acid anhydride group and one carboxyl group), pyromellitic dianhydride, 5-norbornene-bridged-2,3-dicarboxylic anhydride, naphthoic anhydride, naphthalenetetracarboxylic dianhydride, maleic anhydride, succinic anhydride, chlorendic anhydride, etc. Among these, succinic anhydride, maleic anhydride, and phthalic anhydride are preferred, and if biodegradability is considered, succinic anhydride and maleic anhydride are more preferred. In addition, when introducing, for example, -SO3 - In the case of, methods for reacting a compound having a hydroxyl group or an amino group as the above reactive group X with SO3 or an SO3·Lewis base complex in an aprotic polar solvent can be cited. As the above Lewis base, tertiary amines, pyridine, DMF, etc. can be used. In addition, as the above aprotic polar solvent, acetonitrile, etc. are preferred. These reactions can be carried out by known methods.

[0067] As a method for ionic bonding using a polyvalent metal salt, a method of dropping a powder or solution of a polyvalent metal salt into a medium in which a product (hereinafter also referred to as precursor A.) obtained by introducing a monovalent anionic substituent into a compound having two or more reactive groups X is dissolved, and precipitating or depositing it while performing a bonding treatment; or a method of dropping a solution in which precursor A is dissolved into a powder of a polyvalent metal salt or a solution in which a polyvalent metal salt is dissolved, and precipitating or depositing it while performing a bonding treatment can be cited.

[0068] Specifically, for example, first, a solution in which precursor A is dissolved in water or a mixed solvent of water and a hydrophilic organic solvent is prepared. At this time, heating may be carried out as needed to improve solubility. Secondly, a solution containing a polyvalent metal salt is added and stirred. Alternatively, a solution in which precursor A is dissolved can be added to a solution containing a polyvalent metal salt and stirred.

[0069] Examples of the above polyvalent metal salts include calcium salts, strontium salts, magnesium salts, barium salts, radium salts, lead salts, zinc salts, nickel salts, iron salts, copper salts, cadmium salts, cobalt salts, manganese salts, aluminum salts, gallium salts, indium salts, thallium salts, etc. Considering the metals contained in seawater, environmental aspects, safety, and versatility, calcium salts, magnesium salts, and aluminum salts are preferred, and if considering the environment in seawater, calcium salts and magnesium salts are more preferred. As the above polyvalent metal salts, specifically, calcium chloride, calcium sulfate, calcium carbonate, calcium hydroxide, calcium oxide, magnesium chloride, magnesium sulfate, magnesium carbonate, magnesium hydroxide, magnesium oxide, aluminum sulfate, potassium aluminum sulfate (potassium alum), etc. are cited. Considering solubility in water, processability, cost, etc., calcium chloride, magnesium chloride, and aluminum sulfate are preferred.

[0070] The concentration of the polyvalent metal salt in the solution containing the polyvalent metal salt is preferably 1 to 40% by mass, more preferably 10 to 30% by mass. The solvent of the above solution is preferably water; lower alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and mixed solvents thereof can be mixed solvents with other organic solvents as long as they can dissolve the salt in a concentration that does not dissolve the particles.

[0071] In addition, as long as the reactivity of the above polyvalent metal salt is good and it reacts even in a solid state, it can be used in powder form without using a medium, or it can be dispersed and used in a small amount of medium.

[0072] By doing so, ionic bonding treatment can be carried out, and the target marine biodegradable linker (A) that cannot be slowly dissolved can be precipitated or deposited. The treatment time is preferably 0.5 to 24 hours, more preferably 1 to 12 hours.

[0073] At this time, in order to control the particle size of the precipitate or deposit, a surfactant or a polymer stabilizer can be dissolved in at least one of the solution in which the precursor A is dissolved and the solution containing the polyvalent metal salt.

[0074] When the target marine biodegradable linker (A) is precipitated or deposited, heating can be carried out. The heating can be carried out when the solution in which the precursor A is dissolved and the solution containing the polyvalent metal salt are mixed, or can be carried out during stirring after mixing, or can be carried out in both. The heating temperature is preferably 15 to 100 °C, more preferably 40 to 80 °C.

[0075] After the treatment, the particles can be washed and dried as needed, thereby obtaining the marine biodegradable linker (A). The washing can be carried out by a usual method. For example, methods such as removing the solvent after the bonding treatment and adding water for centrifugation can be cited. The drying can be carried out by a usual method. For example, it can be carried out by spray drying, vacuum drying, freeze drying, etc. It should be noted that the obtained marine biodegradable linker (A) can be surface-treated by a known device as needed, or can be pulverized to adjust the particle size.

[0076] Regarding the compound (B1), as long as it is a compound containing two or more reactive groups Y that react with the reactive group X, there is no particular limitation. Regarding the compound (B2), as long as it is a cyclic compound that can be ring-opened polymerized, that is, a cyclic compound that generates a reactive group Y in the molecule by ring-opening, there is no particular limitation. In addition, regarding the compound (C), as long as it is a compound containing two or more reactive groups X in the molecule other than the marine biodegradable linker (A), there is no particular limitation.

[0077] Regarding the reactive group X, as described above. The reactive group Y is not particularly limited as long as it reacts with the reactive group X, and from the viewpoints of reactivity and chemical stability, a group selected from a hydroxyl group, an amino group, a carboxyl group, and an isocyanate group is preferred. Among these, a carboxyl group or an isocyanate group is more preferred.

[0078] Examples of the compound having two or more reactive groups X or reactive groups Y include polyols, polyamines, polycarboxylic acids or their acid chlorides, polyisocyanates, and the like.

[0079] The above-mentioned polyol is not particularly limited as long as it is a compound containing two or more hydroxyl groups, and a polyol having 2 to 20 carbon atoms is preferred. Specific examples thereof include ethylene glycol, glycerol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2-butene-1,4-diol, 1,2,3-butanetriol, 1,2,4-butanetriol, 1,5-pentanediol, 2,4-pentanediol, 1,2,5-pentanetriol, 2-hydroxy-2-ethyl-1,3-propanol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,3,5-cyclohexanetriol, 1,6-hexanediol, 2,5-hexanediol, 3-methyl-1,5-pentanediol, 1,7-heptanediol, 1,4-benzenedimethanol, 3,6-diazaoctane-1,8-diol, 2,6-dihydroxynaphthalene, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, 1,18-octadecanediol, phloroglucinol, pyrogallol, 1,2,4-benzenetriol, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, polyethylene glycol, and the like.

[0080] The above-mentioned polyamine is not particularly limited as long as it is a compound containing two or more amino groups, and a polyamine having 2 to 20 carbon atoms is preferred. Specific examples thereof include aliphatic polyamines such as 1,4-butanediamine, hexamethylenediamine, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,5-diaminopentane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane, 3,3-diaminodipropylamine, 1,4-cyclohexanediamine, spermine, spermidine, triethylenetetramine; aromatic polyamines such as 1,4-benzenediamine, 1,2-diphenylethylenediamine, o-toluidine, and the like.

[0081] The above-mentioned polycarboxylic acids are not particularly limited as long as they are compounds containing two or more carboxyl groups, and polycarboxylic acids having 2 to 20 carbon atoms are preferred. Specific examples thereof include aromatic dicarboxylic acids such as terephthalic acid, 1,3,5-benzenetricarboxylic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and biphenyldicarboxylic acid; aliphatic dicarboxylic acids such as oxalic acid, malonic acid, fumaric acid, maleic acid, succinic acid, adipic acid, sebacic acid, 1,2,3-propanetricarboxylic acid, aconitic acid, malic acid, and citric acid. These carboxylic acids can be used as they are, and if necessary, in order to improve the reactivity, products derived into acid chlorides or active esters can be used.

[0082] The above-mentioned polyisocyanates are not particularly limited as long as they are compounds containing two or more isocyanate groups, and polyisocyanates having 7 to 20 carbon atoms are preferred. Specific examples thereof include aliphatic diisocyanates such as hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI), isophorone diisocyanate (IPDI), cyclohexane-1,4-diisocyanate, and methylene bis(4-cyclohexylisocyanate); aromatic diisocyanates such as toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylene diisocyanate, and 1,4-phenylene diisocyanate. Considering biodegradability in the environment, HDI and PDI, which are linear aliphatic isocyanates, are preferred.

[0083] Specific examples of the compound (B2) include lactones such as lactide, ε-caprolactone, β-propiolactone, β-butyrolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, glycolide, coumarin, cyclopentadecanolide, and cyclohexadecanolide; lactams such as 2-piperidone, ε-caprolactam, N-methyl-ε-caprolactam, ω-heptalactam, ω-octalactam, ω-laurin lactam, and laurolactam.

[0084] Regarding the compound (B1) and the compound (C), from the viewpoint of promoting biodegradability, those without a ring structure are preferred.

[0085] Regarding the compound (B1) and the compound (C), from the viewpoint of biodegradability, bifunctional ones are preferred, and from the viewpoint of adjusting physical properties and biodegradability, compounds with trifunctionality or higher can be used.

[0086] The marine biodegradable linker (A), the compound (B1), and the compound (C) preferably do not contain a ring structure in any molecule. In addition, the marine biodegradable linker (A), the compound (B1), and the compound (C) are preferably all bifunctional.

[0087] There is no particular limitation on the combination of the reactive group X and the reactive group Y. From the viewpoints of processability, reactivity, and physical properties of the polymer compound, any one of the following combinations (1) to (6) is preferred, any one of (1) to (4) is more preferred, any one of (1) or (2) is further preferred, and the combination of (1) is most preferred.

[0088] (1) A polyester-based polymer compound in which the reactive group X is a hydroxyl group and the reactive group Y is a carboxyl group. In this case, the marine biodegradable linker (A) and the compound (C) are polyols, and the compound (B1) is a polycarboxylic acid. Alternatively, the marine biodegradable linker (A) is a polyol, and the compound (B2) is a lactone.

[0089] (2) A polyurethane-based polymer compound in which the reactive group X is a hydroxyl group and the reactive group Y is an isocyanate group. In this case, the marine biodegradable linker (A) and the compound (C) are polyols, and the compound (B1) is a polyisocyanate.

[0090] (3) A polyamide-based polymer compound in which the reactive group X is an amino group and the reactive group Y is a carboxyl group. In this case, the marine biodegradable linker (A) and the compound (C) are polyamines, and the compound (B1) is a polycarboxylic acid. Alternatively, the marine biodegradable linker (A) is a polyamine, and the compound (B2) is a lactam.

[0091] (4) A polyurea-based polymer compound in which the reactive group X is an amino group and the reactive group Y is an isocyanate group. In this case, the marine biodegradable linker (A) and the compound (C) are polyamines, and the compound (B1) is a polyisocyanate.

[0092] (5) A polyester-based polymer compound in which the reactive group X is a carboxyl group and the reactive group Y is a hydroxyl group. In this case, the marine biodegradable linker (A) and the compound (C) are polycarboxylic acids, and the compound (B1) is a polyol.

[0093] (6) A polyamide-based polymer compound in which the reactive group X is a carboxyl group and the reactive group Y is an amino group. In this case, the marine biodegradable linker (A) and the compound (C) are polycarboxylic acids, and the compound (B1) is a polyamine.

[0094] The metal ion equivalent in the marine biodegradable polymer compound of the present invention is preferably 1 to 100 eq / 10 5 g, and more preferably 2 to 50 eq / 10 5 g in consideration of biodegradability and mechanical properties in seawater, and most preferably 10 to 20 eq / 10 5g. If the equivalent amount of metal ions is within the above range, it has good biodegradability and does not impair mechanical properties, so it is preferred. It should be noted that the equivalent amount of metal ions is the value measured by inductively coupled plasma mass spectrometry (ICP-MS).

