WO2023100257A1 - 炭化水素基を有する海洋生分解促進剤及び海洋生分解性組成物 - Google Patents

炭化水素基を有する海洋生分解促進剤及び海洋生分解性組成物 Download PDF

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WO2023100257A1
WO2023100257A1 PCT/JP2021/043924 JP2021043924W WO2023100257A1 WO 2023100257 A1 WO2023100257 A1 WO 2023100257A1 JP 2021043924 W JP2021043924 W JP 2021043924W WO 2023100257 A1 WO2023100257 A1 WO 2023100257A1
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monovalent
marine
acid
carbon atoms
hydrocarbon group
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English (en)
French (fr)
Japanese (ja)
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俊文 橋場
和寿 早川
直弘 上村
恵里奈 松坂
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Nisshinbo Holdings Inc
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Nisshinbo Holdings Inc
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Priority to JP2023564314A priority Critical patent/JPWO2023100257A1/ja
Priority to PCT/JP2021/043924 priority patent/WO2023100257A1/ja
Priority to CN202180104429.3A priority patent/CN118339235A/zh
Priority to EP21966343.2A priority patent/EP4442747A4/en
Priority to US18/712,536 priority patent/US20250011570A1/en
Publication of WO2023100257A1 publication Critical patent/WO2023100257A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/018—Additives for biodegradable polymeric composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0033—Additives activating the degradation of the macromolecular compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable

Definitions

  • the present invention relates to a marine biodegradation accelerator having a hydrocarbon group and a marine biodegradable composition.
  • Non-Patent Document 1 On the other hand, general biodegradable resins exhibit high biodegradability in environments such as soil and sludge where many microorganisms responsible for decomposition exist, but in environments such as the ocean where the concentration of microorganisms is extremely low There is a drawback that it is difficult to decompose (Non-Patent Document 1).
  • PCL polycaprolactone
  • PHA polyhydroxyalkanoic acid
  • the present invention has been made in view of the above-mentioned circumstances, and particularly provides a biodegradation accelerator for promoting biodegradation of resins and the like in the ocean, and a marine biodegradable composition containing the biodegradation accelerator. With the goal.
  • a hydrophobic powdery material composed of a compound in which a valence organic anion and a metal cation having a valence of 2 or more are bonded by an ionic bond does not dissolve in freshwater, but gradually dissolves in seawater despite being hydrophobic.
  • the material first decomposes in seawater, and (1) pores are formed in the resin material, and the specific surface area of the resin and (2) primary decomposition has the effect of promoting secondary decomposition, that is, biodegradation by microorganisms, resulting in resin materials in the ocean.
  • the present inventors have completed the present invention by finding that biodegradation can be promoted.
  • the present invention provides marine biodegradation accelerators and marine biodegradable compositions having the following hydrocarbon groups.
  • Monovalent carboxylic acid having a monovalent hydrocarbon group of 10 to 25 carbon atoms
  • monovalent sulfonic acid having a monovalent hydrocarbon group of 10 to 25 carbon atoms
  • 1 having a monovalent hydrocarbon group of 10 to 25 carbon atoms
  • a marine biodegradation accelerator which is a hydrophobic and thermoplastic powder, consisting of A marine biodegradation accelerator in which the powder dissolves in a 3% by mass sodium chloride aqueous solution or exhibits hydrophilicity in a 3% by mass sodium chloride aqueous solution.
  • the marine biodegradation accelerator of 2 is a monovalent fatty acid having a monovalent hydrocarbon group of 10 to 25 carbon atoms. 4. 3.
  • the marine biodegradation accelerator of 3 wherein the monovalent carboxylic acid is capric acid, lauric acid, myristic acid, palmitic acid, or stearic acid. 5.
  • the marine biodegradation accelerator of 2 wherein the monovalent carboxylic acid is an amino acid derivative having a monovalent hydrocarbon group of 10 to 25 carbon atoms. 6.
  • the marine biodegradation accelerator according to any one of 1 to 10 which is a powder having an average particle size of 0.1 to 10,000 ⁇ m. 12.
  • a marine biodegradable resin composition comprising the marine biodegradation accelerator of any one of 1 to 13 and a resin. 15.
  • Marine biodegradable resin composition, wherein said resin is a biodegradable resin. 16.
  • the marine biodegradation accelerator of the present invention dissolves or becomes hydrophilic in seawater, compositions and molded articles containing it promote biodegradation in the ocean and are useful for marine pollution countermeasures.
  • an environmentally friendly composition and molded article can be obtained.
  • the marine biodegradation accelerator of the present invention includes a monovalent carboxylic acid having a monovalent hydrocarbon group having 10 to 25 carbon atoms, a monovalent sulfonic acid having a monovalent hydrocarbon group having 10 to 25 carbon atoms, and 10 to 25 carbon atoms.
  • the monovalent hydrocarbon group preferably has 12 to 25 carbon atoms, more preferably 14 to 25 carbon atoms, and is best in consideration of safety such as powder melting temperature, hydrophobicity, and irritation. is 14-20 carbon atoms. If the number of carbon atoms is less than 10, the melting temperature is too high, making it difficult to melt and mix with the resin described later. On the other hand, if the number of carbon atoms exceeds 25, the melting temperature may decrease.
  • the monovalent organic anion is preferably derived from the monovalent carboxylic acid or monovalent sulfonic acid, more preferably from the monovalent carboxylic acid.
  • the monovalent carboxylic acid is preferably a fatty acid having a monovalent hydrocarbon group of 10 to 25 carbon atoms or an amino acid derivative having a monovalent hydrocarbon group of 10 to 25 carbon atoms. These monovalent organic anions are preferred due to their ability to attract less fungi in the ocean.
  • the monovalent organic anion preferably does not contain a ring structure.
  • a ring structure may be introduced within a range that does not impair biodegradability and its control.
  • the divalent or higher metal cations are not particularly limited, but are magnesium ions, calcium ions, aluminum ions, strontium ions, barium ions, radium ions, scandium ions, titanium ions, vanadium ions, chromium ions, manganese ions, and iron ions.
