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WO2004048471A1 - Composition de resine biodegradable - Google Patents

Composition de resine biodegradable Download PDF

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Publication number
WO2004048471A1
WO2004048471A1 PCT/JP2003/015004 JP0315004W WO2004048471A1 WO 2004048471 A1 WO2004048471 A1 WO 2004048471A1 JP 0315004 W JP0315004 W JP 0315004W WO 2004048471 A1 WO2004048471 A1 WO 2004048471A1
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WO
WIPO (PCT)
Prior art keywords
group
biodegradable resin
aliphatic polyester
acid
resin composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2003/015004
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English (en)
Japanese (ja)
Inventor
Yoshimichi Okano
Hiroshi Katayama
Junichi Narita
Ichiro Takeishi
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Daicel Corp
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Daicel Chemical Industries Ltd
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Publication date
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Priority to JP2004555030A priority Critical patent/JPWO2004048471A1/ja
Priority to AU2003302415A priority patent/AU2003302415A1/en
Publication of WO2004048471A1 publication Critical patent/WO2004048471A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • 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
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy 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
    • C08G63/16—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
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters

Definitions

  • the present invention relates to a specific aliphatic polyester copolymer having an ester bond based on an aliphatic dicarboxylic acid residue, an aliphatic diol residue, and an optionally added aliphatic hydroxycarboxylic acid residue, and other biodegradable products.
  • the present invention relates to a biodegradable resin composition comprising a hydrophilic resin.
  • the composition has practicable physical properties and is excellent in biodegradability, and also suppresses powder blowing to the molded product surface due to bleeding out of the oligomer and the accompanying deterioration in appearance.
  • PBS polyethylene succinate
  • PCL polycaprolactone
  • biodegradable aliphatic polyesters include plate materials, containers, housings, films, yarns, and the like, and high strength, heat resistance, and biodegradability according to the application are required as basic performance.
  • PLA is a molded product that has been stretched or highly crystallized and has a high melting point near 170 ° C and high heat resistance, but it is hard or brittle. Composting equipment is required because the product has low elongation and is hard to decompose in the soil.
  • PBS and PES have sufficient heat resistance at a melting point of around 100 ° C, but have a low biodegradation rate, are not practically sufficient, and have poor mechanical properties. Lack of flexibility.
  • PCL has excellent flexibility, its application is limited due to its low melting point of 60T: its heat resistance, but its biodegradation rate is very fast.
  • an aliphatic polyester such as polybutylene succinate polypolyprolactone copolymer (PBSC) described in Japanese Patent No. 2997756 can be used.
  • PBSC polybutylene succinate polypolyprolactone copolymer
  • force-prolactone units By introducing force-prolactone units into the polyester copolymer, practical flexibility and appropriate biodegradability can be achieved, and by controlling the content of force-prolactone units, however, it has been found that it is possible to maintain sufficient heat resistance by setting the melting point to 80 ° C. or higher and to control biodegradability (Patent Document 1). Also, there have been many proposals for improving biodegradable high molecular weight aliphatic polyesters.
  • Japanese Patent Application Laid-Open No. 8-311181 discloses that an aliphatic dicarboxylic acid or an ester thereof, an aliphatic diol, an oxycarboxylic acid, an oxycarboxylic acid ester or a lactone are subjected to a polycondensation reaction in the presence of a catalyst to obtain a number average molecular weight.
  • a biodegradable high molecular weight aliphatic polyester copolymer having a molecular weight of 15,000 to 80,000 is disclosed (Patent Document 2).
  • JP-A-9-1272789 discloses an aliphatic polyester having a number average molecular weight of 1 to 300,000 by copolymerizing an aliphatic diol, an aliphatic dicarboxylic acid, and an aliphatic hydroxycarboxylic acid, and a number average molecular weight of 3
  • a resin composition in which 10,000 or more polylactic acids are melt-blended is disclosed (Patent Document 3).
  • WO 02-44249 discloses a weight-average molecular weight of 40 synthesized by a polycondensation reaction of a mixture of three components of an aliphatic diol, an aliphatic dicarboxylic acid, and an aliphatic hydroxycarboxylic acid or an anhydrous cyclic compound thereof (lactones). It is disclosed that by using a high molecular weight aliphatic polyester copolymer of 2,000 or more and other biodegradable resin, the molecular weight stability at the time of forming a film or the like is good and the molding is good. (Patent Document 4).
  • Patent No. 29977756 (Claims 1-3, Examples 1-5)
  • An object of the present invention is to use a high-molecular-weight aliphatic polyester copolymer containing oligomers to provide excellent mechanical properties and biodegradability, as well as powder blowing to the surface and accompanying deterioration in appearance.
  • An object of the present invention is to provide a biodegradable resin composition used for a biodegradable resin molded article having no problem. Disclosure of the invention
  • the inventors of the present invention added a specific amount of another biodegradable resin such as polylactic acid containing a specific amount of D-form with low crystallinity to a high-molecular-weight aliphatic polyester copolymer containing oligosaccharide.
  • a treatment such as annealing, a biodegradable resin molded product with excellent mechanical properties and biodegradability is obtained, with no powder blowing over the surface over time, with little accompanying deterioration in appearance.
  • the present invention was completed. That is, the first aspect of the present invention is that a molecular chain is a repeating unit represented by the following general formulas (1) and (2):
  • R 1 represents a divalent aliphatic group having 1 to 12 carbon atoms.
  • R 2 represents a divalent aliphatic group having 2 to 12 carbon atoms.
  • R 3 represents a divalent aliphatic group having 1 to 10 carbon atoms.
  • the present invention provides an aliphatic polyester-based biodegradable resin composition comprising:
  • the second aspect of the present invention is that the aliphatic polyester copolymer (a) is a low molecular weight aliphatic polyester copolymer having a weight average molecular weight of 5,000 or more, which is a polymer intermediate of the aliphatic polyester copolymer (a). 0.1 to 5 parts by weight of the general formula (7) per 100 parts by weight of the combined (a ')
  • X 1 and X 2 each represent a reactive group capable of forming a covalent bond by acting with a hydroxyl group or a hydroxyl group
  • R 7 represents a single bond, an aliphatic group or an aromatic group having 1 to 20 carbon atoms
  • X 1 and X 2 may have the same chemical structure or may have different chemical structures
  • biodegradable resin composition which has a low molecular weight obtained by reacting a bifunctional linking agent (e) represented by the following formula:
  • a third aspect of the present invention provides the first or second biodegradable resin composition of the present invention, wherein the general formula (1) is a succinic acid residue and / or an adipic acid residue.
  • a fourth aspect of the present invention provides the biodegradable resin composition according to any one of the first to third aspects of the present invention, wherein the general formula (2) is an ethylene glycol residue and / or a 1,4-butanediol residue. I do.
