WO2004099315A1 - 生分解性ポリエステル樹脂組成物及びその製造方法並びにこれを用いてなる発泡体及び成形体 - Google Patents
生分解性ポリエステル樹脂組成物及びその製造方法並びにこれを用いてなる発泡体及び成形体 Download PDFInfo
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- WO2004099315A1 WO2004099315A1 PCT/JP2003/005914 JP0305914W WO2004099315A1 WO 2004099315 A1 WO2004099315 A1 WO 2004099315A1 JP 0305914 W JP0305914 W JP 0305914W WO 2004099315 A1 WO2004099315 A1 WO 2004099315A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- 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
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- 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
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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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
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use 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; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/008—Additives improving gas barrier properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
Definitions
- the present invention relates to a biodegradable polyester resin composition, a method for producing the same, and a foam and a molded article using the same.
- the present invention provides a biodegradable polyester that has excellent mechanical strength and heat resistance, has no problem in operability, has rheological properties advantageous for molding foams and molded articles, and has excellent gas barrier properties.
- the present invention relates to a resin composition, a method for producing the same, and a foam and a molded article using the same. Background art
- Polylactic acid has a characteristic that it has a higher melting point than other biodegradable resins and is superior in heat resistance.
- the melt viscosity is low, for example, foam breakage occurs during extrusion foam molding, and a sufficient expansion ratio cannot be obtained, or bubbles do not stabilize during inflation molding or blow molding.
- the production efficiency in injection molding and the like is poor due to the low crystallization speed. Therefore, in order to be put to practical use, it is necessary to improve the melt viscosity, develop strain hardening when measuring elongational viscosity, and further improve the crystallization rate.
- a method of adding a polymer having a high degree of polymerization or a method of using a polymer having a long-chain branch is effective for causing a resin composition to exhibit strain hardening property.
- a biodegradable polyester having a weight average molecular weight of 500,000 or more has not been put to practical use.
- a method for producing long-chain branched polylactic acid a method in which a polyfunctional initiator is added during polymerization is known (JP-A-10-77778, JP-A-20).
- JP _ A—2 0 0 1 _ 8 9 6 4 6 has high rigidity and biodegradability by melting and kneading the organic layered clay mineral into resin with the average particle size of 1 / _im or less. It is disclosed that a resin having an improved speed can be obtained.
- this document not only has no specific description for reducing the average particle size of the layered clay mineral to 1 / im or less, but also has no description of various conditions for forming, and the formability is improved. It is unknown whether it was.
- JP—A—10—3 2 4 7 6 6 describes that a biodegradable polyester resin synthesized from a dibasic acid and dalicol is cross-linked by combining with a compound having an unsaturated bond with an organic peroxide. It discloses that it can be effectively foamed.
- This method is an example of a method of impregnating resin fine particles with these crosslinking agents at a temperature lower than the melting point of the resin.When divinylbenzene is used as a crosslinking aid, it is described in detail.
- biodegradable polyesters having a heat resistance enhanced mainly by one and / or 0-hydroxycarboxylic acid unit are known.
- this biodegradable polyester has a drawback that the crystallization rate is low and the operability is poor in various molding processes such as injection molding.
- a method of adding an inorganic fine powder but it is not sufficient.
- biodegradable polyesters have insufficient gas barrier properties, particularly barrier properties against oxygen, and have not been used for applications requiring gas barrier properties such as food containers.
- a method for improving gas barrier properties a method of dispersing a layered silicate in a resin has been proposed. It is believed that the gas component is blocked by the layered silicate in the resin, and the gas barrier property is improved because the gaseous component travels around the layered silicate.
- the effect on polyamide resin is disclosed in JP-B-3 284 552
- the application to aliphatic polyesters is disclosed in JP-A-200. 1—164,097.
- simply mixing the layered silicate with the resin does not provide rheological properties suitable for various moldings, and has a problem of poor operability.
- the present invention solves the above problems, has excellent mechanical strength and heat resistance, has a high crystallization rate, has no problem in operability, and has rheological properties advantageous for molding of foams and molded articles.
- An object of the present invention is to provide a biodegradable polyester resin composition having excellent gas barrier properties, a method for producing the same, and a foam and a molded article using the same. Disclosure of the invention
- the present invention provides 100 parts by mass of a biodegradable polyester resin containing 50 mol% or more of 0;-and / or 3-hydroxycarboxylic acid units, and (meth) acrylic acid ester compound 0.01
- a gist of the present invention is a biodegradable polyester resin composition containing 0.1 to 10 parts by mass and a layered silicate of 0.05 to 20 parts by mass.
- the present invention also provides a method for producing the biodegradable polyester resin composition of the present invention, wherein the layered silicate is melt-kneaded to the biodegradable polyester resin composition, and then the (meth) acrylate compound and the peroxide are added. Or a solution or dispersion of a (meth) acrylic ester compound or a solution or dispersion of a (meth) acrylic ester compound and a peroxide, which is to be melted and kneaded.
- the gist of the present invention is a biodegradable resin foam obtained by subjecting the biodegradable polyester resin composition of the present invention to foam molding.
- biodegradable polyester resin composition of the present invention is injection-molded and pressed.
- the gist of the present invention is a biodegradable resin molded article formed by any one of molding and blow molding.
- FIG. 1 is a graph showing the relationship between elongation time [s] and elongational viscosity [Pa ⁇ s] for obtaining the strain hardening coefficient (a 2 / a,). Incidentally, it ai is the slope of the extension early in the linear region of until a bending point M, a 2 is the extension late slope after the bending point M and a ⁇ .
- FIG. 2 is a graph showing the relationship between the degree of crystallinity (0) and the time (minutes) for obtaining the crystallization rate index.
- the crystallization rate index is indicated by the time (minutes) required to reach half the degree of crystallinity finally reached.
- the biodegradable polyester resin composition of the present invention needs to be a specific composition containing a biodegradable polyester resin, a (meth) acrylate compound and a layered silicate.
- a (meth) acrylate compound By blending a (meth) acrylate compound with a biodegradable polyester resin having excellent heat resistance, the crystallization rate is increased and moldability is improved.
- the biodegradable polyester resin composition of the present invention configured as described above has a high melt viscosity, excellent elongational viscosity, excellent strain hardening property at a given time, and a high crystallization rate.
- these effects cannot be obtained simply by mixing a biodegradable polyester resin, a (meth) acrylate compound and a layered silicate.
- the problem of operability can be solved by producing the biodegradable polyester resin composition constituted as described above by the production method of the present invention. It has excellent mechanical strength and good appearance.
- the details will be described.