  • the powder composed of the hydrophobizing compound dissolves in a 3% by mass sodium chloride aqueous solution, or exhibits hydrophilicity in a 3% by mass sodium chloride aqueous solution.
  • the powder composed of the hydrophobizing compound was dispersed in a 3% by mass sodium chloride aqueous solution so that the powder was 0.1% by mass, and after 15 days, the dispersion liquid had a wavelength of 560 nm.
  • the rate is SD1 (%)
  • the marine biodegradation accelerator is dispersed in water so that it becomes 0.1% by mass, and the transmittance of light with a wavelength of 560 nm after 15 days has passed is WD1 (%)
  • WD1/SD1 is preferably 0.9 or less, more preferably 0.8 or less, and even more preferably 0.6 or less. If it is 0.9 or less, it can be confirmed that the particles of the marine biodegradation accelerator change in shape, are dissolved, and become transparent.
  • the lower limit of WD1/SD1 is not particularly limited, it is usually about 0.1. From the viewpoint of environmental impact consideration and biodegradation promoting effect, it is preferable that at least WD1/SD1 ⁇ 0.9 is satisfied for about 15 days.
  • the powder composed of the hydrophobizing compound was dispersed in water and an aqueous sodium chloride solution (sodium chloride concentration: 3% by mass) to a concentration of 0.1% by mass, and stirred at room temperature for 15 days.
  • the hydrophobizing compound preferably has a molecular weight of 5,000 or less, and a molecular weight of 100 to 5,000, when designed to sufficiently satisfy the solubility in water and salt water and the microbial degradability in the environment from environmental considerations. Those having a molecular weight of 150 to 3,000, 200 to 2,000 are more preferred, and those having a molecular weight of 250 to 1,000 are most preferred.
  • the molecular weight means the number average molecular weight (Mn) of a polymer, and Mn is a value measured by gel permeation chromatography in terms of polystyrene. For anything other than polymers, formula weights are meant.
  • the powder composed of the hydrophobizing compound preferably has an average particle size of 0.1 to 10,000 ⁇ m, preferably 1.0 to 5,000 ⁇ m, and more preferably 3.0 to 3,000 ⁇ m. is more preferred.
  • the particle size is preferably 3.0 to 500 ⁇ m.
  • the average particle size is the volume average particle size (MV) by laser diffraction/scattering method.
  • the powder composed of the hydrophobizing compound is a thermoplastic powder, and has a melting temperature of 60 to 230°C, preferably 60 to 200°C. If the melting temperature is within the above range, it can be thermally melted together with the resin and mixed uniformly, so that it is possible to evenly and efficiently generate starting points for biodegradation in the ocean. Further, uniformity is also preferable in that variations in physical properties such as strength can be controlled.
  • the melting temperature is more preferably 70°C to 180°C, still more preferably 90°C to 160°C.
  • the shape of the powder is not particularly limited, and may be physically or chemically controlled such as spherical, approximately spherical, flattened or dimpled, or physically pulverized. From the viewpoint of controlling the diameter distribution, it is preferable to physically or chemically control the shape such as a spherical shape, a substantially spherical shape, a flat shape, or a dimpled shape.
  • the particle group composed of the marine biodegradation accelerator may be formed into pellets by compression molding or melt molding.
  • a contact angle of 50° or more is 50° or more after 30 seconds from dropping water droplets on the melt-molded body of the particle group composed of the powder.
  • the melt molded body is a sheet for contact angle measurement, which is formed by heating and melting particles to form a molded body. In this case, the hydrophobizing effect, the solubility in seawater, and the degradability are sufficiently exhibited.
  • the contact angles are preferably 60° or more, 70° or more, and 80° or more, in this order, because the above effect can be easily obtained.
  • the upper limit of the contact angle is not particularly limited, but realistic values are 170° or less, 160° or less, 150°C or less, and 140° or less.
  • the contact angle preferably satisfies 50° to 160°, more preferably 50° to 150°. It is more preferable to satisfy 60° to 140°, and most preferably 70° to 130°.
  • the contact angle can be measured using a contact angle meter (for example, Drop Master 300 manufactured by Kyowa Interface Science Co., Ltd.).
  • the hydrophobizing compound includes a monovalent carboxylic acid having a monovalent hydrocarbon group of 10 to 25 carbon atoms, a monovalent sulfonic acid having a monovalent hydrocarbon group of 10 to 25 carbon atoms, a monovalent A compound consisting of a monovalent organic anion and a monovalent cation derived from one selected from monovalent sulfate esters having a hydrocarbon group and monovalent phosphate esters having a monovalent hydrocarbon group having 10 to 25 carbon atoms (hereinafter , also referred to as a raw material compound A) is reacted with a polyvalent metal salt containing a divalent or higher valent metal cation to bind the monovalent organic anion with the divalent or higher metal cation.
  • the monovalent cations include monovalent metal ions such as hydrogen ions, lithium ions, sodium ions, potassium ions, and silver ions; and monovalent organic ions such as ammonium cations.
  • monovalent metal ions such as hydrogen ions, lithium ions, sodium ions, potassium ions, and silver ions
  • monovalent organic ions such as ammonium cations.
  • sodium ion, potassium ion, and ammonium cation are preferred, sodium ion and potassium ion are more preferred, and sodium ion is still more preferred, from the viewpoints of environment, biological safety, versatility, cost, and the like.
  • the molecular weight of the raw material compound A is preferably 100-2,500. When the molecular weight is within the above range, physical properties as a resin such as thermal meltability and compatibility with other resins are maintained, and the resin is compatible with seawater and easily decomposed.
  • the lower limit of the molecular weight is preferably 150 or more and 200 or more in that order.
  • the upper limit is preferably 2,000 or less, 1,500 or less, 1,000 or less, and 500 or less in this order.
  • the molecular weight of the raw material compound A is preferably 150-800, more preferably 150-600, even more preferably 200-500.
  • the raw material compound A is preferably one that dissolves in water at room temperature or at 80°C or lower. If it is such a material, it will blend well with seawater, and a favorable biodegradation rate will be obtained.