  • a fifth aspect of the present invention is that, when the general formula (3) is ⁇ -force prolactone, 4-methylcaprolactone, 3,5,5-trimethylcaprolactone, 3,3,5-trimethylcaprolactone,) 3-propiolactone
  • the present invention provides the biodegradable resin composition according to any one of the first to fourth aspects of the present invention, which is a group based on at least one selected from the group consisting of acetylbutyrolactone, ⁇ -valerolactone, and enantholactone.
  • a sixth feature of the present invention is that the reactive group of the bifunctional linking agent (e) represented by the general formula (7) is an isocyanate group, an isothiocyanate group, an epoxy group, an oxazoline group, an oxazolone group or an oxazinone.
  • a biodegradable resin composition according to the second aspect of the present invention which is a group, an aziridine group, or a mixed group thereof.
  • a seventh aspect of the present invention is that the mole fraction of the repeating unit (3) contained in the aliphatic polyester copolymer (a) or the low molecular weight aliphatic polyester copolymer (a ′) is 0.25 or less. And a biodegradable resin composition according to any one of the first to sixth aspects of the present invention.
  • An eighth aspect of the present invention is the first to seventh aspects of the present invention, wherein the weight composition ratio of the aliphatic polyester copolymer (a) and the other biodegradable resin (b) is 99.9 / 0.1 to 70Z30. Provided is a biodegradable resin composition.
  • a ninth aspect of the present invention provides the biodegradable resin composition according to any one of the first to eighth aspects of the present invention, wherein the other biodegradable resin (b) is an aliphatic polyester (bl).
  • a tenth aspect of the present invention is the biodegradable composition according to the ninth aspect of the present invention, wherein the aliphatic polyester (bl) is polylactic acid (PLA), poly ( ⁇ -force prolactone) (PCL), or a mixture thereof.
  • the aliphatic polyester (bl) is polylactic acid (PLA), poly ( ⁇ -force prolactone) (PCL), or a mixture thereof.
  • PLA polylactic acid
  • PCL poly ( ⁇ -force prolactone)
  • An eleventh aspect of the present invention provides the tenth biodegradable resin composition of the present invention, wherein the polylactic acid (PLA) is a polylactic acid copolymer containing 5 to 50% of a D-form.
  • a twelfth aspect of the present invention is the method according to the present invention, wherein the molded product after 60 days from the film formation is immersed and stirred in hexane for 60 seconds, and the extraction amount of the oligomer having a molecular weight of 500 or less is 1 Omg / 2500 cm 2 or less.
  • a biodegradable resin composition according to any one of items 1 to 11 is provided. BEST MODE FOR CARRYING OUT THE INVENTION
  • the molecular chain is a repeating unit represented by the following general formulas (1) and (2):
  • R 1 represents a divalent aliphatic group having 1 to 12 carbon atoms.
  • R 2 represents a divalent aliphatic group having 2 to 12 carbon atoms.
  • R 3 represents a divalent aliphatic group having 1 to 10 carbon atoms.
  • the high molecular weight aliphatic polyester copolymer (a) according to the present invention has the above composition, and has a low molecular weight aliphatic polyester copolymer (a ′) having a weight average molecular weight of 5,000 or more.
  • a ' General formula of 0.1 to 5 parts by weight per 100 parts by weight (7):
  • X 1 and X 2 each represent a reactive group capable of forming a covalent bond by acting with a hydroxyl group or a hydroxyl group
  • R 7 represents a single bond, an aliphatic group or an aromatic group having 1 to 20 carbon atoms
  • X 1 and X 2 may have the same chemical structure or may have different chemical structures
  • Linked by a bifunctional linking agent represented by It may be set to be 000 or more.
  • the component (A) which gives the aliphatic dicarboxylic acid residue of the formula (1) includes aliphatic dicarboxylic acid, an anhydride thereof, or a mono- or diester thereof, and is represented by the following general formula (4). .
  • R 1 represents a divalent aliphatic group having 1 to 12 carbon atoms
  • R 4 and R 5 represent a hydrogen atom, or an aliphatic group or an aromatic group having 1 to 6 carbon atoms.
  • R 4 and R 5 May be the same or different.
  • the divalent aliphatic group represented by R 1 is preferably a 2 to 8 chain or cyclic alkylene group, and includes one (CH 2 ) 2 —, one (CH 2 ) 4 —, one (CH 2 ) 6- and the like, and a linear lower alkylene group having 2 to 6 carbon atoms.
  • R 1 can have a substituent inert to the reaction, for example, an alkoxy group or a keto group, and R 1 can contain a hetero atom such as oxygen or zeo in the main chain. It may contain a structure separated by an ether bond, a thioether bond or the like.
  • R 4 and R 5 are hydrogen atoms, they represent aliphatic dicarboxylic acids.
  • Aliphatic dicarboxylic acids include, for example, succinic acid, daltaric acid, adipic acid, pimelic acid, azelaic acid, suberic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, sebacic acid, diglycolic acid, ketopimelic acid, malonic acid, methyl Malonic acid and the like.
  • aliphatic group represented by R 4 and R 5 in addition to a linear or branched alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, such as a cyclohexyl group having 5 to 5 carbon atoms 12 cycloalkyl groups.
  • R 4 and R 5 are lower alkyl groups having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms.
  • dialkyl esters include, for example, dimethyl succinate, getyl succinate, dimethyl dartrate, getyl dallate, dimethyl adipate, getyl adipate, dimethyl pimerate, dimethyl azelate, dimethyl suberate, getyl suberate Dimethyl sebacate, dimethyl sebacate, dimethyl decane dicarboxylate, dimethyl dodecane dicarbonate, dimethyl diglycolate, dimethyl ketopimelate, dimethyl malonate, dimethyl methyl malonate, and the like. These may be used alone or in combination of two or more.
  • the component (B) which gives the aliphatic diol residue of the formula (2) includes aliphatic diol.
  • the aliphatic diol is represented by the following general formula (4 ′).
  • R 2 represents a divalent aliphatic group having 2 to 12 carbon atoms.
  • divalent aliphatic group examples include a linear or cyclic alkylene group having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms.
  • Preferred alkylene groups are straight-chain lower alkylene groups having 2 to 6 carbon atoms, such as-(CH 2 ) 2 —, 1 (CH 2 ) 3 —, and — (CH 2 ) 4 _.
  • the divalent aliphatic group R 2 can have a substituent inert to the reaction, for example, an alkoxy group or a keto group.
  • R 2 can contain a hetero atom such as oxygen or zeolite in the main chain, and can also have a structure separated by, for example, an ether bond or a thioether bond.
  • Examples of the aliphatic diol include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,3-butanediol, 2-methylbutanepandiol, 1,4-butanediol, neopentyl glycol, Pentame Tylene glycol, hexamethylene glycol, octamethylene glycol, decamethylene glycol, dodecamethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, diethylene glycol, dipropylene glycol, triethylene glycol, Tetraethylene glycol, pentaethylene glycol, polyethylene glycol having a molecular weight of 1,000 or less can be used. These may be used alone or in combination of two or more. A small amount of trifunctional alcohol such as 1,1,1-tris (hydroxymethyl) propane may be used in combination.
