Classifications

• • 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
  • C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
• • 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
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

• the present invention relates to a biodegradable resin composition. More specifically, the present invention relates to a biodegradable resin composition containing a polyester and a polyester carbonate.
• plastic materials such as polyethylene, polypropylene, polyethylene terephthalate, and nylon have been used and consumed in large quantities as molding materials. Some of these plastic materials are recycled, but generally, after being collected, they are incinerated or buried underground. However, because collection requires a great deal of effort and expense, or because collection is difficult, they are sometimes left uncollected. In response to these environmental issues, there is a growing demand for the development of polymeric materials that decompose in the natural environment, and among these, biodegradable plastics, which can be decomposed by microorganisms, are particularly expected to be environmentally compatible materials and new types of functional materials.
• Polyester carbonate resin (hereinafter also referred to as "PEC") is known as a biodegradable plastic (for example, Patent Documents 1 and 2).
• PEC Polyester carbonate resin
• Patent Documents 1 and 2 a biodegradable plastic
• biodegradability is considered to be an important characteristic of resins.
• various developments are being carried out regarding biodegradable resin compositions.
• polyester carbonate has excellent mechanical strength, there is room for improvement in terms of melt fluidity, for example, when molding precision molded objects. Therefore, the present invention provides a biodegradable resin composition that has excellent melt fluidity while maintaining good mechanical strength, and a molded object using the biodegradable resin composition.
• the present inventors have found that the above-mentioned problems can be solved by adding a polyester (hereinafter also referred to as "PE") containing a structural unit (A) represented by general formula (1) and a structural unit (B) represented by general formula (2) to a polyester carbonate containing a structural unit (A) represented by general formula (1) and a structural unit (B) represented by general formula (2), and have arrived at the present invention. That is, the present invention provides the following aspects.
• PE polyester
• a biodegradable resin composition comprising: a polyester carbonate (PEC) containing a structural unit (A) derived from a monomer represented by the following general formula (1) and a structural unit (B) derived from a monomer represented by the following general formula (2).
• n represents an integer of 4 to 16.
• R 1 OOC-(CH 2 )m-COOR 2 (2) (In general formula (2), R 1 and R 2 are each independently selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms, and m represents an integer of 2 to 16.)
• ⁇ 2> The resin composition according to ⁇ 1>, wherein the mass ratio (PE:PEC) of the polyester (PE) to the polyester carbonate (PEC) is 0.1:99.9 to 50:50.
• ⁇ 3> The resin composition according to ⁇ 1> or ⁇ 2>, wherein the polyester (PE) has a hydroxyl value (OH value) of 30 to 140 mgKOH/g.
• ⁇ 4> The resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein the polyester (PE) has a weight average molecular weight (Mw) of 3,000 to 8,000.
• Mw weight average molecular weight
• PEC polyester carbonate
• ⁇ 6> The monomer represented by the general formula (1) contains 1,4-butanediol
• ⁇ 7> The resin composition according to any one of ⁇ 1> to ⁇ 6>, wherein at least one of the monomer represented by the general formula (1) and the monomer represented by the general formula (2) is derived from a biomass resource.
• ⁇ 8> A molded article comprising the biodegradable resin composition according to any one of ⁇ 1> to ⁇ 7>.
• the present invention can provide a biodegradable resin composition that has good mechanical strength and excellent melt fluidity.
• the present invention can also provide a molded article using the biodegradable resin composition.
• a numerical range expressed using "to” means a range including the numerical values before and after "to” as the lower and upper limits.
• a lower limit or an upper limit in this specification means a range including the lower limit or upper limit.
• the biodegradable resin composition of the present invention contains a structural unit (A) derived from a monomer represented by the following general formula (1) and a structural unit (B) derived from a monomer represented by the following general formula (2): , a polyester carbonate ( PEC).
• a structural unit (A) derived from a monomer represented by the following general formula (1) and a structural unit (B) derived from a monomer represented by the following general formula (2): , a polyester carbonate ( PEC).
• HO-( CH2 )n-OH (1) In general formula (1), n represents an integer of 4 to 16.)
• R 1 OOC-(CH 2 )m-COOR 2 (2) In general formula (2), R 1 and R 2 are each independently selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms, and m represents an integer of 2 to 16.
