WO2007029574A1 - 生分解性樹脂組成物及びそれより得られる成形体 - Google Patents
生分解性樹脂組成物及びそれより得られる成形体 Download PDFInfo
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- WO2007029574A1 WO2007029574A1 PCT/JP2006/317057 JP2006317057W WO2007029574A1 WO 2007029574 A1 WO2007029574 A1 WO 2007029574A1 JP 2006317057 W JP2006317057 W JP 2006317057W WO 2007029574 A1 WO2007029574 A1 WO 2007029574A1
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- WIPO (PCT)
- Prior art keywords
- acid
- biodegradable
- resin
- resin composition
- wax
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- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
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- 235000019792 magnesium silicate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
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- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
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- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
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- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- ZBPYFGWSQQFVCJ-UHFFFAOYSA-N pentadecane-1,15-diol Chemical compound OCCCCCCCCCCCCCCCO ZBPYFGWSQQFVCJ-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000012165 plant wax Substances 0.000 description 1
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- 229920000118 poly(D-lactic acid) Polymers 0.000 description 1
- 229920001432 poly(L-lactide) Polymers 0.000 description 1
- 229920001181 poly(butylene adipate-co-butylene terephthalate) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
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- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
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- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
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- 235000015067 sauces Nutrition 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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- 238000009987 spinning Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
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- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
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- 239000011667 zinc carbonate Substances 0.000 description 1
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Classifications
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
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- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
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- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
- B29C49/06—Injection blow-moulding
- B29C49/061—Injection blow-moulding with parison holding means displaceable between injection and blow stations
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/08—Biaxial stretching during blow-moulding
- B29C49/10—Biaxial stretching during blow-moulding using mechanical means for prestretching
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- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
- B29K2067/003—PET, i.e. poylethylene terephthalate
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- B29K2079/00—Use of polymers having nitrogen, with or without oxygen or carbon only, in the main chain, not provided for in groups B29K2061/00 - B29K2077/00, as moulding material
- B29K2079/08—PI, i.e. polyimides or derivatives thereof
- B29K2079/085—Thermoplastic polyimides, e.g. polyesterimides, PEI, i.e. polyetherimides, or polyamideimides; Derivatives thereof
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- B29K2091/00—Use of waxes as moulding material
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- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/26—Scrap or recycled material
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- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2279/00—Use of polymers having nitrogen, with or without oxygen or carbon only, in the main chain not provided for in groups B29K2261/00 - B29K2277/00, as reinforcement
- B29K2279/08—PI, i.e. polyimides or derivatives thereof
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- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/712—Containers; Packaging elements or accessories, Packages
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29L2031/00—Other particular articles
- B29L2031/767—Printing equipment or accessories therefor
- B29L2031/7678—Ink or toner cartridges
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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
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L91/06—Waxes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1303—Paper containing [e.g., paperboard, cardboard, fiberboard, etc.]
- Y10T428/1307—Bag or tubular film [e.g., pouch, flexible food casing, envelope, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
Definitions
- the present invention relates to a biodegradable resin composition and a molded article obtained therefrom.
- biodegradable coagulates such as polylactic acid have attracted attention from the viewpoint of environmental conservation.
- Polylactic acid is one of the biodegradable fats that has good transparency and the highest heat resistance and can be mass-produced from plant-derived materials such as corn and sweet potato. It is highly useful because it is cheap and can contribute to the reduction of petroleum raw materials.
- biodegradable resin is not yet satisfactory as a container or packaging material that requires barrier properties against gases and moisture.
- JP-A-2002-338796 includes adding a layered silicate organically treated with specific ammonia ions to biodegradable resin.
- a layered silicate organically treated with specific ammonia ions are listed.
- JP-A-2002-068201 discloses a method of coating a biodegradable plastic with a metal oxide such as silicon oxide by a chemical vapor deposition method. None of these methods, however, is superior in terms of gasnolianess, but it cannot be said that it is sufficient in terms of environmental considerations and plant material origin.
- an object of the present invention is to provide a biodegradable rosin having improved moisture barrier properties.
- the gist of the present invention is as follows. [0007] (1) A biodegradable resin composition comprising 100 parts by mass of biodegradable polyester resin and 0.1 to 15 parts by mass of jojoba oil and Z or polar wax.
- a molded body which is formed of any one of the biodegradable resin compositions (1) to (3).