  • Examples of the raw material compound A include monovalent carboxylic acid or its salt, monovalent sulfonic acid or its salt, monovalent sulfate or its salt, and monovalent phosphate or its salt.
  • the monovalent carboxylic acid salt is a salt composed of an anion and a monovalent cation derived from a monovalent carboxylic acid having a monovalent hydrocarbon group with 10 to 25 carbon atoms.
  • the monovalent carboxylate include salts composed of an anion and a monovalent cation derived from a fatty acid having a monovalent hydrocarbon group of 10 to 25 carbon atoms, and an amino acid having a monovalent hydrocarbon group of 10 to 25 carbon atoms.
  • a salt or the like composed of an anion derived from the derivative and a monovalent cation is preferable.
  • fatty acids include undecylenic acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, palmitoleic acid, margaric acid, stearic acid, isostearic acid, oleic acid, vaccenic acid, ricinoleic acid, linoleic acid, linolenic acid, and eleostearin.
  • the fatty acid salt is preferably a monovalent metal salt, and specific examples thereof include undecylenates such as potassium undecylenate and sodium undecylenate; laurates such as potassium laurate and sodium laurate; potassium myristate and myristin.
  • Pentadecylate salts such as potassium pentadesylate and sodium pentadecylate; Palmitate salts such as potassium palmitate and sodium palmitate; Margarates such as potassium margarate and sodium margarate; Potassium stearate , stearates such as sodium stearate; isostearates such as potassium isostearate and sodium isostearate; oleates such as potassium oleate and sodium oleate; linoleates such as potassium linoleate and sodium linoleate; linolenic acid salts such as potassium acid and sodium linolenate; arachidates such as potassium arachidate and sodium arachidate; arachidonates such as potassium arachidonate and sodium arachidonate; behenates such as potassium behenate and sodium behenate docosahexaenoates such as sodium docosahexaenoate; coconut oil fatty acid salts such as potassium coconut oil and sodium coconut oil; Of these
  • the amino acid derivative salt those having 12 to 25 carbon atoms are more preferable, and those having a monovalent hydrocarbon group having 14 to 20 carbon atoms are preferable.
  • the salt of the amino acid derivative is preferably a monovalent salt, more preferably a monovalent metal salt.
  • amino acid derivatives examples include sarcosine derivatives such as lauroyl sarcosine, myristoyl sarcosine, palmitoyl sarcosine, and coconut fatty acid sarcosine; Glutamic acid derivatives such as glutamic acid; Glycine derivatives such as lauroylglycine, myristoylglycine, palmitoylglycine, palmitoylmethylglycine, coconut oil fatty acid acylglycine, and cocoylglycine; Laurylmethylalanine, myristoylmethylalanine, cocoylalanine, coconut oil fatty acid methylalanine, etc.
  • sarcosine derivatives such as lauroyl sarcosine, myristoyl sarcosine, palmitoyl sarcosine, and coconut fatty acid sarcosine
  • Glutamic acid derivatives such as glutamic acid
  • Glycine derivatives such as lau
  • Lysine derivatives such as lauroyl lysine, myristoyl lysine, palmitoyl lysine, stearoyl lysine and oleyl lysine;
  • Aspartic acid derivatives such as lauroyl aspartic acid, myristoyl aspartic acid, palmitoyl aspartic acid and stearoyl aspartic acid;
  • Taurine derivatives such as myristoyl taurine, myristoyl methyl taurine, palmitoyl taurine, palmitoyl methyl taurine, stearoyl taurine, and stearoyl methyl taurine;
  • C10-25 monovalent hydrocarbon groups such as proline derivatives such as lauroyl proline, myristoyl proline, and palmitoyl proline and derivatives of amino acids having In particular, N-acyl derivatives of amino acids are preferred.
  • a sarcosic acid derivative having a monovalent hydrocarbon group of 10 to 25 carbon atoms or a glutamic acid derivative having a monovalent hydrocarbon group of 10 to 25 carbon atoms is preferable.
  • lauroyl sarcosine, myristoyl sarcosine, palmitoyl sarcosine, myristoyl glutamic acid, and stearoyl glutamic acid are the best from the viewpoint of melting temperature and safety to the human body.
  • amino acid derivative salts examples include sarcosine derivative salts such as potassium lauroyl sarcosine, sodium lauroyl sarcosinate, potassium myristoyl sarcosine, sodium myristoyl sarcosine, potassium palmitoyl sarcosine, sodium palmitoyl sarcosine, potassium coconut oil fatty acid sarcosine, sodium coconut oil fatty acid sarcosine; lauroyl glutamic acid; Potassium, sodium lauroyl glutamate, potassium myristoyl glutamate, sodium myristoyl glutamate, sodium palmitoyl glutamate, potassium palmitoyl glutamate, potassium stearoyl glutamate, sodium stearoyl glutamate, potassium cocoyl glutamate, sodium cocoyl glutamate, potassium cocoyl glutamate, cocoyl glutamate, potassium cocoyl glutamate, cocoyl glutamate, potassium cocoyl glutamate, cocoy
  • amino acid derivative salts having a hydrocarbon group such as proline derivative salts such as sodium lauroylproline, sodium myristoylproline, and sodium palmitoylproline.
  • proline derivative salts such as sodium lauroylproline, sodium myristoylproline, and sodium palmitoylproline.
  • N-acyl derivative salts of amino acids are preferred.
  • sarcosine derivative salts of lauric acid, myristic acid, or palmitic acid and glutamic acid derivative salts of lauric acid, myristic acid, palmitic acid, or stearic acid are the best from the viewpoint of melting temperature and safety to the human body.
  • the sulfonate preferably has a monovalent hydrocarbon group having 12 to 20 carbon atoms. Moreover, the sulfonate is preferably a monovalent salt, more preferably an ammonium salt or a monovalent metal salt. Specific examples include sodium laurylsulfonate, ammonium laurylsulfonate, sodium myristylsulfonate, ammonium myristylsulfonate, sodium cetylsulfonate, ammonium cetylsulfonate, sodium stearylsulfonate, ammonium stearylsulfonate, and sodium oleylsulfonate.