• the polyester (PE) and polyester carbonate (PEC) contained in the biodegradable resin composition of one embodiment of the present invention may have the same structural unit (A) and the same structural unit (B), or either one of the structural units (A) and the structural unit (B) may be the same, or the structural units (A) and the structural units (B) may be different.
• a polyester (PE) and a polyester carbonate (PEC) contain the same structural unit (A) and structural unit (B).
• the biodegradable resin composition may contain one type of monomer represented by the general formula (1) and one type of monomer represented by the general formula (2) alone, or may contain two or more types in combination.
• n may be an integer from 4 to 16, 4 to 14, 4 to 12, 4 to 10, 4 to 8, 4 to 6, or 4.
• monomers represented by the general formula (1) include aliphatic dihydroxy compounds such as 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,15-pentadecanediol, and 1,16-hexadecanediol.
• R1 and R2 are each independently selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms.
• the number of carbon atoms of the alkyl group that can be selected as R1 and R2 may be 1 to 4, 1 to 3, 1 or 2, 2 to 5, 2 to 4, 2 or 3, 3 to 5, 3 or 4, or 4 or 5.
• the alkyl group that can be selected as R1 and R2 may be a linear or branched alkyl group, and specific examples thereof include a methyl group, an ethyl group, a propyl group such as an n-propyl group or an isopropyl group, and a butyl group such as an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.
• m may be an integer from 2 to 16, 2 to 14, 2 to 12, 2 to 10, 2 to 8, 2 to 6, 2 to 4, or 2.
• the monomer represented by the general formula (2) include aliphatic dibasic acids such as succinic acid, glutaric acid, adipic acid, azelaic acid, suberic acid, sebacic acid, and dodecanoic acid (lauric acid). These aliphatic dibasic acids may be their esters or acid anhydrides.
• n represents an integer of 4 to 6
• R 1 and R 2 are each independently selected from a hydrogen atom and an alkyl group having 1 to 3 carbon atoms
• m represents an integer of 2 to 4.
• the monomer represented by the general formula (1) contains 1,4-butanediol
• the monomer represented by the general formula (2) contains succinic acid or adipic acid.
• the monomer represented by the general formula (1) and the monomer represented by the general formula (2) may be made using raw materials derived from fossil resources such as petroleum and coal, or may be made using raw materials derived from biomass resources such as plants.
• at least one of the monomer represented by the general formula (1) and the monomer represented by the general formula (2) is derived from a biomass resource.
• both the monomer represented by the general formula (1) and the monomer represented by the general formula (2) are derived from a biomass resource.
• Biomass resources include the stored energy from sunlight converted into starch or cellulose by plants through photosynthesis, the bodies of animals that grow by eating plants, and products made by processing plants or animals.
• Specific examples include wood, rice straw, rice bran, old rice, corn, sugar cane, cassava, sago palm, soybean pulp, corn cobs, tapioca waste, bagasse, vegetable oil residue, potatoes, buckwheat, soybeans, oils and fats, waste paper, papermaking residues, fishery residues, livestock waste, sewage sludge, and food waste.
• plant resources such as wood, rice straw, old rice, corn, sugarcane, cassava, sago palm, soybean pulp, corn cob, tapioca waste, bagasse, vegetable oil residue, potato, buckwheat, soybean, oils and fats, waste paper, and papermaking residue are preferred, more preferred are wood, rice straw, old rice, corn, sugarcane, cassava, sago palm, potato, oils and fats, waste paper, and papermaking residue, and most preferred are corn, sugarcane, cassava, and sago palm.
• the mass ratio (PE:PEC) of the polyester (PE) to the polyester carbonate (PEC) is preferably 0.1:99.9 to 50:50, and is also preferably 0.1:99.9 to 40:60, 1.0:99.0 to 30:70, 1.0:99.0 to 20:80, 1.0:99.0 to 10:90, or 1.0:99.0 to 5.0:95.0.
• PE:PEC ratio By setting the PE:PEC ratio within the above range, it is possible to prepare a biodegradable resin composition that has excellent melt fluidity while maintaining good mechanical strength.
• the weight average molecular weight (Mw) of the polyester (PE) is preferably 3,000 to 8,000, more preferably 3,500 to 7,000, and even more preferably 4,000 to 6,000.
• Mw weight average molecular weight
• the weight average molecular weight (Mw) of the polyester carbonate (PEC) is preferably 100,000 to 300,000, more preferably 130,000 to 280,000, and even more preferably 150,000 to 260,000.