[0095] The number-average molecular weight of the marine biodegradable polymer compound of the present invention is preferably 3,000 to 1,000,000. Considering biodegradability, mechanical properties, and moldability, it is more preferably 10,000 to 500,000, further preferably 20,000 to 200,000, and most preferably 40,000 to 100,000. It should be noted that the number-average molecular weight is the polystyrene conversion measured value using gel permeation chromatography (GPC).

[0096] Regarding the content ratio of structural unit A to structural unit C (A:C), from the viewpoints of mechanical properties and biodegradability, expressed as a molar ratio, it is preferably 0.1:99.9 to 90:10, more preferably 1:99 to 50:50, further preferably 2:98 to 20:80, and most preferably 3:97 to 10:90.

[0097] The weight reduction rate of the marine biodegradable polymer compound after being immersed in seawater for 60 days is preferably 5% or more, more preferably 10% or more, and most preferably 20% or more.

[0098] The marine biodegradable polymer compound of the present invention may be a product with blocked ends. That is, a capping agent can be used to block the terminal group X or terminal group Y remaining in the polymer compound. As for the capping agent, as long as it has reactivity with the substituents at the terminals, it can be arbitrarily selected from monocarboxylic acids, monoacyl chlorides, monoesters, monoisocyanates, monoalcohols, monoamines, monoepoxides, etc. for the purpose of improving thermal stability, physical properties, etc. Specific examples thereof include aliphatic carboxylic acids having 1 to 20 carbon atoms such as formic acid, acetic acid, and stearic acid, acyl chlorides of the above aliphatic carboxylic acids, and acid esters of the above aliphatic carboxylic acids; aromatic carboxylic acids having 7 to 20 carbon atoms such as benzoic acid, 4-methylbenzoic acid, 4-hexylbenzoic acid, and naphthoic acid, acyl chlorides of the above aromatic carboxylic acids, and acid esters of the above aromatic carboxylic acids; aliphatic isocyanates having 1 to 20 carbon atoms such as methyl isocyanate and octadecyl isocyanate; aromatic isocyanates having 7 to 20 carbon atoms such as phenyl isocyanate and 4-butylphenyl isocyanate; aliphatic alcohols having 1 to 20 carbon atoms such as methanol, ethanol, and stearyl alcohol; aromatic alcohols having 7 to 20 carbon atoms such as benzyl alcohol and 3-phenyl-1-propanol; fatty acid amines having 1 to 20 carbon atoms such as methylamine, ethylamine, and stearylamine; aromatic amines having 6 to 20 carbon atoms such as aniline, benzylamine, and 4-phenyl-1-butylamine; epoxides having 2 to 20 carbon atoms such as 1,2-epoxyheptane, 1,2-epoxyhexane, 1,2-epoxydecane, and 1,2-epoxy-5-hexene, etc. From the viewpoints of imparting hydrophobicity, environmental load, and reactivity, as the above capping agent, aliphatic carboxylic acids having 6 to 20 carbon atoms, acyl chlorides of the above aliphatic carboxylic acids, acid esters of the above aliphatic carboxylic acids, and aliphatic isocyanates having 6 to 20 carbon atoms are preferred, and aliphatic carboxylic acids having 10 to 18 carbon atoms and their acyl chlorides are more preferred.

[0099] [Method for manufacturing marine biodegradable polymer compound]

[0100] The marine biodegradable polymer compound can be obtained by polymerizing a marine biodegradable linker (A), a compound (B1), and a compound (C) or a marine biodegradable linker (A) and a compound (B2). It should be noted that the marine biodegradable linker (A), the compounds (B1), (B2), and (C) can each be used alone in one kind, or two or more kinds can be used in combination.

[0101] Before polymerization, it is preferred to mix the marine biodegradable linker (A), the compound (B1), and the compound (C) or the marine biodegradable linker (A) and the compound (B2). When mixing the marine biodegradable linker (A), the compound (B1), and the compound (C), they can be mixed simultaneously, or the marine biodegradable linker (A) can be mixed into the mixture after mixing the compound (B1) and the compound (C).

[0102] After mixing, a catalyst may be added as needed. Specific examples of the catalyst will be described later.

[0103] Regarding the polymerization, it is preferable to melt the marine biodegradable linker (A), the compound (B1), and the compound (C) or the marine biodegradable linker (A) and the compound (B2), and heat these compounds in a molten state to polymerize them. At this time, regarding the melting temperature of the marine biodegradable linker (A), from the viewpoints of processability and biodegradability, it is preferably 200 °C or lower, more preferably 180 °C or lower. It should be noted that regarding the compounds (B1), (B2), and (C), their melting temperatures may not be 180 °C or lower, and it is preferable to heat them to the temperature at which all the raw material compounds are melted to polymerize them.

[0104] The above polymerization is preferably addition polymerization or condensation polymerization, more preferably condensation polymerization.

[0105] When polymerizing the marine biodegradable linker (A), the compound (B1), and the compound (C), these compounds are preferably used in an amount such that the ratio of the reactive group equivalents of the marine biodegradable linker (A) and the compound (C) to the reactive group equivalent of the compound (B1) ([(A)+(C)]:(B1)) is 0.75 to 1.25. When polymerizing the marine biodegradable linker (A) and the compound (B2), regarding these compounds, from the viewpoints of mechanical properties and biodegradability, it is preferably used in an amount such that the ratio of the reactive group equivalents of the marine biodegradable linker (A) and the compound (B2) ((A) / (B2)) is 0.001 to 0.1.

[0106] In addition, when polymerizing the marine biodegradable linker (A), the compound (B1), and the compound (C), regarding the usage ratio of the marine biodegradable linker (A) to the compound (C) ((A):(C)), from the viewpoints of mechanical properties and biodegradability, expressed as a molar ratio, it is preferably 0.1:99.9 to 90:10, more preferably 1:99 to 50:50, further preferably 2:98 to 20:80, and most preferably 3:97 to 10:90.

[0107] When the marine biodegradable polymer compound of the present invention is a polyester-based polymer compound, that is, when the reactive group X is a hydroxyl group and the reactive group Y is a carboxyl group, or when the reactive group X is a carboxyl group and the reactive group Y is a hydroxyl group, the polymerization method of known polyesters can be referred to. For example, the method described in Fibers and Industry, Vol. 40, No. 4.5, pp. 259-261, 1984 can be referred to.

[0108] In addition, in the polymerization reaction of the polyester, for promoting the reaction as needed, polycondensation catalysts such as antimony trioxide, germanium catalyst, titanium catalyst, etc. can be used; catalysts generally used in transesterification such as magnesium acetate, manganese acetate, etc. If considering the environmental load, a metal-free catalyst is preferred. The usage amount of the above catalyst is preferably about 0.01 to 5 parts by mass relative to 100 parts by mass of the compound (B1).

[0109] When the marine biodegradable polymer compound of the present invention is a polyamide-based polymer compound, that is, when the reactive group X is an amino group and the reactive group Y is a carboxyl group, or when the reactive group X is a carboxyl group and the reactive group Y is an amino group, the polymerization method of a known polyamide can be referred to. For example, the methods described in Japanese Patent Publication No. 52-12233 and Japanese Patent Publication No. 5-71056 can be referred to.

[0110] In addition, in the polymerization reaction of the polyamide, for promoting the reaction as needed, polycondensation catalysts such as metal salts, ammonium salts, esters of phosphoric acid, phosphorous acid or hypophosphorous acid can be used. The usage amount of the above catalyst is preferably about 0.01 to 1.0 parts by mass relative to 100 parts by mass of the compound (B1).

[0111] When the marine biodegradable polymer compound of the present invention is a polyurethane-based polymer compound, that is, when the reactive group X is a hydroxyl group and the reactive group Y is an isocyanate group, or when the reactive group X is an isocyanate group and the reactive group Y is a hydroxyl group, the polymerization method of a known polyurethane can be referred to. For example, the methods described in the Network Polymer Symposium, Vol. 39, No. 1, pp. 10-19, 2018 can be referred to.

[0112] Regarding the reaction of the above-mentioned marine biodegradable polyol and diisocyanate, in order to shorten the reaction time and lower the reaction temperature caused by the improvement of reactivity, amine-based catalysts such as 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), N,N-dimethylcyclohexylamine (DMCA), and triethylamine can be used; tin catalysts such as dibutyltin dilaurate, tetramethyltin, tetrabutyltin, tetraoctyltin, tributyltin chloride, dibutyltin dichloride, dimethyltin oxide, trimethyltin chloride, dimethyltin dichloride, trioctyltin chloride, dibutyltin oxide, dibutyltin diacetate, butyltin trichloride, dioctyltin dichloride, dioctyltin oxide, dioctyldilauryltin, and dioctyltin diacetate. In addition, zinc complexes, iron complexes, bismuth complexes, and zirconium complexes similar to the above-mentioned tin complexes can also be used as catalysts. If considering the environmental load, metal-free catalysts are preferred. The usage amount of the above-mentioned catalyst is preferably about 0.01 to 5 parts by mass relative to 100 parts by mass of the compound (B1).

[0113] When the marine biodegradable polymer compound of the present invention is a polyurea-based polymer compound, that is, when the reactive group X is an amino group and the reactive group Y is an isocyanate group, or when the reactive group X is an isocyanate group and the reactive group Y is an amino group, the polymerization method of known polyurea can be referred to. For example, the method described in Japanese Patent Application Laid-Open No. 2004-27148 can be referred to.

[0114] In addition, in the polymerization reaction of polyurea, if necessary, in order to promote the reaction, polycondensation catalysts such as transesterification catalysts composed of salts, alcoholates, and organometallic compounds of metals such as lithium, sodium, magnesium, aluminum, potassium, titanium, cobalt, germanium, zinc, rubidium, strontium, tin, antimony, cesium, barium, and lead can be used. The usage amount of the above-mentioned catalyst is preferably about 0.00001 to 0.1 parts by mass relative to 100 parts by mass of the compound (B1).

[0115] In any polymerization reaction, the polymerization temperature is preferably about 130 to 300 °C, more preferably about 160 to 230 °C. The polymerization time is preferably about 0.5 to 24 hours, more preferably about 1 to 12 hours.

[0116] In the case of terminally blocking the marine biodegradable polymer compound, after the polymerization is completed, the above-mentioned blocking agent can be added for blocking, or the above-mentioned blocking agent can be added to the polymerization solution before or during the polymerization reaction for blocking. Regarding the terminal blocking method, in the case of adding the blocking agent for blocking after the polymerization is completed, for example, a method can be cited in which the marine biodegradable polymer compound is melted and the blocking agent is added thereto for reaction. At this time, the temperature for melting the marine biodegradable polymer compound is not particularly limited, and is usually about 130 to 280 °C. The reaction time is not particularly limited, and is usually about 1 to 6 hours. In the case of adding the blocking agent to the polymerization solution before or during the polymerization reaction for blocking, for example, a method can be cited in which the blocking agent is added to the mixture of the above-mentioned raw material compounds, and the terminal is blocked simultaneously with the polymerization reaction. In this case, the blocking agent can be added before the start of the reaction, can be added after dissolving the raw materials other than the blocking agent, or can be added during the polymerization reaction. In order to increase the molecular weight, it is preferably added after dissolving the raw materials other than the blocking agent, or added during the polymerization reaction. In all methods, the addition amount of the above-mentioned blocking agent is preferably about 0.05 to 10% by mass, more preferably about 0.1 to 5% by mass, in all the raw material compounds. The above-mentioned blocking agent can be used alone as one kind, or two or more kinds can be combined and used.