  • alkylsulfonates such as ammonium oleylsulfonate; dodecylbenzenesulfonates such as ammonium dodecylbenzenesulfonate and sodium dodecylbenzenesulfonate; monoalkyls having 12 to 20 carbon atoms such as disodium monoalkylsuccinatesulfonate succinate sulfonate; naphthalenesulfonic acid formalin condensate salt such as naphthalenesulfonic acid formalin condensate sodium salt; olefin sulfonate having 12 to 20 carbon atoms such as sodium tetradecenesulfonate and ammonium tetradecenesulfonate; Isethionate salts such as potassium lauroyl isethionate, sodium lauroyl isethionate, sodium myristoyl isethionate, sodium palmitoyl isethionate, sodium
  • sulfate salts examples include alkyl sulfates, polyoxyethylene aryl ether sulfates, polyoxyethylene alkyl ether sulfates, polyoxyalkylene alkyl ether sulfates, polyoxyalkylene alkenyl ether sulfates, and polyoxyethylene.
  • Castor oil ether sulfate and the like can be mentioned.
  • the sulfate ester salt is preferably a monovalent salt, more preferably an ammonium salt or a monovalent metal salt.
  • the alkyl sulfate ester salt preferably has an alkyl group with 12 to 20 carbon atoms.
  • Specific examples include potassium lauryl sulfate, sodium lauryl sulfate, ammonium lauryl sulfate, potassium myristyl sulfate, sodium myristyl sulfate, ammonium myristyl sulfate, sodium cetyl sulfate, ammonium cetyl sulfate, sodium stearyl sulfate, ammonium stearyl sulfate, sodium oleyl sulfate, and ammonium oleyl sulfate. mentioned.
  • the polyoxyethylene aryl ether sulfate salt preferably has an HLB value of 16 or less, more preferably 12 or less. Specific examples thereof include polyoxyethylene polycyclic phenyl ether sulfate salts such as sodium polyoxyethylene polycyclic phenyl ether sulfate and ammonium polyoxyethylene polycyclic phenyl ether sulfate; sodium polyoxyethylene aryl ether sulfate; mentioned.
  • the polyoxyethylene alkyl ether sulfate ester salt preferably has an HLB value of 16 or less, more preferably 12 or less. Specific examples include polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene lauryl ether sulfate, ammonium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene myristyl ether sulfate, ammonium polyoxyethylene myristyl ether sulfate, and polyoxyethylene cetyl ether sulfate.
  • the polyoxyalkylene alkyl ether sulfate ester salt preferably has an HLB value of 16 or less, more preferably 12 or less. Specific examples thereof include sodium sulfate ester of polyoxyethylene-polyoxypropylene block copolymer, sodium sulfate ester of polyoxyethylene-polyoxybutylene block copolymer, and polyoxyethylene-polyoxypropylene block copolymer. Sulfuric acid ester sodium salts of coalesced alkyl ethers and the like can be mentioned.
  • the polyoxyalkylene alkenyl ether sulfate preferably has an HLB value of 16 or less, more preferably 12 or less.
  • polyoxyethylene castor oil ether sulfate ester and its salt preferably have an HLB value of 16 or less, more preferably 12 or less.
  • polyoxyethylene castor oil ether sulfate, polyoxyethylene castor oil ether sulfate ammonium, and the like include polyoxyethylene castor oil ether sulfate, polyoxyethylene castor oil ether sulfate ammonium, and the like.
  • Examples of the phosphate ester salts include alkyl phosphate salts.
  • alkyl phosphate ester salt one having an alkyl group of 12 to 20 carbon atoms is preferable.
  • Specific examples include decyl phosphate such as potassium decyl phosphate; undecyl phosphate such as potassium undecyl phosphate; lauryl phosphate such as potassium lauryl phosphate; myristyl phosphate such as potassium myristyl phosphate; Potassium, cetyl phosphate such as sodium cetyl phosphate; stearyl phosphate such as potassium stearyl phosphate, and the like.
  • the active functional group means a functional group capable of undergoing a condensation reaction, such as a hydroxy group, an amino group, and a carboxy group.
  • compounds having a hydroxyl group such as monohydric alcohols, monovalent amino compounds, (poly)alkylene glycol ethers, and (poly)alkylene glycol esters are preferred.
  • monovalent anionic substituent to be introduced into the compound having the active functional group -COO - is preferable because it is easy to introduce.
  • the monohydric alcohol is an alcohol having a monovalent hydrocarbon group of 10 to 25 carbon atoms and one hydroxy group, more preferably 12 to 20 carbon atoms. Further, the monohydric alcohol may be linear, branched or cyclic, but the linear one is preferred.
  • the monohydric alcohol examples include hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, icosanol, henicosanol, docosanol, tricosanol, tetracosanol, pentacosanol, hexacosanol, heptacosanol, octacosanol, nonacosanol, triacontanol and the like.
  • the monovalent amino compound is a compound having a monovalent hydrocarbon group of 10 to 25 carbon atoms and one amino group, more preferably 12 to 20 carbon atoms. Further, the monovalent amino compound may be linear, branched or cyclic, and more preferably linear. Specific examples include aminohexane, aminoheptane, aminooctane, aminononane, aminodecane, aminoundecane, aminododecane, aminotridecane, aminotetradecane, aminopentadecane, aminohexadecane, aminoheptadecane, aminooctadecane, aminononadecane, and aminoicosane. etc.
  • the (poly)alkylene glycol ether preferably has an HLB value of 16 or less, more preferably 12 or less, and even more preferably 8 or less. Specific examples include (poly)ethylene glycol monododecyl ether, (poly)ethylene glycol monomyristyl ether, (poly)ethylene glycol monocetyl ether, (poly)ethylene glycol monostearyl ether, (poly)ethylene glycol monooleyl ether.