• the weight average molecular weight (Mw) of the polyester carbonate (PEC) according to one embodiment of the present invention may have a lower limit of 190,000 or more, 200,000 or more, or more than 210,000.
• the upper limit of Mw may be any value within the above range.
• the weight average molecular weight (Mw) means the weight average molecular weight calculated in terms of polystyrene, and can be measured by the method described in the examples below.
• the hydroxyl value (OH value) of the polyester (PE) is preferably 30 to 140 mgKOH/g, more preferably 55 to 85 mgKOH/g, and further preferably 60 to 80 mgKOH/g.
• the hydroxyl value (OH value) in the range of 30 mgKOH/g or more, the affinity with polyester carbonate (PEC) can be improved and the physical properties of the resulting biodegradable resin composition can be maintained well.
• the hydroxyl value (OH value) in the range of 140 mgKOH/g or less, the hydrolysis property of the resulting biodegradable resin composition can be prevented from becoming too high.
• the hydroxyl value (OH value) means a value measured in accordance with JIS K-1557.
• the method for producing the biodegradable resin composition of the present invention is not particularly limited, but the biodegradable resin composition of one embodiment of the present invention can be produced, for example, by a stepwise method including the first-stage reaction and the second-stage reaction shown below.
• a method for obtaining a biodegradable resin composition in a stepwise manner for example, the methods described in JP-A-8-134196 and JP-A-8-301999 can be referred to.
• a compound containing the structural unit (A) derived from the monomer represented by the general formula (1) and a compound containing the structural unit (B) derived from the monomer represented by the general formula (2) are subjected to a polycondensation reaction in the presence of a catalyst to obtain a polyester (PE) as a prepolymer.
• the polyester (PE) obtained in the first reaction step and a carbonic acid diester are subjected to a polycondensation reaction in the presence of a catalyst to obtain a polyester carbonate (PEC).
• the catalyst used in the first and second reactions may be a basic compound catalyst, an ester exchange catalyst or a mixed catalyst comprising both.
• the basic compound catalyst include alkali metal compounds, alkaline earth metal compounds, and nitrogen-containing compounds.
• a salt of zinc, tin, zirconium, or lead is preferably used, and these can be used alone or in combination.
• Specific examples include zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin chloride (II), tin chloride (IV), tin acetate (II), tin acetate (IV), dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead acetate (II), lead acetate (IV), etc.
• Examples of the carbonate diester used in the second reaction include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, etc.
• diphenyl carbonate is particularly preferred.
• Unreacted monomers and carbonate diesters may remain in the biodegradable resin composition of one embodiment of the present invention.
• the acceptable residual monomer concentration is 0 ppm to 5000 ppm, preferably 1 ppm to 3000 ppm.
• the acceptable residual carbonate diester concentration is 0 ppm to 5000 ppm, preferably 1 ppm to 1000 ppm.
• phenol by-produced during the polycondensation reaction may remain.
• the acceptable residual phenol concentration is 1 ppm to 5000 ppm, and preferably 10 ppm to 3000 ppm.
• a cyclic dimer consisting of succinic acid and 1,4-butanediol may remain.
• the acceptable concentration of the cyclic dimer is 1.0 mass% or less, preferably 0.6 mass% or less.
• the concentration of the cyclic dimer in the biodegradable resin composition may be reduced by immersing and extracting the pellet-shaped biodegradable resin composition in a solvent that has low solubility in the biodegradable resin composition, such as water or acetone at 20°C to less than 100°C.
• the biodegradable resin composition of one embodiment of the present invention may be used in combination with resins other than polyester (PE) and polyester carbonate (PEC).
• resins are not particularly limited, but examples include at least one resin selected from the group consisting of polycarbonate resin, (meth)acrylic resin, polyamide resin, polystyrene resin, cycloolefin resin, acrylonitrile-butadiene-styrene copolymer resin, vinyl chloride resin, polyphenylene ether resin, polysulfone resin, polyacetal resin, and methyl methacrylate-styrene copolymer resin.
• Various known resins can be used, and one type can be used alone or two or more types can be used in combination.
• the biodegradable resin composition according to one embodiment of the present invention preferably contains an antioxidant as an additive.
