Crosslinked marine biodegradable polymer compound comprising different anionic polymer compounds, and method for producing same

Abstract

The main chain is linear or branched, and has a total of two or more monovalent anionic groups at the ends of the main chain. An anionic polymer compound (A) that does not have an ionic group in a side chain and an anionic polymer compound (B) that has a monovalent anionic group in a side chain of two or more repeating units are bonded to each other via a bivalent or higher metal cation.

Description

Technical Field

[0001] This invention relates to cross-linked marine biodegradable polymer compounds comprising different anionic polymer compounds and methods for their manufacture. Background Technology

[0002] In recent years, environmental pollution (marine pollution) and adverse effects on ecosystems caused by microplastics have become a problem, prompting various initiatives to mitigate the environmental burden. Among these, the development and widespread adoption of biodegradable resins have garnered significant attention.

[0003] On the other hand, while general biodegradable resins exhibit high biodegradability in environments with abundant decomposing microorganisms, such as soil and mud, they are difficult to decompose in marine environments with extremely low microbial concentrations (Non-Patent Literature 1). Furthermore, for resins such as polycaprolactone (PCL) and polyhydroxyalkanoic acid (PHA) that have been reported to be biodegradable in the ocean, it is known that their decomposition rate varies greatly depending on the type of seawater. Reports indicate that various factors, such as the presence or absence of decomposing bacteria, bacterial count, salinity, pH, water temperature, dissolved oxygen concentration, and dissolved organic carbon content, influence this rate (Non-Patent Literature 2).

[0004] Furthermore, starch-based resins, as biodegradable resins, have also been put into practical use. Although they are commercially available, single starch raw materials have very poor physical properties. Therefore, they are almost always mixed with polyester resins such as polybutylene adipate / terephthalate (PBAT) and polylactic acid (PLA), which are difficult to biodegrade in the ocean. As a result, even starch-based resins tend to have significantly reduced biodegradability in the ocean.

[0005] Under such circumstances, there is a need to develop materials that can reliably decompose in any type of seawater while maintaining their physical properties, act as decomposition promoters for resins that are difficult to biodegrade in seawater, and reduce environmental impact.

[0006] Existing technical documents

[0007] Non-patent literature

[0008] Non-patent literature 1: Hideshige Takada, "The Current Status, International Trends and Countermeasures of Microplastic Pollution", Journal of the Waste Recycling Society, Vol. 29, No. 4, pp. 261-269, 2018

[0009] Non-patent literature 2: Rong Jingzhang et al., "Decomposition of Biodegradable Plastics in Seawater", Fisheries Science, Vol. 40, No. 2, pp. 143-149, 2003. Summary of the Invention

[0010] The problem that the invention aims to solve

[0011] This invention was made in view of the above-mentioned actual situation, and its purpose is to provide heat. Polymer compounds with excellent mechanical properties that induce biodegradability in the ocean and marine biodegradable resin compositions using the same.

[0012] Methods for solving problems

[0013] To solve the aforementioned problems, the inventors conducted repeated and in-depth research, and as a result, discovered that: An anionic polymer compound A, with a straight or branched main chain, having a total of two or more monovalent anionic groups at the end of the main chain, and no ionic groups on the side chains; and an anionic polymer compound B, with monovalent anionic groups on the side chains of two or more repeating units, are polymer compounds bonded by divalent or higher metal cations. It exhibits excellent mechanical properties and high biodegradability in the marine environment.

[0014] It was further discovered that by combining this material with resin, especially biodegradable resin, the material undergoes a first decomposition in seawater, resulting in (1) the formation of pores in the resin material, an increase in the specific surface area of ​​the resin, and the promotion of the proliferation of microorganisms responsible for decomposition; (2) the promotion of secondary decomposition, i.e., biodegradation by microorganisms, through the first decomposition. As a result, the biodegradation of the resin material in the ocean can be promoted, thus completing the present invention.

[0015] That is, the present invention provides the following marine biodegradable polymer compounds and methods for manufacturing the same.

[0016] 1. Marine biodegradable polymer compounds, wherein an anionic polymer compound A, whose main chain is linear or branched and has a total of two or more monovalent anionic groups at the end of the main chain and no ionic groups in the side chains, and an anionic polymer compound B, whose side chains of two or more repeating units have monovalent anionic groups, are bonded by divalent or higher metal cations.

[0017] 2. The polymer compound according to 1, wherein the mass ratio of anionic polymer compound A to anionic polymer compound B is 99:1 to 10:90.

[0018] 3. The polymer compound according to 1 or 2, wherein the main chain of the anionic polymer compound A is linear.

[0019] 4. The polymer compound according to any one of 1 to 3, wherein the anionic polymer compound B comprises repeating units that do not have ionic groups.

[0020] 5. The polymer compound according to any one of 1 to 4, wherein the anionic polymer compound B has aliphatic unsaturated carbon-carbon bonds in the main chain.

[0021] 6. The polymer compound according to any one of 1 to 5, wherein the monovalent anionic group of the anionic polymer compound A is a carboxylate anion.

[0022] 7. The polymer compound according to any one of 1 to 6, wherein the monovalent anionic group of the anionic polymer compound B is a carboxylate anion or a sulfonate anion.

[0023] 8. The polymer compound according to any one of 1 to 7, wherein the monovalent anionic group of the anionic polymer compound B is bonded to the ring.

[0024] 9. The polymer compound according to any one of 1 to 8, wherein the number average molecular weight of the anionic polymer compound A is 500 to 10,000, and the number average molecular weight of the anionic polymer compound B is 500 to 10,000.

[0025] 10. The polymer compound according to any one of 1 to 9, wherein the repeating unit of the anionic polymer compound A is bonded by at least one bond selected from ester bonds, amide bonds, ether bonds and urethane bonds, and the repeating unit of the anionic polymer compound B is bonded by at least one bond selected from ester bonds, amide bonds, ether bonds and urethane bonds.

[0026] 11. The polymer compound according to any one of 1 to 10, wherein the value obtained by dividing the number average molecular weight of the anionic polymer compound B by the average number of monovalent anionic groups in one molecule is 100 to 5000.

[0027] 12. The polymer compound according to any one of 1 to 11, wherein the content of the divalent or higher metal cation is 1 to 300 eq / 10. 5 g.

[0028] 13. The polymer compound according to any one of 1 to 12, wherein the divalent or higher metal cation is a calcium ion, a magnesium ion, or an aluminum ion.

[0029] 14. A marine biodegradation promoter comprising any one of the marine biodegradable polymer compounds described in any one of 1 to 13.

[0030] 15. A marine biodegradable resin composition comprising the marine biodegradation promoter and resin described in 14.

[0031] 16. The marine biodegradable resin composition according to 15, wherein the resin is a biodegradable resin.

[0032] 17. The marine biodegradable resin composition according to 15 or 16, wherein the content of the marine biodegradation promoter is 1 to 50% by mass, and the content of the resin is 50 to 99% by mass.

[0033] 18. A molded article obtained from any one of the marine biodegradable resin compositions described in any one of 15 to 17.

[0034] 19. A method for manufacturing a marine biodegradable polymer compound, comprising the following steps: crosslinking an anionic polymer compound A, having a main chain that is straight or branched, having a total of two or more monovalent anionic groups at the end of the main chain, and having no ionic groups on the side chains, and an anionic polymer compound B, having monovalent anionic groups on the side chains of at least two repeating units, with divalent or higher metal cations.

[0035] The effects of the invention

[0036] The marine biodegradable polymer compound of the present invention is a crosslinked polymer compound containing an anionic polymer compound having a monovalent anionic group at the end and an anionic polymer compound having a monovalent anionic group on the side chain of the repeating unit, thereby possessing both thermal and chemical properties. Mechanical properties and marine biodegradability. Furthermore, the marine biodegradable polymer compound, upon contact with seawater, slowly dissolves in seawater or exhibits hydrophilicity, thus promoting the biodegradation of resin compositions and molded articles containing it in the ocean, and can be used in marine pollution countermeasures. The marine biodegradable polymer compound possesses marine biodegradability, thus promoting the biodegradation of compositions and molded articles containing it in the ocean, and can be used in marine pollution countermeasures. By using a marine biodegradation promoter containing the marine biodegradable polymer compound of the present invention, environmentally friendly compositions and molded articles can be obtained. Detailed Implementation

[0037] [Marine biodegradable polymer compounds]

[0038] The marine biodegradable polymer compounds of the present invention are anionic polymer compounds A, whose main chain is linear or branched, have a total of two or more monovalent anionic groups at the end of the main chain, and have no ionic groups on the side chains, and anionic polymer compounds B, whose side chains of two or more repeating units have monovalent anionic groups, are bonded together by divalent or higher metal cations. It should be noted that in the present invention, the term "main chain" refers to the molecular chain that forms the structural backbone of the polymer. It should also be noted that the main chain may have a ring structure. Furthermore, the term "side chain" refers to a substituent bonded to the main chain.

[0039] In the marine biodegradable polymer compound of the present invention, the mass ratio of anionic polymer compound A to anionic polymer compound B is preferably A:B = 99:1 to 10:90, more preferably 95:15 to 15:85, and even more preferably 90:10 to 20:80. If the mass ratio of anionic polymer compound A to anionic polymer compound B is within the aforementioned range, it can combine the softness from anionic polymer compound A with the thermophysical and mechanical properties from anionic polymer compound B, and also exhibits good biodegradability.

[0040] Anionic polymer compound A can be linear or branched. The thermal properties of the cross-linked polymer compound... From the perspective of mechanical properties, it is preferred that the anionic polymer compound A is linear or branched and has a total of 2 to 10 monovalent anionic groups at the end of the main chain, more preferably has a total of 2 to 4 monovalent anionic groups at the end of the main chain, and even more preferably has a linear anionic polymer compound A and has a total of 2 monovalent anionic groups at the end of the main chain.

[0041] Anionic polymer compound B may contain repeating units without ionic groups, provided that two or more repeating units have monovalent anionic groups. In this case, the arrangement of the monomers in anionic polymer compound B is not particularly limited; random copolymers, alternating copolymers, block copolymers, etc., are all acceptable. Furthermore, anionic polymer compound B can be linear or branched, depending on the thermal properties of the crosslinked polymer compound. From the perspective of mechanical properties, a linear chain is preferred.

[0042] Furthermore, the anionic polymer compound B may have aliphatic unsaturated carbon-carbon bonds in its main chain. In this case, as a range that can balance strength and biodegradability, the number of aliphatic unsaturated carbon-carbon bonds is preferably 0.1 to 50 per molecule on average, more preferably 0.5 to 25, and even more preferably 1 to 10.