  • the (poly)alkylene glycol ester preferably has an HLB value of 16 or less, more preferably 12 or less, and even more preferably 8 or less. Specific examples include (poly)ethylene glycol monolaurate, (poly)ethylene glycol monomyristate, (poly)ethylene glycol monopalmitate, (poly)ethylene glycol monostearate, (poly)ethylene glycol.
  • the number average molecular weight (Mn) of the polyalkylene glycol ether and (poly)alkylene glycol ester preferably has a lower limit of 100 or more, 300 or more, 400 or more, and 500 or more in that order, and the upper limit is 10,000 or less. , 6,000 or less, 4,000 or less, 3,000 or less, and 2,000 or less, in this order.
  • a method for introducing a monovalent anionic substituent into the compound having the active functional group for example, when introducing -COO- , the compound having the active functional group and a divalent carboxylic acid anhydride are combined with a monovalent metal.
  • a monovalent metal examples include a method of esterifying in the presence of a salt, and a method of reacting these with a monovalent metal to form a metal alkoxide, followed by esterification using a divalent carboxylic acid anhydride.
  • the divalent carboxylic anhydride succinic anhydride, maleic anhydride, and phthalic anhydride are preferable, and succinic anhydride and maleic anhydride are more preferable in consideration of biodegradability.
  • hydrophobic compound examples include calcium laurate, magnesium laurate, aluminum laurate, calcium myristate, magnesium myristate, aluminum myristate, calcium palmitate, magnesium palmitate, aluminum palmitate, calcium stearate, and stearic acid.
  • metal soaps such as magnesium, aluminum stearate, calcium ricinoleate, magnesium ricinoleate, aluminum ricinoleate; N-acyl amino acid derivative salts such as magnesium stearoyl glutamate and aluminum stearoyl glutamate; and a salt compound obtained from a calcium salt, a salt compound obtained by esterifying stearyl alcohol and succinic anhydride in the presence of a sodium salt, a calcium salt, and the like.
  • Methods for producing the hydrophobized compound include the following methods (1) and (2).
  • (1) A method comprising the steps of forming a W/O emulsion containing one raw material compound A in water droplets, and binding using a polyvalent metal salt (Method 1).
  • (2) A method in which a solution of a polyvalent metal salt is dropped into a medium in which one type of raw material compound A is dissolved, and precipitation or precipitation is performed while performing a bonding treatment, or one type of compound is added to a medium in which a polyvalent metal salt is dissolved.
  • a method of dropping a solution in which the raw material compound A is dissolved and depositing or precipitating while performing a bonding treatment (Method 2).
  • Method 1 is a method including a step of forming a W/O emulsion containing one raw material compound A in water droplets, and a step of ion bonding treatment using a polyvalent metal salt.
  • a solution is prepared by dissolving one raw material compound A in water or a mixed solvent of water and a hydrophilic organic solvent. At this time, you may heat as needed.
  • the solution and a hydrophobic organic solvent are mixed and emulsified using a stirring device, a homogenizer, or the like.
  • the solution may be added to the hydrophobic organic solvent, or the hydrophobic organic solvent may be added to the solution.
  • a surfactant or polymer stabilizer may be dissolved in a hydrophobic organic solvent and used.
  • a raw material compound A, a hydrophobizing agent, water, a surfactant, a hydrophobic organic solvent, and other necessary components are collectively placed in a container and stirred.
  • An apparatus, homogenizer, or the like may be used for emulsification.
  • Heating may be performed when forming the W/O emulsion. By heating, the solubility can be increased, so that the raw material compound A can be homogenized and the W/O emulsion can be stabilized.
  • the heating temperature is preferably 15 to 100°C, more preferably 40 to 80°C.
  • an ionic bonding treatment is performed.
  • the binding treatment can be performed by adding a solution containing a polyvalent metal salt to the W/O emulsion and stirring.
  • the W/O emulsion may be added to the solution containing the polyvalent metal salt and stirred.
  • polyvalent metal salts examples 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, and manganese salts.
  • calcium salts and magnesium salts are preferred from the viewpoints of being metals contained in seawater, environmental aspects, safety and versatility.
  • Specific examples of the polyvalent metal salt include calcium chloride, calcium sulfate, calcium carbonate, calcium hydroxide, calcium oxide, magnesium chloride, magnesium sulfate, magnesium carbonate, magnesium hydroxide, and magnesium oxide. Calcium chloride and magnesium chloride are preferred in terms of solubility, handleability, cost, and the like.
  • 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 water; a lower alcohol solvent such as methanol, ethanol, 1-propanol, 2-propanol, or a mixed solvent thereof.
  • the salt is dissolved so as to obtain the desired concentration within a range that does not dissolve the particles. If possible, a mixed solvent with another organic solvent may be used.
  • the bonding process may be performed while heating if necessary.
  • the heating may be performed when adding the solution containing the polyvalent metal salt to the dispersion, when stirring after the addition, or during both of them.
  • the heating temperature is preferably 10 to 100°C, more preferably 40 to 80°C.
  • the treatment time is preferably 0.5 to 24 hours, preferably 1 to 12 hours. Heating can increase the solubility of the hydrophobizing agent.
  • the bonding treatment is also performed at the same time as the hydrophobizing treatment.
  • the particles can be washed and dried as necessary to obtain a particle group composed of the hydrophobized compound. Washing can be performed by a usual method, for example, a method of removing the solvent after the binding treatment, adding water and centrifuging. Drying can be performed by a usual method, for example, spray drying, vacuum drying, freeze drying and the like.
  • the resulting hydrophobized compound particle group may be subjected to surface treatment or pulverization using known equipment as necessary to adjust the particle size.
  • Method 2 is a method in which a polyvalent metal salt solution is added dropwise to a medium in which one type of raw material compound A is dissolved, and precipitation or precipitation is performed while performing a bonding treatment, or a raw material compound is added to a medium in which a polyvalent metal salt is dissolved.
  • a solution in which A dissolves is added dropwise, and precipitation or precipitation is performed while performing a bonding treatment.
  • a solution A is prepared by dissolving one raw material compound A in water or a mixed solvent of water and a hydrophilic organic solvent. At this time, in order to improve the solubility, it may be heated as necessary.