[0117] [Marine biodegradable resin composition]

[0118] The marine biodegradable resin composition of the present invention contains the above-mentioned marine biodegradable polymer compound.

[0119] The above-mentioned marine biodegradable polymer compound can be used as a main raw material, and as an additive, it can be used in combination with other resins. The above-mentioned other resin is not particularly limited, and a biodegradable resin is preferred. When used in combination with other resins as an additive, the above-mentioned marine biodegradable polymer compound functions as a marine biodegradation promoter. At this time, a resin composition that promotes biodegradation in the ocean is formed. In addition, in order to adjust the physical properties and processability of the resin composition, as the above-mentioned other resin, a plurality of resins can also be combined and used.

[0120] As the above-mentioned other resins, polyethylene, polyester, polypropylene, polyethylene terephthalate, vinyl chloride, polystyrene, polyurethane, epoxy resin, chlorinated polyethylene resin, chlorinated polypropylene resin, modified nylon resin, phenolic resin, silicone resin, polyvinyl acetate, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, styrene-maleic resin, styrene-butadiene resin, butadiene resin, acrylonitrile-butadiene resin, poly(meth)acrylonitrile resin, (meth)acrylamide resin, bio-PET, bio-polyamide, bio-polycarbonate, bio-polyurethane, polyvinyl alcohol, polybutylene adipate / terephthalate, polyethylene glycol terephthalate succinate, bio-polybutylene succinate, polylactic acid blend, starch blend polyester resin, polybutylene terephthalate succinate, polylactic acid, polyhydroxyalkanoic acid, etc. can be mentioned. If consideration is given to reducing the environmental load, resins with high biodegradability are particularly preferred.

[0121] In addition, as the above-mentioned biodegradable resins, resins derived from petroleum such as polycaprolactone, poly(ε-caprolactone / butylene succinate), polybutylene succinate (PBS), poly(butylene succinate / adipate) (PBSA), poly(butylene adipate / terephthalate) (PBAT), poly(butylene succinate / carbonate), polyethylene terephthalate copolymer, poly(ethylene glycol terephthalate / succinate), poly(tetramethylene adipate / terephthalate), polyethylene succinate, polyvinyl alcohol, polyglycolic acid, glycolic acid / ε-caprolactone copolymer, glycolic acid / propylene carbonate copolymer, etc.; resins with a part of the raw materials derived from biomass such as (polylactic acid / polybutylene succinate)-type block copolymer, (polylactic acid / polycaprolactone) copolymer, (polylactic acid / polyether) copolymer, polylactic acid blend PBAT, lactic acid / glycolic acid copolymer, bio-polybutylene succinate, poly(butylene succinate / adipate), starch blend polyester resin, poly(butylene terephthalate succinate), etc.; resins with 100% of the raw materials derived from biomass such as polyhydroxybutyric acid, polyhydroxyvaleric acid, polyhydroxyoctanoic acid, poly(3-hydroxybutyrate / 4-hydroxybutyrate) (P3HB4HB), poly(3-hydroxybutyrate / 3-hydroxyvalerate) (PHBV), etc. polyhydroxyalkanoic acid, polylactic acid (PLA), etc.; resins derived from natural polymers such as cellulose, cellulose acetate, cellulose ester resin, starch, esterified starch, chitosan, etc.

[0122] Among these, as the biodegradable resin, a resin having biodegradability in soil or compost but poor biodegradability in the ocean is preferred. For example, a biodegradable resin selected from polycaprolactone, (bio)PBS, PBSA, PBAT, poly(tetramethylene adipate / terephthalate), poly(butylene succinate / carbonate), PHBH, PHBV and other polyhydroxyalkanoates, PLA, cellulose, starch, chitosan and other resins derived from natural polymers is combined with the above-mentioned marine biodegradable polymer compound. As the above-mentioned biodegradable resin, a resin derived from PBSA, PBS, PBAT, PLA, or starch is particularly preferred.

[0123] In addition, when considering the reduction of environmental load, as the raw material of the combined resin, a raw material derived from biomass is preferred, and a raw material that is most preferably 100% derived from biomass is more preferred.

[0124] The marine biodegradable resin composition of the present invention may contain a solvent. The above solvent may be a solvent that does not dissolve the above marine biodegradable polymer compound but remains as particles and simultaneously dissolves the resin that will become the matrix, or may be a solvent that dissolves both the above resin and the marine biodegradable polymer compound. By appropriately adjusting them, it can also be effectively used as a molded body, coating, ink, surface treatment agent, etc. produced by film formation such as casting. As preferred solvents, for example, water, formic acid, hexane, heptane, acetonitrile, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, dimethyl sulfone, acetone, methyl ethyl ketone, diethyl ketone, acetophenone, dimethyl ether, dipropyl ether, tetrahydrofuran, chloroform, dichloromethane, trichloroethylene, dichloroethylene, dichloroethane, tetrachloroethane, chlorobenzene, methanol, ethanol, n-propanol, isopropanol, butanol, pentanol, hexafluoroisopropanol, methyl ethylene glycol, methyl triglycol, hexyl ethylene glycol, phenyl ethylene glycol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, benzene, toluene, xylene, etc. can be cited. These can be used alone or in combination of two or more.

[0125] When using a solvent, the total concentration of the resin and the marine biodegradable polymer compound in the above resin composition is preferably 0.5 to 90% by mass, more preferably 1 to 80% by mass, further preferably 5 to 60% by mass, and most preferably 10 to 50% by mass. In addition, the ratio of the marine biodegradable polymer compound to the above resin is expressed by a mass ratio, and is preferably 99:1 to 10:90, more preferably 97:3 to 40:60, further preferably 95:5 to 50:50, and most preferably 90:10 to 60:40.

[0126] In addition, the marine biodegradable resin composition of the present invention may not contain a solvent. In this case, the above resin may be heat-melted, and an unmelted marine biodegradable polymer compound may be added thereto and mixed, or both the above resin and the marine biodegradable polymer compound may be melted and mixed.

[0127] In the marine biodegradable resin composition of the present invention, the content of the marine biodegradable polymer compound is preferably 1 to 50% by mass, more preferably 3 to 50% by mass, further preferably 5 to 45% by mass, further preferably 7 to 40% by mass, and most preferably 10 to 35% by mass. On the other hand, the content of the resin is preferably 50 to 99% by mass, more preferably 50 to 97% by mass, further preferably 55 to 95% by mass, further preferably 60 to 93% by mass, and most preferably 65 to 90% by mass. By including the marine biodegradable polymer compound within the above range, it is possible to effectively utilize it as a marine biodegradation promoter that promotes the progress of biodegradation in seawater while maintaining the physical properties of the biodegradable resin. The above marine biodegradable polymer compounds may be used singly or in combination of two or more.

[0128] The marine biodegradable resin composition of the present invention may contain, as needed, additives such as antioxidants, mold release agents, release agents, surface modifiers, hydrophobizing agents, water repellent agents, hydrophilizing agents, dyes, colorants, heat stabilizers, light stabilizers, weather resistance improvers, antistatic agents, antifogging agents, lubricants, anti-blocking agents, hardening agents, softening agents, compatibilizers, flame retardants, fluidity improvers, plasticizers, dispersants, antibacterial agents, fillers, metal deactivators, etc. The content of these additives is not particularly limited as long as the effects of the present invention are not impaired, and is preferably about 0.1 to 50 parts by mass relative to 100 parts by mass of the resin.

[0129] In the case where the above marine biodegradable resin composition contains a solvent, for example, it can be prepared by adding the resin, the marine biodegradable polymer compound, and the above additives used as needed to the solvent simultaneously or in any order and mixing. In addition, in the case where the above marine biodegradable resin composition does not contain a solvent, for example, the above resin may be melted, and the marine biodegradable polymer compound and the above additives used as needed may be added and mixed thereto simultaneously or in any order, or the above resin and the marine biodegradable polymer compound may be heated and melted together and mixed, and the above additives may be added and mixed as needed.

[0130] [Molded article]

[0131] By using the above resin composition for molding, a molded article in which the marine biodegradable polymer compound is dispersed or dissolved in the above resin can be obtained. When the above resin composition contains a solvent, the resin composition can be directly used for molding. When the above resin composition does not contain a solvent, the resin or the resin and the marine biodegradable polymer compound in the resin composition can be heat-melted and then molded.

[0132] Examples of the shape of the above molded article include a film shape, a fibrous shape, a plate shape, a foamed molded article shape, and other shapes suitable for the use. The molding method is not particularly limited, and various conventionally known molding methods can be used. Specific examples thereof include blow molding, injection molding, extrusion molding, compression molding, melt extrusion molding method, solution casting molding method, calendering molding method, etc.

[0133] Regarding the marine biodegradable resin composition of the present invention, it can be used as a raw material for plastic molded articles, and can also be used as various additives in molded articles such as liquids, coating films, films, plates, papers, etc. When used as a raw material for plastic molded articles, it can be suitably used as a raw material for films, packaging, containers, trays, laminates, adhesives, coating materials, medical, fibers such as clothes, fishing lines, fishing nets and other marine use materials, etc. In addition, when used as an additive, for example, it can be used as a light scattering agent, a light filter material, a coloring agent, cosmetics, an absorbent, an adsorbent, ink, an adhesive, an electromagnetic wave shielding material, a fluorescence sensor, a biological marker, a recording material, a recording element, a polarizing material, a drug carrier for drug delivery system (DDS), a biosensor, a DNA chip, an inspection drug, a fired porous molded article, an anti-adhesive agent, screen printing, offset printing, color overprinting, intaglio printing, rubbing printing, a coater, inkjet, etc. used in printing ink additives, marker pens, ballpoint pens, fountain pens, fountain pens, all-purpose pens and other pen ink additives, crayons, painting tools, erasers and other stationery additives, brush coating, spraying, electrostatic coating, electrodeposition coating, flow coating, roll coating, dip coating and other coating additives, especially additives for coatings used in marine applications such as hull coatings.

[0134] Examples

[0135] Hereinafter, synthesis examples, examples and comparative examples are listed to illustrate the present invention more specifically, but the present invention is not limited to the following examples.

[0136] It should be noted that in the following Examples and Comparative Examples, in terms of the equivalent of metal ions, the target substance was heated and degraded in nitric acid or aqua regia, and measured by emission spectrometry using ICP-MS (ICPE-9820 manufactured by Shimadzu Corporation). In terms of the molecular weight of the marine biodegradable polymer compound and the polymer compound, the target substance was dissolved in chloroform, and measured as the number average molecular weight (Mn) in terms of polystyrene by using a GPC measuring device (COM-20A, LC-20A, SIL-20A, RID-20A, CTO-20A) manufactured by Shimadzu Corporation, with chloroform used as the mobile phase and Shodex k-806M manufactured by Showa Denko K.K. used as the column.

[0137] [1] Synthesis and Evaluation of Marine Biodegradable Linker

[0138] [Example 1-1] Synthesis of Marine Biodegradable Linker A1

[0139] In a 1 L flask, 295 g of succinic acid and 305 g of 1,4-butanediol were added, and heated and stirred at 230 °C for 6 hours. Then, the content was taken out onto a stainless-steel tray with a Teflon (registered trademark) sheet to obtain a solid resin.

