Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/46—Polyesters chemically modified by esterification
  • C08G63/48—Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/78—Preparation processes
  • C08G63/82—Preparation processes characterised by the catalyst used
  • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
• • 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
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2230/00—Compositions for preparing biodegradable polymers
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/08—Stabilised against heat, light or radiation or oxydation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/30—Applications used for thermoforming
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

• the present invention relates to plasticizers for biodegradable resins, biodegradable resin compositions, and molded articles thereof.
• General-purpose plastics such as vinyl chloride resin (PVC) are used in a wide range of applications, and such general-purpose plastics are generally softened by adding a plasticizer before being used.
• PVC vinyl chloride resin
• general-purpose plastics are difficult to decompose, there is a movement to switch from general-purpose plastics to biodegradable resins from the viewpoint of "sustainability" in recent years.
• Patent Documents 1 to 3 When the plasticizer disclosed in Patent Documents 1 to 3 is added to a biodegradable resin, although a plasticizing effect is obtained, the glass transition temperature of the biodegradable resin composition is lowered and the heat resistance is impaired. I was afraid.
• the problem to be solved by the present invention is to provide a plasticizer capable of sufficiently plasticizing a biodegradable resin and imparting excellent heat resistance to molded articles of the biodegradable resin composition.
• the present invention relates to a biodegradable resin plasticizer which is a polyester represented by the following formula (1) or (2).
• B 11 represents an aliphatic monocarboxylic acid residue having 7 to 20 carbon atoms.
• B 12 represents an aliphatic monocarboxylic acid residue having 7 to 20 carbon atoms.
• B 21 represents an aliphatic monoalcohol residue having 6 to 10 carbon atoms.
• B 22 represents an aliphatic monoalcohol residue having 6 to 10 carbon atoms.
• G represents an alkylene glycol residue having 3 to 10 carbon atoms or an oxyalkylene glycol residue having 3 to 10 carbon atoms.
• A represents an alkylenedicarboxylic acid residue having 6 to 12 carbon atoms.
• m and n each represent the number of repeating units in parentheses, and m and n are each independently an integer of 1 or more.
• a and G may be the same or different for each parenthesized repeating unit.
• a plasticizer capable of sufficiently plasticizing a biodegradable resin and imparting excellent heat resistance to molded articles of the biodegradable resin composition.
• the biodegradable resin plasticizer of the present invention is a polyester represented by the following formula (1) or (2).
• the polyester represented by the following formula (1) and the polyester represented by the following formula (2) may be collectively referred to as "the polyester of the present invention”.
• B 11 represents an aliphatic monocarboxylic acid residue having 7 to 20 carbon atoms.
• B 12 represents an aliphatic monocarboxylic acid residue having 7 to 20 carbon atoms.
• B 21 represents an aliphatic monoalcohol residue having 6 to 10 carbon atoms.
• B 22 represents an aliphatic monoalcohol residue having 6 to 10 carbon atoms.
• G represents an alkylene glycol residue having 3 to 10 carbon atoms or an oxyalkylene glycol residue having 3 to 10 carbon atoms.
• A represents an alkylenedicarboxylic acid residue having 6 to 12 carbon atoms.
• m and n each represent the number of repeating units in parentheses, and m and n are each independently an integer of 1 or more.
• a and G may be the same or different for each parenthesized repeating unit.
• the term “carboxylic acid residue” refers to the remaining organic groups other than the carboxyl group of the carboxylic acid. Incidentally, the number of carbon atoms in the “carboxylic acid residue” does not include the carbon atoms in the carboxy group.
• the term “alcohol residue” refers to an organic group remaining after removing a hydroxyl group from an alcohol.
• glycol residue refers to the organic group remaining after removing the hydroxyl group from the glycol.
• Aliphatic monocarboxylic acid residues having 7 to 20 carbon atoms of B 11 and B 12 include, for example, caprylic acid residue, capric acid residue, lauric acid residue, myristic acid residue, pentadecylic acid residue, palmitic acid residue, Examples include acid residues, margaric acid residues, stearic acid residues, arachidic acid residues and the like.