- the biodegradable polyester resin composition of the present invention comprises 100 parts by mass of a biodegradable polyester resin containing 50 mol% or more of ⁇ _ and ⁇ or ⁇ -hydroxycarboxylic acid units, and (meth) acrylic acid ester It is necessary to contain 0.01 to 10 parts by mass of the compound and 0.05 to 20 parts by mass of the layered silicate.
- the biodegradable polyester resin as the main component contains 50 mol% or more of ⁇ - and / or -hydroxycarboxylic acid units. If the content of mono- and / or 3-hydroxycarboxylic acid units is less than 50 mol%, biodegradability and heat resistance will be reduced.
- the ⁇ - and / or ⁇ -hydroxycarboxylic acid units include D-lactic acid, L-lactic acid or a mixture thereof, glycolic acid, 3-hydroxybutyric acid, 3-hydroxyvaleric acid, and 3-hydroxycaproic acid. Lifting Can be Among them, a biodegradable polyester resin containing D-lactic acid, L-lactic acid or a mixture thereof is preferable because of its excellent mechanical strength and heat resistance.
- a resin composition comprising polylactic acid, polyglycolic acid, poly (3-hydroxybutyric acid), poly (3-hydroxyvaleric acid), poly (3-hydroxycabronic acid), a copolymer or a mixture thereof, or the like is used. It is preferable to contain 50 mol% or more in the product.
- the biodegradable polyester resin in the present invention is produced by commonly using a known melt polymerization method or a solid phase polymerization method. Microbial production of poly (3-hydroxybutyric acid) and poly (3-hydroxyvaleric acid) is also possible.
- biodegradable polyester resin of the present invention other biodegradable resins may be copolymerized or if necessary, as long as the heat resistance of poly ( ⁇ - and / or] 3-hydroxycarboxylic acid) is not significantly impaired. You may mix them.
- Other biodegradable resins include aliphatic polyesters composed of diols and dicarboxylic acids represented by poly (ethylene succinate) and poly (butylene succinate), and poly ( ⁇ -caprolactone).
- butylene succinate butyrene terephthalate copolymers (butylene succinate butyrene terephthalate) exhibiting biodegradation even when containing aromatic components (butylene terephthalate)
- polysaccharides such as polyesteramides, polyestercarbonates, and starch may be mentioned.
- the molecular weight of the biodegradable polyester resin in the present invention is not particularly limited, but the weight average molecular weight is preferably 50,000 or more and 100,000 or less, and more preferably 100,000 or more and 100,000 or less. It is preferred that If the weight average molecular weight is less than 50,000, melting of the resin composition The viscosity is undesirably too low. If the weight average molecular weight exceeds 100,000, the moldability of the resin composition rapidly decreases, which is not preferable.
- the (meth) acrylic acid ester compound in the present invention has a high reactivity with a biodegradable resin, has little residual monomer, has relatively low toxicity, and has little coloration of the resin.
- Compounds having at least one (meth) acrylic group or having at least one (meth) acrylic group and at least one dalicidyl or pier group are preferred.
- Specific compounds include glycidyl methacrylate, glycidyl acrylate, glycerol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, aryloxypolyethylene diol monoacrylate, aryl Roxypolyethylene glycol monomethacrylate, polyethylene glycol dimethacrylate, polyethylene dalicol diacrylate, polypropylene glycol dimethacrylate, polypropylene glycol diacrylate, and polytetramethylene glycol dimethacrylate.
- the mixing ratio of the (meth) acrylate compound is required to be 0.01 to 10 parts by mass with respect to 100 parts by mass of the biodegradable polyester resin. Preferably, it is 5 parts by mass. If the compounding ratio of the (meth) acrylate compound is less than 0.01 part by mass, the effects of improving mechanical strength, heat resistance, and dimensional stability, which are the objects of the present invention, cannot be obtained. If the compounding ratio of the acrylate compound exceeds 10 parts by mass, the degree of crosslinking is too strong to operate. It is inferior in business.
- a peroxide in combination, since the crosslinking reaction is promoted and the strain hardening property is easily developed.
- peroxides include benzoyl peroxide, bis (butyl peroxy) trimethylcyclohexane, bis (butyl peroxy) cyclododecane, butyl bis (butyl peroxy) valerate, dicumyl peroxide, and butyl peroxide.
- the mixing ratio of the peroxide is preferably from 0.02 to 20 parts by mass, more preferably from 0.05 to 10 parts by mass, based on 100 parts by mass of the biodegradable polyester resin. Although the mixing ratio of the peroxide may exceed 20 parts by mass, it is disadvantageous in terms of cost. In addition, since peroxide decomposes when mixed with a resin, even if it is used at the time of compounding, it may not be contained in the obtained resin composition. .
- the blending ratio of the layered silicate in the present invention is required to be 0.05 to 20 parts by mass with respect to 100 parts by mass of the biodegradable polyester resin, and is 0.1 to 10 parts by mass. Is preferred. If the mixing ratio of the layered silicate is less than 0.05 parts by mass, sufficient mechanical strength and heat resistance cannot be obtained, and if it exceeds 10 parts by mass, it becomes brittle or disadvantageous in cost. Although the gas barrier property is improved by blending the layered silicate, the effect hardly changes even when blended in an amount of 10 parts by mass or more.
- layered silicates include smectite, vermiculite, And swellable fluorine mica.
- smectite events include montmorillonite, beidelight, hectrite, and savonite.
- swellable fluorine mica include Na-type tetrafluoride mica, Na-type teniolite, and Li-type teniolite.
- kanemite, macaite, magadite, Keniite Layered silicates that do not contain aluminum or magnesium, such as iron, can also be used.
- the layered silicate that improves gas barrier properties is preferably one having a large aspect ratio, such as montmorillonite or swellable fluoromica, and particularly preferably swellable fluoromica.
- the layered silicate may be a natural product or a synthetic product.
- the method for producing the synthetic product may be any of a melting method, an infusion method, a hydrothermal method, and the like. These phyllosilicates may be used alone, or two or more of them having different mineral types, localities, production methods, particle sizes, etc. may be used in combination.
- the layered silicate in the present invention is preferably subjected to an organic cation treatment in advance.
- the organic cation include an ammonium ion such as an ammonium ion, a quaternary ammonium ion, and a phosphonium ion generated by the conversion of primary to tertiary amines.
- the primary amine include octylamine, dodecylamine, and octadecylamine.
- the secondary amine include dioctylamine, methyloctadecylamine, dioctadecylamine, and the like.
- Tertiary amines include trioctylamine, dimethyldodecylamine, didodecylmonomethylamine and the like.
- quaternary ammonium ions tetraethylammonium, octadecyltrimethylammonium, dimethyldioctadecylammonium, dimethyl Droxityl methyl octadecyl ammonium, methyl dodecyl bis (polyethylene glycol) ammonium, methyl getyl (polypropylene glycol) ammonium and the like.