[0043] From a physical and safety perspective, the monovalent anionic groups contained in anionic polymer compound A are preferably carboxylate anions, sulfonate anions, or phosphate anions, more preferably carboxylate anions or sulfonate anions, and even more preferably carboxylate anions. The monovalent anionic groups contained in anionic polymer compound A may be the same or different from each other.

[0044] From a physical and safety perspective, the monovalent anionic groups contained in anionic polymer compound B are preferably carboxylate anions, sulfonate anions, or phosphate anions, more preferably carboxylate anions or sulfonate anions, and even more preferably sulfonate anions. The monovalent anionic groups contained in anionic polymer compound B may be the same or different from each other.

[0045] The monovalent anionic groups contained in anionic polymer compound B can be directly bonded to the main chain or bonded through linker groups. If thermal... The mechanical properties are preferably directly bonded to the main chain, or bonded by a linker group having 1 to 25 atoms, more preferably directly bonded to the main chain. When the monovalent anionic group is directly bonded to the main chain, it is further preferred that the main chain includes a ring, and the monovalent anionic group is bonded to that ring. The ring can be an alicyclic ring or an aromatic ring, preferably an aromatic ring. Furthermore, the ring can contain only carbon atoms or be a heterocyclic ring containing other atoms, preferably containing only carbon atoms. When the monovalent anionic group is bonded by a linker group, the structure of the linker group can be linear, branched, or cyclic, preferably linear or branched, more preferably linear. Furthermore, there is no particular limitation on the atoms constituting the linker group, but carbon, oxygen, nitrogen, boron, sulfur, phosphorus, and silicon are preferred, more preferably carbon, oxygen, nitrogen, and sulfur.

[0046] There is no particular limitation on the molecular weight of anionic polymer compound A, based on thermal properties. From the perspective of mechanical properties and biodegradability, a number-average molecular weight of 200 to 100,000 is preferred, a number-average molecular weight of 300 to 50,000 is more preferred, and a number-average molecular weight of 500 to 10,000 is even more preferred.

[0047] There is no particular limitation on the molecular weight of anionic polymer compound B, based on thermal properties. From the perspective of mechanical properties and biodegradability, a number-average molecular weight of 200 to 100,000 is preferred, a number-average molecular weight of 300 to 50,000 is more preferred, and a number-average molecular weight of 500 to 10,000 is even more preferred.

[0048] In addition, from the thermal properties of the cross-linked polymer compound From a mechanical property perspective, it is preferable that the number-average molecular weight of the anionic polymer compound B divided by the average number of monovalent anionic groups in one molecule is 100 to 5000, more preferably 200 to 3000, and even more preferably 300 to 1000. Furthermore, a repeating unit may contain two or more monovalent anionic groups; repeating units having monovalent anionic groups and repeating units not having monovalent anionic groups may each contain one type, or may contain two or more types.

[0049] Based on the combination of anionic polymer compound A and anionic polymer compound B, the heat can be further improved. Mechanical properties. Specifically, the sum of the weighted average of the number-average molecular weights of component A (containing the marine biodegradable polymer compound) and component B (containing the anionic polymer compound) is preferably 500 to 50,000, more preferably 1,000 to 30,000, even more preferably 1,500 to 10,000, and most preferably 2,000 to 8,000.

[0050] Furthermore, at this time, as a combination of anionic polymer compound A and anionic polymer compound B, it is preferable to combine anionic polymer compound A with a number average molecular weight of 200 to 20,000 with anionic polymer compound B with a number average molecular weight of 300 to 30,000; more preferably, anionic polymer compound A with a number average molecular weight of 500 to 10,000 with anionic polymer compound B with a number average molecular weight of 500 to 20,000; and even more preferably, anionic polymer compound A with a number average molecular weight of 500 to 3,000 with anionic polymer compound B with a number average molecular weight of 1,500 to 5,000.

[0051] Anionic polymer compound A from heat From the viewpoint of mechanical properties and biodegradability, it is preferable to use at least one bond selected from ester bonds, amide bonds, ether bonds, and carbamate bonds to bond the repeating units; more preferably, ester bonds or amide bonds are used; and even more preferably, ester bonds are used. Additionally, the repeating units are heat-resistant... From the viewpoint of mechanical properties and biodegradability, aliphatic, aromatic, or combinations thereof with 1 to 20 carbon atoms are preferred, aliphatic, aromatic, or combinations thereof with 1 to 10 carbon atoms are more preferred, and aliphatic with 1 to 10 carbon atoms are even more preferred.

[0052] Anionic polymer compound B from heat From the viewpoint of mechanical properties and biodegradability, it is preferable to use at least one bond selected from ester bonds, amide bonds, ether bonds, and carbamate bonds to bond the repeating units; more preferably, ester bonds or amide bonds are used; and even more preferably, ester bonds are used. Additionally, the repeating units are heat-resistant... From the viewpoint of mechanical properties and biodegradability, aliphatic, aromatic, or combinations thereof with 1 to 20 carbon atoms are preferred, aliphatic, aromatic, or combinations thereof with 1 to 10 carbon atoms are more preferred, and combinations of aliphatic and aromatic with 1 to 10 carbon atoms are even more preferred.

[0053] For the anionic polymer compound A, it is preferable that its relative biodegradability of cellulose is 40% or more, more preferably 50% or more, further preferably 60% or more, and most preferably 80% or more. It should be noted that the relative biodegradability of cellulose in this invention refers to the maximum degradation rate relative to the maximum degradation rate of cellulose within 2 years after immersion in seawater. The relative biodegradability of cellulose can be determined using ASTM D6691, known marine biodegradation test methods, and BOD modified accordingly.

[0054] With regard to the anionic polymer compound B, it is preferable that its relative biodegradability of cellulose is 40% or more, more preferably 50% or more, further preferably 60% or more, and most preferably 80% or more.

[0055] Anionic polymer compound A preferably has a softening point or melting point. Anionic polymer compound A is preferably a solid or liquid at room temperature. Specifically, as a lower limit for the softening point or melting point, it is preferably -80°C or higher, -40°C or higher, 0°C or higher, 40°C or higher, and 80°C or higher; as an upper limit, it is preferably 180°C or lower, 150°C or lower, and 120°C or lower. Considering processability, it is preferable to have a softening point or melting point in the range of -80 to 180°C, more preferably -40 to 120°C.

[0056] The anionic polymer compound B preferably has a softening point or melting point. The anionic polymer compound B is preferably a solid or liquid at room temperature. Specifically, as a lower limit for the softening point or melting point, it is preferably above 0°C, above 25°C, above 40°C, above 80°C, and above 100°C, respectively; as an upper limit, it is preferably below 180°C, below 150°C, and below 120°C, respectively. Considering processability, it is preferable to have a softening point or melting point in the range of 0–180°C, more preferably 25–120°C.

[0057] The anionic polymer compound A is preferably dissolved in water or a solvent mixed with water, and more specifically, preferably dissolved in water or a solvent mixed with water at concentrations of 1%, 5%, 10%, 20%, 30%, and 50% or more by mass in sequence. Furthermore, the water or the solvent mixed with water can be a cooled product or a heated product.

[0058] The anionic polymer compound B is preferably dissolved in water or a solvent mixed with water, and more specifically, preferably dissolved in water or a solvent mixed with water at concentrations of 1%, 5%, 10%, 20%, 30%, and 50% or more by mass in sequence. Furthermore, the water or the solvent mixed with water can be a cooled product or a heated product.

[0059] Examples of solvents that can be mixed with water include lower alcohol solvents such as methanol, ethanol, 1-propanol, and 2-propanol, as well as amphiphilic solvents such as acetone, acetonitrile, tetrahydrofuran (THF), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and N-methylpyrrolidone (NMP). From the viewpoints of miscibility, solubility, and processability with water, ethanol, acetonitrile, THF, and NMP are preferred, and ethanol and acetonitrile are more preferred.

[0060] There are no particular limitations on the method for manufacturing anionic polymer compound A. For example, it can be manufactured by introducing the monovalent anionic group into a compound (hereinafter also referred to as polymer compound A) through a linker, in which the main chain is linear or branched, has a total of two or more active functional groups such as hydroxyl, amino, or thiol groups at the end of the main chain, and does not have ionic groups in the side chains.

[0061] As polymer compound A, commercially available products and synthetic products can be used. Examples of commercially available products include KURARAY POLYOL P-1010, P-2010, P-2020, P-2050, P-520, C-590, F-1010 (manufactured by Kuraray Co., Ltd.), Placusel 210B, 220N, 308 (manufactured by Daicel Co., Ltd.), polypropylene glycol, diol type 1000, polypropylene glycol, triol type 300 (manufactured by Fujifilm Wako Pure Chemicals Co., Ltd.), poly(propylene glycol) bis(2-aminopropyl ether) 400, poly(propylene glycol) bis(2-aminopropyl ether) 2000 (manufactured by Sigma-Aldrich Nippon Co., Ltd.), etc. In the synthesis of polymer compound A, for example, two or more suitable raw materials can be selected from di- or more carboxylic acids, di- or more alcohols, di- or more amines, di- or more isocyanates, etc., and obtained by polycondensation or addition polymerization. For example, polyester polyols can be obtained by polycondensation of di- or more carboxylic acids and di- or more alcohols, polyamide polyamines can be obtained by polycondensation of di- or more carboxylic acids and di- or more amines, and polyurethane polyols can be obtained by addition polymerization of di- or more isocyanates and di- or more alcohols. The synthesis is not limited to these combinations; three or more raw materials with different functional groups can be used, or two or more different raw materials having the same functional group can be used simultaneously. Furthermore, when using ternary or more raw materials, it is preferable that the total mass of the ternary or more raw materials is 0.01 to 50 mol%, more preferably 0.05 to 30 mol%, and most preferably 0.1 to 15 mol%. In this case, derivatives of the raw materials can be used instead of individual raw materials to facilitate the reaction. In addition, base catalysts such as diazabicycloundecene (DBU) and triethylamine, as well as metal catalysts such as dibutyltin dilaurate and tetraisopropoxytitanium, can be used in the reaction.

[0062] Examples of dicarboxylic acids or more include oxalic acid, malonic acid, fumaric acid, maleic acid, succinic acid, adipic acid, sebacic acid, 1,2,3-propanetricarboxylic acid, aconitic acid, malic acid, citric acid, phthalic acid, isophthalic acid, terephthalic acid, 1,3,5-benzenetricarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyl dicarboxylic acid, trimellitic acid, and pyromellitic acid.