- biodegradability excellent in moisture barrier properties by containing 100 parts by mass of biodegradable polyester resin and 0.1 to 15 parts by mass of jojoba oil and Z or polar wax.
- a greave composition is provided.
- the molded body made of this resin composition can be composted when discarded, and can be reused as a fertilizer. If we use coconut oil, which is a plant-derived raw material, as a biodegradable polyester resin, the ratio of plant-derived materials will increase in the entire coconut resin composition, contributing to the prevention of oil resources from drying out and being environmentally friendly. It becomes a fee.
- the biodegradable polyester resin in the resin composition of the present invention includes an aliphatic polyester mainly composed of a- and Z- or hydroxycarboxylic acid units, an aliphatic dicarboxylic acid component and an aliphatic group. Examples thereof include polyesters having a diol component.
- Examples of a and Z or ⁇ -hydroxycarboxylic acid units include D-lactic acid, L-lactic acid, or mixtures thereof, glycolic acid, 3-hydroxybutyric acid, 3-hydroxyvaleric acid, 3-hydroxycabronic acid Etc., and mixtures and copolymers thereof. Particularly preferred are D-lactic acid and L-lactic acid.
- Examples of the aliphatic carboxylic acid include oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, suberic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, aicosanedioic acid, hydrogenated dimer acid Saturated aliphatic dicarboxylic acids such as fumaric acid, maleic acid, itaconic acid, mesaconic acid, citraconic acid, dimer acid and the like, and derivatives thereof
- Examples of the conductor include lower alkyl ester compounds and acid anhydrides.
- 1,4-cyclohexanedicarboxylic acid 1,3 cyclohexanedicarboxylic acid, 1,2 cyclohexanedicarboxylic acid, 2,5-norbornene dicarboxylic acid, and alicyclic dicarboxylic acids such as tetrahydrophthalic acid.
- succinic acid and adipic acid are particularly preferred from the viewpoint of biodegradability, with adipic acid, succinic acid, hydrous succinic acid, adipic acid and sebacic acid being preferred.
- Aliphatic diols include ethylene glycol, 1,2 propanediol, 1,3 propanediol, 1,2 butanediol, 1,3 butanediol, 1,4-butanediol, 2-methyl-1, 3 Propanediol, 2, 2 Jetyl 1, 3 Propanedyl 2 Amino-2 ethyl 1, 3 Propanediol, 2 Amino 2-methyl 1, 3-propanediol, 2 Ethyl 2-methyl-1, 3 Propanediol, 2 Butyl 2 Ethyl 1,3 propanediol, neopentyl glycol, 3-methyl-1,5 pentanediol, 1,5 pentanediol, 1,6 hexanediol, 1,7 heptanediol, 1,8 octanediol, 1,9-nonanediol, 1,10 decandiol, 1,11
- the polyester resin may be copolymerized with an aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid, as long as it does not impair biodegradability. It is contained in the biodegradable polyester resin referred to in the invention.
- biodegradable polyester resin examples include poly (D lactic acid) and poly (L-lactic acid).
- Polylactic acid may form a stereocomplex.
- the biodegradable polyester resin it is preferable to use a resin containing 50% by mass or more of a plant-derived raw material resin, since the plant-derived degree is high and the effect of reducing petroleum resources is high. . More preferably, it contains 60% by mass or more of rosin that also has plant-derived raw material power, and more preferably 80% by mass or more.
- Polyester rosin that can also be used as plant-derived raw materials includes poly (butylene succinate) in addition to polylactic acid. Polylactic acid is particularly preferred as a rosin that also has plant-derived raw material power, because moldability, transparency, and heat resistance are improved.
- the biodegradable polyester resin is produced by a known melt polymerization method, or, if necessary, by further using a solid phase polymerization method.
- Poly (3-hydroxybutyric acid) and poly (3-hydroxyvaleric acid) can be produced by microorganisms.
- the biodegradable polyester resin used in the present invention may be partially cross-linked, or may be modified with an epoxy compound or the like.
- a terminal blocking agent can be added to block the terminal of the resin.
- a carpositimide compound Oxazoline compound, epoxy compound, isocyanate compound and the like As the end-capping agent, a carpositimide compound Oxazoline compound, epoxy compound, isocyanate compound and the like.
- the addition amount of the terminal blocker is not particularly limited, but is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the resin.