- examples of the phosphonium ion include tetraethylphosphonium, tetrabutylphosphonium, hexadecyltributylphosphonium, tetrakis (hydroxymethyl) phosphonium, and 2-hydroxyoxylrifenylphosphonium.
- Layered silicates treated with onium ions having at least one hydroxyl group in the molecule have a high affinity for polyester resins, especially biodegradable polyester resins, and are particularly preferred because the dispersibility of the layered silicates is improved. .
- These organic cations may be used alone or in combination of two or more.
- the layered silicate is dispersed in water or alcohol, and then the organic cation is added in the form of a salt and mixed by stirring. After the inorganic ions are exchanged with organic cations, filtration, washing and drying are performed.
- a compatibilizer may be used to improve the dispersibility in the polyester resin.
- the amount added is preferably from 0.01 to 10 parts by mass, more preferably from 0.02 to 5 parts by mass, per 100 parts by mass of the biodegradable polyester resin. If the blending ratio of the compatibilizer exceeds 10 parts by mass, the biodegradable polyester resin The heat resistance and mechanical strength of the fat composition may decrease.
- the compatibilizer include compounds such as polyalkylene oxides, aliphatic polyesters, polyhydric alcohol esters, and polycarboxylic acid esters, which are compatible with both polyester resins, especially biodegradable polyester resins and layered silicates. Is used.
- polyalkylene oxides examples include polyethylene glycol, polypropylene glycol, polybutylene glycol, and copolymers thereof.One or two of the terminal hydroxyl groups may be alkoxy-blocked, and may be a monocarboxylic acid or a monocarboxylic acid. It may be esterified with a dicarboxylic acid.
- the aliphatic polyester include polylactic acid, polydaricholic acid, poly (3-hydroxybutyric acid), poly (3-hydroxyvaleric acid), polyhydroxycarboxylic acid such as poly (3-hydroxycabronic acid), and poly ( ⁇ -force).
- examples thereof include aliphatic polyesters composed of a diol represented by a copolymer and a dicarboxylic acid.
- the terminal lipoxyl group may be esterified with an alcohol, or may be hydroxyl-substituted with a diol.
- polyhydric alcohol ester examples include glycerin esters such as monoglyceride, diglyceride, and triglyceride, which are esters of glycerin and a fatty acid, and pentaerythritol ester.
- polyvalent carboxylic acid ester examples include citrates such as tributyl citrate and tributyl acetate.
- the above-mentioned compatibilizer preferably has a boiling point of 250 ° C. or higher. New If the boiling point is less than 250 ° C, gas may be generated during molding or bleed out from the resulting molded product.
- the number average molecular weight is preferably in the range of 200 to 500,000, more preferably 500 to 200,000.
- the molecular weight is less than 200, gas generation during molding or bleeding out from the molded product is likely to occur, and the mechanical strength and heat resistance of the molded product may be impaired. On the other hand, if the molecular weight exceeds 50,000, the effect of improving the dispersibility of the layered silicate tends to decrease.
- Examples of the method for adding the compatibilizer include a method of directly impregnating the above compound into the layered silicate, a method of mixing the above compound in the presence of water or an organic solvent, and then removing the water or the organic solvent by filtration or the like.
- Examples of the method include adding the polyester resin and the layered silicate at the time of melting and mixing, and adding the polyester resin together with the layered silicate at the time of the synthesis of the polyester resin. Is preferably used.
- the preferred dispersion state of the layered silicate in the biodegradable polyester resin of the present invention is a complete delamination type in which the layered silicate layers are separated one by one, or an interlayer insertion type in which resin molecules are inserted between the layers. Alternatively, there are mixed types. Quantitatively, it is preferable that the average thickness of the single layer or lamination of the layered silicate observed by a transmission electron microscope is 1 to 100 nm, more preferably 1 to 50 nm, and further preferably 1 to 20 nm.
- the interlayer distance of the layered silicate observed by X-ray diffraction is preferably at least 2.5 nm, more preferably at least 3 nm, still more preferably at least 4 nm, and most preferably the interlayer distance. Is not observed. like this
- a method for controlling the dispersibility of the layered silicate in the kneading method, a change in kneading conditions, use of the above-described compatibilizer, introduction of a polar group into the resin, and the like can be mentioned.
- the dispersibility can be further increased and the gas barrier property can be improved.
- the strain hardening coefficient force s is preferably from 1.05 to 50, and more preferably from 1.5 to 30.
- the strain hardening coefficient is less than 1.05, foam breakage is likely to occur during extrusion foam molding, and the molded body is liable to be uneven in thickness.
- the strain hardening coefficient exceeds 50, gel is likely to be generated at the time of molding, and the fluidity is unpreferably reduced.
- the strain hardening coefficient refers to the time obtained by elongational viscosity measurement at a temperature 10 ° C higher than the melting point, and the logarithmic plot of the elongational viscosity until the inflection point M appears.
- the slope of the linear region at the beginning of stretching a! It is the ratio (a 2 / ai) of the slope a 2 at the later stage of extension after the inflection point.
- the biodegradable polyester resin composition of the present invention preferably has a crystallization rate index of 30 (min) or less.
- the resin was melted at 200 ° C. using a DSC device, and when the resin was isothermally crystallized at 130 ° C. from this molten state, the final It is the time (minutes) required to reach half of the crystallinity ( ⁇ ) that reaches the target.
- the lower limit of the crystallization rate index is preferably about 0.1 (minute).
- the crystallization rate index decreases as the amount of the crosslinking agent and / or the amount of peroxide increases, and the crystallization rate can be increased. Further, the content is further improved by adding 0.05 part by mass or more of the layered silicate.
- the crystallization speed can be further increased by a further synergistic effect. Further, the crystallization rate can be increased by increasing the number of functional groups of the crosslinking agent.
- the biodegradable polyester resin composition of the present invention is obtained by blending a biodegradable polyester resin, a (meth) acrylate compound and a layered silicate at a blending ratio of the present invention, and using a general extruder. It is obtained by melt-kneading. However, it is difficult to promote the crosslinking reaction and develop strain hardening properties simply by melt-kneading them. Therefore, in the present invention, a peroxide is used in the production of the biodegradable polyester resin composition, or a solution or dispersion of the (meth) acrylate compound is used, and the biodegradable polyester resin is prepared in advance. And the layered silicate are melt-kneaded.
- a biodegradable polyester resin and a layered silicate are charged and kneaded by a dry blend or a quantitative feeder from the vicinity of an inlet of a kneader.
- the (meth) acrylic acid ester compound is charged and melt-kneaded in the middle of the kneader.
- a peroxide it is preferable to use a peroxide at the same time. If the peroxide is solid, use a powder feeder to In the case of a body, supply using a pressurized pump. Alternatively, a solution or dispersion of the (meth) acrylate compound is injected.