  • 1,1,1-tris (hydroxymethyl) propane may be used in combination.
  • the component (C) that gives the aliphatic hydroxycarboxylic acid residue of the formula (3) includes a hydroxycarboxylic acid or a hydroxycarboxylic acid ester represented by the following general formula (5), or a compound represented by the following general formula (6). Lactones.
  • R 3 represents a divalent aliphatic group having 1 to 10 carbon atoms
  • R 6 represents a hydrogen atom or an aliphatic group or an aromatic group having 1 to 6 carbon atoms.
  • R 3 represents a divalent aliphatic group having 1 to 10 carbon atoms.
  • examples of the divalent aliphatic group R 3 include a chain or cyclic alkylene group having 2 to 10, preferably 2 to 8 carbon atoms.
  • R 3 can have a substituent inert to the reaction, for example, an alkoxy group or a keto group.
  • R 3 can contain a hetero atom such as oxygen or zeolite in the main chain, and can also have a structure separated by, for example, an ether bond or a thioether bond.
  • R 6 is hydrogen, or an aliphatic group or an aromatic group.
  • an aliphatic group As a linear or branched lower alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms such as a cyclohexyl group, and an aromatic group, Phenyl, benzyl and the like.
  • hydroxycarboxylic acid examples include glycolic acid, L-lactic acid, D-lactic acid, D, L-lactic acid, 2-methyllactic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxy-n-butyric acid, and 2-hydroxy-1-carboxylic acid. Examples thereof include 3,3-dimethylbutyric acid, 2-hydroxy-1-methylbutyric acid, 2-hydroxy-3-methylbutyric acid, hydroxybivalic acid, hydroxyisocabronic acid, and hydroxycabronic acid.
  • the hydroxycarboxylic acid may be a cyclic dimer ester (lactide) having two molecules bonded thereto. Specific examples thereof include those obtained from glycolic acid and those obtained from lactic acid.
  • hydroxycarboxylic acid ester examples include a methyl ester and an ethyl ester of the above-mentioned hydroxycarboxylic acid, and an acetic acid ester.
  • Examples of the lactones include those represented by the general formula (6).
  • examples of the divalent aliphatic group R 3 include a linear or branched alkylene group having 4 to 10 carbon atoms, preferably 4 to 8 carbon atoms.
  • R 3 can have a substituent inert to the reaction, for example, an alkoxy group or a keto group.
  • R 3 can contain a hetero atom such as oxygen or zeolite in the main chain, and can also have a structure separated by, for example, an ether bond or a thioether bond.
  • lactones include, for example, / 3-propiolactone; 3-butyrolactone, a-ptyrolactone,] 3-valerolactone, ⁇ -valerolactone, ⁇ 5-forceprolactone, ⁇ -forceprolactone , 4-methylcaprolactone, 3,5,5-trimethylcaprolactone, 3,3,5-trimethylcaprolactone, and other various methylating prolactones; / 3-methyl-1- ⁇ -valerolactone, enanthlactone, laurolactone, etc. Cyclic monomeric ester of hydroxycarboxylic acid; cyclic dimer of hydroxycarboxylic acid such as glycolide, L-lactide, D-lactide, etc.
  • the aliphatic polyester copolymer (a) obtained by the polymerization reaction of the above-mentioned component (A), the component (B), and the component (C) optionally added, or a low-molecular-weight aliphatic polyester described later.
  • the polymer (a ') may be random or block.
  • the monomers may be charged at once (random), dividedly (blocked), polymerized dicarboxylic acid-diol polymer with lactones, or polylactone mixed with dicarboxylic acid and diol.
  • the synthesis step depends on the type of raw materials used. Thus, for example, it can be divided into an esterification step in which the first half of the dehydration reaction mainly proceeds and a polycondensation step in which the second half of the ester exchange reaction mainly proceeds.
  • the esterification step is carried out at a reaction temperature of 80 °: ⁇ 250 ° C, preferably 100 ° C to 240 ° C, more preferably 145 ° C to 230, for 0.5 to 5 hours, preferably 1 to 4 hours, 760 It is desirable to carry out under conditions of ⁇ 100 To rr.
  • the catalyst does not require necessarily for aliphatic dicarboxylic acid or diester to 1 mole is used as a starting material, 10- 7 to 10- 3 mol, preferably in an amount of 10 6 to 5 X 10- 4 mole May be used.
  • the latter half polycondensation step is desirably completed in 2 to 10 hours, preferably 3 to 6 hours by raising the reaction temperature while depressurizing the reaction system, and finally 180 ° C to 270 ° C. It is desirable that the degree of reduced pressure be 3 Torr or less, preferably 1 Torr or less, at a reaction temperature of 190 ° C., preferably 190 ° to 240 ° C.
  • this step preferably better to use a general ester exchange reaction catalyst, with respect to the aliphatic dicarboxylic acid or diester to 1 mole used as a starting material, 1 0 7 to 1 0 3 mol, preferably 1 0 - 6 ⁇ 5 X 1 0 used in an amount of one 4 mol.
  • the amount of catalyst is less than this range, the reaction does not proceed well, and the reaction takes a long time. On the other hand, if it exceeds this range, it causes thermal decomposition, cross-linking and coloring of the polymer at the time of polymerization, and also causes thermal decomposition and the like in the molding process of the polymer.
  • the catalyst examples include various compounds of metals, for example, carboxylate, carbonate, borate, oxide, hydroxide, hydride, alcoholate, acetyl acetonate chelate and the like.
  • the metals include alkali metals such as lithium and potassium; alkaline earth metals such as magnesium, calcium and barium; typical metals such as tin, antimony and germanium; lead, zinc, cadmium, manganese, cobalt, nickel, Transition metals such as zirconium, titanium, and iron; and lanthanoid metals such as bismuth, niobium, lanthanum, samarium, europium, palladium, erbium, and ytterbium.
  • a nitrogen-containing basic compound, boric acid, boric acid ester, or the like is also used.
  • the alkali metal compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium hydrogen carbonate, lithium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate, Sodium stearate, lithium stearate, sodium borohydride, sodium borohydride, lithium benzoate, sodium dihydrogen phosphate, potassium dihydrogen phosphate And lithium dihydrogen phosphate.
  • Alkaline earth metal compounds include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, magnesium carbonate, carbonate
  • Examples include strontium, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, and strontium stearate.
  • Typical metal compounds include dibutyltin hydroxide, dibutyltin dilaurate, antimony trioxide, germanium oxide, bismuth hydroxide carbonate, bismuth acetate acetate and the like.
  • Transition metal compounds include lead acetate, zinc acetate, zinc acetyl acetate, cadmium acetate, manganese acetate, manganese acetyl acetate, cobalt acetate, cobalt acetylacetonate, nickel acetate, nickel acetyl acetate, Examples include zirconium acetate, zirconium acetyl acetate, titanium acetate, tetrabutoxy titanate, tetraisopropoxy titanate, titanium hydroxyacetyl acetate, iron acetate, iron acetyl acetate, and niobium acetate.