• Aliphatic monocarboxylic acid residues having 7 to 20 carbon atoms of B 11 and B 12 may have a secondary hydroxyl group and/or a tertiary hydroxyl group in the fatty chain, and a 12-hydroxystearic acid residue, etc. include.
• B 11 and B 12 are preferably aliphatic monocarboxylic acid residues having 11 to 17 carbon atoms, more preferably lauric acid residues, myristic acid residues, palmitic acid residues or stearic acid residues. At least one of B 11 and B 12 of the polyester represented by the formula (1) is an aliphatic monocarboxylic acid residue having 11 to 17 carbon atoms, so that it has a sufficient effect as a plasticizer for biodegradable resins. can demonstrate.
• Examples of aliphatic monoalcohol residues having 6 to 10 carbon atoms for B 21 and B 22 include normal octanol, 2-ethylhexanol, isononyl alcohol and the like.
• B 21 and B 22 are preferably C 7-10 aliphatic monoalcohol residues, more preferably C 8 or 9 aliphatic monoalcohol residues.
• alkylenedicarboxylic acid residue having 6 to 12 carbon atoms of A examples include azelaic acid residue, sebacic acid residue, dodecanedicarboxylic acid residue, cyclohexanedicarboxylic acid residue, hexahydrophthalic acid residue, and the like. be done.
• the alkylenedicarboxylic acid residue having 6 to 12 carbon atoms of A is preferably an alkylenedicarboxylic acid residue having 7 to 10 carbon atoms, more preferably an azelaic acid residue, a sebacic acid residue or a dodecanedioic acid residue. group, more preferably a sebacic acid residue.
• the alkylene glycol residue having 3 to 10 carbon atoms for G includes 1,2-propylene glycol residue, 1,3-propylene glycol residue, 1,2-butanediol residue, and 1,3-butanediol residue. group, 2-methyl-1,3-propanediol residue, 1,4-butanediol residue, 1,5-pentanediol residue, 2,2-dimethyl-1,3-propanediol (neopentyl glycol) residue, 2,2-diethyl-1,3-propanediol (3,3-dimethylol-pentane) residue, 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylolheptane ) residue, 3-methyl-1,5-pentanediol residue, 1,6-hexanediol residue, cyclohexanedimethanol residue, 2,2,4-trimethyl-1,3
• the alkylene glycol residue having 3 to 10 carbon atoms of G is preferably an alkylene glycol residue having 3 to 6 carbon atoms, more preferably a 1,2-propanediol residue or a 1,3-butanediol residue. group, 1,4-butanediol residue, neopentyl glycol residue, 2-methyl-1,3-propanediol residue, 3-methyl-1,5-pentanediol residue, 1,6-hexanediol residue or a diethylene glycol residue.
• the oxyalkylene glycol residue having 3 to 10 carbon atoms of G is, for example, one obtained by replacing one of the carbon atoms of the alkylene glycol residue having 3 to 10 carbon atoms with an oxygen atom, diethylene glycol residue, tri Examples include ethylene glycol residue, tetraethylene glycol residue, dipropylene glycol residue, tripropylene glycol residue and the like.
• the oxyalkylene glycol residue having 3 to 10 carbon atoms of G is preferably an oxyalkylene glycol residue having 4 to 6 carbon atoms, more preferably a diethylene glycol residue or a triethylene glycol residue.
• each of m and n is, but not limited to, 15, for example.
• the polyester of the present invention may be used, for example, as a mixture of polyester resins in which m in formula (1) is different from each other and/or a mixture of polyester resins in which n in formula (2) is different from each other.
• the average value of m is in the range of 1-9, for example, and the average value of n is in the range of 1-9, for example.
• the average values of m and n can be confirmed from the number average molecular weight of the polyester.
• the number average molecular weight (Mn) of the polyester of the present invention is, for example, 500 to 5,000, preferably 1,000 to 3,500, more preferably 1,200 to 2,800, more preferably 1,600 to 2,400.
• Mn number average molecular weight
• the above number average molecular weight (Mn) is a value converted to polystyrene based on gel permeation chromatography (GPC) measurement, and is measured by the method described in Examples.
• the acid value of the polyester of the present invention is preferably 2.0 or less, more preferably 1.0 or less.