- the present invention it is preferable to dissolve or disperse the (meth) acrylate compound and / or peroxide in a medium and to pour the mixture into a kneading machine because the operability is remarkably improved. That is, a solution or dispersion of a (meth) acrylate compound is injected during melt-kneading of a biodegradable polyester resin and a peroxide, or (meth) acrylic acid is melt-kneaded of a biodegradable polyester resin. It is preferable to inject and melt and knead a solution or dispersion of the ester compound and the peroxide.
- a general medium is used, and is not particularly limited, but a plastic having excellent compatibility with the aliphatic polyester of the present invention. Agents are preferred, and biodegradable ones are preferred.
- one or more plastics selected from aliphatic polycarboxylic acid ester derivatives, aliphatic polyhydric alcohol ester derivatives, aliphatic oxyester derivatives, aliphatic polyether derivatives, aliphatic polyether polycarboxylic acid ester derivatives, and the like. Agents and the like.
- Specific compounds include dimethyl adipate, dibutyl adipate, triethylene glycol diacetate, methyl acetyl ricinoleate, acetyl tryptyl citrate, polyethylene glycol, dibutyl diglycol succinate and the like.
- the amount of the plasticizer to be used is preferably 30 parts by mass or less, more preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the resin. If the reactivity of the cross-linking agent is low, it is not necessary to use a plasticizer, but if the reactivity is high, it is preferable to use 0.1 parts by mass or more.
- the kneading temperature is preferably in the range of (melting point of resin + 5 ° C.) to (melting point of resin + 100 ° C.), and the kneading time is preferably 20 seconds to 30 minutes. When the temperature is lower than this range or for a short time, kneading or reaction becomes insufficient, and when the temperature is higher or longer, decomposition or coloring of the resin may occur.
- the biodegradable polyester resin composition of the present invention is produced by melt-kneading a biodegradable polyester resin, a (meth) acrylate compound, a peroxide, and a layered silicate as raw materials.
- peroxides are generally decomposed during melt-kneading, and thus the peroxide is not necessarily contained in the obtained resin composition.
- a medium such as a plasticizer when adding the peroxide, but this medium may also volatilize during melt-kneading, so the medium is always contained in the obtained resin composition. Not necessarily.
- a pigment, a heat stabilizer, an antioxidant, a weathering agent, a flame retardant, a plasticizer, a lubricant, a release agent may be used as long as the properties are not significantly impaired.
- Various additives such as a mold agent, an antistatic agent, and a filler may be added.
- the heat stabilizer and antioxidant for example, hindered phenols, phosphorus compounds, hindered amines, zeo compounds, copper compounds, alkali metal halides, or mixtures thereof can be used.
- Inorganic fillers include talc, calcium carbonate, zinc carbonate, wollastonite, silica, alumina, magnesium oxide, calcium silicate, sodium aluminate Aluminum, calcium aluminate, sodium aluminosilicate, magnesium silicate, glass balloon, carbon black, zinc oxide, antimony trioxide, zeolite, 'hide mouth talcite, metal fiber, metal powder, ceramic whiskers, Potassium titanate, boron nitride, graphite, glass fiber, carbon fiber, and the like.
- the organic filler include naturally occurring polymers such as starch, cellulose fine particles, wood flour, okara, fir husk, and bran, and modified products thereof.
- the method of mixing the above additives and other thermoplastic resins with the biodegradable polyester resin composition of the present invention is not particularly limited. Kneading may be performed by a known kneading method using a single-screw extruder, a twin-screw extruder, a roll kneader, a Brabender or the like. It is also effective to use a static mixer or a dynamic mixer together. In addition, the above additives and other thermoplastic resins may be added during the polymerization of the biodegradable resin.
- a foaming method for producing a foam from the biodegradable polyester resin composition of the present invention all general methods can be applied. For example, using an extruder, a decomposable foaming agent that decomposes at the melting temperature of the resin is preliminarily blended with the resin, and extruded from a slit nozzle to form a sheet, or extruded from a round nozzle to form a sheet. Can be in the form of a land.
- Examples of the decomposable foaming agents include azo compounds represented by azodicarbonamide dibarium azodicarboxylate, nitroso compounds represented by N, N 'dinitrosopentamethylenetetramine, and 4,4' — Examples thereof include hydrazine compounds typified by oxybis (benzenesulfonyl hydrazide) and hydrazicarbonamide, and inorganic blowing agents such as sodium hydrogen carbonate. Also, It is also possible to inject a volatile foaming agent in the middle of the extruder to foam it.
- examples of the foaming agent include inorganic compounds such as nitrogen, carbon dioxide, and water, various hydrocarbons such as methane, ethane, and butane, organic solvents such as fluorocarbon compounds, and various alcohols such as ethanol and methanol. And the like.
- a method of preparing fine particles of the resin composition in advance, impregnating the above-described blowing agent with an organic solvent, water, or the like, and then expanding the temperature or pressure to produce expanded fine particles can be applied.
- Specific applications of the biodegradable foam sheet and foam board produced by the extrusion foaming method include, as it is, it can be used as it is for decorative boards and various pods, and can be folded and used for lunch boxes, various decorative boxes and cushioning materials. It can be drawn and used for food containers such as tray cups, garden pots, car interior materials, mannequins and toys.
- the foamed fine particles can be molded and used for various cushioning materials, or can be used as they are as cushioning materials.
- the biodegradable foam sheet or foam board produced by the extrusion foaming method is subjected to deep drawing such as vacuum molding, air pressure molding, and vacuum pressure molding to produce food containers, agricultural and horticultural containers, and blister packs.
- Containers and press-through pack containers can be manufactured.
- the deep drawing temperature and the heat treatment temperature are preferably in the range of (Tg + 20 ° C) to (Tin ⁇ 20 ° C). If the deep drawing temperature is less than (Tg + 20 ° C), deep drawing may be difficult or the heat resistance of the obtained container may be insufficient. If the temperature exceeds 0 ° C), uneven wall thickness may occur, or the orientation may be lost, resulting in reduced impact resistance.
- the extrusion temperature must be equal to or higher than the melting point (Tm) or the flow starting temperature of the biodegradable polyester resin composition, preferably 180 to 230 ° C, more preferably 190 to 2 ° C. It is in the range of 20 ° C. If the molding temperature is too low, molding becomes unstable or easily overloaded. If the molding temperature is too high, problems such as reduction in the strength of the extruded molded body obtained by decomposition of the biodegradable polyester resin and coloring of the molded body occur. Extrusion molding can produce biodegradable sheet pipes and the like. However, in order to enhance the heat resistance, the biodegradable polyester resin composition has a glass transition temperature (Tg) or higher, (Tm (20 ° C) or lower.