- the molecular weight of the biodegradable polyester resin is not particularly limited, but it is an index. It can be preferably used if the melt flow rate (MFR) in C, 20.2N (2.16 kg) is in the range of 0.1 to 50 g / 10 min. More preferably, it is in the range of 0.2 to 40 gZlO minutes.
- MFR melt flow rate
- the biodegradable resin composition of the present invention contains jojoba oil and / or polar wax in addition to biodegradable polyester resin.
- jojoba oil is an ester collected from natural jojoba (scientific name: Simmondasia Chinensis) seeds by pressing, distillation, etc., and is composed of higher unsaturated fatty acids and higher unsaturated alcohols.
- the Jojoba is an evergreen shrub that grows naturally in the dry areas of the southeastern United States (Arizona and California) and northern Mexico (Sonora and Baja). Currently, it is cultivated in the dry areas of Israel, Australia, Argentina, etc. in addition to the US and Mexico.
- jojoba oil used in the present invention include hydrogenation of crude jojoba oil that has been used as it has been pressed as described above, purified jojoba oil purified by molecular distillation, and purified jojoba oil. Any of hydrogenated jojoba oil, jojoba alcohol, jojoba cream and the like that can be mixed with rosin can be used.
- Jojoba oil is not mixed with water, and is therefore suitable for improving the steam-nozzle property. Since the boiling point is as high as 420 ° C, it is stable even when mixed with a resin that requires melt kneading at high temperatures.
- the polar wax used in the present invention may be a deviation between natural wax and synthetic wax! /.
- Examples of natural waxes include petroleum wax, montan wax, animal wax, and vegetable wax.
- any non-polar wax having a structure mainly composed of saturated aliphatic hydrocarbons such as paraffin wax and micro wax may be used. If it is modified to wax, etc., it has polarity. Sometimes. As long as the montan wax has a structure having a polarity, the polarity can be imparted by, for example, ester candy or partial candy. Plant waxes include those containing a mixture of higher fatty acids and higher alcohol esters, such as strong lunaba wax, rice wax, and candelilla wax. Synthetic waxes include fatty acids, fatty acid esters, fatty acid amides, and the like. For example, castor oil, hydrogenated castor oil, esterified product of sebacic acid, 12-hydroxystearic acid and its ester compounds, amide compounds and saponified products.
- these waxes have polarity, they have the effect of maintaining the translucency of the resin when mixed with the biodegradable polyester resin, and the resin having an excellent appearance. This effect is remarkable when polylactic acid is used as the biodegradable polyester resin.
- the wax is not mixed with water, the wax is suitable for improving the moisture barrier property of the biodegradable resin composition.
- the boiling point is generally high, the stability is good, so it can exist stably even when mixed with a resin that normally needs to be melt-kneaded at high temperatures.
- jojoba oil and polar wax may be used singly or in combination.
- the blending amount needs to be 0.1 to 15 parts by mass with respect to 100 parts by mass of the biodegradable polyester resin.
- jojoba oil or polar wax may be added during polymerization of biodegradable polyester resin, Examples thereof include a method of adding at the time of kneading and a method of adding at the time of molding a molded product using the same coagulant.
- a method of adding pellets in which jojoba oil or polar wax is previously adjusted to a high concentration that is, a so-called master batch method may be used.
- the preferred addition time is melt kneading or molding.
- an addition method when adding at the time of melt-kneading or molding dry blend with rosin in advance and then supply to a general kneader or molding machine And a method of adding from the middle of kneading using a side feeder.
- the biodegradable resin composition of the present invention includes a heat stabilizer, an antioxidant, a light-proofing agent, a pigment, and a weathering agent other than those defined in the present invention within a range not impairing the effects of the present invention.
- flame retardants, plasticizers, lubricants, mold release agents, antistatic agents, fillers, dispersants and the like may be added.
- heat stabilizer and the anti-oxidation agent examples include phosphite organic compounds, hindered phenol compounds, benzotriazole compounds, triazine compounds, hindered amine compounds, iodo compounds, copper compounds, and alkali metals. Halides or mixtures thereof can be used. These additives are generally added at the time of melt-kneading or polymerization.
- Fillers include inorganic fillers and organic fillers.
- Inorganic fillers include talc, calcium carbonate, zinc carbonate, wollastonite, silica, alumina, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, glass balloon, carbon Examples thereof include black, dumbbell oxide, antimony trioxide, zeolite, hydrated talcite, metal fiber, metal whisker, ceramic whisker, potassium titanate, boron nitride, graphite, glass fiber, and carbon fiber.