• an antioxidant generally commercially available ones can be used, but it is preferable to contain at least one of an acid phenol-based antioxidant and a phosphite-based antioxidant, for example.
• Phenolic antioxidants include 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 4,4',4''-(1-methylpropanyl-3-ylidene)tris(6-tert-butyl-m-cresol), 6,6'-di-tert-butyl-4,4'-butylidene-m-cresol, ocladecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentane, pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 3,9-bis ⁇ 2-[3-
• Phosphite antioxidants include 2-ethylhexyl diphenyl phosphite, isodecyl diphenyl phosphite, triisodecyl phosphite, triphenyl phosphite, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxy-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and 2,2'-methylenebis(4,6-di-tert-butylphenyl)2-ethylhexyl phosphite.
• phosphite examples include tris(2,4-di-tert-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra-C12-15-alkyl(propane-2,2-diylbis(4,1-phenylene))bis(phosphite), 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and preferably 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane.
• the antioxidant any one of the above may be used alone, or a mixture of two or more of them may be used.
• the antioxidant is preferably contained in an amount of 1 ppm by weight to 3000 ppm by weight based on the total weight of the biodegradable resin composition.
• the content of the antioxidant is more preferably 50 ppm by weight to 2500 ppm by weight, even more preferably 100 ppm by weight to 2000 ppm by weight, particularly preferably 150 ppm by weight to 1500 ppm by weight, and even more preferably 200 ppm by weight to 1200 ppm by weight.
• the biodegradable resin composition according to one embodiment of the present invention preferably contains a release agent as an additive.
• the release agent include ester compounds, for example, glycerin fatty acid esters such as mono- and diglycerides of glycerin fatty acid, glycol fatty acid esters such as propylene glycol fatty acid esters and sorbitan fatty acid esters, higher alcohol fatty acid esters, and full esters or mono fatty acid esters of aliphatic polyhydric alcohols and aliphatic carboxylic acids.
• an ester of an aliphatic polyhydric alcohol and an aliphatic carboxylic acid is used as the release agent, either a monoester or a full ester can be used, but an ester other than the full ester, such as a monoester, may also be used.
• the release agent include the following. That is, sorbitan fatty acid esters such as sorbitan stearate, sorbitan laurate, sorbitan oleate, sorbitan trioleate, sorbitan tribehenate, sorbitan stearate, sorbitan tristearate, and sorbitan caprylate; propylene glycol fatty acid esters such as propylene glycol monostearate, propylene glycol monooleate, propylene glycol monobehenate, propylene glycol monolaurate, and propylene glycol monopalmitate; higher alcohol fatty acid esters such as stearyl stearate; Glycerol fatty acid ester monoglycerides including: glycerol monohydroxystearates such as glycerol monostearate and glycerol mono 12-hydroxystearate, monoglycerides such as glycerol monooleate, glycerol monobehenate, glyce
• the release agent is preferably contained in an amount of 1 ppm by weight to 5,000 ppm by weight based on the total weight of the resin composition.
• the content of the release agent is more preferably 50 ppm by weight to 4,000 ppm by weight, even more preferably 100 ppm by weight to 3,500 ppm by weight, particularly preferably 500 ppm by weight to 13,000 ppm by weight, and even more preferably 1,000 ppm by weight to 2,500 ppm by weight.
• additives may be added to the biodegradable resin composition of one embodiment of the present invention.
• the content of other additives other than the antioxidant and the release agent is preferably 10 ppm by weight to 5.0% by weight, more preferably 100 ppm by weight to 2.0% by weight, and even more preferably 1000 ppm by weight to 1.0% by weight, but is not limited thereto.
• the above-mentioned additives may adversely affect the transmittance, and therefore it is preferable not to add them in excess, and for example, the total amount added is within the above-mentioned range.
• the biodegradable resin composition of the present invention can be easily decomposed by microorganisms in soil, compost, seawater, rivers, lakes, etc., and can be widely used, for example, in cases where recycling is difficult.
• it since it has excellent moldability, it can be processed into various molded products such as films, sheets, laminates, fibers, nonwoven fabrics, threads, and laminates.
• Specific examples of applications in which the present invention can be used are given below.