  • the rare earth compound include lanthanum acetate, samarium acetate, palladium europium acetate, erpium acetate, ytterbium acetate, and the like.
  • nitrogen-containing basic compound examples include aliphatic ethers such as tetraethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide.
  • borate ester examples include trimethyl borate, trihexyl borate, triheptyl borate, triphenyl borate, tritolyl borate, and trinaphthyl borate.
  • the above-mentioned raw materials of the trifunctional or higher functional polycarboxylic acid, polyhydric alcohol, and polyhydroxycarboxylic acid can be used.
  • the feed ratio of the raw materials (A) and (B) is selected so as to satisfy the following conditional expression (1). It is desirable.
  • [A] represents the number of moles of the component (A)
  • [B] represents the number of moles of the component (B).
  • a bifunctional linking agent (e) represented by the above formula (7) is added to the low-molecular-weight aliphatic polyester copolymer (a ') in a molten state, so that the weight average molecular weight is 4 You may make it raise to 000 or more.
  • the copolymer (a ') obtained in the polymerization step has a weight average molecular weight of 5,000 or more, preferably 10,000 or more, and the sum of the acid value and the hydroxyl value is between 1.0 and 45.
  • the acid value is 30 or less.
  • the sum of the acid value and the hydroxyl value of the copolymer (a ') is proportional to the concentration of the terminal group of the copolymer (a'), and when the weight average molecular weight is 5,000 or more, Virtually, the sum of the acid value and the hydroxyl value is 45 or less.
  • the molecular weight of the copolymer (a ') is low, and a large amount of the coupling agent is required to increase the molecular weight to the desired molecular weight by adding the coupling agent. Required.
  • problems such as gelation are likely to occur.
  • the sum of the acid value and the hydroxyl value is 1.0 or less, the viscosity of the molten state becomes high because the molecular weight of the copolymer (a ') is high.
  • the amount of the linking agent used is extremely small, it is difficult to make the reaction uniform, and problems such as gelation are liable to occur.
  • the melting temperature is raised for the purpose of causing a uniform reaction, problems such as thermal decomposition, cross-linking and coloring of the polymer occur.
  • the linking agent (e) used in the present invention is represented by the above formula (7).
  • formulas (9) to (11) capable of forming a covalent bond by reacting substantially only with a hydroxyl group are represented by the above formula (7).
  • R 8 to R 1Q represent a divalent aliphatic group or an aromatic group, and the hydrogen directly bonded to the ring may be substituted with an aliphatic group and Z or an aromatic group.
  • It can be selected from a group of cyclic reaction groups having up to 8 members.
  • X 1 and X 2 may have the same chemical structure or may have different chemical structures.
  • linking agent (e) various linking agents described in WO 02-44249, such as a series of diisocyanate compounds, can be used.
  • the acid value of the low molecular weight aliphatic polyester copolymer (a ′) as a precursor is 2.0 or less, preferably 1.0 or less. If the acid value is greater than 2.0, the concentration of the hydroxyl terminal of the copolymer (a ') is low and the ligation reaction cannot be carried out efficiently, or after the ligation reaction, that is, the acid value of the final product. And the molecular weight tends to decrease during molding.
  • the reactive groups X 1 and X 2 of the linking agent (e) can react with substantially only a lipoxyl group to form a covalent bond, thereby forming a 3- to 8-membered ring represented by the above formulas (12) to (15).
  • the acid value of the copolymer (a ') is preferably from 0.5 to 30.
  • the acid value is smaller than 0.5, the amount of the linking agent used is extremely small, so that it is difficult to perform a uniform reaction. If the acid value is larger than 30, problems such as the inability to lower the acid value of the final product and the risk of gelation due to the use of a large amount of the linking agent arise.
  • the diisocyanate 1 and the compound are preferably aliphatic diisocyanate compounds, and specifically, hexamethylene diisocyanate, lysine diisocyanate methyl ester (OCN- (CH 2 ) 4-CH (-NCO ) (-COOCH 3 ) ⁇ , uniquelyosinate.
  • the aliphatic polyester resin containing a urethane bond has a weight average molecular weight of 40,000 or more, and usually 70,000 to 350,000, preferably Is in the range of 70,000 to 250,000.
  • the reaction between the linking agent (e) and the low molecular weight aliphatic polyester copolymer (a ′) can be easily stirred in a state where the copolymer (a ′) is in a uniform molten state or contains a small amount of solvent. It is desirable to be carried out under conditions.
  • the amount of the coupling agent (e) used is desirably 0.1 to 5 parts by weight based on 100 parts by weight of the copolymer (a '). If the amount of the linking agent (e) is smaller than this, it is difficult to obtain a final product having a desired molecular weight, and if it is larger, problems such as gelation are likely to occur.
  • the reaction for increasing the molecular weight using the linking agent (e) is carried out at a temperature equal to or higher than the melting point of the copolymer (a '), and is lower than 270 ° C, preferably lower than 250 ° C, more preferably lower than 23 ° C. It can be performed below 0 ° C.
  • This reaction can be carried out in the same reactor as the polycondensation reaction by adding the linking agent (e) to the reactor in which the low molecular weight aliphatic polyester was produced. In addition, it can be carried out by mixing the low-molecular-weight aliphatic polyester and the linking agent using an ordinary extruder or a static mixer.
  • the molecular chain is represented by the following general formula: one (one CO—R 1 —COO—R 2 —O —) —
  • R 1 represents a divalent aliphatic group having 1 to 12 carbon atoms
  • R 2 represents a divalent aliphatic group having 2 to 12 carbon atoms.
  • R 3 represents a divalent aliphatic group having 1 to 10 carbon atoms.
  • the feed ratio of the raw materials (A) and (C) be selected so as to satisfy the following conditional expression (ii), including the case where the repeating unit (Q) is represented by .
  • [C] ([A] + [C]) in the above formula represents the mole fraction of the component (C) contained in the aliphatic polyester copolymer (a) or (a ′), and the repeating unit ( When it consists of P) and a repeating unit (Q), it indicates the mole fraction of the repeating unit Q.
  • the above range is preferably from 0.0002 to 0.30, more preferably from 0.0002 to 0.20, more preferably from 0.0002 to 0.18. When this value is smaller than 0.0002, the obtained polymer has high crystallinity and is inflexible and hard, and the biodegradability is slow and insufficient.
  • the obtained polymer has a low melting point and extremely low crystallinity, so that it has no heat resistance and is not suitable for practical use.
  • the charging ratios of the raw materials (A), (B) and (C) are selected so as to satisfy the following conditional expression (ii ').
  • [C] / ([A] + [B] + [C]) in the above formula represents the mole fraction of the component (C) contained in the aliphatic polyester copolymer (a) or (a ′). If this value is less than 0.0002, the resulting polymer is hard with high crystallinity and inflexibility, and the biodegradability is slow and insufficient in terms of biodegradability. (Depending on the type of (C), etc.) On the other hand, if it is larger than 0.25, the obtained polymer has a low melting point and extremely low crystallinity, so that it has no heat resistance and is not suitable for practical use (in some cases, depending on the type of component (C), etc.). Is).