• the hydroxyl value of the polyester of the present invention is preferably 15 or less, more preferably 10 or less.
• the viscosity of the polyester of the present invention is preferably 7,000 mPa ⁇ s or less, more preferably 5000 mPa ⁇ s or less. The acid value, hydroxyl value and viscosity of the polyester of the present invention are confirmed by the methods described in Examples.
• the properties of the polyester of the present invention vary depending on the number average molecular weight, composition, etc., but it is usually liquid, solid, pasty, etc. at room temperature.
• the polyester of the present invention is obtained using a reaction raw material containing one or more selected from, for example, monocarboxylic acids, monoalcohols, glycols and dicarboxylic acids.
• the reaction raw material means a raw material that constitutes the polyester of the present invention, and does not contain a solvent or a catalyst that does not constitute the polyester.
• the method for producing the polyester of the present invention is not particularly limited, and it can be produced by a known method, and can be produced by the following production method.
• the reaction raw materials for the polyester of the present invention may contain one or more selected from monocarboxylic acids, monoalcohols, glycols and dicarboxylic acids, and may contain other raw materials.
• preferably 90% by mass or more of the total amount of the reaction raw material is one or more selected from monocarboxylic acids, monoalcohols, glycols and dicarboxylic acids, more preferably monocarboxylic acids, It consists only of one or more selected from monoalcohols, glycols and dicarboxylic acids.
• the monocarboxylic acid used in the production of the polyester of the present invention is a monocarboxylic acid corresponding to the aliphatic monocarboxylic acid residue having 7 to 20 carbon atoms of B 11 and B 12 , and one type of monocarboxylic acid is used. may be used, or two or more may be used in combination.
• the monoalcohol used in the production of the polyester of the present invention is a monoalcohol corresponding to the aliphatic monoalcohol residue having 6 to 10 carbon atoms of B 21 and B 22 , and the monoalcohol used may be used alone. Well, you may use 2 or more types together.
• the glycol used for producing the polyester of the present invention is a glycol corresponding to an alkylene glycol residue having 3 to 10 carbon atoms or an oxyalkylene glycol residue having 3 to 10 carbon atoms of G, and one type of glycol is used. may be used, or two or more may be used in combination.
• the dicarboxylic acid used in the production of the polyester of the present invention is a dicarboxylic acid corresponding to the alkylenedicarboxylic acid residue having 6 to 12 carbon atoms of A, and the dicarboxylic acid to be used may be used alone or in combination of two or more. may be used together.
• the polyester represented by the formula (1) in which m is 1 or more can be obtained, for example, by the method shown below.
• Method 1 A method in which the monocarboxylic acid, dicarboxylic acid and glycol constituting each residue of the polyester represented by formula (1) are charged all at once and reacted.
• Method 2 Dicarboxylic acid and glycol constituting each residue of the polyester represented by the formula (1) are reacted under conditions in which the equivalent weight of the hydroxyl group is greater than the equivalent weight of the carboxyl group to convert the hydroxyl group to the end of the main chain.
• the polyester represented by the formula (2) in which n is 1 or more can be obtained, for example, by the method shown below.
• Method 3 A method in which the monoalcohol, dicarboxylic acid and glycol constituting each residue of the polyester represented by formula (2) are charged all at once and reacted.
• Method 4 The dicarboxylic acid and glycol constituting each residue of the polyester represented by the formula (2) are reacted under conditions where the equivalent weight of the carboxyl group is greater than the equivalent weight of the hydroxyl group to form a carboxyl group on the main chain.
• a hydrogenated vegetable oil fatty acid may be used as the aliphatic monocarboxylic acid used in the production of the polyester represented by the formula (1).
• the hydrogenated vegetable oil fatty acid include hydrogenated coconut oil fatty acid, hydrogenated palm kernel oil fatty acid, hydrogenated palm oil fatty acid, hydrogenated olive oil fatty acid, hydrogenated castor oil fatty acid, and hydrogenated rapeseed oil fatty acid. These are obtained by hydrolyzing and hydrogenating oils obtained from palm, palm kernel, palm, olive, castor and rapeseed, respectively, and all contain aliphatic monocarboxylic acids having 8 to 21 carbon atoms. It is a mixture of two or more long chain aliphatic monocarboxylic acids.