[0063] Examples of alcohols comprising two or more groups include ethylene glycol, glycerol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2-buten-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, pentaerythritol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,3,5-cyclohexanetriol, 1,6-hexanediol, 2,5-hexanediol, and 3-methyl-1 5-Pentanediol, 1,7-Heptanediol, 1,4-Benzenediethanol, 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, Phloroglucinol, 1,2,4-Phosphorylbenzene, 4,4'-Dihydroxybiphenyl, 4,4'-Dihydroxydiphenylmethane, 4,4'-Dihydroxydiphenyl ether, polyethylene glycol, etc.

[0064] Examples of amines consisting of two or more atoms include ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-butanediamine, 1,5-diaminopentane, 1,6-diaminohexane (hexamethylenediamine), 1,7-diaminoheptane, 1,8-diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane, 3,3-diaminodipropylamine, tris(3-aminopropyl)amine, 3,3'-diaminobenzidine, 1,4-cyclohexanediamine, spermine, spermidine, triethylenetetramine, 1,4-phenylenediamine, 1,2-diphenylethylenediamine, and o-toluidine.

[0065] Examples of binary or higher isocyanates include hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI), isophorone diisocyanate (IPDI), cyclohexane-1,4-diisocyanate, methylene bis(4-cyclohexyl isocyanate), toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymeric MDI, xylene diisocyanate, and 1,4-phenyl diisocyanate.

[0066] Regarding anionic polymer compound B, commercially available products and synthetic products can be used. Examples of commercially available products include Z-221 (Mitsubishi Chemical Industry Co., Ltd.). In the synthesis of anionic polymer compound B, it can be obtained through the following reactions: polymerization of a monomer having a monovalent anionic group or a functional group that can be converted to anionic groups through appropriate treatment; and reaction of a polymer compound containing repeating units having reactive sites with a compound (hereinafter also referred to as compound b) that is reactive to the reactive sites and has a monovalent anionic group or a functional group that can be converted to a monovalent anionic group through appropriate treatment.

[0067] Specific examples of the monomers mentioned above include sodium 5-sulfoisophthalate, sodium 4-sulfoisophthalate, 4-sulfonnaphthalene-2,6-dicarboxylic acid, methyl trimellitic acid, pyromellitic dianhydride, 4,4'-biphthalic anhydride, methacrylic acid, methyl methacrylate, styrene sulfonic acid, etc.

[0068] Examples of polymerization reactions using the monomers include condensation and addition polymerization of the monomers with di- or more carboxylic acids, di- or more alcohols, di- or more amines, di- or more isocyanates, etc. Examples of di- or more carboxylic acids, di- or more alcohols, di- or more amines, and di- or more isocyanates include compounds identical to those described above. For example, condensation polymerization with sodium 5-sulfoisophthalate, terephthalic acid, and 1,4-butanediol, and addition polymerization with pyromellitic dianhydride and hexamethylenediamine are preferred. In these cases, derivatives of the reactants can be used instead of their respective raw materials to facilitate the reaction. Furthermore, base catalysts such as DBU and triethylamine, and metal catalysts such as dibutyltin dilaurate and tetraisopropoxytitanium can be used in the reactions.

[0069] Examples of unsaturated polymer compounds that include repeating units with reactive sites include unsaturated polyester compounds, unsaturated polyamide compounds, and unsaturated polyurethane compounds, which contain repeating units with aliphatic unsaturated carbon-carbon bonds. These unsaturated polymer compounds can be synthesized by using maleic acid, fumaric acid, citrate, succinic acid, 2-pentenic acid, methylene succinic acid, allyl malonic acid, isopropyl succinic acid, 2,4-hexadienoic acid, alkynyl dicarboxylic acid, and other unsaturated polycarboxylic acids; unsaturated polyols such as 2-buten-1,4-diol and 3-hexen-1,6-diol; unsaturated polyamines such as 2-buten-1,4-diamine and 3-hexen-1,6-diamine; and unsaturated polyisocyanates such as 2-buten-1,4-diisocyanate and 3-hexen-1,6-diisocyanate. Preferred examples include unsaturated polyesters obtained by polycondensation of maleic acid and 1,4-butanediol, and unsaturated polyamides obtained by polycondensation of sebacic acid, maleic acid, and hexamethylenediamine. In these cases, derivatives of the respective raw materials can be used instead to facilitate the reaction. Furthermore, base catalysts such as DBU and triethylamine, and metal catalysts such as dibutyltin dilaurate and tetraisopropoxytitanium can be used in the reaction. In addition to the unsaturated polymer compounds mentioned above, free radical initiators and radiation can be used to temporarily create polymer compounds with free radical sites in the system for polyolefin and polyether polymers.

[0070] As compounds in compound b that are reactive to aliphatic unsaturated carbon-carbon bonds, when the reaction with unsaturated bonds is a conjugated addition reaction, examples include thiocarboxylic acids such as 3-mercaptopropionic acid, amino acids such as 5-aminopentanoic acid and 6-aminohexanoic acid, aminosulfonic acids such as 2-aminoethanesulfonic acid, aminophosphoric acids such as ethanolamine phosphoric acid, malonic acid, organocopper acid complexes, and other nucleophilic organic acids and their derivatives. When the reaction with unsaturated bonds is a free radical reaction, examples include carboxylic acids and sulfonic acids with unsaturated bonds such as acrylic acid, 3-pentenoic acid, carboxystyrene, and styrenesulfonic acid. When the reaction with unsaturated bonds is a Diels-Alder reaction, examples include pyrrolic carboxylic acids such as 1-methyl-2-pyrrolic acid. When the reaction with unsaturated bonds is a photocycloaddition reaction, examples include carboxylic acids with unsaturated bonds such as acrylic acid and 3-pentenoic acid. Compounds that are reactive to free radical sites in compound b include carboxylic acids and sulfonic acids with unsaturated bonds, such as acrylic acid, 3-pentenoic acid, carboxystyrene, and styrenesulfonic acid.

[0071] There are no particular limitations on the reaction between the polymer compound containing the repeating unit with the reactive site and compound b. However, considering reactivity, selectivity, the physical properties of the products, and safety, 3-mercaptopropionic acid, 5-aminovaleric acid, 6-aminohexanoic acid, and malonic acid derivatives are preferred in conjugate addition reactions, with 3-mercaptopropionic acid being the most preferred. In the reaction, commonly used catalysts can be used as needed. For example, base catalysts such as DBU and TEA can be used in conjugate addition reactions; transition metal catalysts such as organorruthenium complexes and organotitanium complexes can be used in free radical reactions; Lewis acid catalysts such as ytterbium trifluoromethanesulfonate and scandium trifluoromethanesulfonate can be used in Diels-Alder reactions; and photosensitizers such as thiophene and benzophenone can be used in photocyclization addition reactions. In this case, derivatives of the reactants can be used instead of the reactants to facilitate the reaction.

[0072] [Marine biodegradable polymer compounds]

[0073] The marine biodegradable polymer compound of the present invention is formed by anionic polymer compound A and anionic polymer compound B bonded together by divalent or higher metal cations.

[0074] There is no particular limitation on the divalent or higher metal cations mentioned, and examples 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, and radium ions. Among these, calcium ions, beryllium ions, magnesium ions, strontium ions, barium ions, zinc ions, and aluminum ions are preferred, and calcium ions, magnesium ions, and aluminum ions are more preferred. Only one divalent or higher metal cation may be used, or multiple cations may be combined.

[0075] The marine biodegradable polymer compounds of the present invention may each contain only one type of anionic polymer compound A and anionic polymer compound B, or may contain multiple different types, and may also contain other anions besides these. Examples of other anions include polyvalent anions, fatty acid anions, amino acid anions, amino acid derivative anions, sulfonate anions, etc.

[0076] Examples of such polyvalent anions include 1,5-naphthalenedisulfonic acid, ethanedisulfonic acid, monoethyl phosphate, malic acid, aspartic acid, glutamic acid, succinic acid, adipic acid, sebacic acid, terephthalic acid, isophthalic acid, etc.

[0077] Examples of fatty acid anions include hexanoic acid, heptanoic acid, caprylic acid, octanoic acid, nonanoic acid, decanoic acid, undecenoic acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, palmitoleic acid, heptadecanic acid, stearic acid, isostearic acid, oleic acid, isoleic acid, ricinoleic acid, linoleic acid, linolenic acid, tung oil acid, hydroxystearic acid, arachidic acid, eicosatrienoic acid, arachidonic acid, eicosapentaenoic acid, docosanoic acid, docosahexaenoic acid, docosahexaenoic acid, nervonic acid, hexacosanoic acid, linaloic acid, triacontanic acid, coconut oil fatty acids, and palm oil fatty acids.

[0078] Examples of amino acid anions or amino acid derivative anions include: alanine, leucine, arginine, lysine, asparagine, methionine, aspartic acid, phenylalanine, cysteine, proline, glutamine, serine, glutamic acid, threonine, glycine, tryptophan, histidine, tyrosine, isoleucine, and other amino acid anions; sarcosine derivatives (capryloylsarcosine, lauroylsarcosine, myristoylsarcosine, palmitoylsarcosine, coconut fatty acid sarcosine, etc.); glutamic acid derivatives (capryloylglutamic acid, lauroylglutamic acid, myristoylglutamic acid, palmitoylglutamic acid, stearoylglutamic acid, coconut fatty acylglutamic acid, coconut acylglutamic acid, acylglutamic acid, dilauryloylglutamic acid, etc.); and glycine derivatives (lauroylglycine, myristoylglycine, palmitoylglycine, palmitoylmethylglycine, coconut fatty acyl...). Anions of amino acid derivatives with hydrocarbon groups, such as glycine, coconutoylglycine, alanine derivatives (lauroyl methyl alanine, myristoyl methyl alanine, coconutoyl alanine, coconut oil fatty acid methyl alanine, etc.), lysine derivatives (lauroyl lysine, myristoyl lysine, palmitoyl lysine, stearoyl lysine, oleyl lysine, acylated lysine, etc.), aspartic acid derivatives (lauroyl aspartic acid, myristoyl aspartic acid, palmitoyl aspartic acid, stearoyl aspartic acid, etc.), taurine derivatives (lauroyl taurine, lauroyl methyl taurine, myristoyl taurine, myristoyl methyl taurine, palmitoyl taurine, palmitoyl methyl taurine, stearoyl taurine, stearoyl methyl taurine, etc.), and proline derivatives (lauroyl proline, myristoyl proline, palmitoyl proline, etc.).