  • the molar fraction of component (C) is 0.25 or less, preferably 0.0002 to 0.14, particularly preferably 0.0002 to 0.18.
  • the high molecular weight aliphatic polyester copolymer (a) according to the present invention has a weight average molecular weight of 40,000 or more, usually 70,000 to 350,000, preferably 70,0. The range is from 00 to 250,000.
  • the melting point is usually as high as 80 ° C or more, and the difference between the melting point and the decomposition temperature is as large as 100 ° C or more, and thermoforming is easy.
  • R 1 and R 2 in the general formula (1) are (CH 2 ) 2 or (CH 2 ) 4 , and R 3 is (CH 2 ) 5 Those have high melting points and high crystallinity.
  • R 1 and R 2 in the general formula (1) are (CH 2 ) 2 or (CH 2 ) 4 , and R 3 is (CH 2 ) Those with 5 have a high melting point and high crystallinity.
  • the high molecular weight aliphatic polyester copolymer (a) according to the present invention has an oligomer content of 1,000 to 20,000 m, preferably 1,000 to 15, having a molecular weight of 500 or less, as measured by the method described below. , 00 Oppm, particularly preferably from 1,000 to 10,000 Oppm.
  • another biodegradable resin (b) is added to the aliphatic polyester copolymer (a) in order to suppress the bleed-out.
  • the other biodegradable resin (b) synthetic and / or natural polymers are used.
  • Examples of the synthetic polymer include aliphatic polyesters, polyamides, polyamide esters, biodegradable cellulose esters, polypeptides, polyvinyl alcohol, and mixtures thereof.
  • an aliphatic polyester resin as the other biodegradable resin (b), preferably a poly (hydroxyalkylene (1 to 10 carbon atoms) carboxylic acid), particularly a polylactic acid (PLA), It is also used for the purpose of controlling the rate of biodegradability and controlling the physical properties.
  • the weight ratio of the aliphatic polyester copolymer (a) to the polylactic acid is 99.9 / 0.1 to 0.1. 7030, preferably 9575 to 80/20, more preferably 90/10 to 80/20.
  • the weight ratio of polylactic acid is less than 0.1, no inhibition of pre-adhesion and no effect of delaying biodegradation are observed, and if it exceeds 30, the aliphatic polyester copolymer (a) loses its original characteristic flexibility. This may result in brittle molded products.
  • the polylactic acid has an MFR (according to ASTM D-1238; load of 2160 g, at a temperature of 190) of from 0.1 to; L00 gZl for 0 minutes, preferably 1 to 50 g / 10 minutes, particularly preferably 2 ⁇ 10 gZl 0 min is used.
  • the type of polylactic acid is a D, L-polylactic acid copolymer, preferably a D-form content of 5 to 50%, particularly preferably 10 to 20%. is there.
  • a copolymer in such a range as the polylactic acid a molded article having a high toughness obtained from the composition with the aliphatic polyester copolymer (a) can be obtained.
  • the melting point of polylactic acid is 160 ° C or less, preferably amorphous.
  • Poly force prolactone (PCL) is 160 ° C or less, preferably amorphous.
  • the other biodegradable resin (b) poly (hydroxyalkylene (C 1-10) carboxylic acid), more preferably polylactone, particularly preferably polyprolactone (PCL) is used. In addition to suppression, it is also used for the purpose of controlling the biodegradation rate and controlling the physical properties.
  • the weight ratio of the aliphatic polyester copolymer (a) to the polyprolactone is 99.9X0. 1-70 / 30, preferably 95 / 5-80Z20, more preferably 9 0Z10 to 8020. If the weight ratio of the polyfunctional prolactone is too small, the effect of suppressing pre-adhesion and the effect of delaying biodegradation are not recognized. If it is too large, the heat resistance may be impaired.
  • polyforce prolactone those having a weight average molecular weight of 60,000 to 400,000, preferably 100,000 to 300,000, particularly preferably 140,000 to 200,000 are used.
  • polyprolactone examples include water; divalent or higher valent glycols such as ethylene dalicol, propylene glycol, and glycerin; and divalent or higher valent dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, and butanetetracarboxylic acid.
  • Acids Polycaprolactone using dicarboxylic or higher hydroxycarboxylic acids as initiators such as glycolic acid, lactic acid, and malic acid can be used.
  • the above polylactic acid alone may be used as the other biodegradable resin (b), but polylactic acid and the above polyprolactone can be used in combination.
  • the weight ratio of polylactic acid to polyprolactone is such that polylactic acid: polyprolactone is 100: 0 to 0: 100, preferably 90:10 to 50:50, and more preferably 80:20 to 60: 40.
  • the biodegradable cellulose ester that can be used as the other biodegradable resin (b) include organic acid esters such as cellulose acetate, cellulose butylate, and cellulose propionate; and cellulose nitrate, cellulose sulfate, and cellulose phosphate.
  • Inorganic acid esters; hybrid esters such as cellulose acetate butyrate, cellulose acetate phthalate and cellulose nitrate acetate can be exemplified.
  • cellulose esters can be used alone or in combination of two or more.
  • organic acid esters, cellulose acetate propionate, and cellulose acetate butyrate are preferred, and cellulose acetate containing a plasticizer is more preferred.
  • a cellulose acetate having a degree of acetylation of 40.03 to 62.5% that is, a cellulose acetate having a degree of acetyl substitution of 1.5 to 3.0 per repeating unit is considered to be useful.
  • cellulose acetate containing a plasticizer cellulose acetate having an acetylation degree of 48.8 to 62.5, particularly 50 to 62.5%, is useful. is there.
  • polypeptide examples include polyamino acids such as polymethylglutamic acid and polyamide esters.
  • polyamide ester examples include resins synthesized from ⁇ -force prolacton and ⁇ -force prolactam.
  • Examples of the natural polymer include starch, cellulose, paper, pulp, cotton, hemp, wool, silk, leather, carrageenan, chitin / chitosan, natural linear polyester resin, and a mixture thereof.
  • starch derived from a natural product, processed (modified) starch or a mixture of both can be used. More specifically, natural starches such as potato starch, corn starch, sweet potato starch, wheat starch, rice starch, tapio starch, sago starch, cassava starch, legume starch, kuzu starch, bracken starch, lotus starch, and heshi starch. These degradation products, amylose-degraded starch, and amylobectin-degraded starch are exemplified.
  • Starch can be used after solubilization if necessary.
  • starch can be heated by adding water to a viscous liquid for use.
  • a liquid that has been plasticized with ethylene glycol or glycerin instead of water and used as a liquid can also be used.
  • the processed starch include those obtained by subjecting natural starch to various physical denaturation, such as ⁇ -starch, fractionated amylose, and moisture-heat-treated starch.