• the vegetable oil fatty acid described above which has not been hydrogenated may be used as long as the effects of the present invention are not impaired. Also, the vegetable oil fatty acid is not limited to the above.
• the resulting polyester is composed of two or more polyesters represented by the formula (1). Obtained as a mixture.
• the polyester of the present invention is preferably a polyester prepared from an alkylene glycol having 3 to 10 carbon atoms, an alkylenedicarboxylic acid having 8 to 14 carbon atoms, and a hydrogenated vegetable oil fatty acid as reaction raw materials.
• hydrogenated vegetable oil fatty acid as aliphatic monocarboxylic acid, sebacic acid as alkylenedicarboxylic acid, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol and alkylene glycol as alkylene glycol
• all reaction raw materials can be biomass-derived raw materials.
• the reaction of the reaction raw materials may optionally be carried out in the presence of an esterification catalyst, for example, at a temperature of 180 to 250° C. for 10 to 25 hours.
• an esterification catalyst for example, at a temperature of 180 to 250° C. for 10 to 25 hours.
• Conditions such as the temperature and time of the esterification reaction are not particularly limited and may be set as appropriate.
• esterification catalyst examples include titanium-based catalysts such as tetraisopropyl titanate and tetrabutyl titanate; tin-based catalysts such as dibutyltin oxide; and organic sulfonic acid-based catalysts such as p-toluenesulfonic acid.
• the amount of the esterification catalyst used may be set appropriately, but it is usually used in the range of 0.001 to 0.1 parts by mass with respect to 100 parts by mass of the total amount of the reaction raw materials.
• Biodegradable resin composition contains the biodegradable resin plasticizer and biodegradable resin of the present invention.
• Biodegradable resins contained in the biodegradable resin composition of the present invention include polylactic acid (PLA), polyethylene succinate (PES), polyethylene terephthalate-succinate (PETS), polybutylene succinate (PBS), and polybutylene.
• Adipate-terephthalate (PBAT), polyethylene adipate-terephthalate (PEAT), polybutylene succinate-terephthalate (PBST), polyethylene succinate-terephthalate (PEST), polybutylene succinate-adipate (PBSA), polybutylene succinate-carbonate (PEC), polybutylene succinate-adipate-terephthalate (PBSAT), polyethylene succinate-adipate-terephthalate (PESAT), polytetramethylene adipate-terephthalate (PTMAT), polyhydroxybutyric acid (PHB), polyhydroxybutyric acid-hydroxyhexane acid (PHBH), polyhydroxybutyric acid-hydroxyvalerate (PHBV), polycaprolactone (PCL), polycaprolactone-butylene succinate (PCLBS), cellulose acetate and the like.
• the biodegradable resin to be used may be determined according to the intended use, and the above biodegradable resins may be used singly or in combination of two or more
• the biodegradable resin is preferably the group consisting of polylactic acid, polybutylene succinate, polybutylene adipate terephthalate, polyhydroxybutyric acid-hydroxyhexanoic acid, polyhydroxybutyric acid-hydroxyvalerate, polybutylene succinate adipate and polyethylene terephthalate succinate. It is one or more selected from.
• the biodegradable resin composition of the present invention may contain non-biodegradable resins as long as the effects of the present invention are not impaired.
• the non-biodegradable resin is not particularly limited, and includes polyolefin, polyester, polysulfide, polyvinyl chloride, modified polysulfide, silicone resin, modified silicone resin, acrylic urethane resin, epoxy resin, polyurethane, acrylic resin, polyester, and unsaturated resin. A polyester etc. are mentioned.
• the content of the biodegradable resin plasticizer of the present invention in the biodegradable resin composition of the present invention is preferably It is in the range of 1 to 50 parts by mass, more preferably in the range of 1 to 30 parts by mass, still more preferably in the range of 1 to 20 parts by mass, and particularly preferably in the range of 1 to 15 parts by mass.