[0079] Examples of sulfonate anions include alkyl sulfonic acids (lauryl sulfonic acid, myristyl sulfonic acid, cetyl sulfonic acid, stearyl sulfonic acid, oleyl sulfonic acid, etc.), dodecylbenzene sulfonic acid, dialkyl succinate sulfonic acid, monoalkyl succinate sulfonic acid, naphthalene sulfonic acid, olefin sulfonic acid, alkyl hydroxyethanesulfonic acid (lauroyl hydroxyethanesulfonic acid, myristoyl hydroxyethanesulfonic acid, palmitoyl hydroxyethanesulfonic acid, stearyl hydroxyethanesulfonic acid, etc.), and dialkyl sulfosuccinic acid (dihexyl sulfosuccinic acid, dioctyl sulfosuccinic acid, didecyl sulfosuccinic acid, diisobutyl sulfosuccinic acid, etc.).

[0080] The metal ion equivalent (content of divalent or higher metal cations) in the marine biodegradable polymer compound is preferably 1–300 eq / 10 5 g, more preferably 10–200 eq / 10 considering biodegradability and mechanical properties in seawater. 5 g, further optimized to 20–100 eq / 10 5 g. If the metal ion equivalent is within the stated range, it exhibits good biodegradability without impairing mechanical properties, and is therefore preferred. Furthermore, the metal ion equivalent is a value determined using inductively coupled plasma mass analysis (ICP-MS).

[0081] Marine biodegradable polymer compounds can be formulated into amorphous or crystalline polymer compounds based on the mixing ratio of anionic polymer compound A and anionic polymer compound B. The marine biodegradable polymer compound is solid at room temperature. Specifically, the lower limit of its softening point is preferably above 0°C, above 40°C, and above 80°C; the upper limit is preferably below 250°C, below 200°C, below 180°C, and below 160°C. Preferably, it has a softening point in the range of 40–200°C, more preferably 60–180°C, and even more preferably 80–160°C.

[0082] The marine biodegradable polymer compound preferably has a relative biodegradability of cellulose of 40% or more, more preferably 50% or more, further preferably 60% or more, and most preferably 80% or more.

[0083] [Methods for manufacturing marine biodegradable polymer compounds]

[0084] Marine biodegradable polymer compounds can be manufactured using a method that includes the following steps: crosslinking anionic polymer compound A and anionic polymer compound B with a divalent or higher metal salt (hereinafter also referred to as a multivalent metal salt).

[0085] Examples of crosslinking treatment methods include: adding a powder or solution or dispersion of a polyvalent metal salt dropwise to a solution or dispersion containing anionic polymer compound A and anionic polymer compound B, thereby performing a bonding treatment while simultaneously causing precipitation or sedimentation; adding a powder or solution or dispersion of a polyvalent metal salt dropwise to a molten liquid containing anionic polymer compound A and anionic polymer compound B, thereby performing a bonding treatment; and adding a solution or dispersion containing anionic polymer compound A and anionic polymer compound B dropwise to a powder of a polyvalent metal salt or a solution or dispersion in which a polyvalent metal salt is dissolved, thereby performing a bonding treatment while simultaneously causing precipitation or sedimentation. These methods can be performed individually or in combination.

[0086] As a preferred example, firstly, a solution is prepared in which anionic polymer compound A and anionic polymer compound B are dissolved in water, an organic solvent, or a mixture thereof, or a molten liquid is prepared by heating anionic polymer compound A and anionic polymer compound B to melt them. Heating may be performed as needed to improve solubility and reduce the viscosity of the molten liquid. Secondly, a solution containing a polyvalent metal salt is added to the obtained solution or molten liquid, and the mixture is stirred. Alternatively, a solution or molten liquid containing anionic polymer compound A and anionic polymer compound B may be added to the solution containing the polyvalent metal salt and stirred.

[0087] Examples of 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, and thallium salts. Considering the metals present in seawater, environmental factors, safety, and versatility, calcium salts, magnesium salts, and aluminum salts are preferred. Considering the environmental conditions in seawater, calcium salts and magnesium salts are even more preferred. Specific examples of polyvalent metal salts include calcium chloride, calcium sulfate, calcium carbonate, calcium hydroxide, calcium oxide, magnesium chloride, magnesium sulfate, magnesium carbonate, magnesium hydroxide, magnesium oxide, aluminum sulfate, sodium aluminum sulfate (sodium alum), and potassium aluminum sulfate (potassium alum). Considering solubility in water, processability, and cost, calcium chloride, magnesium chloride, and aluminum sulfate are preferred.

[0088] The concentration of the polyvalent metal salt in the solution containing the polyvalent metal salt is preferably 1-40% by mass, more preferably 10-30% by mass. The solvent of the solution is preferably a lower alcohol solvent such as water, methanol, ethanol, 1-propanol, 2-propanol, acetone, acetonitrile, THF, DMF, DMSO, NMP, or a mixture thereof. As long as the salt can be dissolved within a range that does not dissolve the resin to achieve the target concentration, a mixture of other organic solvents may be used.

[0089] In addition, as long as the polyvalent metal salt is highly reactive and reacts even in a solid state, it can be used in powder form without the use of a medium, or dispersed in a small amount of medium.

[0090] During crosslinking, in order to control the particle size and spherical shape of the precipitates or sediments, the surfactant and polymeric stabilizer can be dissolved in at least one of a solution containing anionic polymer compounds A and B and a solution containing a polyvalent metal salt.

[0091] There are no limitations on the methods for preparing solutions or dispersions containing anionic polymer compound A and anionic polymer compound B. Examples include mixing a monovalent salt of anionic polymer compound A and a monovalent salt of anionic polymer compound B with water or an organic solvent; and mixing an acidic polymer compound A and an acidic polymer compound B, which are proton-bonded to the monovalent anionic groups of anionic polymer compound A and anionic polymer compound B, with water or an organic solvent, and then adding a monovalent base. These methods can be performed individually or in combination. Furthermore, when performed in combination, the order in which they are performed is not particularly limited.

[0092] As the monovalent countercation constituting the monovalent salt of the anionic polymer compound A and the monovalent salt of the anionic polymer compound B, lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion, francium ion, ammonium ion, methylammonium ion, ethylammonium ion, aniline-onium ion, pyridinium ion, dimethylammonium ion, diethylammonium ion, trimethylammonium ion, triethylammonium ion, etc., are preferred from the viewpoints of safety, environmental impact, and operability. Sodium ion, potassium ion, and ammonium ion are more preferred, and sodium ion and potassium ion are even more preferred.

[0093] Examples of monovalent bases include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, lithium methoxide, sodium methoxide, potassium methoxide, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, ammonia, methylamine, ethylamine, TEA, and DBU. Lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium bicarbonate, sodium bicarbonate, or potassium bicarbonate are preferred. Considering safety and environmental impact, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, or potassium bicarbonate are particularly preferred.

[0094] By adding a base containing a metal with a divalent or higher valence to water or an organic solvent containing acidic polymer compound A and acidic polymer compound B, marine biodegradable polymer compounds can also be generated in a chain reaction following the formation of anionic polymer compound A and anionic polymer compound B.

[0095] Examples of bases containing divalent or higher metals include magnesium hydride, strontium hydride, calcium hydride, barium hydride, magnesium methoxide, calcium methoxide, strontium methoxide, barium methoxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium oxide, strontium oxide, calcium oxide, barium oxide, magnesium carbonate, strontium carbonate, calcium carbonate, barium carbonate, magnesium bicarbonate, strontium bicarbonate, calcium bicarbonate, and barium bicarbonate. Considering solubility in water, reactivity, and cost, calcium hydride, calcium methoxide, calcium hydroxide, and barium hydroxide are preferred, with calcium hydroxide being more preferred.

[0096] As a preferred example, a solution in which acidic polymer compound A and acidic polymer compound B are dissolved in water, an organic solvent, or a mixture thereof, or a molten liquid in which acidic polymer compound A and acidic polymer compound B are melted by heating, is prepared. Heating may be performed as needed to improve solubility and reduce the viscosity of the molten liquid. Next, a solution of a base containing a metal with a valence of divalent or higher is added to the obtained solution or molten liquid, and the mixture is stirred. Alternatively, a solution or molten liquid in which acidic polymer compound A and acidic polymer compound B are dissolved in a solution of a base containing a metal with a valence of divalent or higher may be added, and the mixture is stirred.

[0097] Examples of bases containing divalent or higher metals include magnesium hydride, strontium hydride, calcium hydride, barium hydride, magnesium methoxide, calcium methoxide, strontium methoxide, barium methoxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium oxide, strontium oxide, calcium oxide, barium oxide, magnesium carbonate, strontium carbonate, calcium carbonate, barium carbonate, magnesium bicarbonate, strontium bicarbonate, calcium bicarbonate, and barium bicarbonate. Considering solubility in water, reactivity, and cost, calcium hydride, calcium methoxide, calcium hydroxide, and barium hydroxide are preferred, with calcium hydroxide being more preferred.

[0098] In addition, it is not necessary to crosslink anionic polymer compound A and anionic polymer compound B at the same time. For example, by crosslinking a portion of the anionic polymer compound of one, adding the anionic polymer compound of the other, and further crosslinking, a marine biodegradable polymer compound can also be obtained.

[0099] By subjecting anionic polymer compound A and anionic polymer compound B to the aforementioned crosslinking treatment, the target marine biodegradable polymer compound, which is no longer slowly dissolving, is precipitated, deposited, or obtained as a bulk by means of metal cation bonding between anionic polymer compound A and anionic polymer compound B. The treatment time is preferably 0.5 to 24 hours, more preferably 1 to 12 hours.

[0100] Heating can be performed to precipitate or deposit the target marine biodegradable polymer compound. Heating can be performed by mixing a solution in which anionic polymer compound A and anionic polymer compound B are dissolved, or a molten liquid of anionic polymer compound A and anionic polymer compound B, with a solution containing a polyvalent metal salt; or by stirring after mixing; or by both. Alternatively, heating can be performed by mixing a solution in which acidic polymer compound A and acidic polymer compound B are dissolved, or a molten liquid of acidic polymer compound A and acidic polymer compound B, with a solution containing a base containing a metal with a divalent or higher valence; or by stirring after mixing; or by both. The heating temperature is preferably 5–200°C, more preferably 10–150°C, and even more preferably 20–100°C.