  • Acetylated starch other chemically modified starch derivatives, such as esterification Ester starch that has been processed, etherified starch that has been etherified, cross-linked starch that has been processed with a cross-linking agent, and starch that has been aminated with 2-dimethylaminoethyl chloride.
  • Preferred starches are granular starch, plasticized starch plasticized with water and Z or a plasticizer, a mixture of granular starch and plasticized starch plasticized with water and Z or a plasticizer.
  • the weight composition ratio of the aliphatic polyester copolymer (a) and the starch is 95/5 to 20/80, preferably 90 to 10/40/60.
  • Resin additives include plasticizers, heat stabilizers, lubricants, anti-blocking agents, nucleating agents, photolytic agents, biodegradation accelerators, antioxidants, UV stabilizers, antistatic agents, flame retardants, droplet agents, and antibacterial agents Agents, deodorants, fillers, coloring agents, or mixtures thereof.
  • plasticizer examples include an aliphatic dibasic acid ester, a fluoric acid ester, a hydroxy polycarboxylic acid ester, a polyester plasticizer, a fatty acid ester, an epoxy plasticizer, and a mixture thereof.
  • phthalic acid esters such as di-2-ethylhexyl phthalate (DOP), dibutyl phthalate (DBP), diisodecyl phthalate (DIDP), and di-2-ethyl ethyl adipate
  • DOP di-2-ethylhexyl phthalate
  • DBP dibutyl phthalate
  • DIDP diisodecyl phthalate
  • Adipates such as xyl (DOA) and diisodecyl adipate (DI DA); azelates such as azelaic acid-di-2-ethylhexyl (DOZ); tri-l-ethylhexyl acetyl citrate; tributyl acetyl citrate
  • polyester-based plasticizers such as polypropylene glycol adipate, etc., and these are used alone or
  • the amount of the plasticizer to be added varies depending on the application, but is generally 3 to 30 parts by weight based on 100 parts by weight of the aliphatic polyester copolymer (a). Is preferable. When it is a molded product, the content is preferably in the range of 5 to 15 parts by weight. If the amount is less than 3 parts by weight, the elongation at break and the impact strength may decrease, and if it exceeds 30 parts by weight, the strength at break and the impact strength may decrease.
  • Heat stabilizers include aliphatic carboxylate salts. As the aliphatic carboxylic acid, an aliphatic hydroxycarboxylic acid is particularly preferred. As the aliphatic hydroxycarboxylic acid, naturally occurring ones such as lactic acid and hydroxybutyric acid are preferable.
  • the salt examples include salts of sodium, calcium, aluminum, barium, magnesium, manganese, iron, zinc, lead, silver, copper and the like. These can be used as one kind or as a mixture of two or more kinds.
  • the amount of addition is in the range of 0.5 to 10 parts by weight based on 100 parts by weight of the copolymer.
  • the impact strength (Izod impact value) is improved, and the effects of elongation at break, breaking strength and impact strength are reduced.
  • lubricant those generally used as an internal lubricant and an external lubricant can be used.
  • fatty acid esters, hydrocarbon resins and the like are used.
  • a lubricant When selecting a lubricant, it is necessary to select a lubricant whose melting point is lower than the melting point of lactone resin and other biodegradable resins. For example, in consideration of the melting point of the aliphatic polyester resin, a fatty acid amide of 16 Ot: or less is selected as the fatty acid amide. W 200
  • 0.05 to 5 parts by weight of a lubricant is added to 100 parts by weight of the resin. If the amount is less than 0.05 part by weight, the effect is not sufficient, and if it exceeds 5 parts by weight, it is not wound around a roll or the like, and the physical properties are deteriorated.
  • ethylene bisstearic acid amide, stearic acid amide, oleic acid amide, and erlic acid amide which are highly safe and registered with the FDA (US Food and Drug Administration), preferable.
  • photodegradation accelerator examples include benzophenones such as benzoins, benzoin alkyl ethers, benzophenone, and 4,4-bis (dimethylamino) benzophenone, and derivatives thereof; Acetophenone and its derivatives; quinones; thioxanthones; photoexciting materials such as phthalocyanine, analytic titanium oxide, ethylene carbon monoxide copolymer, and sensitizers of aromatic ketones and metal salts. Is exemplified. These photolysis accelerators can be used alone or in combination of two or more.
  • biodegradation accelerator examples include oxo acids (eg, oxo acids having about 2 to 6 carbon atoms such as glycolic acid, lactic acid, citric acid, tartaric acid, and malic acid), saturated dicarboxylic acids (eg, oxalic acid, malonic acid, etc.).
  • Organic acids such as acids, succinic acid, succinic anhydride, and dartaric acid, etc .; lower saturated dicarboxylic acids having about 2 to 6 carbon atoms); lower alkyls of these organic acids and alcohols having about 1 to 4 carbon atoms. Esters are included.
  • biodegradation promoters include organic acids having about 2 to 6 carbon atoms, such as citric acid, tartaric acid, and malic acid, and coconut shell activated carbon. These biodegradation accelerators can be used alone or in combination of two or more.
  • Examples of the filler include various fillers, such as calcium carbonate and talc, myrgic acid, and silica silicate.
  • Inorganic fillers such as lucidum, finely divided silica (anhydride), white carbon (hydrated), asbestos, porcelain clay (fired), maltstone, various titanium oxides, glass fibers, etc., and organic materials such as particles of natural materials Fillers can be mentioned.
  • the particle diameter is preferably from 0.1 to 7 m.
  • the finely divided silica as the inorganic filler may be silica produced by a wet method or silica produced by high-temperature hydrolysis of silicon tetrachloride in oxyhydrogen, but the particle size is 50 nm or less. Is preferable, and when low haze is required, a further 10 nm level is preferable.
  • the biodegradability is further improved and the melt strength (viscosity) is increased, so that drawdown during melt molding is prevented, and moldability such as vacuum molding, blow molding, and inflation molding is possible. Is improved.
  • the amount of the filler added is not particularly limited, but the weight ratio of the filler Z copolymer (a) to the aliphatic polyester copolymer (a) is preferably 5 to 50/95 to 50. More preferably, it is 10 to 45Z90 to 55, more preferably 20 to 40/80 to 60, particularly preferably 25 to 35Z75 to 65.
  • the resin will blow powder, while if it is too small, drawdown, necking, uneven thickness, and noticeable irregularities will occur during molding.
  • Organic fillers include finely divided particles of paper having a diameter of 50 microns or less and made from paper.
  • the addition amount and particle size of the organic filler are the same as in the case of the inorganic filler.
  • Examples of the bulking agent include wood flour and glass balloon.
  • the amount of filler added is the same as for inorganic fillers.
  • a general method can be preferably used as a method for kneading the aliphatic polyester copolymer (a) with the other biodegradable resin (b) and / or other additives.
  • the raw material resin pellet powder is used.
  • the body and solid flakes are dry-mixed with a Henschel mixer or a Ripon mixer, and then mixed with a single-screw or twin-screw extruder, Banbury mixer, kneader, mixing roll, etc. It can be supplied to a known melt mixer and melt-kneaded.