  • a solution B containing a polyvalent metal salt is added and stirred.
  • a solution obtained by dissolving one raw material compound A in a solution containing a polyvalent metal salt may be added and stirred.
  • the solution containing the polyvalent metal salt the same one as described in the description of Method 1 can be used.
  • the binding treatment can be performed, and the target hydrophobized compound, which gradually becomes insoluble, precipitates or precipitates.
  • the treatment time is preferably 0.5 to 24 hours, preferably 1 to 12 hours.
  • a surfactant or polymer stabilizer may be dissolved in at least one of the solutions A and B for the purpose of controlling the particle size of the precipitate or precipitate.
  • Heating may be performed when precipitating or precipitating the target hydrophobized compound. Heating may be performed when the solution A and the solution B are mixed, may be performed when stirring after mixing, or may be performed during both of them. Since the solubility of the raw material compound A can be increased by heating, it is possible to homogenize the polymerization and the molecular weight distribution by bonding, and to stabilize the bonding.
  • the heating temperature is preferably 15 to 100°C, more preferably 40 to 80°C.
  • the particles can be washed and dried as necessary to obtain hydrophobized compound particles. Washing can be performed by a usual method, for example, a method of removing the solvent after the binding treatment, adding water and centrifuging. Drying can be performed by a usual method, for example, spray drying, vacuum drying, freeze drying and the like.
  • the resulting hydrophobized compound particle group may be subjected to surface treatment or pulverization using known equipment as necessary to adjust the particle size.
  • the marine biodegradation accelerator of the present invention in combination with a resin, particularly a biodegradable resin, a resin composition that promotes biodegradation in the ocean can be obtained. Moreover, for the purpose of adjusting the physical properties and handleability of the resin composition, it is also possible to use a combination of a plurality of types of resins.
  • the biodegradable resin means a resin that is decomposed by the action of microorganisms in the natural world and finally decomposed into inorganic substances such as water and carbon dioxide.
  • Resins that can be combined with the marine biodegradation accelerator of the present invention include polyethylene, polyester, polypropylene, polyethylene terephthalate, vinyl chloride, polystyrene, polyurethane, epoxy resins, chlorinated polyethylene resins, chlorinated polypropylene resins, modified nylon resins, and phenol.
  • 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 terephthalate succinate, bio-polybutylene succinate, polylactic acid blend, starch blend polyester resin, polybutylene Examples thereof include terephthalate succinate, polylactic acid, and polyhydroxyalkanoic acid. Considering the reduction of the burden on the environment, highly biodegradable resins are particularly preferred.
  • the biodegradable resins include polycaprolactone, poly(caprolactone/butylene succinate), polybutylene succinate (PBS), poly(butylene succinate/adipate) (PBSA), poly(butylene adipate/terephthalate) ( PBAT), poly(butylene succinate/carbonate), polyethylene terephthalate copolymer, poly(ethylene terephthalate/succinate), poly(tetramethylene adipate/terephthalate), polyethylene succinate, polyvinyl alcohol, polyglycolic acid, glycolic acid/caprolactone copolymer, etc.
  • polylactic acid/polybutylene succinate block copolymer, (polylactic acid/polycaprolactone) copolymer, (polylactic acid/polyether) copolymer, polylactic acid blend PBAT, lactic acid/glycolic acid copolymer, Bio-polybutylene succinate, poly(butylene succinate/adipate), starch-blend polyester resin, poly(butylene terephthalate succinate) and other resins partially derived from biomass; polyhydroxybutyric acid, polyhydroxyvaleric acid, polyhydroxycapryl acids, poly(hydroxybutyrate/hydroxyhexanoate) (PHBH), poly(3-hydroxybutyrate/4-hydroxybutyrate) (P3HB4HB), poly(hydroxybutyrate/hydroxyvaleric acid) (PHBV), etc.
  • biomass-derived resins such as polyhydroxyalkanoic acid and polylactic acid (PLA); and resins derived from natural polymers such as cellulose, cellulose acetate, cellulose ester resins, starch, esterified starch, and chitosan.
  • resins that have biodegradability in soil or compost as biodegradable resins but have poor biodegradability in the ocean such as polycaprolactone, (bio) PBS, PBSA, PBAT, poly(tetramethylene adipate/ terephthalate), poly(butylene succinate/carbonate), polyhydroxyalkanoic acids such as PHBH and PHBV, and biodegradable resin components selected from resins derived from natural polymers such as PLA, cellulose, starch, and chitosan. It is preferable to combine the marine biodegradation accelerators.
  • the biodegradable resin resins derived from PBSA, PBS, PBAT, PLA, and starch are particularly preferred.
  • a particularly preferred combination of the marine biodegradation accelerator of the present invention and a biodegradable resin includes calcium palmitate, calcium stearate, calcium myristoyl sarcosinate, calcium palmitoyl sarcosine, calcium stearoyl glutamate, and a biodegradable resin as the marine biodegradation accelerator.
  • examples include those selected from PBSA, PBS, PBAT, and resins derived from starch.
  • the raw material of the resin to be combined is preferably biomass-derived, more preferably 25% or more is biomass-derived raw material, and 50% or more is biomass-derived raw material. More preferably, 80% or more of the raw material is biomass-derived raw material, most preferably.
  • the resin composition of the present invention may contain a solvent.
  • the solvent may dissolve the resin forming the matrix while leaving the marine biodegradation accelerator as particles without dissolving the marine biodegradation accelerator, or may dissolve both the resin and the marine biodegradation accelerator. By appropriately adjusting these, it becomes possible to use it as a molding by forming a film by casting or the like, as a coating material, an ink, a surface treatment agent, or the like.
  • Preferred solvents include water, hexane, heptane, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, dimethylsulfone, acetone, methylethylketone, diethylketone, acetophenone, dimethylether, dipropylether, tetrahydrofuran, chloroform, chloride Methylene, trichloroethylene, ethylene dichloride, dichloroethane, tetrachloroethane, chlorobenzene, methanol, ethanol, n-propanol, isopropanol, butanol, pentanol, methyl glycol, methyltriglycol, hexyl glycol, phenyl glycol, ethylene glycol, propylene glycol, phenol , cresol, polyethylene glycol, benzene, toluene, xylene and the like. These may be used individually by 1 type
  • the total concentration of the resin and the marine biodegradation accelerator in the resin composition is preferably 0.5 to 90% by mass, more preferably 1 to 80% by mass, and 5 to 60% by mass. More preferably, 10 to 50% by mass is most preferable.