[0140] Next, 500 g of the obtained resin was pulverized and added to a 3 L flask. 500 g of acetonitrile, 100 g of succinic anhydride, and 125 g of sodium carbonate were added, and heated and stirred at 70 °C for 4 hours. The reaction solution was cooled to room temperature, and the precipitate was removed by filtration. The obtained filtrate was concentrated, and the solvent was further removed under reduced pressure to obtain a polymer compound substituted with COONa at one terminal or both terminals. The number average molecular weight of the obtained compound was determined by the terminal quantification method using 1 1H-NMR, and the result was 620.

[0141] The obtained polymer compound was dissolved in a mixed solvent of 500 g of ion-exchanged water and 500 g of acetonitrile, and 320 g of a 20 mass% calcium chloride aqueous solution was added thereto, and stirred well. A white precipitate was formed, so the supernatant was removed, and the precipitate was recovered. After washing with water, the residual solvent was removed under reduced pressure to produce a marine biodegradable linker A1 containing an ionic bond in the molecule and having hydroxyl groups at both terminals. Its number average molecular weight was measured by GPC, and the result was 1800 (average number of metal cations 1.50).

[0142] [Example 1-2] Synthesis of Marine Biodegradable Linker A2

[0143] In a 1-L flask, 152 g of adipic acid, 173 g of terephthalic acid, and 275 g of 1,4-butanediol were added, and the mixture was heated and stirred at 230 °C for 6 hours. Then, the content was taken out onto a stainless-steel tray with a Teflon (registered trademark) sheet, and a solid resin was thus obtained.

[0144] Next, 500 g of the obtained resin was pulverized and added to a 3-L flask. 500 g of acetonitrile, 100 g of succinic anhydride, and 160 g of potassium carbonate were added, and the mixture was heated and stirred at 70 °C for 4 hours. The reaction solution was cooled to room temperature, and the precipitate was removed by filtration. The obtained filtrate was concentrated, and then the solvent was removed under reduced pressure, whereby a polymer compound substituted with COOK at one or both ends was obtained. Using the 1 end-group quantification method by 1H-NMR, the number-average molecular weight of the obtained compound was determined to be 600.

[0145] The obtained polymer compound was dissolved in a mixed solvent of 500 g of ion-exchanged water and 500 g of acetonitrile, and 320 g of a 20 mass% aqueous calcium chloride solution was added thereto, followed by sufficient stirring. A white precipitate was formed, so the precipitate was recovered by removing the supernatant, washed with water, and then the remaining solvent was removed under reduced pressure, thereby producing a marine biodegradable linker A2 containing an ionic bond in the molecule and having hydroxyl groups at both ends. By GPC measurement, its number-average molecular weight was 2200 (average number of metal cations: 2.06).

[0146] [Example 1-3] Synthesis of marine biodegradable linker A3

[0147] 500 g of Kuraray polyol P-510 (manufactured by Kuraray Co., Ltd., Mn = 500) was added to a 3-L flask. Next, 500 g of acetonitrile, 100 g of succinic anhydride, and 125 g of sodium carbonate were added, and the mixture was heated and stirred at 70 °C for 4 hours. The reaction solution was cooled to room temperature, and the precipitate was removed by filtration. The obtained filtrate was concentrated, and then the solvent was removed under reduced pressure, whereby a polymer compound substituted with COONa at one or both ends was obtained. Using the 1 end-group quantification method by 1H-NMR, the number-average molecular weight of the obtained compound was determined to be 590.

[0148] The obtained polymer compound was dissolved in a mixed solvent of 500 g of ion-exchanged water and 500 g of acetonitrile, and 280 g of a 20 mass% aqueous magnesium chloride solution was added thereto, followed by sufficient stirring. A white precipitate was formed, so the precipitate was recovered by removing the supernatant, washed with water, and then the remaining solvent was removed under reduced pressure, thereby producing a marine biodegradable linker A3 containing an ionic bond in the molecule and having hydroxyl groups at both ends. By GPC measurement, its number-average molecular weight was 1600 (average number of metal cations: 1.22).

[0149] [Examples 1-4] Synthesis of Marine Biodegradable Linker A4

[0150] 300 g of succinic acid, 300 g of butanediamine, and 180 g of ion-exchanged water were added to an autoclave with an internal volume of 1 L. After sufficient nitrogen replacement, the temperature was raised to 270 °C while stirring. While maintaining the closed state, stirring was continued at 270 °C for 1 hour, and then the pressure was released to atmospheric pressure. Then, the content was taken out to a stainless-steel tray with a Teflon (registered trademark) sheet, and thus a solid resin was obtained.

[0151] Next, 500 g of the obtained resin was pulverized and added to a 3 L flask. Then, 500 g of acetonitrile, 100 g of succinic anhydride, and 125 g of sodium carbonate were added, and the mixture was heated and stirred at 70 °C for 4 hours. The reaction solution was cooled to room temperature, and the precipitate was removed by filtration. The obtained filtrate was concentrated, and then the solvent was removed under reduced pressure, thereby obtaining a polymer compound substituted with COONa at one end or both ends. The number-average molecular weight of the obtained compound was determined by the end-group quantification method using 1 1H-NMR, and the result was 620.

[0152] The obtained polymer compound was dissolved in a mixed solvent of 500 g of ion-exchanged water and 500 g of acetonitrile, and 320 g of a 20 mass% calcium chloride aqueous solution was added thereto, and the mixture was stirred well. A white precipitate was formed, so the supernatant was removed to recover the precipitate. After washing with water, the remaining solvent was removed under reduced pressure, thereby producing a marine biodegradable linker A4 containing an ionic bond in the molecule and having amino groups at both ends. The number-average molecular weight was measured by GPC, and the result was 1800 (average number of metal cations: 1.50).

[0153] [Examples 1-5] Synthesis of Marine Biodegradable Linker A5

[0154] 250 g of succinic acid, 350 g of hexamethylenediamine, and 150 g of ion-exchanged water were added to an autoclave with an internal volume of 1 L. After sufficient nitrogen replacement, the temperature was raised to 270 °C while stirring. While maintaining the closed state, stirring was continued at 270 °C for 1 hour, and then the pressure was released to atmospheric pressure. Then, the content was taken out to a stainless-steel tray with a Teflon (registered trademark) sheet, and thus a solid resin was obtained.

[0155] Next, 500 g of the obtained resin was pulverized and added to a 3 L flask. Then, 500 g of acetonitrile, 100 g of succinic anhydride, and 125 g of sodium carbonate were added, and the mixture was heated and stirred at 70 °C for 4 hours. The reaction solution was cooled to room temperature, and the precipitate was removed by filtration. The obtained filtrate was concentrated, and then the solvent was removed under reduced pressure, thereby obtaining a polymer compound substituted with COONa at one end or both ends. Using 1The number-average molecular weight of the obtained compound was determined by the terminal quantification method of 1H-NMR, and the result was 600.

[0156] The obtained polymer compound was dissolved in a mixed solvent of 500 g of ion-exchanged water and 500 g of acetonitrile, and 320 g of a 20 mass% calcium chloride aqueous solution was added thereto, followed by sufficient stirring. A white precipitate was formed, so the precipitate was recovered by removing the supernatant, washed with water, and the remaining solvent was removed under reduced pressure, thereby producing a marine biodegradable linker A5 containing an ionic bond in the molecule and having amino groups at both ends. The number-average molecular weight thereof was measured by GPC, and the result was 1700 (average number of metal cations 1.36).

[0157] [Example 1-6] Synthesis of marine biodegradable linker A6

[0158] 500 g of poly(propylene glycol) bis(2-aminopropyl ether) (manufactured by Sigma-Aldrich, Mn = 400) was added to a 3 L flask. Next, 500 g of acetonitrile, 126 g of succinic anhydride and 159 g of sodium carbonate were added, and the mixture was heated and stirred at 70 °C for 4 hours. The reaction solution was cooled to room temperature, and the precipitate was removed by filtration. The obtained filtrate was concentrated, and then the solvent was removed under reduced pressure, thereby obtaining a polymer compound substituted with COONa at one or both ends. Using 1 The number-average molecular weight of the obtained compound was determined by the terminal quantification method of 1H-NMR, and the result was 510.

[0159] The obtained polymer compound was dissolved in a mixed solvent of 500 g of ion-exchanged water and 500 g of acetonitrile, and 320 g of a 20 mass% calcium chloride aqueous solution was added thereto, followed by sufficient stirring. A white precipitate was formed, so the precipitate was recovered by removing the supernatant, washed with water, and the remaining solvent was removed under reduced pressure, thereby producing a marine biodegradable linker A6 containing an ionic bond in the molecule and having amino groups at both ends. The number-average molecular weight thereof was measured by GPC, and the result was 1500 (average number of metal cations 1.42).

[0160] [Example 1-7] Synthesis of marine biodegradable linker A7

[0161] 500 g of Placcel 220N (manufactured by Daicel Corporation, Mn = 2000) was added to a 3 L flask. Next, 500 g of acetonitrile, 60 g of succinic anhydride and 70 g of sodium carbonate were added, and the mixture was heated and stirred at 70 °C for 4 hours. Then, the reaction solution was cooled to room temperature, and the precipitate was removed by filtration. Hydrochloric acid was added to the obtained filtrate, and extraction was carried out with toluene. The toluene containing the extract was concentrated, and then the solvent was removed under reduced pressure, thereby obtaining a polymer compound substituted with COOH at the end. Using 1The number-average molecular weight of the obtained compound was determined by the terminal quantification method of 1H-NMR, and the result was 2120.

[0162] The obtained polymer compound was dissolved in a mixed solvent of 500 g of ion-exchanged water and 500 g of acetonitrile, and 210 g of a 10 mass% aqueous sodium bicarbonate solution was added thereto to neutralize the single terminal or both terminals. Then, 80 g of a 20 mass% aqueous calcium chloride solution was added and stirred well. A white precipitate was formed, so the precipitate was recovered by removing the supernatant, washed with water, and the remaining solvent was removed under reduced pressure, thereby producing a marine biodegradable linker A7 containing an ionic bond in the molecule and having carboxyl groups at both terminals. The number-average molecular weight thereof was measured by GPC, and the result was 5200 (average number of metal cations 1.36).

[0163] [Example 1-8] Synthesis of marine biodegradable linker A8

[0164] In a 1 L flask, 350 g of adipic acid and 250 g of butanediol were added, and heated and stirred at 230 °C for 6 hours. Then, the content was taken out onto a stainless steel tray with a Teflon (registered trademark) sheet to obtain a solid resin.

[0165] Next, 500 g of the obtained resin was pulverized, added to a 3 L flask, 500 g of acetonitrile, 110 g of succinic anhydride and 171 g of potassium carbonate were added, and heated and stirred at 70 °C for 4 hours. The reaction solution was cooled to room temperature, and the precipitate was removed by filtration. Hydrochloric acid was added to the obtained filtrate, and extraction was carried out with toluene. The toluene containing the extract was concentrated, and then the solvent was removed under reduced pressure, thereby obtaining a polymer compound with the terminals substituted by COOH. The number-average molecular weight of the obtained compound was determined by the terminal quantification method using 1 1H-NMR, and the result was 1200.