- biodegradable sheets or pipes manufactured by the extrusion method include: raw sheet for deep drawing, raw sheet for batch foaming, cards such as credit cards, underlays, clear files, Straws, hard pipes for agriculture and horticulture.
- the biodegradable sheet is subjected to deep drawing such as vacuum forming, compressed air forming, and vacuum compressed air forming to produce food containers, agricultural and horticultural containers, blister pack containers, and press-through pack containers.
- the deep drawing temperature and the heat treatment temperature are preferably (Tg + 20 ° C.) to (Tm ⁇ 20 ° C.). If the deep drawing temperature is less than (Tg + 20 ° C), deep drawing may be difficult or the heat resistance of the obtained container may be insufficient. Conversely, if the deep drawing temperature is (Tm-20 ° C) Exceeding C) may cause uneven wall thickness or loss of orientation, resulting in reduced impact resistance.
- the form of the food container, agricultural, horticultural container, blister pack container, and press-through pack container is not particularly limited. It is preferable that the container is deep drawn to a depth of 2 mm or more to accommodate chemicals, etc.
- the thickness of the container is not particularly limited. It is more preferably 0 to 500 xm.
- Specific examples of food containers include fresh food trays, instant food containers, fast food containers, and lunch boxes.
- Specific examples of agricultural and horticultural containers include nursery pots.
- specific examples of the blister pack container include packaging containers for various product groups such as office supplies, toys, and dry batteries in addition to food.
- blow molding method for producing a molded product from the biodegradable polyester resin composition of the present invention.
- the blow molding method include a direct blow method in which a raw material chip is directly molded, an injection blow molding method in which a preformed body (a bottomed parison) is molded by injection molding and then blow molding, and a stretch blow molding method. Can also be adopted. Either the hot parison method, in which blow molding is performed continuously after forming the preform, or the cold parison method, in which the preform is cooled and taken out and then heated again to perform blow molding, can be employed. The forming temperature must be (Tg + 20 ° C) to (Tm-20 ° C).
- the molding temperature is less than (Tg + 20 ° C)
- molding may be difficult or the heat resistance of the resulting container may be insufficient.
- the blow molding temperature may be (Tm-20 ° C). Exceeding C) is not preferable because uneven thickness is caused and problems such as blowdown due to viscosity decrease occur.
- an injection molding method for producing an injection molded article from the biodegradable polyester resin composition of the present invention a general injection molding method is used. Gas injection molding, injection press molding and the like.
- the cylinder temperature at the time of injection molding must be ⁇ or higher than the flow start temperature, and is preferably 180 to 230 ° (:, more preferably 190 to 220 °). It is in the range of C. If the molding temperature is too low, shorts are generated and the molding becomes unstable or easily overloaded, while if the molding temperature is too high, the biodegradable polyester resin is decomposed and obtained. This is not preferable because it causes problems such as a decrease in the strength of the molded product, coloring, etc.
- the mold temperature needs to be (Tm_20 ° C) or less.
- Tm_20 ° C the temperature at which crystallization is promoted in the mold for the purpose of increasing heat resistance.
- Tg the temperature at which crystallization is promoted in the mold for the purpose of increasing heat resistance
- the foam When the foam is injection-molded, it is possible to knead the resin and the foaming agent in advance, or to add the foaming agent in the middle of the extruder to mold. In this case, a general molding method can be applied.
- the form of the injection-molded article manufactured by the above-mentioned injection molding method is not particularly limited, and specific examples include dishes, bowls, bowls, chopsticks, spoons, forks, knife and other tableware, fluid containers, container caps, and the like.
- Office supplies such as rulers, writing utensils, clear cases, CD cases, etc., daily necessities such as triangle corners for kitchens, trash cans, washbasins, toothbrushes, combs, hangers, etc., agriculture such as flowerpots, nursery pots, etc.
- Examples include resin parts for electrical appliances such as various toys, air conditioner panels, refrigerator trays, and various housings, and resin parts for automobiles 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 to accommodate the fluid.
- the thickness of the container is not particularly limited, but is preferably 0.1 mm or more, more preferably 0.1 to 5 mm, from the viewpoint of strength.
- Specific examples of fluid containers include beverage cups and beverage bottles such as dairy products, soft drinks and alcoholic beverages, soy sauce, sauces, mayonnaise, ketchup, temporary storage containers for seasonings such as cooking oil, shampoo Containers such as rinses, containers for cosmetics, containers for agricultural chemicals, and the like.
- Elongational viscosity (1) Using an elongational viscosity measurement device RME (manufactured by Rheometrics), prepare a test piece of 60 mmX 7 mmX lmm (thickness). And, after supporting the both ends by metal belt clamps, at 1 0 ° C a temperature higher than the melting point of the resin composition, the elongation deformation measurement sample is rotated at a strain rate of 0. 1 sec 1 addition, during deformation The extensional viscosity was determined by detecting the torque applied to the pinch roller.
- RME elongational viscosity measurement device
- Crystallization rate index (min) Using a DSC device (Pyrisl DSC manufactured by Pachinkin Elmer Co., Ltd.), as shown in Fig. 2, from 20 ° C at a heating rate of 500 ° C / min. After the temperature was raised to 200 ° C, it was kept at 200 ° C for 5 minutes. Next, the temperature was lowered from 200 ° C. to 130 ° C. at a temperature lowering rate of 500 ° C./min, and the temperature was maintained at 130 ° C. to crystallize. Then, assuming that the finally reached crystallinity was 1, the time when the crystallinity reached 0.5 was determined as the crystallization rate index (min).
- Expansion ratio Calculated from the ratio of the foam density (D1), which is the mass of the foam divided by the volume that increases when the foam is immersed in water, and the true resin density (DO) It is an indicator of weight reduction and cushioning performance.
- Molding cycle (second) It is an index of injection moldability, using an injection molding device (TOSHIBA MACHINE Co., IS-100E), molding temperature of 200 ° C, mold Injection molding was performed on a release cup mold (diameter: 38 mm, height: 300 mm) at a temperature of 110 ° C, and the cycle time until the cup was successfully released was examined.
- TOSHIBA MACHINE Co., IS-100E injection molding device
- Blow moldability Using a professional molding machine (ASB-500HT, manufactured by Nissei SB Co., Ltd.), at a molding temperature of 200 ° C, a diameter of 30 mm, a height of 100 mm, and a thickness of 3. A 5 mm briform was produced. The obtained briform was heated to a surface temperature of 80 ° C and formed into a bottle-shaped mold (diameter: 90 mm, height: 250 mm). Was formed. Then, the appearance of the obtained molded body was evaluated as follows.