• Specific examples of the material include various bags such as shopping bags, packaging materials for magnetic tape cassettes for videos and audios, packaging materials for flexible disks, plate-making materials, packaging bands, adhesive tape, tape, yarn, cups, trays, cartons, lunch boxes, containers for prepared foods, food and confectionery packaging materials, food wrap materials, internal coating materials for food and drink packages, shrink film for PET bottles, fresh food trays, fast food containers and lunch boxes, garbage bags, cups, plates, chopsticks, spoons, forks, straws, wrap materials for cosmetics and perfumery products, shopping bags, diapers, sanitary napkins, wrap materials for medicines, pharmaceutical packaging materials, packaging materials for surgical patches used for stiff shoulders, sprains, etc., various packaging materials for food, electronics, medical care, medicines, cosmetics, etc., parts of artificial hair and wig components, artificial turf, body bags, etc., and when the material has a film-like shape, it can also be heat-sealed.
• an agricultural mulch film it is used to cover the soil surface to keep the soil warm and to remove weeds, to prevent damage from pests, to create a fine uneven surface to diffuse sunlight and create an environment suitable for growing vegetables and fruits and for raising seedlings, etc. Films that are spread on the outside of greenhouses are used to prevent the generation of fog and mist, to improve heat retention, to prevent dust, etc.
• Other agricultural materials include materials used in the fields of agriculture, civil engineering, and fisheries, such as multipurpose films, pots and strings for plants, fertilizer coating materials, sustained-release covering materials, horticultural films, agricultural chemical wrap films, greenhouse films, fertilizer bags, seedling pots for transplanting, seedling raising pots, waterproof sheets, sandbag bags, construction films, weed prevention sheets, vegetation nets made of tapes and yarns, water-retaining films for greening wastelands and deserts, sandbags, vegetation nets, fishing lines, fishing nets, seaweed nets, and artificial bait. They can also be used for other purposes, such as garbage bags and compost bags.
• the material can be used in medical and sanitary products, for example, as medical materials such as sutures and bandages, and as sanitary materials such as disposable diapers and some sanitary products (polymer absorbents, waterproof films). It can also be used as disposable leisure goods for golf, fishing, marine sports, etc., and as a water treatment material such as a precipitant, dispersant, and detergent.
• the biodegradable resin composition according to one embodiment of the present invention preferably has a weight average molecular weight (Mw) of 150,000 or more, more preferably 155,000 or more, and even more preferably 160,000 or more.
• the weight average molecular weight (Mw) is preferably 300,000 or less, more preferably 280,000 or less, and even more preferably 260,000 or less.
• the biodegradable resin composition according to another embodiment of the present invention preferably has a weight average molecular weight (Mw) of 160,000 or more, more preferably 170,000 or more, and even more preferably 180,000 or more.
• the weight average molecular weight (Mw) is preferably 250,000 or less, more preferably 240,000 or less, and even more preferably 230,000 or less.
• the weight average molecular weight (Mw) is preferably 150,000 or more, more preferably 155,000 or more, and even more preferably 160,000 or more.
• the weight average molecular weight (Mw) is preferably 200,000 or less, more preferably 190,000 or less, and even more preferably 180,000 or less.
• the biodegradable resin composition according to yet another embodiment of the present invention preferably has a weight average molecular weight (Mw) of 90,000 or more, more preferably 100,000 or more, and even more preferably 120,000 or more.
• the weight average molecular weight (Mw) is preferably 200,000 or less, more preferably 190,000 or less, and even more preferably 180,000 or less.
• the biodegradable resin composition according to one embodiment of the present invention preferably has a melt volume flow rate (MVR) of 5.50 cm3 /10 min or more, more preferably 6.00 cm3 /10 min or more, and even more preferably 6.50 cm3 /10 min or more.
• MVR melt volume flow rate
• the biodegradable resin composition according to another embodiment of the present invention preferably has a melt volume flow rate (MVR) of 15.0 cm3 /10 min or more, more preferably 15.2 cm3 /10 min or more.
• the biodegradable resin composition according to yet another embodiment of the present invention preferably has a melt volume flow rate (MVR) of 4.50 cm3 /10 min or more, more preferably 5.00 cm3 /10 min or more, and even more preferably 7.50 cm3 /10 min or more.
• MVR melt volume flow rate
• the MVR molding is possible even when the MVR exceeds 100 cm3 /10 min, but the upper limit may be, for example, 200 cm3 /10 min or less, or 150 cm3 /10 min or less.
• the method for measuring MVR is as described in the Examples below.