- Examples of the organic filler include naturally occurring polymers such as starch, cellulose fine particles, wood flour, okara, fir shell, bran, kenaf, and modified products thereof.
- the biodegradable resin composition of the present invention includes polyamide (nylon), polyethylene, polypropylene, polybutadiene, polystyrene, AS resin, ABS resin, poly (acrylic), as long as the effects of the present invention are not impaired. Acid), poly (acrylic acid ester), poly (methacrylic acid), poly (methacrylic acid ester), polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyarylate, and their co-polymers Non-biodegradable rosin such as coalescence may be added.
- a general kneader such as a single screw extruder, a twin screw extruder, a roll kneader, or a Brabender can be used.
- a twin screw extruder it is preferable to use a twin screw extruder to improve the dispersibility of jojoba oil, polar wax, and other additives.
- the biodegradable resin composition of the present invention can be formed into various molded articles by known molding methods such as injection molding, blow molding, and extrusion molding.
- the injection molding method in addition to a general injection molding method, a gas injection molding method, an injection press molding method, or the like can be adopted.
- the cylinder temperature at the time of injection molding needs to be equal to or higher than the melting point (Tm) of the biodegradable polyester resin or the flow start temperature, preferably in the range of 180 to 230 ° C, more preferably 190 to 220. It is in the range of ° C. If the molding temperature is too low, the fluidity of the resin is reduced, which tends to cause molding defects and overload of the equipment. On the other hand, if the molding temperature is too high, the biodegradable polyester resin is decomposed, and problems such as a decrease in strength and coloring of the molded product are likely to occur.
- the mold temperature is preferably (Tg ⁇ 10 ° C.) or less when the glass transition temperature (Tg) or less of the biodegradable resin composition is used.
- Tg glass transition temperature
- Tg or more and (Tm—30 ° C) or less.
- blow molding method examples include a direct blow method in which molding is performed directly from raw material chips, an injection blow molding method in which blow molding is performed after a preformed body (bottom parison) is first molded by injection molding, or stretch blow molding.
- examples include molding methods.
- the hot parison method in which blow molding is continuously performed after the preform is molded
- the cold parison method in which V preform is preliminarily cooled and taken out from the molding apparatus and heated again to perform blow molding. Either method can be adopted.
- the extrusion temperature needs to be equal to or higher than the Tm or flow start temperature of the raw biodegradable polyester resin, preferably in the range of 180 to 230 ° C, more preferably in the range of 190 to 220 ° C. It is a range. If the molding temperature is too low, the operation may become unstable or overloaded. On the other hand, when the molding temperature is too high, the biodegradable polyester resin component is decomposed, and problems such as strength reduction and coloring are likely to occur in the extruded molded body. Sheets and pipes can be produced by extrusion.
- Specific applications of the sheet or pipe obtained by the extrusion method include: raw sheet for deep drawing, raw sheet for batch-type foaming, cards such as credit cards, underlay, tarier file, straw Agricultural and horticultural hard pipes. Also, the sheet In addition, food containers, agricultural and horticultural containers, blister pack containers, press-through pack containers, and the like can be manufactured by performing deep drawing such as vacuum forming, pressure forming, and vacuum / pressure forming.
- the deep drawing temperature and the heat treatment temperature are preferably (Tg + 20 ° C.) to (Tg + 100 ° C.). If the deep drawing temperature is less than (Tg + 20 ° C), deep drawing may be difficult.
- the form of food containers, agricultural horticultural containers, blister pack containers, and press-through pack containers is not particularly limited, but is deeply drawn to a depth of 2 mm or more to accommodate food, goods, drugs, etc. It is preferable.
- the thickness of the container is not particularly limited, but is preferably 150 to 500 / ⁇ ⁇ , more preferably 50 m or more from the viewpoint of strength.
- Specific examples of food containers include fresh food trays, instant food containers, first food containers, lunch boxes and the like.
- a specific example of a container for agriculture and horticulture is a seedling pot.
- Specific examples of blister pack containers include food packaging containers, as well as packaging containers for various products such as office supplies, toys, and dry batteries.