- ASB-500HT professional molding machine
- Oxygen permeability coefficient (ml'mm / rri'day'MPa): Pressing a resin pellet into a sheet with a thickness of 300a using a press machine, and measuring the differential pressure gas permeability The oxygen transmission coefficient was measured using an apparatus (GTR-Tech, GTR-30XAU) under the conditions of 20 ° C. and 90% RH. Then, the oxygen permeability coefficient was determined by the following equation.
- Oxygen permeability coefficient (ml'mm / rri'day'MPa)
- the oxygen permeability coefficient is an index of gas barrier properties. The smaller the value, the better the gas barrier properties.
- A Polylactic acid (weight average molecular weight: 140,000, L-form: 99%, D-form: 1%, melting point: 168. (:, MFR 11 g / 10 min)
- PE GDMJ Polyethylene glycol dimethacrylate
- TMPTM Trimethylpropane trimester
- P EGDA Polyethylene glycol diacrylate
- GM Daricidyl methacrylate
- Lucentite SAN Swellable heptrite in which interlayer ions have been replaced by dimethyldioctadecylmonium ion (Cope Chemical Co., Ltd., average particle size: 0.11 ⁇ ).
- Lucentite SEN A swellable heptrite in which interlayer ions have been replaced by dihydroxyethylmethyl dodecyl ammonium ion (manufactured by COOP Chemicals, average particle size: 0.1 lim).
- Esven E Montmorillonite in which interlayer ions have been replaced with trimethyloxydecyl ammonium ions (Hogyyun Co., Ltd., average particle size 2.5 nm)
- biodegradable polyester resin A: polylactic acid (weight average molecular weight: 140,000, L form: 99%, D form: 1%, melting point: 168 ° C, MFR llg / l 0 min) 100 parts by mass 4 parts by mass of Esven E as a layered silicate and 1.0 part by mass of fine powder talc (manufactured by Hayashi Kasei Co., Ltd., average particle size 2.5 um) —30, Die hole diameter: 4mmX3H, kneading temperature: 200 ° C), dry-blended and supplied to the extrusion feeder.
- polylactic acid weight average molecular weight: 140,000, L form: 99%, D form: 1%, melting point: 168 ° C, MFR llg / l 0 min
- Esven E as a layered silicate
- fine powder talc manufactured by Hayashi Kasei Co., Ltd., average particle size 2.5 um
- PEGDM of I was used as a (meth) acrylic acid ester compound in the ratio shown in Table 1, and this PEGDM, di-tert-butyl peroxide as a liquid peroxide, and a plasticizer as a plasticizer were used.
- a mixed solution was prepared so as to have a ratio of acetyl triptyl citrate and a force of 1: 2: 5 parts by mass, and the obtained mixed solution was supplied from the middle of the kneader using a liquid constant-rate supply pump.
- the dry-blended resin and the mixed solution were melt-kneaded, extruded, processed into a pellet, and dried to obtain a biodegradable polyester resin composition.
- This biodegradable polyester resin composition and a carbon dioxide gas as a foaming agent having a concentration of 1.0% by mass are twin-screw extruded and foamed (PCM-30, manufactured by Ikegai Co., Ltd., die lip width: 1.2 mm). (X length 40 mm), and a foamed sheet was produced under the conditions of a kneading temperature of 200 ° C and a die temperature of 160 ° C.
- Table 1 shows the physical properties of the obtained resin composition and foam.
- Example 13 since the (meth) acrylate compound and the layered silicate were blended within the scope of the present invention, the crystallization rate was high and the operability was good. In addition, a biodegradable polyester resin composition having a large strain hardening coefficient and an excellent flexural modulus was obtained. In addition, since the (meth) acrylate compound was melt-kneaded after mixing the layered silicate with the polyester resin, a resin composition having excellent operability and moldability was obtained. The foam using the biodegradable polyester resin composition had independent appearance and uniform thickness and good appearance.
- Table 1 shows the physical properties of the obtained resin composition and foam.
- the mixing ratio of the (meth) acrylate compound was set to 12 parts by mass, which was larger than the range of the present invention. Other than that, an attempt was made to produce a foamed sheet in the same manner as in Example 1, but the viscosity was too high to extrude the resin composition, and the sheet could not be obtained.
- Comparative Example 1 did not contain a (meth) acrylic acid ester compound, so that the mechanical strength represented by the flexural modulus could not be improved, and the strain hardening coefficient was low. In addition, even when this resin composition was subjected to a foaming treatment, foam breaks occurred, resulting in a foamed sheet having a non-uniform thickness.
- ⁇ Comparative Example 2 shows that the (meth) acrylic acid ester compound is As described above, the viscosity increased too much, and the resin composition could not be extruded stably as described above, and the resin composition could not be produced.
- Example 1 the types and mixing ratios of the biodegradable polyester resin and the (meth) acrylate compound were changed as shown in Tables 2-1 and 2-2. The rest was the same as in Example 1 to obtain a biodegradable polyester resin composition.
- the obtained biodegradable polyester resin composition and a carbon dioxide gas as a foaming agent having a concentration of 1.0% by mass are twin-screw extruded and foamed (PCM-45, Ikegai Co., Ltd., die lip: width 0.7 mm). (X length: 65 mm), and a foamed sheet was produced under the conditions of a kneading temperature of 200 ° C and a die temperature of 160 ° C.
- Tables 2-1 and 2-2 show the physical properties of the obtained resin composition and foam.
- Examples 4 to 8 the type of the (meth) acrylate compound was changed, and in Examples 7 to 13, the type of the biodegradable polyester resin was changed. Since the compounding ratio of the silicate and the (meth) acrylic acid ester compound was within the range of the present invention, the crystallization rate was high, the strain hardening coefficient was large, the flexural modulus was excellent, and a closed-cell, uniform foam was obtained. It was obtained. Examples 14 to 18
- Table 3-1 shows the types and mixing ratios of layered silicates. Other than that, a biodegradable polyester resin composition was obtained in the same manner as in Example 1. '
- the concentration of the obtained biodegradable polyester resin composition is 1.0% by mass.
- Table 3-1 shows the physical properties of the obtained resin composition and foam.
- Examples 14 to 16 vary the type of layered silicate
- Examples 17 and 18 vary the amount of layered silicate added. Both of them are biodegradable polyester resin and layered silicate. And (meth) acrylic acid ester compound were within the range of the present invention, so that the crystallization rate was high, the strain hardening coefficient was large, the flexural modulus was excellent, and the closed foam was uniform. A foam was obtained. Further, as shown in Example 16, when Somasif MEE was used as the layered silicate, the gas barrier properties were particularly improved. Further, as shown in Examples 16 to 18, the larger the amount of the layered silicate added, the better the gas-nollability.