[0101] After processing, the particles are washed and dried as needed to obtain marine biodegradable polymer compounds. Washing can be carried out using conventional methods, such as removing the solvent after treatment or centrifuging with water. Drying can be carried out using conventional methods, such as spray drying, vacuum drying, or freeze drying. Furthermore, the obtained marine biodegradable polymer compounds can be surface-treated or pulverized to adjust the particle size, as needed, using known equipment.

[0102] In the case of marine biodegradable polymer compounds, at least one monovalent anionic group that is not bonded between the anionic polymer compounds by a divalent metal cation may be blocked with a closed segment group.

[0103] By selecting the closed-chain segment group, multiple effects can be introduced into both single raw materials and composite raw materials (marine biodegradable resin compositions) using this raw material, including adjustments to melt temperature and melt viscosity, crystallinity, microbial adhesion and biodegradability, resin tensile strength, flexural strength, elasticity, etc., improved compatibility with resin, adjustment of hydrophobicity, water repellency, adhesion, and plasticity. This improves both the biodegradability and physical properties of the marine biodegradable resin composition. It is desirable for the organic anion that forms the closed-chain segment to have a structure that is biodegradable in the ocean; therefore, a closed-chain segment group with a molecular weight of 5000 or less is preferred. For example, when the rate of biodegradability in the ocean and the maintenance of average physical properties are important, a molecular weight of 2500 or less is preferred, and more preferably 1000 or less.

[0104] Specifically, the closed-chain segment preferably has a hydrocarbon group with 3 or more carbon atoms, more preferably has a hydrocarbon group with 6 or more carbon atoms, even more preferably has a hydrocarbon group with 10 or more carbon atoms, and most preferably has a hydrocarbon group with 12 or more carbon atoms. There is no particular limit on the upper limit of the number of carbon atoms in the hydrocarbon group, but it is preferably 30 or less, more preferably 25 or less, and even more preferably 20 or less.

[0105] The closed-chain segment group is preferably an organic anion selected from carboxylate anions having 3 or more carbon groups, sulfonate anions having 3 or more carbon groups, sulfate anions having 3 or more carbon groups, and phosphate anions having 3 or more carbon groups. Among these, monovalent organic anions derived from carboxylic acids having 3 or more carbon groups are preferred, and more preferably monovalent organic anions derived from fatty acids having 3 or more carbon groups or amino acid derivatives having 3 or more carbon groups.

[0106] End-capping can be performed using at least one end-capping agent selected from carboxylic acids having 3 or more carbon groups, salts of such carboxylic acids, sulfonic acids having 3 or more carbon groups, salts of such sulfonic acids, sulfates having 3 or more carbon groups, salts of such sulfates, phosphates having 3 or more carbon groups, and salts of such phosphates. End-capping can be performed by adding the end-capping agent to a solution containing polymer compound A or B, followed by bonding treatment with polyvalent metal ions.

[0107] As a capping agent, the preferred options are the acid compounds or chlorine compounds described in paragraphs

[0029] to

[0044] of Japanese Patent Application Publication No. 2021-191810.

[0108] [Marine Biodegradable Resin Composition]

[0109] The marine biodegradable resin composition of the present invention comprises the marine biodegradable polymer compound.

[0110] The marine biodegradable polymer compound can be used as a main raw material or as an additive in combination with other resins. There are no particular limitations on the other resins, but biodegradable resins are preferred. When used as an additive in combination with other resins, the marine biodegradable polymer compound functions as a marine biodegradation promoter. In this case, the composite resin becomes a resin composition that promotes biodegradation in the ocean. Furthermore, to adjust the physical properties and processability of the resin composition, multiple resins can be used in combination as the other resins mentioned above.

[0111] Other resins mentioned include polyethylene, polyester, polypropylene, polyethylene terephthalate, 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 acid 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 blends, starch-blended polyester resins, polybutylene terephthalate succinate, polylactic acid, polyhydroxyalkanoic acid, etc. Resins with high biodegradability are particularly preferred when considering the reduction of environmental impact and the promotion of marine biodegradability.

[0112] In addition, examples of biodegradable resins include polycaprolactone, poly(caprolactone / butylene succinate), polybutylene succinate (PBS), poly(butylene glycol succinate / adipate) (PBSA), poly(butylene glycol adipate / terephthalate) (PBAT), poly(butylene glycol succinate / carbonate), polyethylene terephthalate copolymer, poly(ethylene glycol terephthalate / succinate), poly(tetramethylene adipate / terephthalate), polyethylene succinate, polyvinyl alcohol, polyglycolic acid, glycolic acid / caprolactone copolymer, glycolic acid / propylene carbonate copolymer, etc., resins whose raw materials are derived from petroleum; (polylactic acid / polybutylene succinate-based) block copolymers, (polylactic acid / polycaprolactone) copolymers, ( Resins containing a portion of biomass-derived raw materials include polylactic acid / polyether copolymers, polylactic acid blends (PBAT), lactic acid / glycolic acid copolymers, bio-based polybutylene succinate, poly(butylene glycol succinate / adipate), starch-blended polyester resins, and poly(butylene terephthalate succinate). Resins containing 100% biomass-derived raw materials include polyhydroxybutyric acid (PHBH), polyhydroxyvalerate, polyhydroxyoctanoic acid (PHOV), poly(hydroxybutyrate / hydroxyhexanoate) (PHBH), poly(3-hydroxybutyrate / 4-hydroxybutyrate) (P3HB4HB), and poly(hydroxybutyrate / hydroxyvalerate) (PHBV). Resins containing cellulose, cellulose acetate, cellulose ester resins, starch, esterified starch, and chitosan are derived from natural polymers. These can be used individually or in combination.

[0113] Among these, the preferred biodegradable resin is one that is biodegradable in soil or compost but poorly biodegradable in the ocean. For example, a combination of a biodegradable resin selected from natural polymers such as polycaprolactone, PBS, PBSA, PBAT, poly(1,4-butanediol adipate / terephthalate), poly(butanediol succinate / carbonate), PHBH, PHBV, PLA, cellulose, starch, and chitosan with the aforementioned marine biodegradable polymer compound is preferred. Resins derived from PBSA, PBS, PBAT, PLA, and starch are particularly preferred as the biodegradable resin.

[0114] In addition, considering the reduction of environmental impact, the raw materials for the composite resin are preferably derived from biomass or more, more preferably from biomass or more, and most preferably from biomass or more.

[0115] The marine biodegradable resin composition of the present invention may contain a solvent. The solvent may be a solvent that dissolves the resin, leaving it as a particle residue while simultaneously forming the matrix, without dissolving the marine biodegradable polymer compound; or it may be a solvent that dissolves both the resin and the marine biodegradable polymer compound. By appropriately adjusting these components, it can also be effectively used as a molded article, coating, ink, surface treatment agent, etc., produced by film formation such as casting. Preferred solvents include, 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, tetrachloroethane, chlorobenzene, methanol, ethanol, n-propanol, isopropanol, butanol, pentanol, hexafluoroisopropanol, methyl ethylene glycol, methyl triethylene glycol, hexyl ethylene glycol, phenyl ethylene glycol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, benzene, toluene, xylene, etc. These can be used individually or in combination.

[0116] When using a solvent, the total concentration of the resin and the marine biodegradable polymer compound in the resin composition is preferably 0.5 to 90% by mass, more preferably 1 to 80% by mass, even more preferably 5 to 60% by mass, and most preferably 10 to 50% by mass. Furthermore, the ratio of the marine biodegradable polymer compound to the resin, expressed as a mass ratio, is preferably 99:1 to 10:90, more preferably 97:3 to 40:60, even more preferably 95:5 to 50:50, and most preferably 90:10 to 60:40.

[0117] The lower limit of the softening point of the resin composition is preferably 60°C or higher, 70°C or higher, and 80°C or higher, respectively; the upper limit is preferably 300°C or lower, 250°C or lower, 200°C or lower, and 180°C or lower, respectively. Preferably, the softening point is within the range of 60–250°C, more preferably 70–200°C, and even more preferably 80–180°C.

[0118] Furthermore, the marine biodegradable resin composition of the present invention may be solvent-free. In this case, the resin may be thermally melted, and a non-melting marine biodegradable polymer compound may be added and mixed therein, or both the resin and the marine biodegradable polymer compound may be melted and mixed.

[0119] In the marine biodegradable resin composition of the present invention, the content of the marine biodegradable polymer compound is preferably 1-60% by mass, more preferably 3-50% by mass, even more preferably 5-45% by mass, even more preferably 7-40% by mass, and most preferably 10-35% by mass. On the other hand, the content of the resin is preferably 40-99% by mass, more preferably 50-97% by mass, even more preferably 55-95% by mass, even more preferably 60-93% by mass, and most preferably 65-90% by mass. By including the marine biodegradable polymer compound within the aforementioned range, it is possible to effectively utilize it as a marine biodegradation promoter that promotes biodegradation in seawater while maintaining the physical properties of the biodegradable resin. The marine biodegradable polymer compound can be used alone or in combination of two or more.

[0120] The tensile strength of the test piece obtained from the resin composition, compared to that of a blank resin test piece without the marine biodegradable polymer compound of the present invention, is preferably 80% or more, more preferably 85% or more, and even more preferably 90% or more, when the content of the marine biodegradable polymer compound in the resin composition is 10% by mass. Furthermore, when the content of the marine biodegradable polymer compound in the resin composition is 30% by mass, it is preferably 65% ​​or more, more preferably 70% or more, and even more preferably 80% or more.

[0121] The marine biodegradable resin composition of the present invention may, as needed, contain additives such as antioxidants, release agents, stripping agents, surface modifiers, hydrophobic agents, water-repellent agents, hydrophilic agents, pigments, colorants, heat stabilizers, light stabilizers, weather resistance improvers, antistatic agents, antifogging agents, lubricants, antiblocking agents, hardening agents, softening agents, compatibilizers, flame retardants, flowability improvers, plasticizers, dispersants, antibacterial agents, fillers, and metal passivators. The content of these additives is not particularly limited as long as it does not impair the effects of the present invention; preferably, it is about 0.1 to 50 parts by weight relative to 100 parts by weight of the resin.