- Other molded articles produced using the biodegradable rosin composition of the present invention include dishes such as dishes, bowls, bowls, chopsticks, spoons, forks and knives; containers for fluids; for containers Caps; Rulers, writing instruments, clear cases, CD cases, office supplies; kitchen triangle corners, trash cans, washbasins, toothbrushes, combs, hangers, and other daily necessities; Various types of toys; grease components for electrical appliances such as air conditioner panels and various cases; automotive grease components such as bumpers, instrument panels and door trims.
- the form of the fluid container is not particularly limited, but is preferably formed to a depth of 20 mm or more in order to accommodate the fluid.
- the thickness of the container is not particularly limited, but is preferably 0.1 mm or more from the viewpoint of strength, and more preferably 0.1 to 5 mm.
- fluid containers include beverage cups and beverage bottles such as dairy products, soft drinks and alcoholic beverages; containers for conserving seasonings such as soy sauce, sauces, mayonnaise, ketchup, and edible oils; shampoos and rinses Containers for cosmetics; containers for agricultural chemicals, and the like.
- the biodegradable rosin composition of the present invention may be a fiber.
- the fiber production method is special Although not limited to this, a method of melt spinning and stretching the rosin composition is preferred.
- the melt spinning temperature is preferably 160 ° C to 260 ° C. When the temperature is lower than 160 ° C, melt extrusion tends to be difficult. On the other hand, when the temperature exceeds 260 ° C, decomposition of the resin composition becomes remarkable, and high strength fibers tend to be obtained.
- the temperature at which the melt-spun fiber yarn is stretched so as to have the desired fiber diameter is preferably Tg or more.
- the fibers obtained by the above method are used as clothing fibers, industrial material fibers, fibers constituting short fiber nonwoven fabrics, and the like.
- the biodegradable resin composition of the present invention can also be developed into a long-fiber nonwoven fabric.
- the production method is not particularly limited, and examples thereof include a method in which a resin composition is made into a fiber by a high-speed spinning method, and the fiber is deposited and then webbed, and further made into a fabric using means such as heat pressure welding. be able to.
- Resin B terephthalic acid Z adipic acid Z 1,4-butanediol copolymer (manufactured by BASF, product name: Ecoflex, melting point 108 ° C, (190 ° C, load 20. 2N))
- F Oxidized wax (manufactured by Nippon Seiro Co., Ltd., product name: LUVAX0321)
- G Dibutyl sebacate (manufactured by Toyokuni Oil Co., Ltd., product name: DBS)
- the physical property values of the molded body formed with the greave composition were measured as follows.
- a bottle container capable of being covered with a screw cap was manufactured using the cocoa resin composition, and the moisture barrier property was measured using the bottle container. Specifically, after filling the container with water, it was sealed with a screw cap, stored in a thermostatic bath at 50 ° C, and its weight was measured over time to examine the rate of decrease in stored water. Practically, the reduction rate of stored water is preferably 2% by mass or less after 340 hours.
- the biodegradable resin composition was pressed at 190 ° C for about 3 minutes using a desktop test press manufactured by Tester Sangyo Co., Ltd., to produce a 1 mm thick press sheet as a molded body. It was. About this press sheet, it measured using the Nippon Denshoku Industries Co., Ltd. make, model number: NDH-2000 turbidity haze meter. In practice, the haze is preferably 25% or less.
- Dry blend of 100 parts by weight of rosin A and 0.5 part by weight of refined jojoba oil C, manufactured by Ikegai Co., Ltd., model number: PCM-30, twin screw extruder (screw diameter is 30mm ⁇ , average groove depth is 2.5mm), melt kneading at 190 ° C, screw rotation speed 200rpm ( 3.3rps), residence time 1.6 minutes, extruded, processed into pellets, dried, oiled A composition was obtained.
- the obtained resin composition was melted at a cylinder set temperature of 200 ° C using an injection blow molding machine (manufactured by Nissei ASB Machinery Co., Ltd., model number: ASB-50TH) into a 10 ° C mold. After filling and cooling for 10 seconds, a 5 mm thick preform (bottom parison) was obtained. This preform is heated with an electric heater at 120 ° C and placed in a mold set at 25 ° C. By blow molding with strong air, a bottle container with an internal volume of 150 ml and a thickness of 1.1 mm was produced.
- Example 6 Compared with Example 1, the blending amounts and types of coconut and jojoba oils were changed. Other than that, a resin composition was prepared in the same manner as in Example 1, and a container was molded and its physical properties were measured. The results are shown in Table 1. In Example 6, rosin A, rosin B and refined jojoba oil C were dry blended and supplied to a twin screw extruder.