- Table 3-2 shows the physical properties of the obtained resin composition and foam. Comparative Example 4 '
- Somasif MEE was used as the layered silicate, and its mixing ratio was 22 parts by mass, which was larger than the range of the present invention. Other than that, an attempt was made to produce a foam sheet in the same manner as in Example 1, but the viscosity was too low to extrude the resin composition, and the sheet could not be obtained.
- biodegradable polyester resin A: polylactic acid (weight average molecular weight: 140,000, L-form: 9.9%, D-form: 1%, melting point: 168 ° CMFR: 1 g / 10 minutes) 100 parts by mass and layered silica 4 parts by mass of Somasif MEE as a salt, 1.5 parts by mass of fine talc having an average particle diameter of 1.0 m (manufactured by Nippon Talc) as a nucleating agent, and 25-dimethyl-2- as a peroxide Inert solid dilute powder of 1,5-bis (t_butylpropyl) hexine-3 was added to the resin component by 1.0% by mass, and dried with the twin-screw extruder kneader used in Example '1.
- Blend and supply to the extrusion feeder did.
- a mixed solution was prepared such that PEGDM (0.1 part by mass) as the (meth) acrylic acid ester compound and acetyltriptyl citrate as the plasticizer were in a ratio of 1: 5 parts by mass.
- the mixed solution was supplied from the middle of the kneader using a liquid metering pump.
- the dry-blended resin and the mixed solution were melt-kneaded and extruded, processed into a pellet, and dried to obtain a biodegradable polyester resin composition.
- the obtained biodegradable polyester resin composition is charged into a batch foaming apparatus (autoclave 50 Om 1, manufactured by Taiatsu Glass Co., Ltd.), at a temperature of 150 ° C. and a carbon dioxide gas injection pressure of 15 MP. As a, after a carbon dioxide gas injection time of 60 minutes had elapsed, the pressure was released at a stretch to produce a carbon dioxide gas batch foam.
- a batch foaming apparatus autoclave 50 Om 1, manufactured by Taiatsu Glass Co., Ltd.
- Table 4 shows the physical properties of the obtained resin composition and foam.
- Butane gas was used instead of carbon dioxide gas as a blowing agent. Otherwise, the procedure of Example 19 was repeated to prepare a batch foam.
- Table 4 shows the physical properties of the obtained resin composition and foam.
- Example 19 since the thickening effect of the (meth) acrylic acid ester compound was high, the crystallization rate was high, the strain hardening coefficient was large, and a foam having a high magnification was obtained by foaming in an independent cell form.
- Example 20 butane gas was used as the foaming agent, but a foam in the form of an independent cell having a higher expansion ratio was obtained because the foaming agent had high solubility in the resin. ⁇
- the biodegradable polyester resin obtained in Example 19 was converted into a biaxial kneader-type foam sheeting device (TEM48 BS type, manufactured by Toshiba Machine Co., Ltd., die lip interval: 0.3 mm) Melting and kneading at a melting temperature of 210 ° C using a circle die discharge diameter: 160 m ⁇ ), a cooling zone temperature of 140 ° C, a die temperature of 160 ° C, and a carbon dioxide concentration of 2.
- a sheet was prepared at a take-up speed of 1.5 m / min by a sheet width of 64 mm ⁇ 2 pieces under a condition of 0%, discharge amount: 50 Kg / h.
- the obtained foam sheet was a foam sheet composed of uniform independent foam cells having a thickness of 2.0 mm and an expansion ratio of 7.5 times. Further, the flexural modulus was 4.4 GPa, which was excellent in mechanical strength.
- This foamed sheet is molded into a food tray using a thermoforming machine (manufactured by Asano Research Laboratories) by a mold that integrally molds the lid and the container. . 5) was prepared. Specifically, the sheet temperature was set to 130 ° C, and the sheet was moved onto the mold after the heating time passed for 10 seconds. Then, vacuum forming at a mold temperature of 110 ° C. was performed for 5 seconds to obtain a formed body.
- a thermoforming machine manufactured by Asano Research Laboratories
- the obtained molded article was a food tray having a uniform foaming state without molding flaws.
- the expansion ratio of this tray was 7.3 times, the same as the sheet before molding.
- Example 22 uses the biodegradable polyester resin composition obtained in Example 2 and Example 23 uses the biodegradable polyester resin composition obtained in Example 19, and uses an injection molding apparatus.
- Toshiba Machine Co., IS_100E was used to perform injection molding into a mold release die (diameter 38 mm, height 300 mm).
- the molding temperature was set at 200 ° C and the mold temperature was set at 110 ° C, and the cycle time until the cup could be released was examined.
- Table 5 shows the obtained measurement results.
- Comparative Example 5 used the biodegradable polyester resin composition obtained in Comparative Example 1
- Comparative Example 6 used the biodegradable polyester resin composition obtained in Comparative Example 3. Otherwise, injection molding was performed in the same manner as in Example 22, and the cycle time until the dies could be released was examined. Table 5 shows the obtained measurement results. '' Comparative Example 7
- Example 1 Only the biodegradable polyester used in Example 1 was used without blending the (meth) acrylic acid compound and the layered silicate. Otherwise, injection molding was performed in the same manner as in Example 22. However, the operability was poor and the operation could not be performed.
- Comparative Example 5 since the (meth) acrylic acid compound was not blended, the crystallization rate was extremely slow, and the molding cycle was significantly reduced. In Comparative Example 6, since the compounding ratio of the layered silicate was too small, the hot stiffness was insufficient, and a trouble occurred at the time of removing the molded product, and the operability at the time of injection molding was deteriorated. .
- Example 24 uses the biodegradable polyester resin composition obtained in Example 2 and Example 25 uses the biodegradable polyester resin composition obtained in Example 19 in a blow molding apparatus.
- a briform having a diameter of 30 mm, a height of 100 mm, and a thickness of 3.5 mm was produced at a molding temperature of 200 ° C. .
- the obtained preform was heated to a temperature of 80 ° C and blow-molded into a bottle-shaped mold (90 mm in diameter, 25 Omm in height) to obtain a thickness of 0.3.
- a 5 mm compact was obtained.
- Comparative Example 8 used the biodegradable polyester resin composition obtained in Comparative Example 1
- Comparative Example 9 used the biodegradable polyester resin composition obtained in Comparative Example 3.
- the opening was formed in the same manner as in Example 24.
- Table 5 shows the obtained measurement results.
- Example 1 Only the biodegradable polyester used in Example 1 was used without blending the acrylic acid compound and the layered silicate. Otherwise, the blow molding was attempted in the same manner as in Example 24, but the operability was poor and it could not be carried out.