[0166] The prepared polymer compound was dissolved in a mixed solvent of 500 g of ion-exchanged water and 500 g of acetonitrile, and 475 g of a 10 mass% aqueous potassium bicarbonate solution was added thereto to neutralize the single terminal or both terminals. Then, 130 g of a 20 mass% aqueous calcium chloride solution was added and stirred well. A white precipitate was formed, so the precipitate was recovered by removing the supernatant, washed with water, and the remaining solvent was removed under reduced pressure, thereby producing a marine biodegradable linker A8 containing an ionic bond in the molecule and having carboxyl groups at both terminals. The number-average molecular weight thereof was measured by GPC, and the result was 2900 (average number of metal cations 1.28).

[0167] [Example 1-9] Synthesis of marine biodegradable linker A9

[0168] 250 g of succinic acid, 350 g of hexamethylenediamine, and 150 g of ion-exchanged water were added to an autoclave with an internal volume of 1 L. After sufficient nitrogen replacement, the temperature was raised to 270 °C while stirring. While maintaining the closed state, further stirring was carried out at 270 °C for 1 hour, and then the pressure was released to atmospheric pressure. Then, the content was taken out onto a stainless-steel tray with a Teflon (registered trademark) sheet, and thus a solid resin was obtained.

[0169] Next, 500 g of the obtained resin was pulverized and added to a 3 L flask. 500 g of acetonitrile, 200 g of succinic anhydride, and 272 g of potassium carbonate were added, and heating and stirring were carried out at 70 °C for 4 hours. The reaction solution was cooled to room temperature, and the precipitate was removed by filtration. Hydrochloric acid was added to the obtained filtrate, and extraction was carried out with toluene. The toluene containing the extract was concentrated, and further the solvent was removed under reduced pressure, and thus a polymer compound substituted with COOH at the terminal was obtained. The number-average molecular weight of the obtained compound was determined by the terminal quantification method using 1 1H-NMR, and the result was 710.

[0170] The prepared polymer compound was dissolved in a mixed solvent of 100 g of ion-exchanged water and 500 g of acetonitrile, 820 g of a 10 mass% aqueous potassium hydrogen carbonate solution was added thereto, and the single terminal or both terminals were neutralized. Then, 230 g of a 20 mass% aqueous calcium chloride solution was added and stirred well. A white precipitate was formed, so the supernatant was removed to recover the precipitate. After washing with water, the remaining solvent was removed under reduced pressure, and thus a marine biodegradable linker A9 containing an ionic bond in the molecule and having carboxyl groups at both terminals was produced. The number-average molecular weight thereof was measured by GPC, and the result was 1800 (average number of metal cations 1.22).

[0171] [Example 1-10] Synthesis of marine biodegradable linker A10

[0172] In a 1 L flask, 295 g of succinic acid and 305 g of 1,4-butanediol were added, and heating and stirring were carried out at 230 °C for 6 hours. Then, the content was taken out onto a stainless-steel tray with a Teflon (registered trademark) sheet, and thus a solid resin was obtained.

[0173] Next, 500 g of the obtained resin was pulverized and added to a 3 L flask. 500 g of acetonitrile, 100 g of succinic anhydride, and 125 g of sodium carbonate were added, and heating and stirring were carried out at 70 °C for 4 hours. The reaction solution was cooled to room temperature, and the precipitate was removed by filtration. The obtained filtrate was concentrated, and further the solvent was removed under reduced pressure, and thus a polymer compound substituted with COONa at the single terminal or both terminals was obtained. The number-average molecular weight of the obtained compound was determined by the terminal quantification method using 1 1H-NMR, and the result was 610.

[0174] The prepared polymer compound was dissolved in a mixed solvent of 500 g of ion-exchanged water and 500 g of acetonitrile, and 370 g of a 30 mass% aqueous aluminum sulfate solution was added thereto, followed by thorough stirring. A white precipitate was formed. Thus, the supernatant was removed to recover the precipitate. After washing with water, the remaining solvent was removed under reduced pressure, whereby a marine biodegradable linker A10 containing an ionic bond in the molecule and having hydroxyl groups at all terminals was produced. The number-average molecular weight thereof was measured by GPC, and the result was 2600 (average number of metal cations: 1.10).

[0175] [Comparative Example 1-1] Synthesis of Marine Biodegradable Linker B1

[0176] In a 1 L flask, 319 g of succinic acid and 244 g of 1,4-butanediol were added, and the mixture was heated and stirred at 230 °C for 6 hours. Then, the content was taken out onto a stainless steel tray with a Teflon (registered trademark) sheet, whereby a solid resin was obtained.

[0177] Next, 500 g of the obtained resin was pulverized and added to a 3 L flask. Then, 500 g of chloroform, 2.5 g of succinic anhydride, and 4.0 g of potassium carbonate were added, and the mixture was heated and stirred at 70 °C for 24 hours. The reaction solution was cooled to room temperature, and the precipitate was removed by filtration. The obtained filtrate was concentrated, and further the solvent was removed under reduced pressure, whereby a polymer compound substituted with COOK at one terminal or both terminals was obtained. The number-average molecular weight of the obtained compound was determined by the terminal quantification method using 1 1H-NMR, and the result was 22000.

[0178] The prepared polymer compound was melted at 120 °C, and 7.0 g of a 20 mass% aqueous calcium chloride solution was added thereto, followed by thorough stirring. By removing the water, a marine biodegradable linker B1 containing an ionic bond in the molecule and having hydroxyl groups at both terminals was produced. The number-average molecular weight thereof was measured by GPC, and the result was 42000 (average number of metal cations: 0.90).

[0179] [Comparative Example 1-2] Synthesis of Marine Biodegradable Linker B2

[0180] 336 g of adipic acid, 269 g of hexamethylenediamine, and 150 g of ion-exchanged water were added to an autoclave with an internal volume of 1 L. After sufficient nitrogen replacement, the temperature was raised to 265 °C while stirring. While maintaining the closed state, the mixture was further stirred at 265 °C for 1 hour, and then the pressure was released to atmospheric pressure. Then, the mixture was stirred at 270 °C for 2 hours. Then, the content was taken out onto a stainless steel tray with a Teflon (registered trademark) sheet, whereby a solid resin was obtained.

[0181] Next, 500 g of the obtained resin was pulverized and added to a 3 L flask. Next, 500 g of chloroform, 2.6 g of succinic anhydride, and 4.1 g of potassium carbonate were added, and the mixture was heated and stirred at 70 °C for 24 hours. The reaction solution was cooled to room temperature, and the precipitate was removed by filtration. The obtained filtrate was concentrated, and then the solvent was removed under reduced pressure, thereby obtaining a polymer compound in which the single terminal or both terminals were replaced with COOK. The number-average molecular weight of the obtained compound was determined by the terminal quantification method using 1 1H-NMR, and the result was 24,000.

[0182] The prepared polymer compound was melted at 180 °C, 7.2 g of a 20 mass% calcium chloride aqueous solution was added thereto, and the mixture was sufficiently stirred. By removing the water, a marine biodegradable linker B2 containing an ionic bond in the molecule and having amino groups at both terminals was prepared. Its number-average molecular weight was measured by GPC, and the result was 50,000 (average number of metal cations 1.07).

[0183] [Marine biodegradation evaluation]

[0184] For the marine biodegradable linkers A1 to A10, a seawater biodegradation test was carried out by the following method. It should be noted that as a control material, microcrystalline cellulose (Avicel PH-101 manufactured by Sigma-Aldrich) was used, and the relative biodegradation degree of cellulose was used for evaluation. The results are shown in Table 1.

[0185] <Test method, conditions>

[0186] Biodegradation degree measurement method: Measurement of oxygen consumption using a closed respirometer (refer to ASTM D6691)

[0187] Test device OxiTop IDS (manufactured by WTW)

[0188] Cultivation temperature 30 ± 1 °C, in the dark

[0189] Biodegradation degree (%) = (BOD O - BOD B ) / ThOD × 100

[0190] BOD O : Biochemical oxygen demand for confirming the activity of the test or planting source (measured value: mg)

[0191] BOD B : Average biochemical oxygen demand of the blank test (measured value: mg)

[0192] ThOD: Theoretical oxygen demand required when the test material or control material is completely oxidized (calculated value: mg)

[0193] Relative biodegradability of cellulose (%) = (Maximum biodegradability of test particles / Maximum biodegradability of cellulose) × 100

[0194] Seawater (collected from Tokyo Bay [Chiba Prefecture: Chiba Port])

[0195] After removing foreign substances from the collected seawater using a 10-μm filter, it was aerated at room temperature of 25°C. In addition, as inorganic nutrients, ammonium chloride was added to make it 0.05 g / L, and potassium dihydrogen phosphate was added to make it 0.1 g / L.

[0196] [Table 1]

[0197]

[0198] From the results shown in Table 1, for the marine biodegradable binder of the present invention, the following biodegradability results were obtained: up to 56 days of the culture period, the relative degradation degree of cellulose became 40% or more.

[0199] [2] Synthesis of marine biodegradable polymer compound

[0200] [Example 2-1] Production of marine biodegradable polymer compound AP1

[0201] 100 g of succinic acid, 76.7 g of 1,4-butanediol, and 26.5 g of marine biodegradable binder A1 were placed in a 300-mL flask. Under a nitrogen stream, the temperature of the mantle heater was set to 230°C, and heating and mixing were carried out for 6 hours using a stirrer. Then, the reaction product in the flask was taken out onto a stainless-steel tray with a Teflon (registered trademark) sheet and naturally cooled to obtain the marine biodegradable polymer compound AP1.

[0202] For the marine biodegradable polymer compound AP1, the number-average molecular weight was measured by GPC, and the result was 45,000. The equivalent of calcium ions was measured by ICP-MS, and the result was 10.2 eq / 10 5 g.

[0203] [Example 2-2] Production of marine biodegradable polymer compound AP2

[0204] 100 g of adipic acid, 72.1 g of 1,4-butanediol, and 37.6 g of marine biodegradable binder A2 were placed in a 300-mL flask. Under a nitrogen stream, the temperature of the mantle heater was set to 230°C, and heating and mixing were carried out for 6 hours using a stirrer. Then, the reaction product in the flask was taken out onto a stainless-steel tray with a Teflon (registered trademark) sheet and naturally cooled to obtain the marine biodegradable polymer compound AP2.

[0205] Regarding the marine biodegradable polymer compound AP2, the number average molecular weight was measured by GPC, and the result was 46,000. The equivalent amount of calcium ions was measured by ICP-MS, and the result was 10.8 eq / 10 5 g.

[0206] [Example 2-3] Preparation of Marine Biodegradable Polymer Compound AP3

[0207] Charge 34.9 g of hexamethylene diisocyanate, 100 g of P-510 (manufactured by Kuraray Co., Ltd.), and 22.6 g of marine biodegradable linker A3 into a 300 mL flask. Under a nitrogen stream, set the temperature of the mantle heater to 90 °C and heat and mix for 60 minutes using a stirrer. Then, take out the reaction product in the flask onto a stainless-steel tray with a Teflon (registered trademark) sheet and cool it naturally to obtain the marine biodegradable polymer compound AP3.

[0208] Regarding the marine biodegradable polymer compound AP3, the number average molecular weight was measured by GPC, and the result was 52,000. The equivalent amount of magnesium ions was measured by ICP-MS, and the result was 9.5 eq / 10 5 g.

[0209] [Example 2-4] Preparation of Marine Biodegradable Polymer Compound AP4

[0210] Add 100 g of adipic acid, 76.0 g of hexamethylenediamine, 40 g of ion-exchanged water, and 83.1 g of marine biodegradable linker A4 to an autoclave with an internal volume of 1 L. After sufficient nitrogen replacement, heat to 265 °C while stirring. While maintaining the closed state, further stir at 265 °C for 1 hour, and then release the pressure to atmospheric pressure. Then, stir at 270 °C for 2 hours. Then, take out the content onto a stainless-steel tray with a Teflon (registered trademark) sheet to obtain the marine biodegradable polymer compound AP4.