- Example 2 0.5 parts by mass of polar wax E and a drive blend of resin A were used. And otherwise, it was the same as Example 1, and the rosin composition was obtained. And the bottle container was produced using the obtained rosin composition, and the moisture barrier property was measured. In addition, a press sheet having a thickness of 1 mm was prepared from the resin composition as described above, and the haze was measured. The results are shown in Table 2.
- Example 7 As shown in Table 2, the type and amount of wax were changed as compared with Example 7. Otherwise, a resin composition was prepared in the same manner as in Example 7, and the moisture barrier property of the container was measured. Further, the haze of the sheet was measured. The results are shown in Table 2.
- Example 7 Compared to Example 7, the container was blow-molded using only resin A without adding wax. Obtained. And the moisture barrier property was measured using this container. The haze of the sheet was also measured. The results are shown in Table 2.
- the rosin compositions of Examples 7 to 12 all have a reduced water storage rate in the bottle container as compared with that of Comparative Example 3 which does not have the addition of polar wax. I was good at. In addition, the haze value was low and the transparency was excellent as compared with Comparative Example 4 to which a nonpolar wax was added.
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Abstract
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KR1020087001054A KR101282144B1 (ko) | 2005-09-08 | 2006-08-30 | 생분해성 수지 조성물 및 그것으로부터 얻어진 성형체 |
US11/989,624 US8062721B2 (en) | 2005-09-08 | 2006-08-30 | Biodegradable resin and product molded or formed from the same |
EP20060797032 EP1923427B1 (en) | 2005-09-08 | 2006-08-30 | Biodegradable resin composition and molded body obtained from same |
CN2006800248693A CN101218297B (zh) | 2005-09-08 | 2006-08-30 | 可生物降解树脂组合物以及由其制得的成型体 |
JP2007534356A JP5132312B2 (ja) | 2005-09-08 | 2006-08-30 | 生分解性樹脂組成物及びそれより得られる成形体 |
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- 2006-08-30 KR KR1020087001054A patent/KR101282144B1/ko not_active IP Right Cessation
- 2006-08-30 US US11/989,624 patent/US8062721B2/en not_active Expired - Fee Related
- 2006-08-30 JP JP2007534356A patent/JP5132312B2/ja not_active Expired - Fee Related
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Cited By (7)
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JP2012158761A (ja) * | 2005-10-05 | 2012-08-23 | Unitika Ltd | 生分解性樹脂組成物、その製造方法、それを用いた成形体 |
EP1944333A1 (en) * | 2005-11-04 | 2008-07-16 | Unitika Ltd. | Biodegradable resin foam sheet, biodegradable resin foam article and biodegradable resin molded container |
EP1944333A4 (en) * | 2005-11-04 | 2009-12-02 | Unitika Ltd | FOAM PANEL OF BIODEGRADABLE RESIN, FOAM MATERIAL OF BIODEGRADABLE RESIN AND SHAPED CONTAINER OF BIODEGRADABLE RESIN |
US7972669B2 (en) | 2005-11-04 | 2011-07-05 | Unitika Ltd. | Biodegradable resin foam sheet, biodegradable resin foam article and biodegradable resin molded container |
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JPWO2009110171A1 (ja) * | 2008-03-03 | 2011-07-14 | ユニチカ株式会社 | 生分解性ポリエステル樹脂組成物及びそれからなる成形体 |
US20110178211A1 (en) * | 2008-03-03 | 2011-07-21 | Unitika Ltd. | Biodegradable polyester resin composition and molded body composed of the same |
Also Published As
Publication number | Publication date |
---|---|
EP1923427A1 (en) | 2008-05-21 |
US20090258982A1 (en) | 2009-10-15 |
JP5132312B2 (ja) | 2013-01-30 |
CN101218297A (zh) | 2008-07-09 |
EP1923427B1 (en) | 2011-10-19 |
JPWO2007029574A1 (ja) | 2009-03-19 |
KR20080049006A (ko) | 2008-06-03 |
EP1923427A4 (en) | 2010-09-01 |
US8062721B2 (en) | 2011-11-22 |
KR101282144B1 (ko) | 2013-07-04 |
CN101218297B (zh) | 2011-11-16 |
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