  • the biodegradable molded article of the present invention in which bleeding is suppressed is obtained by molding the kneaded product obtained above by an injection molding method, an extrusion molding method, a cast molding method, an inflation film molding method, or the like.
  • the bleed out of the oligomer can be further effectively suppressed.
  • the annealing temperature is usually from 30 to 60 T, preferably from 35 to 50, and more preferably from 35 to 45 ° C, depending on the composition ratio. If the annealing temperature is less than 30, the effect of further suppressing the bleed-out of the oligomer may not be observed. If the temperature is higher than 60 ° C, the molded article becomes too soft and may be blocked.
  • the annealing time depends on the temperature, but is usually 10 hours or more, preferably 24 to 480 hours, more preferably 72 to 360 hours. If the anneal treatment time is less than 10 hours, the effect of further suppressing the premide out of the oligomer may not be exhibited.
  • the upper limit is not particularly limited, but if it exceeds 480 hours, the expression of the suppressing effect is saturated.
  • the oligomer extraction amount in 60 seconds when immersed stirred in hexane is 1 Smg / ⁇ 500 cm 2 or less, preferably 12mgZ molded article surface one 2500 cm 2 or less, more preferably 1 OmgZ molded article surface one 2500 cm 2 or less, particularly preferably those of 8 MGZ molded article surface one 2500 cm 2 or less.
  • the molded article of the present invention is a molded article for use in which biodegradability is preferred, and includes plate materials, bottles' tanks (beverage bottles, food bottles, industrial large containers, detergent containers, pharmaceutical and agricultural chemical containers), trays, Cup (general purpose cup / food cup Z retort food cup / Other cups), Blister molded products, PTP packaged products, Packaging related materials (tapes, ropes, packing bands), hoses, tubes, containers (beer containers, fresh food containers), cushioning materials, insulation materials ( These are applied products such as fish boxes, others), coating materials, various films, accessories (zippers / pots), water-absorbing polymers, fibers (threads, woven fabrics, non-woven fabrics, nets, and ropes).
  • Products refrigerators, air conditioners, lighting equipment, heating equipment
  • electronic products TV, video and other video-related equipment, radio, stereo, CD, MD audio equipment, telephones, faxes, mobile phones, personal computers, word processors, Printers (copiers, various components of projectors), heavy electrical materials (insulation materials for light electricity (condenser films), magnetic tape films, circuit boards)
  • Plate materials IC sealing materials, bonded magnets, magnetic cards, conductive materials, battery materials (electrode materials, electrolyte materials, separators, battery batteries), resist materials, sensor materials (light, gas , Smell, humidity, temperature, ion), toys and stationery 'sporting goods (golf supplies, ski supplies, fishing supplies, shoes, helmets), mechanical parts (sliding parts (bearing)
  • Plumbing materials board materials (sheets and flat corrugated sheets Z decorative plywood), heat insulation materials, heat insulation, cold insulation materials (foam plastic), adhesives' sealing materials, tiles, medical supplies (separation membranes, sutures, Artificial organs, bioabsorbable materials, contact lenses, syringes 'injection needles, blood collection tubes and specimen testing instruments, infusions' blood transfusion instruments, catheters and tubes), etc.
  • Butanediol-Succinic acid prolactone terpolymer manufactured by Daicel Chemical Industries, Ltd., CBS-051 (Mw20.80,000 in terms of polystyrene, MFR (190 ° C) 1.8, Tml 08 ° C, oligomer Content 560 Oppm)
  • Polylactic acid copolymer (D 2) D-lactic acid content 2.2%, MFR (190 ° C) 9.4 g / 10 min, melting point 164)
  • Polylactic acid copolymer (D13) D-lactic acid content 12.6%, MFR (190 ° C) 2.6 g / 10min, amorphous
  • Polylactic acid copolymer (D3) D-lactic acid content 1.6%, MFR (190) 2.6 g / 10min, melting point 168 ° C
  • PCL Polycaprolactone
  • Weight average molecular weight Measured by GPC and determined in terms of standard polystyrene.
  • Bleed-out amount (mg): Immerse the molded article (2 pieces of A4 size, total area 2 500 cm 2 ) in 500m1 of hexane solvent, stir for 60 seconds, take out the molded article, The hexane solvent was concentrated and dried, and the solid content was dried under reduced pressure at 80 ° C and 400 Torr for 12 hours and weighed.
  • the amount of the additive erlic acid amide in the above extract was analyzed by gas chromatography as necessary.
  • the elongation (%) was the change in the distance between the chucks.
  • the measurement conditions are as follows.
  • Cross head speed 30 Omm / min (However, Young's modulus is measured at 5 mm / min. went. )
  • the measured values are the average of five measurements.
  • 3 days anneal A molded product that has been annealed for 3 days after molding is left at room temperature for 17 days, and 20 days after molding.
  • 10 days anneal A molded product that was annealed for 10 days after molding was left at room temperature for 10 days, and 20 days after molding.
  • the aliphatic polyester copolymer (a) and the other aliphatic polyester (b) were previously melt-kneaded at the ratios shown in Table 1 to obtain a kneaded composition.
  • a molded article was obtained using the kneading composition obtained above.
  • the base point of the elapsed days was set to 0 day for the film formation date (the same applies hereinafter).
  • Table 1 shows the results.
  • the aliphatic polyester copolymer (a) alone was used, and the bleed out of the oligomer occurred over time, and the haze and the parallel light transmittance deteriorated.
  • a polylactic acid copolymer is added as another aliphatic polyester (b)
  • bleeding is suppressed, and deterioration of appearance is suppressed.
  • Copolymer (a) CBS101 CBS101 CBS051 CBS051 CBS101 CBS051
  • the kneading composition was added in the same manner as in Example 1 by adding the aliphatic polyester copolymer (a), the aliphatic polyester (b) of Jo and other o- and the resin additive in the proportions shown in Table 2. Using a kneading composition, a molded product having a thickness of 30 m was obtained using a molding machine.
  • Table 2 shows the results. As can be seen from these results, in Comparative Example 3, although the aliphatic polyester copolymer (a) was used alone and the amount of bleed-out of the oligomer was large over time, the addition of polylactic acid was observed as shown in Examples 5 to 8. Bleed-out is suppressed along with the rate. The addition of the polylactic acid copolymer dilutes and lowers the oligomer content in the resin composition, but the bleed-out amount clearly exceeds the decrease due to the dilution.
  • Copolymer (a) CBS101 CBS101 CBS101 CBS101 CBS101
  • a molded product was obtained in the same manner as in Example 5 except that CBS051 was used instead of CBS101 as the aliphatic polyester copolymer (a). Comparative Example 4 was performed without the addition of the polylactic acid copolymer.
  • bleed-out can be further suppressed, and the amount of other aliphatic polyester (b) necessary for suppressing the bleed-out can be reduced.
  • the molded article obtained from the composition containing D13 having a high D-lactic acid content (D-lactic acid content of 12.6%) has a mixed amount of 15%.