• the molded article produced from the biodegradable resin composition of one embodiment of the present invention has a tensile elongation (%) of preferably 170% or more, more preferably 172% or more, and even more preferably 174% or more, and preferably 200% or less, more preferably 195% or less, and even more preferably 192% or less.
• the molded article produced from the biodegradable resin composition of another embodiment of the present invention has a tensile elongation (%) of preferably 175% or more, more preferably 185% or more, and even more preferably 195% or more, and preferably 230% or less, more preferably 220% or less, and even more preferably 215% or less.
• the molded article produced from the biodegradable resin composition of yet another embodiment of the present invention preferably has a tensile elongation (%) of 200% or more, more preferably 250% or more.
• the tensile elongation (%) is preferably 500% or less, more preferably 480% or less.
• the molded article having a small tensile elongation is not necessarily inferior. For example, even if the tensile elongation is small, a molded article having a high flexural modulus may be highly useful.
• the molded article of one embodiment may have a tensile elongation (%) of 5% or more, 10% or more, or 11% or more, or may be 50% or less, 30% or less, or 20% or less.
• the method for measuring the tensile elongation (%) is as described in the Examples section below.
• the molded article produced from the biodegradable resin composition of one embodiment of the present invention preferably has a maximum tensile strength (MPa) of 33.5 MPa or more, more preferably 34.0 MPa or more, and even more preferably 34.2 MPa.
• the maximum tensile strength (MPa) is preferably 38.0 MPa or less, more preferably 37.5 MPa or less, and even more preferably 37.0 MPa.
• the molded article produced from the biodegradable resin composition of another embodiment of the present invention preferably has a maximum tensile strength (MPa) of 30.0 MPa or more, more preferably 31.5 MPa or more, and even more preferably 33.0 MPa or more.
• the maximum tensile strength (MPa) is preferably 45.0 MPa or less, more preferably 44.5 MPa or less, and even more preferably 43.0 MPa.
• the method for measuring the maximum tensile strength (MPa) is as described in the Examples below.
• the molded article produced from the biodegradable resin composition of one embodiment of the present invention preferably has a tensile yield strength (MPa) of 32.0 MPa or more, more preferably 32.5 MPa or more, and even more preferably 32.8 MPa or more.
• the tensile yield strength (MPa) is preferably 36.0 MPa or less, more preferably 35.5 MPa or less, and even more preferably 35.0 MPa or less.
• the molded article produced from the biodegradable resin composition of another embodiment of the present invention preferably has a tensile yield strength (MPa) of more than 28.0 MPa, more preferably 28.5 MPa or more, and even more preferably 30.0 MPa or more.
• the tensile yield strength (MPa) is preferably 35.0 MPa or less, more preferably 33.5 MPa or less, and even more preferably 32.0 MPa or less.
• the method for measuring the tensile yield strength (MPa) is as described in the Examples section below.
• the molded article produced from the biodegradable resin composition of one embodiment of the present invention preferably has a flexural modulus (Mpa) of 630 Mpa or more, more preferably 632 Mpa or more, and even more preferably 634 Mpa or more.
• the flexural modulus (Mpa) is preferably 670 Mpa or less, more preferably 668 Mpa or less, and even more preferably 664 Mpa or less.
• the molded article produced from the biodegradable resin composition of another embodiment of the present invention preferably has a flexural modulus (Mpa) of 590 Mpa or more, more preferably 592 or more, and even more preferably 594 or more.
• the flexural modulus (Mpa) is preferably 615 Mpa or less, more preferably 613 Mpa or less, and even more preferably 610 Mpa or less.
• the molded article produced from the biodegradable resin composition of yet another embodiment of the present invention preferably has a flexural modulus (Mpa) of 430 Mpa or more, more preferably 450 or more, and even more preferably 465 or more.
• the flexural modulus (Mpa) is preferably 615 Mpa or less, more preferably 613 Mpa or less, and even more preferably 610 Mpa or less.
• the method for measuring the flexural modulus (Mpa) is as described in the Examples below.
• the molded article produced from the biodegradable resin composition of one embodiment of the present invention preferably has a bending stress (Mpa) of 34.0 Mpa or more, more preferably 34.4 Mpa or less, and even more preferably 34.7 Mpa or more.