  • the ratio of the marine biodegradation accelerator to the resin is preferably 99:1 to 10:90, more preferably 97:3 to 40:60, further preferably 95:5 to 50:50, in terms of mass ratio. 90:10 to 60:40 is most preferred.
  • the resin composition of the present invention may not contain a solvent.
  • the resin may be melted with heat and the marine biodegradation accelerator may be added and mixed, or the resin and the marine biodegradation accelerator may be melted and mixed together.
  • the content of the marine biodegradation accelerator is 1 to 50% by mass, and the content of the resin is 50 to 99% by mass.
  • the content of the marine biodegradation accelerator is more preferably 3 to 50% by mass, even more preferably 5 to 45% by mass, even more preferably 7 to 40% by mass, and 10 ⁇ 35% by weight is most preferred.
  • the resin content is more preferably 50 to 97% by mass, even more preferably 55 to 95% by mass, still more preferably 40 to 93% by mass, and most preferably 65 to 90% by mass.
  • the resin composition of the present invention may optionally contain an antioxidant, a release agent, a release agent, a surface modifier, a hydrophobizing agent, a water repellent agent, a hydrophilizing agent, a dye or pigment, a coloring agent, and a heat stabilizer. , light stabilizers, weather resistance improvers, antistatic agents, antifogging agents, lubricants, antiblocking agents, hardening agents, softening agents, compatibilizers, flame retardants, fluidity improvers, plasticizers, dispersants, Additives such as antimicrobial agents, fillers, metal deactivators and the like may also be included. The content of these additives is not particularly limited as long as it does not impair the effects of the present invention, but it is preferably about 0.1 to 50 parts by mass with respect to 100 parts by mass of the resin.
  • the resin composition contains a solvent
  • the resin, the marine biodegradation accelerator and, if necessary, the additive are added to the solvent at the same time or in any order, and mixed. can be done. Further, when the resin composition does not contain a solvent, for example, the resin is melted, and the marine biodegradation accelerator and, if necessary, the additive are added simultaneously or in any order, Alternatively, the resin and the marine biodegradation accelerator may be heated to melt together and mixed, and the additives may be added and mixed as necessary.
  • a molded article in which the marine biodegradation accelerator is dispersed or dissolved in the resin can be obtained.
  • the resin composition contains a solvent
  • molding may be performed using the resin composition as it is, and when the resin composition does not contain a solvent, the resin in the resin composition or the resin and marine biodegradation Molding may be performed after the accelerator is melted by heat.
  • Examples of the shape of the molded product include film-like, fiber-like, plate-like, foam-molded product-like, and other shapes according to the application.
  • the molding method is not particularly limited, and conventionally known various molding methods can be used. Specific examples thereof include blow molding, injection molding, extrusion molding, compression molding, melt extrusion molding, solution casting molding, calendar molding, and the like.
  • the present invention will be described in more detail below with production examples, examples, and comparative examples, but the present invention is not limited to the following examples.
  • the particle size distribution and volume average particle diameter (MV) were measured using MICROTRACK MT3000 (manufactured by Microtrack Bell Co., Ltd.).
  • Example 1-1 Production of Calcium Palmitate Particle Group (Particle Group A1) The components shown below were placed in a 5,000 mL reaction vessel and dissolved at 70°C by stirring with a stirrer. Potassium palmitate 250.0g Ion-exchanged water 2,875.0g
  • Example 1-2 Production of Myristoyl Sarcosine Calcium Particle Group (Particle Group A2) The components shown below were placed in a 5,000 mL reaction vessel and dissolved at 60°C by stirring with a stirrer.
  • Myristoyl sarcosinate sodium 250.0g Ion-exchanged water 2,250.0g
  • Example 1-3 Production of Calcium Myristoyl Glutamate Particles (Particle Group A3) The components shown below were placed in a 5,000 mL reaction vessel and dissolved at 60°C by stirring with a stirrer. Sodium myristoyl glutamate 70.0g Ion-exchanged water 2,730.0g
  • Example 1-4 Production of Magnesium Dodecanesulfonate Particle Group (Particle Group A4) The components shown below were charged in a 3,000 mL reaction vessel and stirred at 40°C with a stirrer to dissolve. rice field. Sodium dodecanesulfonate 150.0 g Ion-exchanged water 600.0g
  • Example 1-5 Production of Aluminum Myristate Particle Group (Particle Group A5) The components shown below were placed in a 5,000 mL reaction vessel and dissolved at 50°C by stirring with a stirrer. Sodium myristate 250.0g Ion-exchanged water 2,875.0g
  • Example 1-6 Production of propylene glycol monostearate derivative calcium particle group (particle group A6) The following components were charged into a 3,000 mL reaction vessel and stirred at 60°C using a stirrer. Dissolved. Propylene glycol monostearate derivative A 120.0 g Ion-exchanged water 1,104.0 g Ethanol 276.0g
  • Example 1-7 Production of Stearyl Alcohol Derivative Calcium Particle Group (Particle Group A7) The components shown below were charged into a 3,000 mL reaction vessel and dissolved by stirring with a stirrer at 75°C. .
  • Stearyl alcohol derivative B 100.0 g Deionized water 1,140.0g Ethanol 760.0g
  • the obtained particle dispersion was passed through a sieve with an opening of 200 ⁇ m and transferred to a 3,000 mL flask. Next, the particle dispersion that passed through the sieve was subjected to centrifugal separation, which was repeated five times, followed by classification and washing operations to obtain PS single spherical polymer particle group B2 with an MV of 10 ⁇ m.