• the biodegradable resin composition of the present invention may contain the biodegradable resin and the biodegradable resin plasticizer of the present invention, and a plasticizer other than the biodegradable resin plasticizer of the present invention (other plasticizers ) and other additives.
• plasticizers examples include benzoic acid esters such as diethylene glycol dibenzoate; dibutyl phthalate (DBP), di-2-ethylhexyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), Phthalates such as diundecyl phthalate (DUP) and ditridecyl phthalate (DTDP); terephthalates such as bis(2-ethylhexyl) terephthalate (DOTP); isophthalates such as bis(2-ethylhexyl) isophthalate (DOIP) acid ester; pyromellitic acid ester such as tetra-2-ethylhexyl pyromellitic acid (TOPM); di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), diisodecyl adipate (D
• the content of the other plasticizer is, for example, 10 to 300 parts per 100 parts by mass of the biodegradable resin plasticizer of the present invention. parts by mass, preferably 20 to 200 parts by mass.
• additives examples include flame retardants, stabilizers, stabilizing aids, colorants, processing aids, fillers, antioxidants (antiaging agents), ultraviolet absorbers, light stabilizers, lubricants, and electrification agents.
• examples include inhibitors, cross-linking aids, and the like.
• the method for producing the biodegradable resin composition of the present invention is not particularly limited.
• the biodegradable resin, the plasticizer for the biodegradable resin of the present invention, and the above-mentioned other additives are melted using a melt-kneader such as a single-screw extruder, twin-screw extruder, Banbury mixer, Brabender, and various kneaders. It can be obtained by a method of kneading.
• the biodegradable resin composition of the present invention can be molded by various molding methods applied to general-purpose plastics.
• the molding method include compression molding (compression molding, laminate molding, stampable molding), injection molding, extrusion molding and co-extrusion molding (film molding by inflation method or T-die method, laminate molding, pipe molding, wire / cable molding , profiled material molding), hot press molding, blow molding (various blow molding), calendar molding, solid molding (uniaxial stretching molding, biaxial stretching molding, roll rolling molding, stretch orientation nonwoven fabric molding, thermoforming (vacuum molding, air pressure molding) molding), plastic processing, powder molding (rotational molding), various non-woven fabric moldings (dry method, adhesion method, entanglement method, spunbond method, etc.), and the like.
• Injection molding, extrusion molding, compression molding or hot press molding are preferably applied. As specific shapes, application to sheets, films, and containers is preferred.
• the molded product obtained above may be subjected to secondary processing.
• the secondary processing includes embossing, painting, adhesion, printing, metallizing (plating, etc.), machining, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, coating etc.).
• a molded article obtained from the biodegradable resin composition of the present invention can exhibit excellent heat resistance because it contains the plasticizer for biodegradable resin of the present invention.
• the molded article is composed of a biodegradable resin and can be decomposed, it is a molded article with a small environmental load.
• Molded articles obtained from the biodegradable resin composition of the present invention are suitably used in a wide range of applications such as packaging materials for packaging liquids, granules, and solids, agricultural materials, and construction materials.
• Specific applications include injection molded products (e.g. fresh food trays, fast food containers, coffee capsule containers, cutlery, outdoor leisure products, etc.), extrusion molded products (e.g. films, sheets, fishing lines, fishing nets, vegetation). nets, secondary processing sheets, water-retaining sheets, etc.), hollow molded products (bottles, etc.), and the like.
• Applications are not limited to the above, agricultural films, coating materials, fertilizer coating materials, nursery pots, laminated films, boards, stretched sheets, monofilaments, nonwoven fabrics, flat yarns, staples, crimped fibers, creased tapes, splits Yarns, composite fibers, blown bottles, shopping bags, garbage bags, compost bags, cosmetic containers, detergent containers, bleach containers, ropes, binding materials, sanitary coverstock materials, cooler boxes, cushioning films, multifilaments, synthetic papers , surgical thread, suture thread, artificial bone, artificial skin, microcapsule, wound dressing, etc. for medical use.
• the values of acid value, hydroxyl value and viscosity are values evaluated by the following methods.
• ⁇ Method for measuring acid value> It was measured by a method according to JIS K0070-1992.
• ⁇ Method for measuring hydroxyl value> It was measured by a method according to JIS K0070-1992.