[0211] Regarding the marine biodegradable polymer compound AP4, the number average molecular weight was measured by GPC, and the result was 62,000. The equivalent amount of calcium ions was measured by ICP-MS, and the result was 18.1 eq / 10 5 g.

[0212] [Example 2-5] Preparation of Marine Biodegradable Polymer Compound AP5

[0213] 100 g of adipic acid, 80.6 g of hexamethylenediamine, 60 g of ion-exchanged water, and 567.1 g of marine biodegradable linker A were added to an autoclave with an internal volume of 1 L. After sufficient nitrogen replacement, the temperature was raised to 265 °C while stirring. While maintaining the closed state, after stirring at 265 °C for 1 hour, the pressure was released to atmospheric pressure. Then, stirring was carried out at 270 °C for 2 hours. Then, the content was taken out to a stainless-steel tray with a Teflon (registered trademark) sheet, and thus the marine biodegradable polymer compound AP5 was obtained.

[0214] For the marine biodegradable polymer compound AP5, the number-average molecular weight was measured by GPC, and the result was 57,000. The equivalent amount of calcium ions was measured by ICP-MS, and the result was 6.1 eq / 10 5 g.

[0215] [Example 2-6] Preparation of marine biodegradable polymer compound AP6

[0216] 100 g of diphenylmethane diisocyanate, 45.7 g of hexamethylenediamine, and 24.2 g of marine biodegradable linker A6 were placed in a 300 mL flask. Under a nitrogen stream, the temperature of the mantle heater was set to 90 °C, and heating and mixing were carried out using a stirrer for 60 minutes. Then, the reaction product in the flask was taken out to a stainless-steel tray with a Teflon (registered trademark) sheet and naturally cooled, and thus the marine biodegradable polymer compound AP6 was obtained.

[0217] Since the marine biodegradable polymer compound AP6 is insoluble in solvents, GPC measurement was not performed. The equivalent amount of calcium ions was measured by ICP-MS, and the result was 11.1 eq / 10 5 g.

[0218] [Example 2-7] Preparation of marine biodegradable polymer compound AP7

[0219] 100 g of terephthalic acid, 56 g of 1,4-butanediol, and 35.1 g of marine biodegradable linker A7 were placed in a 300 mL flask. Under a nitrogen stream, the temperature of the mantle heater was set to 230 °C, and heating and mixing were carried out using a stirrer for 6 hours. Then, the reaction product in the flask was taken out to a stainless-steel tray with a Teflon (registered trademark) sheet and naturally cooled, and thus the marine biodegradable polymer compound AP7 was obtained.

[0220] For the marine biodegradable polymer compound AP7, the number-average molecular weight was measured by GPC, and the result was 68,000. The equivalent amount of calcium ions was measured by ICP-MS, and the result was 2.10 eq / 10 5 g.

[0221] [Example 2-8] Preparation of Marine Biodegradable Polymer Compound AP8

[0222] Charge 100 g of adipic acid, 61.5 g of 1,4-butanediol, and 49.1 g of marine biodegradable linker A8 into a 300 mL flask. Under a nitrogen stream, set the temperature of the mantle heater to 230 °C, and carry out heating and mixing for 6 hours using a stirrer. Then, take out the reaction product in the flask onto a stainless-steel tray with a Teflon (registered trademark) sheet and cool it naturally to obtain the marine biodegradable polymer compound AP8.

[0223] For the marine biodegradable polymer compound AP8, the number-average molecular weight was measured by GPC, and the result was 63000. The equivalent of calcium ions was measured by ICP-MS, and the result was 9.3 eq / 10 5 g.

[0224] [Example 2-9] Preparation of Marine Biodegradable Polymer Compound AP9

[0225] Add 100 g of adipic acid, 79.1 g of hexamethylenediamine, 60 g of ion-exchanged water, and 21.8 g of marine biodegradable linker A9 to an autoclave with an internal volume of 1 L. After sufficient nitrogen replacement, heat it to 265 °C with stirring. While maintaining the closed state, further stir at 265 °C for 1 hour, then release the pressure to atmospheric pressure. Then, stir at 270 °C for 2 hours. Then, take out the content onto a stainless-steel tray with a Teflon (registered trademark) sheet to obtain the marine biodegradable polymer compound AP9.

[0226] For the marine biodegradable polymer compound AP9, the number-average molecular weight was measured by GPC, and the result was 55000. The equivalent of calcium ions was measured by ICP-MS, and the result was 11.6 eq / 10 5 g.

[0227] [Example 2-10] Preparation of Marine Biodegradable Polymer Compound AP10

[0228] Charge 100 g of ε-caprolactone and 14.97 g of marine biodegradable linker A10 into a 300 mL flask. Under a nitrogen stream, set the temperature of the mantle heater to 230 °C, and carry out heating and mixing for 6 hours using a stirrer. Then, take out the reaction product in the flask onto a stainless-steel tray with a Teflon (registered trademark) sheet and cool it naturally to obtain the marine biodegradable polymer compound AP10.

[0229] For the marine biodegradable polymer compound AP10, the number-average molecular weight was measured by GPC, and the result was 25000. The equivalent of calcium ions was measured by ICP-MS, and the result was 5.2 eq / 105 g.

[0230] [Example 2-11] Preparation of Marine Biodegradable Polymer Compound AP11

[0231] Charge 100.0 g of succinic acid, 76.2 g of 1,4-butanediol, and 32.5 g of marine biodegradable linker A10 into a 300 mL flask. Under a nitrogen stream, set the temperature of the mantle heater to 230 °C and heat and mix for 6 hours using a stirrer. Then, take out the reaction product in the flask onto a stainless-steel tray with a Teflon (registered trademark) sheet and cool naturally to obtain the marine biodegradable polymer compound AP11.

[0232] Since the marine biodegradable polymer compound AP11 is insoluble in solvents, GPC measurement was not performed. For the marine biodegradable polymer compound AP11, the equivalent amount of aluminum ions was measured by ICP-MS, and the result was 7.2 eq / 10 5 g.

[0233] [Example 2-12] Preparation of Marine Biodegradable Polymer Compound AP12

[0234] Charge 100 g of adipic acid, 13.4 g of 1,2,3-propanetricarboxylic acid, 68.4 g of 1,4-butanediol, and 30.6 g of marine biodegradable linker A1 into a 300 mL flask. Under a nitrogen stream, set the temperature of the mantle heater to 230 °C and heat and mix for 6 hours using a stirrer. Then, take out the reaction product in the flask onto a stainless-steel tray with a Teflon (registered trademark) sheet and cool naturally to obtain the marine biodegradable polymer compound AP12.

[0235] Since the marine biodegradable polymer compound AP12 is insoluble in solvents, GPC measurement was not performed. For the marine biodegradable polymer compound AP12, the equivalent amount of calcium ions was measured by ICP-MS, and the result was 9.6 eq / 10 5 g.

[0236] [Comparative Example 2-1] Preparation of Polymer Compound BP1

[0237] Charge 100 g of succinic acid, 63.2 g of 1,4-butanediol, and 10.5 g of marine biodegradable linker B1 into a 300 mL flask. Under a nitrogen stream, set the temperature of the mantle heater to 230 °C and heat and mix for 6 hours using a stirrer. Then, take out the reaction product in the flask onto a stainless-steel tray with a Teflon (registered trademark) sheet and cool naturally to obtain the polymer compound BP1.

[0238] For the polymer compound BP1, the number-average molecular weight was measured by GPC and found to be 82,000. The equivalent amount of calcium ions was measured by ICP-MS and the result was 0.41 eq / 10 5 g.

[0239] [Comparative Example 2-2] Production of Polymer Compound BP2

[0240] 100 g of adipic acid, 65.5 g of hexamethylenediamine, 60 g of ion-exchanged water, and 29.4 g of marine biodegradable linker B were added to an autoclave with an internal volume of 1 L. After sufficient nitrogen replacement, the temperature was raised to 265 °C with stirring. While maintaining the closed state, the mixture was further stirred at 265 °C for 1 hour, and then the pressure was released to atmospheric pressure. Then, it was stirred at 270 °C for 2 hours. Then, the content was taken out to a stainless-steel tray with a Teflon (registered trademark) sheet to obtain the polymer compound BP2.

[0241] For the polymer compound BP2, the number-average molecular weight was measured by GPC and found to be 86,000. The equivalent amount of calcium ions was measured by ICP-MS and the result was 0.36 eq / 10 5 g.

[0242] [Comparative Example 2-3] Production of Polymer Compound BP3

[0243] 100 g of succinic acid and 77.9 g of 1,4-butanediol were placed in a 300 mL flask. Under a nitrogen stream, the temperature of the mantle heater was set to 230 °C, and heating and mixing were carried out using a stirrer for 6 hours. Then, the reaction product in the flask was taken out to a stainless-steel tray with a Teflon (registered trademark) sheet and allowed to cool naturally, thereby obtaining the polymer compound BP3.

[0244] For the polymer compound BP3, the number-average molecular weight was measured by GPC and found to be 79,000.

[0245] [Comparative Example 2-4] Production of Polymer Compound BP4

[0246] 100 g of adipic acid, 81.2 g of hexamethylenediamine, and 40 g of ion-exchanged water were added to an autoclave with an internal volume of 1 L. After sufficient nitrogen replacement, the temperature was raised to 265 °C with stirring. While maintaining the closed state, the mixture was further stirred at 265 °C for 1 hour, and then the pressure was released to atmospheric pressure. Then, it was stirred at 270 °C for 2 hours. Then, the content was taken out to a stainless-steel tray with a Teflon (registered trademark) sheet to obtain the polymer compound BP4.

[0247] For the polymer compound BP4, the number-average molecular weight was measured by GPC and found to be 81,000.

[0248] [Comparative Example 2-5] Production of Polymer Compound BP5

[0249] Charge 33.4 g of hexamethylene diisocyanate and 100 g of P-510 (manufactured by Kuraray Co., Ltd.) into a 300 mL flask. Under a nitrogen stream, set the temperature of the mantle heater to 90 °C, and heat and mix for 60 minutes using a stirrer. Then, take out the reaction product in the flask onto a stainless-steel tray with a Teflon (registered trademark) sheet and cool it naturally to obtain polymer compound BP5.

[0250] For polymer compound BP5, the number-average molecular weight was measured by GPC, and the result was 83,000.

[0251] [Comparative Example 2-6] Production of Polymer Compound BP6

[0252] Charge 100 g of ε-caprolactone and 0.81 g of 1,4-butanediol into a 300 mL flask. Under a nitrogen stream, set the temperature of the mantle heater to 230 °C, and heat and mix for 6 hours using a stirrer. Then, take out the reaction product in the flask onto a stainless-steel tray with a Teflon (registered trademark) sheet and cool it naturally to obtain polymer compound BP6.

[0253] For polymer compound BP6, the number-average molecular weight was measured by GPC, and the result was 85,000.

[0254] [3] Synthesis of Terminally Blocked Marine Biodegradable Polymer Compound

[0255] [Example 3-1] Production of Marine Biodegradable Polymer Compound AP1'

[0256] Heat 20 g of marine biodegradable polymer compound AP1 to 180 °C under a nitrogen stream to melt it. As a capping agent, add 0.8 g of phenyl isocyanate and heat for 1 hour. Then, take out the reaction product in the flask onto a stainless-steel tray with a Teflon (registered trademark) sheet and cool it naturally to obtain the terminally blocked marine biodegradable polymer compound AP1'.