- Example 26 uses the biodegradable polyester resin composition obtained in Example 2 and Example 27 uses the biodegradable polyester resin composition obtained in Example 19, and an extruder A molded plate having a width of 50 mm and a thickness of 2.0 mm was produced under the conditions of a molding temperature of 210 ° C (manufactured by Ikegai Co., Ltd., PCM-30).
- Example 26 the crystallization rate was high and the extrudability was good due to the synergistic effect of the content of the layered silicate and the (meth) acrylic acid compound. Comparative Example 1 1, 1 2
- Comparative Example 11 used the biodegradable polyester resin composition obtained in Comparative Example 1
- Comparative Example 12 used the biodegradable polyester resin composition obtained in Comparative Example 3. Except for this, extrusion was performed in the same manner as in Example 26.
- Table 7 shows the measurement results obtained.
- Example 1 Only the biodegradable polyester used in Example 1 was used without blending the (meth) acrylic acid compound and the layered silicate. Except for this, the extrusion molding was attempted in the same manner as in Example 26, but the workability was poor and the extrusion could not be performed.
- Comparative Example 13 shows no strain hardening property because neither (meth) acrylic acid compound nor layered silicate was blended, a low crystallization rate, and no extrusion molding as described above. The desired molded product could not be obtained.
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Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
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PCT/JP2003/005914 WO2004099315A1 (ja) | 2003-05-12 | 2003-05-12 | 生分解性ポリエステル樹脂組成物及びその製造方法並びにこれを用いてなる発泡体及び成形体 |
US10/555,139 US7449510B2 (en) | 2003-05-12 | 2003-05-12 | Biodegradable polyester resin composition, process for producing the same and foamed article and molded article using the same |
CNB038264455A CN100354367C (zh) | 2003-05-12 | 2003-05-12 | 生物降解性聚酯树脂组合物及其制造方法和用它形成的泡沫体及成形物 |
EP03721095A EP1624024B1 (en) | 2003-05-12 | 2003-05-12 | Biodegradable polyester resin composition, process for producing the same and foamed article and molded article using the same |
KR1020057021521A KR100935130B1 (ko) | 2003-05-12 | 2003-05-12 | 생분해성 폴리에스테르 수지 조성물 및 그 제조방법 및 이것을 사용하여 이루어지는 발포체 및 성형체 |
JP2004571580A JP4353902B2 (ja) | 2003-05-12 | 2003-05-12 | 生分解性ポリエステル樹脂組成物及びその製造方法並びにこれを用いてなる発泡体及び成形体 |
DE60314783T DE60314783T2 (de) | 2003-05-12 | 2003-05-12 | Biologisch abbaubaren polyester enthaltende zusammensetzung, herstellungsverfahren dafür und schaum- und formkörper unter deren verwendung |
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PCT/JP2003/005914 WO2004099315A1 (ja) | 2003-05-12 | 2003-05-12 | 生分解性ポリエステル樹脂組成物及びその製造方法並びにこれを用いてなる発泡体及び成形体 |
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US (1) | US7449510B2 (ja) |
EP (1) | EP1624024B1 (ja) |
JP (1) | JP4353902B2 (ja) |
KR (1) | KR100935130B1 (ja) |
CN (1) | CN100354367C (ja) |
DE (1) | DE60314783T2 (ja) |
WO (1) | WO2004099315A1 (ja) |
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- 2003-05-12 DE DE60314783T patent/DE60314783T2/de not_active Expired - Lifetime
- 2003-05-12 KR KR1020057021521A patent/KR100935130B1/ko not_active IP Right Cessation
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Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2006030859A1 (ja) | 2004-09-16 | 2006-03-23 | Asahi Kasei Life & Living Corporation | 耐熱性に優れた脂肪族ポリエステル樹脂組成物 |
WO2006086813A1 (de) * | 2005-02-18 | 2006-08-24 | Alois Zorn | Schaumstoffprodukt |
US8765043B2 (en) | 2005-02-18 | 2014-07-01 | Alois Zorn | Method of producing a foam material product |
TWI397553B (zh) * | 2005-04-26 | 2013-06-01 | Unitika Ltd | 生物分解性樹脂組成物、由該組成物構成之成形體,及該組成物之製造方法 |
CN101128535B (zh) * | 2005-06-07 | 2011-12-21 | 尤尼吉可株式会社 | 生物降解聚酯树脂组合物、其制造方法及该组合物成型所得的成型体 |
WO2007094478A1 (ja) * | 2006-02-14 | 2007-08-23 | Nec Corporation | ポリ乳酸系樹脂組成物及び成形体 |
JP2007262339A (ja) * | 2006-03-30 | 2007-10-11 | Unitika Ltd | ポリ乳酸系ポリエステル樹脂組成物、その製造方法、それを用いた成形体 |
JP2008308562A (ja) * | 2007-06-14 | 2008-12-25 | Unitika Ltd | 生分解性ポリエステル樹脂組成物、その製造方法、それを用いた成形体 |
JP2015502448A (ja) * | 2011-12-26 | 2015-01-22 | エルジー・ハウシス・リミテッドLg Hausys,Ltd. | 生分解性樹脂組成物とこれを用いた生分解性シートの製造方法 |
JP2015052045A (ja) * | 2013-09-06 | 2015-03-19 | 株式会社カネカ | ポリエステル樹脂組成物、ポリエステル樹脂発泡体及びその製造方法 |
JP5993108B1 (ja) * | 2015-03-18 | 2016-09-14 | バンドー化学株式会社 | 発泡用樹脂組成物及び発泡成形体 |
WO2016147883A1 (ja) * | 2015-03-18 | 2016-09-22 | バンドー化学株式会社 | 発泡用樹脂組成物及び発泡成形体 |
US10377872B2 (en) | 2015-03-18 | 2019-08-13 | Bando Chemical Industries, Ltd. | Foamable resin composition and molded foam |
WO2024080263A1 (ja) * | 2022-10-13 | 2024-04-18 | 日精樹脂工業株式会社 | 射出ブロー成形用ポリ乳酸樹脂組成物、ポリ乳酸樹脂組成物の製造方法、射出ブロー成形体及び射出ブロー成形体の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
US7449510B2 (en) | 2008-11-11 |
US20070027247A1 (en) | 2007-02-01 |
JP4353902B2 (ja) | 2009-10-28 |
EP1624024A4 (en) | 2006-06-21 |
CN100354367C (zh) | 2007-12-12 |
KR20060036905A (ko) | 2006-05-02 |
EP1624024A1 (en) | 2006-02-08 |
DE60314783D1 (de) | 2007-08-16 |
KR100935130B1 (ko) | 2010-01-06 |
DE60314783T2 (de) | 2008-04-10 |
EP1624024B1 (en) | 2007-07-04 |
CN1771291A (zh) | 2006-05-10 |
JPWO2004099315A1 (ja) | 2006-07-13 |
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