• ⁇ Method for measuring viscosity> It was measured by a method according to JIS K6901-1986.
• the number average molecular weight of polyester is a value converted to polystyrene based on GPC measurement, and the measurement conditions are as follows.
• [GPC measurement conditions] Measuring device: High-speed GPC device “HLC-8320GPC” manufactured by Tosoh Corporation Column: "TSK GURDCOLUMN SuperHZ-L” manufactured by Tosoh Corporation + "TSK gel SuperHZM-M” manufactured by Tosoh Corporation + “TSK gel SuperHZM-M” manufactured by Tosoh Corporation + “TSK gel SuperHZ-2000” manufactured by Tosoh Corporation + “TSK gel SuperHZ-2000” manufactured by Tosoh Corporation Detector: RI (differential refractometer) Data processing: "EcoSEC Data Analysis version 1.07" manufactured by Tosoh Corporation Column temperature: 40°C Developing solvent: tetrahydrofuran Flow rate: 0.35 mL/min Measurement sample: 7.5 mg of the sample was dissolved in
• Example 1 Synthesis of polyester plasticizer A
• 808 g (4.0 mol) of sebacic acid and 495 g (5.5 mol) of 1,3-butanediol were placed in a reaction vessel having an inner volume of 2 liters and equipped with a thermometer, a stirrer and a reflux condenser.
• a flask was charged, and the temperature was gradually raised to 220° C. while stirring under a nitrogen stream.
• 410 g (2.0 mol) of hydrogenated coconut oil fatty acid and 0.1 g of tetraisopropoxytitanium as an esterification catalyst were added, and water produced was continuously removed.
• the polyester plasticizer A (number average molecular weight: 1,820, viscosity: 690 mPa ⁇ s, acid value: 0.5, hydroxyl value: 6.5) was obtained by distillation under reduced pressure at the same temperature.
• the hydrogenated coconut oil fatty acid contains 5% by mass of octanoic acid (8 carbon atoms), 5% by mass of capric acid (10 carbon atoms), 51% by mass of lauric acid (12 carbon atoms), and myristic acid (12 carbon atoms). 14), 10% by mass of palmitic acid (16 carbon atoms), and 11% by mass of octadecanoic acid (18 carbon atoms).
• biodegradable resin composition (1) 100 parts by mass of polylactic acid (“REVODE 110” manufactured by Zhejiang Hisun Biomaterials Co., Ltd.) and 5 parts by mass of the obtained polyester plasticizer A were mixed to obtain a biodegradable resin composition (1). The following evaluation was performed using the obtained biodegradable resin composition (1). Table 1 shows the results.
• the obtained biodegradable resin composition (1) was made into a press sheet having a thickness of 1 mm with a hot press.
• the tensile strength of this sheet was measured according to JIS K7128-3:1998.
• the obtained biodegradable resin composition (1) was made into a press sheet having a thickness of 1 mm with a hot press.
• the crystallization temperature and glass transition temperature of this sheet were measured using a differential scanning calorimeter (“DSC3+” manufactured by Mettler Toledo, Inc.). Since heat is generated when crystallization occurs, the crystallization temperature was evaluated from the exothermic peak. Moreover, since the baseline shifts when the glass transition occurs, the glass transition temperature was evaluated from the baseline shift.
• Example 2 Synthesis of polyester plasticizer B
• 808 g (4.0 mol) of sebacic acid and 572 g (5.5 mol) of neopentyl glycol were charged into a 2-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser. , and the temperature was raised stepwise to 220° C. while stirring under a nitrogen stream.
• 410 g (2.0 mol) of hydrogenated coconut oil fatty acid and 0.1 g of tetraisopropoxytitanium as an esterification catalyst were added, and water produced was continuously removed.
• polyester plasticizer B (number average molecular weight: 1,780, viscosity: 650 mPa ⁇ s, acid value: 0.5, hydroxyl value: 8.0) was obtained by distillation under reduced pressure at the same temperature.
• a biodegradable resin composition (2) was prepared and evaluated in the same manner as in Example 1, except that plasticizer B was used instead of plasticizer A. Table 1 shows the results.