[0122] When the marine biodegradable resin composition contains a solvent, it can be prepared, for example, by simultaneously or in any order adding the resin, the marine biodegradable polymer compound, and the additives to be used as needed to the solvent. Alternatively, when the marine biodegradable resin composition does not contain a solvent, for example, the resin can be melted, and the marine biodegradable polymer compound and the additives to be used as needed can be added and mixed simultaneously or in any order thereto; or the resin and the marine biodegradable polymer compound can be heated, melted together, and mixed, with the additives added and mixed as needed.

[0123] [Molded body]

[0124] By using the resin composition for molding, it is possible to obtain a molded article in which the marine biodegradable polymer compound is dispersed or dissolved in the resin. When the resin composition contains a solvent, it can be used directly for molding; when the resin composition does not contain a solvent, it can be molded after the resin or the resin and the marine biodegradable polymer compound in the resin composition have been thermally melted.

[0125] Examples of possible shapes for the molded body include film-like, fibrous, sheet-like, foamed, and other shapes suitable for the intended use. As for the molding method, there are no particular limitations, and various conventionally known molding methods can be used. Specific examples include blow molding, injection molding, extrusion molding, compression molding, melt extrusion molding, solution casting, and calendering.

[0126] [use]

[0127] The marine biodegradable polymer compound and marine biodegradable resin composition of the present invention can be used as raw materials for plastic molding products, and can also be used as various additives in molded products such as liquids, coatings, films, sheets, and paper. When used as raw materials for plastic molding products, they can be used as raw materials for general-purpose and marine-purpose materials such as films, packaging, containers, pallets, laminates, adhesives, coating materials, medical and clothing fibers, shoes, belts, tires, pipes, shock-absorbing materials, fishing lines, and fishing nets, and are particularly suitable as raw materials for marine-purpose materials. In addition, when used as an additive, it is widely used as an additive in light scattering agents, filter materials, colorants, cosmetics, absorbents, adsorbents, inks, adhesives, electromagnetic wave shielding materials, fluorescent sensors, biomarkers, recording materials, recording elements, polarizing materials, drug holders for drug delivery systems (DDS), biosensors, DNA chips, diagnostic drugs, sintered porous molded products, anti-blocking agents, printing ink additives used in screen printing, offset printing, color overprinting, gravure printing, rubbing printing, coaters, inkjet printing, etc., for markers, ballpoint pens, fountain pens, fountain pens, multi-purpose pens, etc., for stationery such as crayons, drawing tools, and erasers, for coatings used in brush coating, spraying, electrostatic coating, electrodeposition coating, flow coating, roller coating, dip coating, etc., and especially for coatings used in marine applications such as ship hull coatings.

[0128] Example

[0129] The following examples and comparative examples illustrate the present invention in more detail, but the present invention is not limited to the following examples. Furthermore, in the following examples and comparative examples, the metal ion equivalent was determined by heating and decomposing the target substance in nitric acid or aqua regia, and then measuring it using ICP-MS (ICPE-9820 manufactured by Shimadzu Corporation) with luminescence analysis. In addition, the number-average molecular weight and the number of anionic groups were determined using a nuclear magnetic resonance apparatus (JNEM-ECZ400S manufactured by Nippon Electron Co., Ltd.). 1 The integral value of the peak in H-NMR is calculated.

[0130] [1] Synthesis of anionic polymer compound A

[0131] [Synthetic Example 1-1] Synthesis of Anionic Polymer Compound A-1

[0132] In a 1000 mL reaction vessel, 400 g of polyester glycol (Kuraray Polyol P-1010, manufactured by Kuraray Co., Ltd.), 84 g of succinic anhydride, and 40 g of acetonitrile were added. The mixture was stirred at 130 °C for 2 hours under a nitrogen atmosphere to obtain acidic polymer compound A-1. Anionic polymer compound A-1 was obtained by adding 500 g of acidic polymer compound A-1, 412 g of water, and 88 g of potassium bicarbonate to a 3000 mL round-bottom flask and stirring at room temperature.

[0133] Aniline polymer compound A-1 is a linear chain with monovalent anionic groups at both ends. 1 H-NMR measurements confirmed a number-average molecular weight of 1300.

[0134] [Synthetic Examples 1-2] Synthesis of Anionic Polymer Compound A-2

[0135] In a 1000 mL reaction vessel, 400 g of polyester triol (Kuraray Polyol F-1010, manufactured by Kuraray Co., Ltd.), 126 g of succinic anhydride, and 60 g of acetonitrile were added. The mixture was stirred at 130 °C for 2 hours under a nitrogen atmosphere to obtain acidic polymer compound A-2. Anionic polymer compound A-2 was obtained by adding 500 g of acidic polymer compound A-2, 368 g of water, and 132 g of potassium bicarbonate to a 3000 mL round-bottom flask and stirring at room temperature.

[0136] Aniline polymer compound A-2 is a three-branched polymer with monovalent anionic groups at all its ends. 1 H-NMR measurements confirmed a number-average molecular weight of 1400.

[0137] [Synthetic Examples 1-3] Synthesis of Anionic Polymer Compound A-3

[0138] In a 1000 mL round-bottom flask, 130 g of 1,4-butanediol, 71 g of dimethyl terephthalate, 150 g of dimethyl adipate, and 2.4 g of tetraisopropoxytitanium were added. The mixture was stirred at 160 °C for 6 hours under a nitrogen atmosphere. Then, 32 g of succinic anhydride and 40 g of acetonitrile were added, and the mixture was stirred at 130 °C for 2 hours to obtain the acidic polymer compound A-3. In a 3000 mL round-bottom flask, 350 g of acidic polymer compound A-3, 316 g of water, and 34 g of potassium bicarbonate were added. The mixture was stirred at 80 °C to obtain the anionic polymer compound A-3.

[0139] Aniline polymer compound A-3 is a linear chain with monovalent anionic groups at both ends, which... 1 H-NMR measurements confirmed a number-average molecular weight of 2300.

[0140] [Synthetic Examples 1-4] Synthesis of Anionic Polymer Compound A-4

[0141] In a 1000 mL round-bottom flask, 280 g of hexamethylenediamine, 340 g of sebacic acid, and 80 g of water were added. The mixture was then placed in an autoclave, and after thorough nitrogen replacement, the temperature was raised to 230 °C while stirring. Subsequently, under sealed conditions, the mixture was stirred at 230 °C for 1 hour, then depressurized to atmospheric pressure. The solid components were washed with ethanol and dried. 400 g of the dried resin was pulverized, and 82 g of succinic anhydride, 100 g of potassium carbonate, and 400 g of acetonitrile were added. The mixture was stirred at 70 °C for 4 hours, and then cooled to room temperature to allow the precipitate to form. The precipitate was removed by filtration, and the resulting filtrate was concentrated under reduced pressure to obtain the acidic polymer compound A-4. Finally, in a 3000 mL round-bottom flask, 300 g of acidic polymer compound A-4, 263 g of water, and 37 g of potassium bicarbonate were added and stirred at 80 °C to obtain the anionic polymer compound A-4.

[0142] Aniline polymer compound A-4 is a linear chain with monovalent anionic groups at both ends, which... 1 H-NMR measurements confirmed a number-average molecular weight of 1800.

[0143] [Synthetic Examples 1-5] Synthesis of Anionic Polymer Compound A-5

[0144] In a 1000 mL reaction vessel, 300 g of polyether glycol (polytetramethylene ether glycol manufactured by Mitsubishi Chemical Co., Ltd.), 94 g of succinic anhydride, and 30 g of acetonitrile were added. The mixture was stirred at 130 °C for 2 hours under a nitrogen atmosphere to obtain acidic polymer compound A-5. In a 3000 mL round-bottom flask, 400 g of acidic polymer compound A-5, 1100 g of water, and 100 g of potassium bicarbonate were added and stirred at room temperature to obtain anionic polymer compound A-5.

[0145] Aniline polymer compound A-5 is a linear chain with monovalent anionic groups at both ends, which... 1 H-NMR measurements confirmed a number-average molecular weight of 900.

[0146] Anionic polymer compounds A-1 to A-5 are summarized in Table 1 below.

[0147] [Table 1]

[0148]

[0149] [2] Synthesis of anionic polymer compound B

[0150] [Synthetic Example 2-1] Synthesis of anionic polymer compound B-1

[0151] 204 g of ethylene glycol, 80 g of dimethyl terephthalate, 122 g of sodium dimethyl 5-sulfoisophthalate and 1.0 g of tetraisopropoxytitanium were added to a 1000 mL flask. After stirring at 200 °C for 3 hours under a nitrogen atmosphere, the liquid was distilled off under reduced pressure to obtain the anionic polymer compound B-1.

[0152] pass 1 ¹H-NMR analysis confirmed that the anionic polymer compound B-1 has a number-average molecular weight of 3000 and an average of 6 monovalent anionic groups on its side chains.

[0153] [Synthetic Example 2-2] Synthesis of anionic polymer compound B-2

[0154] 142 g of ethylene glycol, 110 g of dimethyl sebacate, 142 g of sodium dimethyl 5-sulfoisophthalate and 0.7 g of tetraisopropoxytitanium were added to a 1000 mL flask and stirred at 200 °C for 3 hours under a nitrogen atmosphere to obtain the anionic polymer compound B-2.

[0155] pass 1 ¹H-NMR analysis confirmed that the anionic polymer compound B-2 has a number-average molecular weight of 1500 and an average of three monovalent anionic groups on its side chains.

[0156] [Synthetic Examples 2-3] Synthesis of Anionic Polymer Compound B-3

[0157] 195 g of 1,4-butanediol, 110 g of dimethyl adipate, 80 g of sodium dimethyl 5-sulfoisophthalate and 0.9 g of tetraisopropoxytitanium were added to a 1000 mL flask and stirred at 200 °C for 3 hours under a nitrogen atmosphere to obtain the anionic polymer compound B-3.

[0158] pass 1 ¹H-NMR analysis confirmed that the anionic polymer compound B-3 has a number-average molecular weight of 1900 and an average of three monovalent anionic groups on its side chains.

[0159] [Synthetic Examples 2-4] Synthesis of Anionic Polymer Compound B-4

[0160] In a 1000 mL round-bottom flask, 11 g of hexamethylenediamine and 160 g of tetrahydrofuran were added. Then, a solution of 25 g of pyromellitic anhydride and 200 g of tetrahydrofuran was slowly added, and the mixture was stirred at 50 °C for 2 hours under a nitrogen atmosphere. After distilling off the solvent, 22 g of potassium bicarbonate and 200 g of water were added, and the mixture was stirred at room temperature to obtain the anionic polymer compound B-4.