• the bending stress (Mpa) is preferably 37.0 Mpa or less, more preferably 36.8 Mpa or less, and even more preferably 36.6 Mpa or less.
• the molded article produced from the biodegradable resin composition of another embodiment of the present invention preferably has a bending stress (Mpa) of 33.7 or more, more preferably 33.7 Mpa or more, and even more preferably 34.0 Mpa or more.
• the bending stress (Mpa) is preferably 35.5 Mpa or less, more preferably 35.0 Mpa or less, and even more preferably 34.8 Mpa or less.
• the molded article produced from the biodegradable resin composition according to yet another embodiment of the present invention has a bending stress (Mpa) of preferably 26.0 or more, more preferably 26.5 or more, and even more preferably 28.0 or more.
• the bending stress (Mpa) is preferably 35.5 MPa or less, more preferably 35.0 MPa or less, and even more preferably 34.8 MPa or less.
• the method for measuring the bending stress (Mpa) is as described in the Examples section below.
• the molded article produced from the biodegradable resin composition of one embodiment of the present invention preferably has a notched Charpy impact strength (KJ/ m2 ) of more than 8.8 KJ/ m2 , more preferably 8.9 KJ/m2 or more , and even more preferably 9.0 KJ/ m2 or more.
• the notched Charpy impact strength (KJ/ m2 ) is preferably 12.0 KJ/ m2 or less, more preferably 11.5 KJ/m2 or less , and even more preferably 11.0 KJ/m2 or less .
• the molded article produced from the biodegradable resin composition of another embodiment of the present invention preferably has a notched Charpy impact strength (KJ/ m2 ) of more than 8.3 KJ/ m2 , more preferably 8.4 KJ/ m2 or more, and even more preferably 8.5 KJ/m2 or more .
• the notched Charpy impact strength (KJ/ m2 ) is preferably 10.0 KJ/m2 or less , more preferably 9.5 KJ/ m2 or less, and even more preferably 9.0 KJ/m2 or less .
• a molded article produced from the biodegradable resin composition of yet another embodiment of the present invention preferably has a notched Charpy impact strength (KJ/ m2 ) of 7.5 KJ/m2 or more , more preferably 8.0 KJ/m2 or more , and even more preferably 10.0 KJ/ m2 or more.
• the notched Charpy impact strength (KJ/ m2 ) is preferably 15.0 KJ/m2 or less , more preferably 14.0 KJ/ m2 or less, and even more preferably 13.0 KJ/ m2 or less.
• the method for measuring the notched Charpy impact strength (KJ/m 2 ) is as described in the Examples below.
• Hydroxyl value (OH value) The hydroxyl value was measured in accordance with JIS K-1557.
• Test specimen Molding machine: Epson Techform Corporation C,Mobile-0813 Molding temperature: Manifold 150°C, Body 170°C, Tip 70% Mold temperature setting: 40°C Extrusion screw speed: 90 rpm Weighing speed: 2mm/s Injection speed: 20mm/s How to measure: Measuring instrument: Shimadzu Corporation Autograph AGS-X Load cell maximum capacity: 500N Test speed: 0.5mm/min, 25mm/min after elastic deformation Grip distance: 50mm
• Tensile elongation Calculated from the stroke travel distance of the test device based on the initial gripper distance. Maximum tensile strength: Determined from the maximum strength from the start of the test to the breakage of the test piece.
• Tensile yield strength Determined from the first point where the test force decreases by 0.1% relative to the full scale of the load cell. Number of test repetitions: 3
• Notched Charpy impact strength was measured in accordance with JIS K 7111-1: 2012/1eA. The detailed conditions of the test specimen and the measurement method are described below.
• Test specimen Molding machine: Epson Techform Corporation C,Mobile-0813 Molding temperature: Manifold 150°C, Body 170°C, Tip 70% Mold temperature setting: 40°C Extrusion screw speed: 90 rpm Weighing speed: 2mm/s Injection speed: 20mm/s
• Test piece shape rectangular test piece 10mm x 80mm x 2mm Notching machine: Toyo Seiki Co., Ltd.
• notching tool A-4E type Impact direction Edgewise Notch shape: A Notch tip radius: 0.25 Remaining width after notch: Standard 8.0mm measurement: Measuring instrument: Toyo Seiki Co., Ltd. DG-CB Number of test repetitions: 3
• PET2 of Polyester (PE; Prepolymer)>
• a polyester (PE2) was obtained in the same manner as in the above-mentioned Polyester (PE; prepolymer) Polymerization Example 1, except that trimethylolpropane was not used as a raw material.