  • the TD has a large elongation even in weight%.
  • molded articles obtained from a composition containing D2 (D-lactic acid content: 2.2%) or D3 (D-lactic acid content: 1.6%), which has a low D-lactic acid content have a lower mixing amount.
  • the content is 15% by weight, a molded article having a small elongation of TD can be obtained.
  • EA Awake 1000 1000 1000 1000 1000 1000 1000 2 days after molding Preed 0 0 0 0 0 0 20 days after molding Pread X X X X 0 0
  • a molded product having a thickness of 30 m and a thickness of 40 was obtained using a molding machine.
  • the obtained molded article was subjected to an annealing treatment at 40 ° C. for 10 days, then left at room temperature for 10 days, and then subjected to measurement.
  • Table 5
  • the biodegradability is excellent in mechanical properties and biodegradability, and has no problems such as powder blowing and further deterioration of appearance.
  • a resin molded product is obtained.

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Abstract

L'invention concerne une composition de résine biodégradable à base de polyester aliphatique comprenant: un copolymère polyester aliphatique (a) dans lequel la chaîne moléculaire est constituée d'unités récurrentes représentées par les formules générales -CO-R1-CO- (1), dans laquelle R1 représente un groupe aliphatique divalent C1-12, et -O-R2-O- (2), dans laquelle R2 représente un groupe aliphatique divalent C2-12, et contient facultativement des unités récurrentes représentées par la formule CO-R3-O- (3), dans laquelle R3 représente un groupe aliphatique divalent C1-10. Dans ce copolymère, le poids moléculaire moyen est égal ou supérieur à 40'000 et le contenu d'oligomères possédant un poids moléculaire égal ou inférieur à 500 est compris entre 1000 et 20'000 ppm. Cette composition comprend également une autre résine biodégradable (b). En utilisant le copolymère polyester aliphatique à poids moléculaire élevé et contenant des oligomères, on obtient des moulages de résine biodégradable possédant d'excellentes propriétés mécanique et de biodégradabilité, dont la surface ne subit pas de poudrage et qui ne présentent pas de problèmes tels que la détérioration de l'apparence due au poudrage.
PCT/JP2003/015004 2002-11-25 2003-11-25 Composition de resine biodegradable Ceased WO2004048471A1 (fr)

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JP2006096863A (ja) * 2004-09-29 2006-04-13 Daicel Chem Ind Ltd 脂肪族ポリエステル樹脂組成物フィルム及び用途
JP2006274257A (ja) * 2005-03-02 2006-10-12 Daicel Chem Ind Ltd 低分岐度脂肪族ポリエステル共重合体組成物、成形品及びフィルム
KR100657936B1 (ko) * 2004-07-07 2006-12-14 도레이새한 주식회사 나노입자를 함유한 생분해성 폴리에스테르 수지 조성물
JP2007262118A (ja) * 2006-03-27 2007-10-11 Toyobo Co Ltd 光散乱シート用生分解性ポリエステル樹脂組成物およびその製造方法
JP2007284595A (ja) * 2006-04-18 2007-11-01 Daicel Chem Ind Ltd 脂肪族ポリエステルフィルム
WO2008073099A1 (fr) * 2006-12-15 2008-06-19 Kimberly-Clark Worldwide, Inc. Polyesters biodégradables utilisés dans la formation de fibres
WO2008073101A1 (fr) * 2006-12-15 2008-06-19 Kimberly-Clark Worldwide, Inc. Acides polylactiques biodégradables s'utilisant dans la formation de fibres
JP2012040360A (ja) * 2010-08-13 2012-03-01 Tyco Healthcare Group Lp 表面腐食性縫合糸
WO2012055973A1 (fr) * 2010-10-27 2012-05-03 Novamont S.P.A. Polyester biodégradable et films d'enveloppement pour l'emballage produits avec celui-ci
US8268738B2 (en) 2008-05-30 2012-09-18 Kimberly-Clark Worldwide, Inc. Polylactic acid fibers
US8461262B2 (en) 2010-12-07 2013-06-11 Kimberly-Clark Worldwide, Inc. Polylactic acid fibers
US8518311B2 (en) 2007-08-22 2013-08-27 Kimberly-Clark Worldwide, Inc. Multicomponent biodegradable filaments and nonwoven webs formed therefrom
ITMI20120737A1 (it) * 2012-05-03 2013-11-04 Univ Pisa Copolimeri a base di poliesteri e plastificanti reattivi per la produzione di film da imballaggio trasparenti e biodegradabili
KR101343735B1 (ko) * 2006-12-15 2013-12-19 킴벌리-클라크 월드와이드, 인크. 섬유 형성용 생분해성 폴리에스테르
WO2019085522A1 (fr) * 2017-11-03 2019-05-09 金发科技股份有限公司 Matériau d'impression 3d d'acide polylactique et fil préparé à partir de celui-ci
JP2019093520A (ja) * 2017-11-27 2019-06-20 スキューズ株式会社 指機構、ロボットハンド及びロボットハンドの制御方法
KR20190096174A (ko) * 2018-02-08 2019-08-19 최만재 인장강도와 유연성이 우수한 생분해성 수술사 및 그 제조방법
WO2023210177A1 (fr) * 2022-04-28 2023-11-02 Dic株式会社 Accélérateur de dégradation de résine biodégradable, composition de résine biodégradable, corps moulé et procédé de dégradation de résine biodégradable
WO2024112154A1 (fr) * 2022-11-25 2024-05-30 에스케이리비오 주식회사 Procédé de préparation de composition de résine de polyester biodégradable et procédé de production de film de polyester biodégradable l'utilisant

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KR102553049B1 (ko) * 2022-03-03 2023-07-07 주식회사 피엘에이코리아 생분해성 소재, 생분해성 섬유 부재, 생분해성 패브릭 부재 및 이들의 제조 방법
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JP2007262118A (ja) * 2006-03-27 2007-10-11 Toyobo Co Ltd 光散乱シート用生分解性ポリエステル樹脂組成物およびその製造方法
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WO2013164743A1 (fr) * 2012-05-03 2013-11-07 Universita' Di Pisa Copolymères à base de polyesters réactifs et de plastifiants pour la fabrication d'un film d'emballage transparent, biodégradable
WO2019085522A1 (fr) * 2017-11-03 2019-05-09 金发科技股份有限公司 Matériau d'impression 3d d'acide polylactique et fil préparé à partir de celui-ci
JP2019093520A (ja) * 2017-11-27 2019-06-20 スキューズ株式会社 指機構、ロボットハンド及びロボットハンドの制御方法
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WO2023210177A1 (fr) * 2022-04-28 2023-11-02 Dic株式会社 Accélérateur de dégradation de résine biodégradable, composition de résine biodégradable, corps moulé et procédé de dégradation de résine biodégradable
JP7401028B1 (ja) * 2022-04-28 2023-12-19 Dic株式会社 生分解性樹脂分解促進剤、生分解性樹脂組成物、成形体および生分解性樹脂の分解方法
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