[0161] pass 1 ¹H-NMR analysis confirmed that the anionic polymer compound B-4 has a number-average molecular weight of 2000 and an average of 13 monovalent anionic groups on its side chains.

[0162] [Synthetic Examples 2-5] Synthesis of Anionic Polymer Compound B-5

[0163] 119.1 g of 1,4-butanediol, 75.6 g of succinic acid, and 25.0 g of maleic acid were added to a 1000 mL flask and stirred at 160 °C for 6 hours under a nitrogen atmosphere. Then, 90.1 g of 3-mercaptopropionic acid and 34.4 g of acetonitrile were added, and the mixture was stirred at 130 °C for 4 hours to obtain the anionic polymer compound B-5.

[0164] pass 1 ¹H-NMR analysis confirmed that the anionic polymer compound B-5 has a number-average molecular weight of 1800 and an average of three monovalent anionic groups.

[0165] The anionic polymer compounds B-1 to B-5 are summarized in Table 2 below.

[0166] [Table 2]

[0167]

[0168] [3] Biodegradability test of anionic polymer compounds

[0169] [Refer to Examples 1-10]

[0170] For anionic polymer compounds A-1 to A-5 and anionic polymer compounds B-1 to B-5, seawater biodegradation tests were conducted using the following method. Furthermore, as a control material, microcrystalline cellulose (Avicel PH-101 manufactured by Sigma-Aldrich) was used, and its relative biodegradability was evaluated. The results are shown in Table 4.

[0171] <Experimental Methods and Conditions>

[0172] Biodegradability determination method: Oxygen consumption is measured using a closed respiration meter (refer to ASTM D6691).

[0173] Experimental setup: OxiTop IDS (manufactured by WTW)

[0174] Incubation temperature: 30±1℃, in the dark

[0175] Biodegradability (%) = (BOD) O -BOD B) / ThOD×100

[0176] BOD O Biochemical oxygen demand (measured value: mg) confirmed by experimental or plant source activity.

[0177] BOD B Mean biochemical oxygen demand (measured value: mg) in the blank test

[0178] ThOD: The theoretical oxygen demand required to completely oxidize the test or control material (calculated value: mg).

[0179] Relative biodegradability of cellulose (%) = (Maximum biodegradability of test particles / Maximum biodegradability of cellulose) × 100

[0180] Seawater (taken from Tokyo Bay [Chiba Prefecture: Chiba Port])

[0181] The collected seawater was filtered through a 10μm filter to remove impurities and then aerated at room temperature (25 degrees Celsius). Additionally, ammonium chloride was added at a concentration of 0.05 g / L and potassium dihydrogen phosphate was added at a concentration of 0.1 g / L as inorganic nutrients.

[0182] [Table 3]

[0183]

[0184] As shown in Table 3, anionic polymer compound A and anionic polymer compound B achieved a relative biodegradability of cellulose of over 40% up to 60 days of culture.

[0185] [4] Synthesis of marine biodegradable polymer compounds

[0186] [Example 1-1] Synthesis of marine biodegradable polymer compound C-1

[0187] In a 1000 mL round-bottom flask, 400 g of a 25% by mass aqueous solution of anionic polymer compound A-1 and 100 g of a 25% by mass aqueous solution of anionic polymer compound B-1 were added and stirred thoroughly until homogeneous. Then, 140 g of a 30% by mass aqueous solution of calcium chloride was added and stirred, resulting in the formation of a precipitate. The precipitate was washed with water and dried under reduced pressure to obtain marine biodegradable polymer compound C-1.

[0188] [Examples 1-2] Synthesis of marine biodegradable polymer compound C-2

[0189] In a 1000 mL round-bottom flask, 200 g of a 50% by mass aqueous solution of anionic polymer compound A-2 and 400 g of a 25% by mass aqueous solution of anionic polymer compound B-2 were added and stirred thoroughly until homogeneous. Then, 175 g of a 30% by mass aqueous solution of calcium chloride was added and stirred, resulting in the formation of a precipitate. The precipitate was washed with water and dried under reduced pressure to obtain marine biodegradable polymer compound C-2.

[0190] [Examples 1-3] Synthesis of marine biodegradable polymer compound C-3

[0191] In a 1000 mL round-bottom flask, 160 g of a 50% by mass aqueous solution of anionic polymer compound A-3 and 480 g of a 25% by mass aqueous solution of anionic polymer compound B-3 were added and stirred thoroughly until homogeneous. Then, 120 g of a 30% by mass aqueous solution of magnesium chloride was added and stirred, resulting in the formation of a precipitate. The precipitate was washed with water and dried under reduced pressure to obtain marine biodegradable polymer compound C-3.

[0192] [Examples 1-4] Synthesis of marine biodegradable polymer compound C-4

[0193] In a 1000 mL round-bottom flask, 320 g of a 50% by weight aqueous solution of anionic polymer compound A-4 and 160 g of a 25% by weight aqueous solution of anionic polymer compound B-1 were added and stirred thoroughly until homogeneous. Then, 110 g of a 30% by weight aqueous solution of calcium chloride was added and stirred, resulting in the formation of a precipitate. The precipitate was washed with water and dried under reduced pressure to obtain marine biodegradable polymer compound C-4.

[0194] [Examples 1-5] Synthesis of marine biodegradable polymer compound C-5

[0195] In a 2000 mL round-bottom flask, 640 g of a 50% by weight aqueous solution of anionic polymer compound A-5 and 160 g of a 25% by weight aqueous solution of anionic polymer compound B-1 were added and stirred thoroughly until homogeneous. Then, 320 g of a 40% by weight aqueous solution of aluminum sulfate was added and stirred, resulting in the formation of a precipitate. The precipitate was washed with water and dried under reduced pressure to obtain the marine biodegradable polymer compound C-5.

[0196] [Examples 1-6] Synthesis of marine biodegradable polymer compound C-6

[0197] In a 1000 mL round-bottom flask, 160 g of a 50% by mass aqueous solution of anionic polymer compound A-1 and 480 g of a 25% by mass aqueous solution of anionic polymer compound B-4 were added and stirred thoroughly until homogeneous. Then, 360 g of a 30% by mass aqueous solution of calcium chloride was added and stirred, resulting in the formation of a precipitate. The precipitate was washed with water and dried under reduced pressure to obtain marine biodegradable polymer compound C-6.

[0198] [Examples 1-7] Synthesis of marine biodegradable polymer compound C-7

[0199] In a 1000 mL round-bottom flask, 120 g of a 50% by mass aqueous solution of anionic polymer compound A-3 and 560 g of a 25% by mass aqueous solution of anionic polymer compound B-5 were added and stirred thoroughly until homogeneous. Then, 130 g of a 30% by mass aqueous solution of calcium chloride was added and stirred, resulting in the formation of a precipitate. The precipitate was washed with water and dried under reduced pressure to obtain marine biodegradable polymer compound C-7.

[0200] [Examples 1-8] Synthesis of marine biodegradable polymer compound C-8

[0201] In a 1000 mL round-bottom flask, 240 g of a 50% by mass aqueous solution of anionic polymer compound A-1, 80 g of a 50% by mass aqueous solution of anionic polymer compound A-2, and 160 g of a 25% by mass aqueous solution of anionic polymer compound B-1 were added and stirred thoroughly until homogeneous. Then, 160 g of a 30% by mass aqueous solution of calcium chloride was added and stirred, resulting in the formation of a precipitate. The precipitate was washed with water and dried under reduced pressure to obtain marine biodegradable polymer compound C-8.

[0202] [Examples 1-9] Synthesis of marine biodegradable polymer compound C-9

[0203] In a 1000 mL round-bottom flask, 320 g of a 50% by mass aqueous solution of anionic polymer compound A-1, 80 g of a 25% by mass aqueous solution of anionic polymer compound B-1, and 80 g of a 25% by mass aqueous solution of anionic polymer compound B-3 were added and stirred thoroughly until homogeneous. Then, 130 g of a 30% by mass aqueous solution of calcium chloride was added and stirred, resulting in the formation of a precipitate. The precipitate was washed with water and dried under reduced pressure to obtain marine biodegradable polymer compound C-9.

[0204] [Comparative Example 1-1] Synthesis of Marine Biodegradable Polymer Compound X-1

[0205] 400 g of a 50% by weight aqueous solution of anionic polymer compound A-2 was added to a 1000 mL pear-shaped flask, followed by 180 g of a 30% by weight aqueous solution of calcium chloride. The mixture was stirred, resulting in the formation of a precipitate. The precipitate was washed with water and dried under reduced pressure to obtain the marine biodegradable polymer compound X-1.

[0206] The marine biodegradable polymer compounds C-1 to C-9 and X-1 are summarized in Table 4 below.

[0207] [Table 4]

[0208]

[0209] [5] Preparation of marine biodegradable resin compositions and confirmation tests in seawater - 1

[0210] (1) Surface changes

[0211] [Examples 2-1 to 2-9, Comparative Examples 2-1 to 2-2]

[0212] In PBSA (Mitsubishi Chemical Co., Ltd. FD-92), a biodegradable resin, marine biodegradable polymer compounds C-1 to C-9 and X-1 were pulverized using a pulverizer (Osaka Chemical Co., Ltd. One Brender WB-1) and graded using a stainless steel sieve (26 μm mesh size). These compounds were melt-blended at 140°C to a concentration of 20% by mass, and then molded at 150°C to produce films with a thickness of 200 μm (Examples 2-1 to 2-9, Comparative Example 2-1). Alternatively, PBSA itself (without the marine biodegradable polymer compounds) was molded at 150°C to produce a film with a thickness of 200 μm (Comparative Example 2-2).

[0213] In addition, the obtained membranes were processed into 10 mm square products and placed in 200 mL of ion-exchanged water and 200 mL of seawater (collected from Tokyo Bay [Chiba Prefecture: Chiba Port]), respectively. After standing at 25°C for 7 days and 30 days, the membranes were removed and their surface and appearance were observed using a scanning electron microscope. The results are shown in Table 5.

[0214] [Table 5]

[0215]

[0216] The results shown in Table 5 suggest that, while the collapse was caused by seawater, the presence of microorganisms in the seawater promoted biodegradation.

[0217] (2) The weight of the composite resin is reduced.

[0218] [Examples 3-1 to 3-9, Comparative Examples 3-1 to 3-2]

[0219] Using the same method as (1), membranes containing marine biodegradable polymer compounds C-1 to C-9 and X-1, respectively, and membranes containing PBSA monopolymer were prepared. The resulting membranes were processed into 20 mm square products, clamped in stainless steel mesh, and immersed in seawater (collected from Tokyo Bay [Chiba Prefecture: Chiba Port]) in a 15 L tank. The weight reduction after immersion was observed after 30, 60, and 90 days. The results are shown in Table 6.