• the physical properties of the obtained polyester (PE2) are shown in Table 1.
• Polymerization Example 1 (PEC1)> 77.025 kg of polyester (PE1) obtained in Polymerization Example 1 of Polyester (PE; Prepolymer), 11.023 kg (51 mol) of diphenyl carbonate (DPC), and 5.860 g (2.7.E-02 mol, 75 ppm relative to the prepolymer) of zinc acetate dihydrate as a catalyst were charged into a 300 L reaction kettle equipped with a condenser and a stirring blade. After replacing the inside of the reactor with nitrogen, the inside temperature of the reactor was controlled to 220°C under normal pressure (101.33 kPa), and phenol produced by the transesterification reaction was condensed and removed using a condenser. The inside of the reactor was then gradually reduced in pressure to 0.25 kPa to obtain polyester carbonate (PEC1). The physical properties of the obtained polyester carbonate (PEC1) are shown in Table 2.
• polyester carbonate (PEC2) was obtained in the same manner as in Polymerization Example 1, except that 71.730 kg of polyester (PE1) obtained in Polymerization Example 1 of the above-mentioned polyester (PE; prepolymer), 8.725 kg (41 mol) of diphenyl carbonate (DPC), and 2.910 g (1.3.E-02 mol, 40 ppm relative to the prepolymer) of zinc acetate dihydrate were used as a catalyst.
• the physical properties of the obtained polyester carbonate (PEC2) are shown in Table 2.
• polyestercarbonate (PEC3) was obtained in the same manner as in Polyestercarbonate Polymerization Example 1, except that 77.025 kg of polyester (PE2) obtained in the above-mentioned Polyester (PE; prepolymer) Polymerization Example 2, 10.734 kg (50 mol) of diphenyl carbonate (DPC), and 5.860 g (2.7.E-02 mol, 75 ppm relative to the prepolymer) of zinc acetate dihydrate were used as raw materials.
• the physical properties of the obtained polyestercarbonate (PEC3) are shown in Table 2.
• Example 1 The polyester carbonate was 99% by mass of the above-mentioned PEC1, and the prepolymer was 1% by mass of the above-mentioned PE2.
• the kneading conditions are shown below.
• the physical properties of the obtained biodegradable resin composition are shown in Table 3.
• Extruder: Toyo Seiki Co., Ltd. small twin-screw segment extruder 2D15W L/D: 17 Temperature settings: C1/C2/die 130°C/150°C/150°C Feeder rotation speed: 10 rpm Discharge rate: 400g/h setting
• Examples 2 to 6, Comparative Examples 1 and 2 Melt kneading was carried out in the same manner as in Example 1, except that the polyester carbonates and polyesters (prepolymers) shown in Tables 3 and 4 were used.
• the physical properties of the resulting biodegradable resin compositions are shown in Tables 3 and 4.
• Examples 7 to 10, Comparative Example 3 Melt kneading was carried out in the same manner as in Example 1, except that the polyester carbonate and polyester (prepolymer) shown in Table 5 were used.
• the physical properties of the obtained biodegradable resin composition are shown in Table 5. In Table 5, "-" indicates that no clear yield point was observed (in this case, the maximum tensile strength can be regarded as the tensile yield strength).
• Examples 1 to 3 and Comparative Example 1 shown in Table 3 are properties of a system in which the Mw of the biodegradable resin composition is large.
• Examples 4 to 6 and Comparative Example 2 shown in Table 4 are properties of a system in which the Mw of the biodegradable resin composition is small.
• Examples 7 to 10 and Comparative Example 3 shown in Table 5 are systems using PEC3 obtained without blending trimethylolpropane (branching agent).
• the molded articles made from the biodegradable resin compositions of Examples 1 to 3, Examples 4 to 6, and Examples 7 to 10 have better mechanical strength overall than the molded articles of Comparative Examples 1, 2, and 3.
• Examples 9 and 10 (containing 30% by mass or more of prepolymer) had extremely low tensile elongation and lost ductility, but had improved flexural modulus and excellent flexural strength.
• the biodegradable resin composition of the present invention had excellent melt fluidity while maintaining good mechanical strength.

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