• Example 3 Synthesis of polyester plasticizer C
• 808 g (4.0 mol) of sebacic acid and 418 g (5.5 mol) of 1,2-propanediol were placed in a reaction vessel having an inner volume of 2 liters and equipped with a thermometer, a stirrer, and a reflux condenser.
• a flask was charged, and the temperature was gradually raised to 220° C. while stirring under a nitrogen stream.
• 410 g (2.0 mol) of hydrogenated coconut oil fatty acid and 0.1 g of tetraisopropoxytitanium as an esterification catalyst were added, and water produced was continuously removed.
• the polyester plasticizer A (number average molecular weight: 1,800, viscosity: 700 mPa ⁇ s, acid value: 0.4, hydroxyl value: 7.0) was obtained by distilling off under reduced pressure at the same temperature.
• a biodegradable resin composition (3) was prepared and evaluated in the same manner as in Example 1, except that plasticizer C was used instead of plasticizer A. Table 1 shows the results.
• polyester plasticizer D (Example 4: Synthesis of polyester plasticizer D) A reaction vessel was charged with 808 g (4.0 mol) of sebacic acid, 292 g (2.75 mol) of diethylene glycol, and 209 g (2.75 mol) of 1,2-propanediol, equipped with a thermometer, a stirrer, and a reflux condenser. The mixture was charged in a four-necked flask having an internal volume of 2 liters and heated stepwise to 220° C. while stirring under a nitrogen stream. Then, 410 g (2.0 mol) of hydrogenated coconut oil fatty acid and 0.1 g of tetraisopropoxytitanium as an esterification catalyst were added, and water produced was continuously removed. After the reaction, polyester plasticizer I (number average molecular weight: 1,740, viscosity: 610 mPa ⁇ s, acid value: 0.4, hydroxyl value: 7.2) was obtained by distilling off under reduced pressure at
• a biodegradable resin composition (4) was prepared and evaluated in the same manner as in Example 1, except that plasticizer D was used instead of plasticizer A. Table 1 shows the results.
• polyester plasticizer E (Example 5: Synthesis of polyester plasticizer E) A reaction vessel was charged with 808 g (4.0 mol) of sebacic acid, 209 g (2.75 mol) of 1,2-propanediol, and 248 g (2.75 mol) of 1,3-butadiol with a thermometer, stirrer, and reflux. The mixture was placed in a 2-liter four-necked flask equipped with a condenser, and the temperature was raised stepwise to 220° C. while stirring under a nitrogen stream. Then, 410 g (2.0 mol) of hydrogenated coconut oil fatty acid and 0.1 g of tetraisopropoxytitanium as an esterification catalyst were added, and water produced was continuously removed. After the reaction, polyester plasticizer I (number average molecular weight: 1,740, viscosity: 610 mPa ⁇ s, acid value: 0.4, hydroxyl value: 7.2) was obtained by distilling off under reduced pressure at
• a biodegradable resin composition (5) was prepared and evaluated in the same manner as in Example 1, except that plasticizer E was used instead of plasticizer A. Table 1 shows the results.
• Example 2 Preparation of biodegradable resin composition (2')
• Example 1 except that DAIFATTY-101 (manufactured by Daihachi Chemical Co., Ltd.), which is a commercially available plasticizer for polylactic acid and is a dibasic acid ester, was prepared and DAIFATTY-101 was used instead of the polyester plasticizer A.
• a biodegradable resin composition (2') was prepared and evaluated in the same manner. Table 1 shows the results.
• Example 6 Preparation of biodegradable resin composition (6)
• PHBV polyhydroxybutyric acid-hydroxyvalerate copolymer
• polyester plasticizer A 5 parts by mass of polyester plasticizer A
• Example 7 Preparation of biodegradable resin composition (7)
• PHBV polyhydroxybutyric acid-hydroxyvalerate copolymer
• polyester plasticizer B 5 parts by mass of polyester plasticizer B
• Example 8 Preparation of biodegradable resin composition (8)
• PHBV polyhydroxybutyric acid-hydroxyvalerate copolymer
• polyester plasticizer C 5 parts by mass of polyester plasticizer C

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