  • PBSA particle group B4 Production of polybutylene succinate adipate (PBSA) particle group (particle group B4) 30.0 g of pellets of biodegradable resin (PBSA, FD-9 manufactured by Mitsubishi Chemical Corporation) were extruded with liquid nitrogen. It was frozen and pulverized with a pulverizer (Wonder Blender WB-1 manufactured by Osaka Chemical Co., Ltd.). The particle size was then adjusted by sieving. By repeating this, a single PBSA particle group B4 with an MV of 5 ⁇ m was obtained.
  • PBSA polybutylene succinate adipate
  • Each particle group was molded by a hot press set to a melting temperature higher than that of each particle group to prepare a film having a thickness of 200 ⁇ m. Then, according to JIS R 3257, pure water was dropped on the film surface, and the contact angle of the pure water was measured using a contact angle meter (Drop Master 300 manufactured by Kyowa Interface Science Co., Ltd.).
  • Solubility test-1 [Examples 3-1 to 3-7, Comparative Examples 3-1 to 3-5] 1.0 g of each particle group was dispersed in water or an aqueous sodium chloride solution (sodium chloride concentration: 3% by mass) so as to be 0.1% by mass, and a solubility test was conducted. Table 2 shows the results. (1) Appearance: The condition was visually confirmed 15 days after dispersion. (2) Shape: After 15 days from dispersing in an aqueous sodium chloride solution, the change in shape compared with the shape before the test was confirmed by particle size distribution measurement.
  • Each particle group is dispersed in an aqueous sodium chloride solution, and the transmittance of light with a wavelength of 560 nm of the dispersion after 15 days is SD1 (%), and each particle group is dispersed in water.
  • the transmittance of light having a wavelength of 560 nm of the dispersion after 24 hours was defined as WD1 (%), and WD1/SD1 was determined.
  • the transmittance was measured using an ultraviolet-visible spectrophotometer (UV-2450 manufactured by Shimadzu Corporation).
  • Table 3 shows the presence or absence of the shape of each particle group in the film and the measurement results of the contact angle of the produced film. The presence or absence of particle shape was visually observed, and the contact angle was measured by the method described in "[3] Measurement of basic physical properties".
  • the obtained film was processed into a 10 mm square, placed in 200 mL of ion-exchanged water and 200 mL of a 3% by mass sodium chloride aqueous solution, and allowed to stand at 25 ° C. for 15 days and 45 days. The surface and appearance of the film were observed with an electron microscope.
  • Table 4 shows the results. SEM photographs of the film of Example 5-2 after 45 days of immersion in water and 45 days after immersion in a 3% by mass sodium chloride aqueous solution are shown in FIGS. 1 and 2, respectively.
  • the obtained film was processed to 10 mm square, placed in 200 mL of ion-exchanged water and 200 mL of a 3% by mass sodium chloride aqueous solution, and allowed to stand at 25 ° C. for 15 days and 45 days. The surface and appearance of the film were observed at . Table 5 shows the results. SEM photographs of the film of Example 6-3 after 45 days of immersion in water and 45 days after immersion in a 3% by mass sodium chloride aqueous solution are shown in FIGS. 3 and 4, respectively.
  • Powder biodegradability test [Examples 7-1 to 7-3, Comparative Examples 7-1 to 7-3] A seawater biodegradation test was performed on the particle groups A1 to A3 and the particle groups B1 to B3 by the following method.
  • a control material microcrystalline cellulose (Avicel PH-101 manufactured by Sigma-Aldrich) was used, and the relative biodegradability of cellulose was evaluated. Table 6 shows the results.
  • BOD O biochemical oxygen demand for test or confirmation of inoculum activity (measured value: mg)
  • BOD B Mean biochemical oxygen demand of blank test (measured value: mg)
  • ThOD The theoretical oxygen demand (calculated in mg) required if the test or control material were completely oxidized.
  • Cellulose relative biodegradability (%) (maximum biodegradability of test particles/maximum cellulose biodegradability) x 100 Seawater (collected from Tokyo Bay [Chiba Prefecture: Chiba Port])] The collected seawater was aerated at a room temperature of 25°C after removing foreign matter with a 10 ⁇ m filter. Further, as inorganic nutrients, 0.05 g/L of ammonium chloride and 0.1 g/L of potassium dihydrogen phosphate were added.
  • Example 8-6 a film having a thickness of 200 ⁇ m
  • the obtained film was processed into 20 mm squares, sandwiched between stainless steel nets, and immersed in seawater (collected from Tokyo Bay [Chiba Prefecture: Chiba Port]) in a 40 L water tank], 30 days, 60 days, and 90 days later. The progress of weight loss after immersion was observed. Table 7 shows the results.
  • BOD O biochemical oxygen demand for test or confirmation of inoculum activity (measured value: mg)
  • BOD B Mean biochemical oxygen demand of blank test (measured value: mg)
  • ThOD The theoretical oxygen demand (calculated in mg) required if the test or control material were completely oxidized.
  • Cellulose relative biodegradability (%) (maximum biodegradability of test particles/maximum cellulose biodegradability) x 100 Seawater (collected from Tokyo Bay [Chiba Prefecture: Chiba Port])] The collected seawater was aerated at a room temperature of 25°C after removing foreign matter with a 10 ⁇ m filter. Further, as inorganic nutrients, 0.05 g/L of ammonium chloride and 0.1 g/L of potassium dihydrogen phosphate were added.
  • the marine biodegradation accelerator of the present invention is considered to have the effect of improving the overall biodegradability and promoting the biodegradability of the biodegradable resin in seawater. be done.
  • the marine biodegradation accelerator of the present invention maintains hydrophobicity in freshwater, while in seawater, it is reduced in molecular weight by biodegradation prior to biodegradable resin, or salt-substituted. By doing so, it becomes easier to dissolve or hydrophilize. Therefore, by adding the marine biodegradation accelerator of the present invention to a resin composition that is biodegradable in soil/compost or a mixed composition that is weakly biodegradable in the sea, it becomes porous in seawater, and microorganisms It is possible to work to help adhesion and promote biodegradation, and as a result, it is possible to improve the overall marine biodegradability and reduce the environmental load.

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