[0220] [Table 6]

[0221]

[0222] The results shown in Table 6 suggest that, while the collapse was caused by seawater, the presence of microorganisms in the seawater promoted biodegradation.

[0223] (3) Tensile strength test

[0224] [Examples 4-1 to 4-9, Comparative Example 4-1]

[0225] Using the same method as (1), membranes containing marine biodegradable polymer compounds C-1 to C-9 and X-1 in PBSA at concentrations of 10%, 20%, or 30% by mass, as well as membranes containing PBSA monopolymer, were prepared. Dumbbell-shaped specimens were prepared from the various membranes according to JIS K 7139-A22 and tested using a universal testing machine (A1 Co., Ltd.). アンド The tensile stress (yield point) was determined using a die-cast MCT-2150. Five measurements were taken for each sample, and the average value was taken as the tensile stress. The results are shown in Table 7.

[0226] [Table 7]

[0227]

[0228] The results shown in Table 7 confirm that the marine biodegradable polymer compound of the present invention has improved mechanical properties compared with X-1.

[0229] (4) Determination of softening point

[0230] [Examples 5-1 to 5-9, Comparative Example 5-1]

[0231] Using the same method as in (1), membranes containing marine biodegradable polymer compounds C-1 to C-9 and X-1 at concentrations of 10%, 20%, or 30% by mass, as well as membranes containing PBSA monohydrate, were prepared. For marine biodegradable polymer compounds C-1 to C-9 and X-1, the softening point was determined using a thermomechanical analyzer (NETZSCH Japan Co., Ltd. TMA4000SE). Specifically, the softening point was defined as the temperature at which a 200 μm thick, 150 mm long, and 3 mm wide test piece was stretched along its edge with a 10 g load and the elongation was observed to be 1 mm within a temperature range of 0–180 °C (heating rate 3 °C / min). The results are shown in Table 8.

[0232] [Table 8]

[0233]

[0234] The results shown in Table 8 confirm that the marine biodegradable polymer compound of the present invention has improved thermal properties compared with X-1.

[0235] [6] Preparation of marine biodegradable resin compositions and confirmation tests in seawater - 2

[0236] (1) Surface changes

[0237] [Examples 6-1 to 6-9, Comparative Examples 6-1 to 6-2]

[0238] Marine biodegradable polymer compounds C-1 to C-9 and X-1 were melt-blended at 140°C to a concentration of 20% by mass in starch-based resin (Mater-Bi EF05B, manufactured by Novamont) using a pulverizer (Osaka Chemical Co., Ltd. WB-1 Blender) and graded using a stainless steel sieve (26 μm mesh size). The mixture was then molded at 150°C to produce films with a thickness of 200 μm (Examples 6-1 to 6-9, Comparative Example 6-1). Alternatively, a film with a thickness of 200 μm was produced by molding the starch-based resin itself (without the marine biodegradable polymer compounds) at 150°C (Comparative Example 6-2).

[0239] In addition, the obtained membranes were processed into 10 mm square products and placed in 200 mL of ion-exchanged water and 200 mL of seawater (collected from Tokyo Bay [Chiba Prefecture: Chiba Port]), respectively. After standing at 25°C for 7 days and 30 days, the membranes were removed and their surface and appearance were observed using a scanning electron microscope. The results are shown in Table 9.

[0240] [Table 9]

[0241]

[0242] The results shown in Table 9 suggest that, while the collapse was caused by seawater, the presence of microorganisms in the seawater promoted biodegradation.

[0243] (2) The weight of the composite resin is reduced.

[0244] [Examples 7-1 to 7-9, Comparative Examples 7-1 to 7-2]

[0245] Using the same method as (1), membranes containing marine biodegradable polymer compounds C-1 to C-9 and X-1, respectively, and membranes containing starch-based resin monomers were prepared. The resulting membranes were processed into 20 mm square products, clamped in stainless steel mesh, and immersed in seawater (collected from Tokyo Bay [Chiba Prefecture: Chiba Port]) in a 15 L tank. The weight reduction after immersion was observed after 30, 60, and 90 days. The results are shown in Table 10.

[0246] [Table 10]

[0247]

[0248] The results shown in Table 10 suggest that, while the collapse was caused by seawater, the presence of microorganisms in the seawater promoted biodegradation.

[0249] (3) Tensile strength test

[0250] [Examples 8-1 to 8-9, Comparative Example 8-1]

[0251] Using the same method as (1), membranes were prepared by adding marine biodegradable polymer compounds C-1 to C-9 and X-1 to starch-based resins to make their concentrations 10%, 20%, or 30% by mass, as well as membranes of starch-based resin monomers.

[0252] According to JIS K 7139-A22, dumbbell-shaped specimens were prepared from various membranes and tested using a universal testing machine ((Kuai) Co., Ltd.). アンド The tensile stress (yield point) was determined using a die-cast MCT-2150. Five measurements were taken for each sample, and the average value was taken as the tensile stress. The results are shown in Table 11.

[0253] [Table 11]

[0254]

[0255] The results shown in Table 11 confirm that the marine biodegradable polymer compound of the present invention has improved mechanical properties compared with X-1.

[0256] (4) Determination of softening point

[0257] [Examples 9-1 to 9-9, Comparative Example 9-1]

[0258] Using the same method as (1), films containing marine biodegradable polymer compounds C-1 to C-9 and X-1 at concentrations of 10%, 20%, or 30% by mass, as well as films containing only the starch-based resin, were prepared. For marine biodegradable polymer compounds C-1 to C-9 and X-1, the softening point was determined using a thermomechanical analyzer (NETZSCH Japan Co., Ltd. TMA4000SE). Specifically, the softening point was defined as the temperature at which a 200 μm thick, 150 mm long, and 3 mm wide test piece was stretched along its edge with a 10 g load and the elongation was observed to be 1 mm within a temperature range of 0–180 °C (heating rate 3 °C / min). The results are shown in Table 12.

[0259] [Table 12]

[0260]

[0261] The results shown in Table 12 confirm that the marine biodegradable polymer compound of the present invention has improved thermal properties compared with X-1.

[0262] Based on the above results, the marine biodegradable polymer compound of the present invention, in seawater, prior to biodegradable resins, is reduced in molecular weight through biodegradation, dissolved by salt displacement, or readily exhibits hydrophilicity. Therefore, by adding a marine biodegradation promoter containing the marine biodegradable polymer compound of the present invention to resin compositions with biodegradability in soil, compost, or low biodegradability in the ocean, the composition becomes textured in seawater, facilitating microbial attachment and promoting biodegradation. As a result, overall marine biodegradability is improved while reducing environmental impact. By combining a marine biodegradability promoter containing the marine biodegradable polymer compound of the present invention with a resin that is biodegradable in soil and compost, the biodegradability of seawater can be improved. In addition, by appropriately modifying the structure of the organic anion, multiple effects can be introduced, such as adjustment of melting temperature and viscosity, adjustment of crystallinity, adjustment of microbial attachment and biodegradability, adjustment of physical properties such as resin tensile strength, flexural strength, and elasticity, improvement of compatibility with resin, adjustment of hydrophobicity, adjustment of hydrophobicity, and adjustment of adhesion and plasticity. Thus, improvements can be achieved in both the biodegradability and physical properties of the marine biodegradable resin composition.

Claims

1. Marine biodegradable polymer compounds, among which, An anionic polymer compound A, whose main chain is straight or branched, has a total of two or more monovalent anionic groups at the end of the main chain, and has no ionic groups in the side chains, and an anionic polymer compound B, whose side chains of two or more repeating units have monovalent anionic groups, are bonded by divalent or higher metal cations.

2. The polymer compound according to claim 1, wherein, The mass ratio of anionic polymer compound A to anionic polymer compound B is 99:1 to 10:

90.

3. The polymer compound according to claim 1, wherein, The main chain of the anionic polymer compound A is linear.

4. The polymer compound according to claim 1, wherein, Anionic polymer compound B contains repeating units that do not have ionic groups.

5. The polymer compound according to claim 1, wherein, Anionic polymer compound B has aliphatic unsaturated carbon-carbon bonds in its main chain.

6. The polymer compound according to claim 1, wherein, The monovalent anionic group of the anionic polymer compound A is a carboxylate anion.

7. The polymer compound according to claim 1, wherein, The monovalent anionic group of the anionic polymer compound B is a carboxylate anion or a sulfonate anion.

8. The polymer compound according to claim 1, wherein, The monovalent anionic group of anionic polymer compound B is bonded to a ring.

9. The polymer compound according to claim 1, wherein, The number average molecular weight of anionic polymer compound A is 500–10000, and the number average molecular weight of anionic polymer compound B is 500–10000.

10. The polymer compound according to claim 1, wherein, Anionic polymer compound A is a compound in which repeating units are bonded together using at least one bond selected from ester bonds, amide bonds, ether bonds, and urethane bonds. Anionic polymer compound B is a compound in which repeating units are bonded together using at least one bond selected from ester bonds, amide bonds, ether bonds, and urethane bonds.

11. The polymer compound according to claim 1, wherein, The value obtained by dividing the number average molecular weight of anionic polymer compound B by the average number of monovalent anionic groups in one molecule is 100 to 5000.

12. The polymer compound according to claim 1, wherein, The content of the divalent or higher metal cations is 1–300 eq / 10 5 g.

13. The polymer compound according to claim 1, wherein, The divalent or higher metal cations are calcium ions, magnesium ions, or aluminum ions.

14. A marine biodegradation promoter comprising any one of the marine biodegradable polymer compounds according to claims 1 to 13.

15. A marine biodegradable resin composition comprising the marine biodegradation promoter and resin as described in claim 14.

16. The marine biodegradable resin composition according to claim 15, wherein, The resin is a biodegradable resin.

17. The marine biodegradable resin composition according to claim 15, wherein, The content of the marine biodegradation promoter is 1-50% by mass, and the content of the resin is 50-99% by mass.

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

19. A method for manufacturing a marine biodegradable polymer compound, comprising the following steps: crosslinking an anionic polymer compound A, having a main chain that is straight or branched, having a total of two or more monovalent anionic groups at the end of the main chain, and having no ionic groups on the side chains, and an anionic polymer compound B, having monovalent anionic groups on the side chains of at least two repeating units, with divalent or higher metal cations.

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