[0257] [Example 3-2] Production of Marine Biodegradable Polymer Compound AP2'

[0258] Instead of using 20 g of marine biodegradable polymer compound AP1, use 20 g of marine biodegradable polymer compound AP2. As a capping agent, instead of using phenyl isocyanate, use 1.0 g of octadecyl isocyanate. Otherwise, the terminally blocked marine biodegradable polymer compound AP2' was obtained in the same manner as in Example 3-1.

[0259] [Example 3-3] Preparation of Marine Biodegradable Polymeric Compound AP3'

[0260] 6.98 g of hexamethylene diisocyanate, 20 g of P-510 (manufactured by Kuraray Co., Ltd.), and 4.52 g of marine biodegradable linker A3 were placed in a 100 mL flask. Under a nitrogen stream, the temperature of the mantle heater was set to 90 °C, and using a stirrer, heating and mixing were carried out for 20 minutes. Then, 0.8 g of cyclohexyl isocyanate was added as a capping agent, and further heating and mixing were carried out for 40 minutes. After that, the reaction product in the flask was taken out onto a stainless-steel tray with a Teflon (registered trademark) sheet and allowed to cool naturally, thereby obtaining the end-capped marine biodegradable polymeric compound AP3'.

[0261] [Example 3-4] Preparation of Marine Biodegradable Polymeric Compound AP4'

[0262] 20 g of adipic acid, 15.2 g of hexamethylenediamine, 8 g of ion-exchanged water, and 16.62 g of marine biodegradable linker A4 were added to an autoclave with an internal volume of 1 L. After sufficient nitrogen replacement, the temperature was raised to 265 °C while stirring. While maintaining the closed state, stirring was further carried out at 265 °C for 1 hour, and then the pressure was released to atmospheric pressure. 0.8 g of benzoyl chloride was added as a capping agent, and stirring was carried out at 270 °C for 2 hours. Then, the content was taken out onto a stainless-steel tray with a Teflon (registered trademark) sheet, and the end-capped marine biodegradable polymeric compound AP4' was obtained.

[0263] [Example 3-5] Preparation of Marine Biodegradable Polymeric Compound AP5'

[0264] 20 g of adipic acid, 16.12 g of hexamethylenediamine, 12 g of ion-exchanged water, and 13.42 g of marine biodegradable linker A4 were added to an autoclave with an internal volume of 1 L. After sufficient nitrogen replacement, the temperature was raised to 265 °C while stirring. While maintaining the closed state, stirring was further carried out at 265 °C for 1 hour, and then the pressure was released to atmospheric pressure. 0.9 g of myristoyl chloride was added as a capping agent, and stirring was carried out at 270 °C for 2 hours. Then, the content was taken out onto a stainless-steel tray with a Teflon (registered trademark) sheet, and the end-capped marine biodegradable polymeric compound AP5' was obtained.

[0265] [Example 3-6] Preparation of Marine Biodegradable Polymeric Compound AP6'

[0266] 20 g of diphenylmethane diisocyanate, 9.14 g of hexamethylenediamine, and 4.84 g of marine biodegradable linker A6 were charged into a 100 mL flask. Under a nitrogen stream, the temperature of the mantle heater was set to 90°C, and using a stirrer, heating and mixing were carried out for 20 minutes. Then, 0.1 g of lauroyl chloride was added as a capping agent, and further heating and mixing were carried out for 40 minutes. After that, the reaction product in the flask was taken out onto a stainless-steel tray with a Teflon (registered trademark) sheet and allowed to cool naturally, thereby obtaining a terminally blocked marine biodegradable polymer compound AP6'.

[0267] [Example 3-7] Preparation of Marine Biodegradable Polymer Compound AP7'

[0268] Instead of using marine biodegradable polymer compound AP1, 20 g of marine biodegradable polymer compound AP7 was used, the melting temperature was set to 210°C, and instead of phenyl isocyanate, 1.0 g of octadecyl isocyanate was used as a capping agent. Otherwise, the terminally blocked marine biodegradable polymer compound AP7' was obtained in the same manner as in Example 3-1.

[0269] [Example 3-8] Preparation of Marine Biodegradable Polymer Compound AP8'

[0270] Instead of using marine biodegradable polymer compound AP1, 20 g of marine biodegradable polymer compound AP8 was used, and instead of phenyl isocyanate, 0.9 g of octadecyl isocyanate was used as a capping agent. Otherwise, the terminally blocked marine biodegradable polymer compound AP8' was obtained in the same manner as in Example 3-1.

[0271] [Example 3-9] Preparation of Marine Biodegradable Polymer Compound AP9'

[0272] 20 g of adipic acid, 15.82 g of hexamethylenediamine, 12 g of ion-exchanged water, and 4.36 g of marine biodegradable linker A9 were added to an autoclave with an internal volume of 1 L. After sufficient nitrogen replacement, the temperature was raised to 265°C with stirring. Maintaining the closed state, stirring was continued at 265°C for 1 hour, and then the pressure was released to atmospheric pressure. 0.8 g of lauroyl chloride was added as a capping agent, and stirring was carried out at 270°C for 2 hours. Then, the content was taken out onto a stainless-steel tray with a Teflon (registered trademark) sheet, thereby obtaining a terminally blocked marine biodegradable polymer compound AP9'.

[0273] [Example 3-10] Preparation of Marine Biodegradable Polymer Compound AP10'

[0274] Instead of using the marine biodegradable polymer compound AP1, use 1020 g of the marine biodegradable polymer compound AP10 as a capping agent, and instead of phenyl isocyanate, use 0.9 g of dodecyl isocyanate. Otherwise, obtain the end-capped marine biodegradable polymer compound AP10' in the same manner as in Example 3-1.

[0275] [Example 3-11] Preparation of Marine Biodegradable Polymer Compound AP11'

[0276] In a 100 mL flask, charge 20 g of succinic acid, 15.24 g of 1,4-butanediol, and 6.5 g of the marine biodegradable linker A1. Under a nitrogen stream, set the temperature of the mantle heater to 230 °C, and using a stirrer, carry out heating and mixing for 1 hour. Then, add 0.2 g of octadecyl isocyanate as a capping agent, and further carry out heating and mixing for 5 hours. After that, take out the reaction product in the flask onto a stainless steel tray with a Teflon (registered trademark) sheet and allow it to cool naturally, thereby obtaining the end-capped marine biodegradable polymer compound AP11'.

[0277] [Example 3-12] Preparation of Marine Biodegradable Polymer Compound AP12'

[0278] In a 100 mL flask, charge 20 g of adipic acid, 2.68 g of 1,2,3-propanetricarboxylic acid, 13.68 g of 1,4-butanediol, and 6.12 g of the marine biodegradable linker A1. Under a nitrogen stream, set the temperature of the mantle heater to 230 °C, and using a stirrer, carry out heating and mixing for 1 hour. Then, add 0.1 g of octadecyl isocyanate as a capping agent, and further carry out heating and mixing for 5 hours. After that, take out the reaction product in the flask onto a stainless steel tray with a Teflon (registered trademark) sheet and allow it to cool naturally, thereby obtaining the end-capped marine biodegradable polymer compound AP12'.

[0279] [Comparative Example 3-1] Preparation of Polymer Compound BP1'

[0280] Instead of using the marine biodegradable polymer compound AP1, use 20 g of the polymer compound BP1. Otherwise, obtain the end-capped polymer compound BP1' in the same manner as in Example 3-1.

[0281] [Comparative Example 3-2] Preparation of Polymer Compound BP2'

[0282] 20 g of adipic acid, 13.1 g of hexamethylenediamine, 12 g of ion-exchanged water and 21.88 g of marine biodegradable linker B were added to an autoclave with an internal volume of 1 L. After sufficient nitrogen replacement, the temperature was raised to 265 °C with stirring. While maintaining the closed state, after stirring at 265 °C for 1 hour, the pressure was released to atmospheric pressure. As a capping agent, 0.8 g of myristoyl chloride was added and stirred at 270 °C for 2 hours. Then, the content was taken out onto a stainless-steel tray with a Teflon (registered trademark) sheet, and thus the end-capped polymer compound BP2' was obtained.

[0283] [Comparative Example 3-3] Preparation of Polymer Compound BP3'

[0284] Instead of using the marine biodegradable polymer compound AP1, 20 g of polymer compound BP3 was used, and instead of phenyl isocyanate, 1.0 g of octadecyl isocyanate was used as a capping agent. Otherwise, the end-capped polymer compound BP3' was obtained in the same manner as in Example 3-1.

[0285] [Comparative Example 3-4] Preparation of Polymer Compound BP4'

[0286] 20 g of adipic acid, 16.24 g of hexamethylenediamine and 8 g of ion-exchanged water were added to an autoclave with an internal volume of 1 L and placed in the autoclave. After sufficient nitrogen replacement, the temperature was raised to 265 °C with stirring. While maintaining the closed state, after stirring at 265 °C for 1 hour, the pressure was released to atmospheric pressure. As a capping agent, 0.9 g of lauroyl chloride was added and stirred at 270 °C for 2 hours. Then, the content was taken out onto a stainless-steel tray with a Teflon (registered trademark) sheet, and thus the end-capped polymer compound BP4' was obtained.

[0287] [Comparative Example 3-5] Preparation of Polymer Compound BP5'

[0288] 6.68 g of hexamethylene diisocyanate and 20 g of P-510 (manufactured by Kuraray Co., Ltd.) were charged into a 100 mL flask. Under a nitrogen stream, the temperature of the mantle heater was set to 90 °C, and using a stirrer, heating and mixing were carried out for 20 minutes. Then, as a capping agent, 0.9 g of octadecyl isocyanate was added, and after further heating and mixing for 40 minutes, the reaction product in the flask was taken out onto a stainless-steel tray with a Teflon (registered trademark) sheet and allowed to cool naturally, and thus the end-capped polymer compound BP5' was obtained.

[0289] [Comparative Example 3-6] Preparation of Polymer Compound BP6'

[0290] Instead of using the marine biodegradable polymer compound AP1, the polymer compound BP620g was used, and instead of phenyl isocyanate, 0.8 g of dodecyl isocyanate was used as the capping agent. Otherwise, the same method as in Example 3-1 was adopted to obtain the end-capped polymer compound BP6'.

[0291] [4] Measurement of basic physical properties

[0292] [Examples 4-1 to 4-24, Comparative Examples 4-1 to 4-12]

[0293] For the marine biodegradable polymer compounds AP1 to AP12, AP1' to AP12', the polymer compounds BP1 to BP6 and BP1' to BP6', the melting temperature, contact angle and tensile stress were measured by the following methods. The results are shown in Tables 2 and 3.

[0294] [Measurement of melting temperature]

[0295] It was measured using a differential scanning calorimeter (DSC6200 manufactured by Seiko Instruments Inc.). Specifically, 10 mg of the measurement sample was accurately weighed, and the accurately weighed measurement sample was placed in an aluminum dish. As a reference, an empty aluminum dish was used, and the temperature was raised at a rate of 10 °C / min in the temperature range of 20 to 300 °C at normal temperature and humidity. From the obtained reverse heat flow curve, the glass transition temperature (Tg) was calculated. At this time, the midpoint of the straight line connecting the intersection points of the respective tangents of the baseline and the curve where heat absorption occurs was obtained and used as Tg. In addition, as the melting temperature, the endothermic (melting) peak point of the obtained curve was calculated.

[0296] [Measurement of contact angle]

[0297] Each marine biodegradable polymer compound and polymer compound were melted at the melting temperature, compression molded to produce a film with a thickness of 150 μm. According to JIS R 3257, water droplets were dropped on the produced film, and the contact angle after 30 seconds was measured using a contact angle meter (Drop Master 300 manufactured by Kyowa Interface Science Co., Ltd.).

[0298] [Measurement of tensile stress]

[0299] According to JIS K 7139-A22, dumbbells were made from various films, and the tensile stress (yield point) was measured using a universal testing machine (MCT-2150 manufactured by A&D Co., Ltd.). Each sample was measured 5 times, and the average value was used as the tensile stress.

[0300] [Table 2]

[0301]

[0302] [Table 3]

[0303]

[0304] [5] Conduct a weight reduction test using seawater

[0305] [Examples 5-1 to 5-24, Comparative Examples 5-1 to 5-12]

[0306] Using marine biodegradable polymer compounds AP1 to AP12, AP1' to AP12', polymer compounds BP1 to BP6 and BP1' to BP6', press molding was carried out at the melting temperature respectively to produce films with a thickness of 200 μm.

[0307] The obtained films were processed into 20 mm square products, clamped on a stainless steel mesh, and immersed in seawater (collected from Tokyo Bay [Chiba Prefecture: Chiba Port]) placed in a 15 L water tank, and the weight reduction process after 30 days, 60 days, and 90 days of immersion was observed.

[0308] The results are shown in Tables 4 and 5.

[0309] [Table 4]

[0310]

[0311] [Table 5]

[0312]

[0313] From the results shown in Tables 4 and 5, it is considered that while the breakdown caused by seawater occurs, the presence of microorganisms in seawater promotes biodegradability.

[0314] [6] Preparation of marine biodegradable resin composition and confirmation test 1 in seawater (weight reduction)

[0315] [Examples 6-1 to 6-12, Comparative Examples 6-1 to 6-7]

[0316] For PBSA (FD-92 manufactured by Mitsubishi Chemical Corporation) as a biodegradable resin, it was pulverized using a pulverizer (Wonder Blender WB-1 manufactured by Osaka Chemical Co., Ltd.), and the marine biodegradable polymer compounds AP1 to AP12 and polymer compounds BP1 to BP6 classified using a stainless steel sieve (mesh size 26 μm) were kneaded at 140 °C respectively so that the concentration became 20% by mass, and press molding was carried out at 150 °C to produce films with a thickness of 200 μm (Examples 6-1 to 6-12, Comparative Examples 6-1 to 6-6). In addition, PBSA itself (without particle groups) was press molded at 150 °C to produce a film with a thickness of 150 μm (Comparative Example 6-7).

[0317] The measurement results of the contact angle of the produced film are shown in Table 6. It should be noted that the contact angle was measured by the method described in "[4] Measurement of Basic Physical Properties".

[0318] In addition, the products obtained by processing the produced film into 10 mm squares were respectively placed in 200 mL of ion-exchanged water and 200 mL of seawater (collected from Tokyo Bay [Chiba Prefecture: Chiba Port]), and left standing at 25 °C for 7 days and 30 days. Then, the film was taken out, and the surface and appearance of the film were observed using a scanning electron microscope. The results are shown in Table 6.

[0319] [Table 6]

[0320]

[0321] From the results shown in Table 6, it is considered that while the collapse was caused by seawater, the biodegradability was promoted due to the presence of microorganisms in seawater.

[0322] [7] Preparation of Marine Biodegradable Resin Composition and Confirmation Test in Seawater 2 (Weight Loss)

[0323] [Examples 7-1 to 7-12, Comparative Examples 7-1 to 7-7]

[0324] For the starch-based resin (Mater-Bi EF05B, manufactured by Novamont) as a biodegradable resin, it was pulverized using a pulverizer (Wonder Blender WB-1 manufactured by Osaka Chemical Co., Ltd.). The marine biodegradable polymer compounds AP1' to AP12' and polymer compounds BP1' to BP6' classified using a stainless steel sieve (mesh size 26 μm) were respectively kneaded at 140 °C so that the concentration became 20% by mass, and compression molding was carried out at 150 °C to produce a film with a thickness of 200 μm (Examples 7-1 to 7-12, Comparative Examples 7-1 to 7-6). In addition, the starch-based resin itself (without particle groups) was compression molded at 150 °C to produce a film with a thickness of 150 μm (Comparative Example 7-7).

[0325] The measurement results of the contact angle of the produced film are shown in Table 7. It should be noted that the contact angle was measured by the method described in "[4] Measurement of Basic Physical Properties".

[0326] In addition, the products obtained by processing the produced film into 10 mm squares were respectively placed in 200 mL of ion-exchanged water and 200 mL of seawater (collected from Tokyo Bay [Chiba Prefecture: Chiba Port]), and left standing at 25 °C for 7 days and 30 days. Then, the film was taken out, and the surface and appearance of the film were observed using a scanning electron microscope. The results are shown in Table 7.

[0327] [Table 7]

[0328]

[0329] From the results shown in Table 7, it is considered that while the seawater-induced breakdown occurred, the presence of microorganisms in the seawater promoted biodegradability.

Claims

1. A marine biodegradable polymer compound, which is a marine biodegradable polymer compound containing the following structural units as essential units: Structural unit A, which is derived from a marine biodegradable linker (A), the marine biodegradable linker containing two or more organic anions with a molecular weight of 100 to 10,000, having a structure in the main chain where the organic anions are bonded through ionic bonds generated by divalent or higher metal cations, and containing two or more reactive groups X in the molecule; and Structural unit B1, which is derived from a compound (B1), the compound having two or more reactive groups Y in the molecule that react with the reactive group X; or structural unit B2, which is derived from a cyclic compound (B2), the cyclic compound being a cyclic compound capable of ring-opening polymerization, and by ring-opening, generating reactive groups Y in the molecule that react with the reactive group X, Among them, In the case of containing structural unit B1, it further contains structural unit C, which is derived from a compound (C) other than the marine biodegradable linker, the compound other than the marine biodegradable linker containing two or more reactive groups X in the molecule.

2. The marine biodegradable polymer compound according to claim 1, wherein The organic anion is selected from carboxylate anions, i.e., -COO - , sulfonate anions, i.e., -SO3 - , sulfate anions, i.e., -O-SO3 - , and phosphate anions, i.e., -P(=O)(OH)-O - and is at least one of them.

3. The marine biodegradable polymer compound according to claim 1, wherein The organic anion has a repeating unit containing at least one bond selected from an ether bond, an ester bond, an amide bond, and a carbonate bond.

4. The marine biodegradable polymer compound according to claim 1, wherein, The divalent or higher metal cation is calcium ion, beryllium ion, magnesium ion, strontium ion, barium ion, zinc ion, aluminum ion, iron ion, copper ion, platinum ion, gold ion, titanium ion, nickel ion, cobalt ion, manganese ion, zirconium ion, ruthenium ion, rhodium ion, palladium ion, scandium ion, gallium ion, indium ion, or radium ion.

5. The marine biodegradable polymer compound according to claim 1, wherein, The equivalent average of metal ions of divalent or higher in the molecule is 1 to 100 eq / 10 5 g.

6. The marine biodegradable polymer compound according to claim 1, wherein The melting temperature of the marine biodegradable linker (A) is 180 °C or lower.

7. The marine biodegradable polymer compound according to claim 1, wherein, The average value of the number of metal cations contained in one molecule of the marine biodegradable linker (A) is greater than 1.

8. The marine biodegradable polymer compound according to claim 1, wherein The relative degradation degree of the cellulose phase of the marine biodegradable linker (A) is 40% or more.

9. The marine biodegradable polymer compound according to claim 1, wherein, The reactive group X and the reactive group Y are each independently a hydroxyl group, an amino group, an isocyanate group, or a carboxyl group.

10. The marine biodegradable polymer compound according to claim 1, wherein The content ratio of structural unit A to structural unit C, that is, A:C expressed as a molar ratio, is 0.1:99.9 to 90:

10.

11. The marine biodegradable polymer compound according to claim 1, which is a polyester, a polyurethane, a polyamide, or a polyurea.

12. The marine biodegradable polymer compound according to claim 1, wherein, Any one or more of the marine biodegradable linker (A), the compound (B1), and the compound (C) is trifunctional or higher.

13. The marine biodegradable polymer compound according to claim 1, wherein, The terminal of the marine biodegradable polymer compound is blocked.

14. An additive, which is composed of the marine biodegradable polymer compound according to any one of claims 1 to 13.

15. A marine biodegradable resin composition, which contains the marine biodegradable polymer compound according to any one of claims 1 to 13.

16. The marine biodegradable resin composition according to claim 15, which further contains a biodegradable resin.

17. The marine biodegradable resin composition according to claim 16, wherein, The content of the marine biodegradable polymer compound is 1 to 99% by mass, and the content of the biodegradable resin is 1 to 99% by mass.

18. A molded article obtained from the marine biodegradable resin composition according to claim 15.

19. A method for manufacturing a marine biodegradable polymer compound, wherein, Polymerize a marine biodegradable linker (A), a compound (B1), and a compound (C) other than the marine biodegradable linker. The marine biodegradable linker (A) contains two or more organic anions with a molecular weight of 100 to 10,000, has a structure in the main chain where the organic anion is bonded by an ionic bond generated by a divalent or higher metal cation, and contains two or more reactive groups X in the molecule. The compound (B1) has two or more reactive groups Y in the molecule that react with the reactive group X. The compound (C) other than the marine biodegradable linker contains two or more reactive groups X in the molecule. Or polymerize the marine biodegradable linker (A) and a cyclic compound (B2). The marine biodegradable linker (A) contains two or more organic anions with a molecular weight of 100 to 10,000, has a structure in the main chain where the organic anion is bonded by an ionic bond generated by a divalent or higher metal cation, and contains two or more reactive groups X in the molecule. The cyclic compound (B2) is a cyclic compound capable of ring-opening polymerization, and by ring-opening, a reactive group Y that reacts with the reactive group X is generated in the molecule.

20. The method for producing a marine biodegradable polymer compound according to claim 19, wherein, The polymerization is a polycondensation.

21. The method for manufacturing a marine biodegradable polymer compound according to claim 19, wherein, It includes a step of mixing the marine biodegradable linker (A), the compound (B1), and the compound (C) or the marine biodegradable linker (A) and the compound (B2) before polymerization.

22. The method for producing a marine biodegradable polymer compound according to claim 19, wherein, The usage ratio of the marine biodegradable linker (A) to the compound (C), expressed as the ratio of (A):(C) in terms of the amount of substance, is 0.1:99.9 to 90:

10.

23. The method for producing a marine biodegradable polymer compound according to any one of claims 19 to 22, wherein, The melting temperature of the marine biodegradable linker (A) is 180°C or lower, and the marine biodegradable linker (A), the compound (B1), and the compound (C) or the marine biodegradable linker (A) and the compound (B2) are melted and polymerized.

24. A compound that contains two or more organic anions with a molecular weight of 100 to 10,000, has a structure in the main chain where the organic anion is bonded by an ionic bond generated by a divalent or higher metal cation, and contains two or more amino groups, carboxyl groups, thiol groups, vinyl groups, or isocyanate groups in the molecule.

Images