WO2006112287A1 - ポリヒドロキシアルカノエート樹脂発泡粒子、およびその成形体と該樹脂発泡粒子の製造方法 - Google Patents
ポリヒドロキシアルカノエート樹脂発泡粒子、およびその成形体と該樹脂発泡粒子の製造方法 Download PDFInfo
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- WO2006112287A1 WO2006112287A1 PCT/JP2006/307549 JP2006307549W WO2006112287A1 WO 2006112287 A1 WO2006112287 A1 WO 2006112287A1 JP 2006307549 W JP2006307549 W JP 2006307549W WO 2006112287 A1 WO2006112287 A1 WO 2006112287A1
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- hydroxyalkanoate
- foamed
- particles
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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
- C08J9/0014—Use of organic additives
- C08J9/0028—Use of organic additives containing nitrogen
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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
- B29C44/34—Auxiliary operations
- B29C44/3461—Making or treating expandable particles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0895—Manufacture of polymers by continuous processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4283—Hydroxycarboxylic acid or ester
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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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
- C08J9/16—Making expandable particles
- C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2230/00—Compositions for preparing biodegradable polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2310/00—Agricultural use or equipment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2340/00—Filter 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
Definitions
- the present invention relates to a polyhydroxyalkanoate coagulated foam particle derived from a plant and having biodegradability, a molded product thereof, and a method for producing the foamed coffin resin particle.
- Aliphatic polyester foamable particles characterized by having a specific melt viscosity see, for example, JP-A-6-248106
- polyisocyanates polyhydric alcohols
- polycarboxylic acids as crosslinking agents
- Polylactic acid foamed particles and molded articles thereof using, for example, International Publication No. 99Z21915 Nonfretsu K JP 2000-169546, JP 2000-17039, JP 2000 00029 (See JP 2001-98044, JP 2002-327037, JP 2003-253107, JP 2004-107430, JP 2004-107505, and JP 2004-149649) There is.
- P3HA resin which also produces microbial power
- P3HA resin expanded particles and molded articles thereof are disclosed in JP-A-2000-31438.
- PHBH poly (3-hydroxybutyrate-toco 3-hydroxyhexanoate)
- PHBH poly (3-hydroxybutyrate-toco 3-hydroxyhexanoate)
- an object of the present invention is to provide a foamed particle molded body obtained by filling a mold with biodegradable resinous foam particles excellent in environmental compatibility derived from plants and then heat-molding it.
- the purpose is to provide a foamed particle molded body that does not shrink and has a wide processing width during molding.
- the first aspect of the present invention is a general formula (1) produced from a microorganism:
- R is an alkyl group represented by C H, and n is an integer of 1 to 15.
- P3HA resin expanded foam particles comprising a resin composition containing a polymer poly P3HA containing a repeating unit represented by formula (I) and an isocyanate compound.
- P3HA is PHBH.
- poly (3 hydroxyhexanoate) is 1 to 20 mol%.
- a second aspect of the present invention relates to a molded article of P3HA foamed resin particles, which is obtained by filling a mold with the above foamed resin particles and heat molding.
- a base resin composed of a resin composition containing P3HA and an isocyanate compound is dispersed together with a dispersant in an aqueous dispersion medium in a sealed container, and then a foaming agent is sealed in the sealed container. After being introduced into the interior and heated above the softening temperature of the base resin, one end of the sealed container is opened, and the base resin and the aqueous dispersion medium are released in an atmosphere at a pressure lower than the pressure of the sealed container.
- the present invention also relates to a method for producing the P3HA foamed resin particles, wherein the base resin is foamed.
- the expanded P3HA resin particles of the present invention are produced by the general formula (1):
- R is an alkyl group represented by C H, and n is an integer of 1 to 15.
- P3HA of the present invention is a compound represented by the general formula (1):
- R is an alkyl group represented by C H, and n is an integer of 1 to 15.
- P3HA in the present invention a homopolymer of 3 hydroxyalkanoate or a copolymer having a combination force of two or more 3 hydroxyalkanoates having different n, that is, G copolymer, tree copolymer, tetra copolymer, etc. Or two of these The above-mentioned blended material is given.
- PHBH which is one of P3HA
- PHBH is prepared by appropriately adjusting the raw materials and culture conditions using Alcaligenes eutrophus AC32, a PHA synthase derived from Ae romonas caviae as a microorganism. Bacteriol., 179, 4821 (1997).
- the isocyanate compound used in the present invention is not particularly limited, but it is preferable that one molecule has two or more isocyanate groups from the viewpoint of reactivity. More preferably, it has 3 or more isocyanate groups.
- Examples of the type include aromatic, alicyclic, and aliphatic isocyanates. More specifically, aromatic isocyanates include tolylene, diphenylmethane, naphthylene, tolidine, xylene and triphenylmethane as skeletons, and cycloaliphatic isocyanates as isophorone and hydrogenated diphenylmethane as skeletons.
- Examples of the isocyanate compound and the aliphatic isocyanate include an isocyanate compound having a hexamethylene and lysine skeleton.
- an isocyanate compound having a hexamethylene and lysine skeleton In addition, a combination of two or more of these isocyanate compounds can be used, but tolylene and diphenylmethane are preferred from the viewpoints of versatility, handleability, and weather resistance, and diphenylmethane polyisocyanate is preferred. used.
- the amount of isocyanate compound used is 0.1 parts by weight or more with respect to 100 parts by weight of P3HA. It is preferable that The upper limit is not particularly limited, but is preferably 20 parts by weight or less. Further, from the standpoint of quality and practical use, it is more preferably 0.3 to 15 parts by weight, and particularly preferably 0.5 to 5 parts by weight.
- the isocyanate compound is less than 0.1 part by weight, the film strength of the resin cannot withstand the foaming force at the time of foaming, and the foamed cells tend to break up and a good foam tends to be difficult to obtain.
- the amount exceeds 20 parts by weight unreacted isocyanate compound remains or the reaction such as crosslinking proceeds excessively, and there is a tendency to reduce foaming force.
- additives may be added to the P3HA resin composition in the present invention as long as the required performance of the obtained expanded particles is not impaired.
- the additive can be used according to the purpose, for example, a colorant such as an acid-proofing agent, an ultraviolet absorber, a dye, a pigment, a plasticizer, a lubricant, a crystallization nucleating agent, an inorganic filler, Of these, biodegradable additives are preferred.
- Additives include inorganic compounds such as silica, talc, calcium silicate, wollastonite, kaolin, clay, mica, zinc oxide, titanium oxide, silicon oxide, sodium stearate, magnesium stearate, calcium stearate and stearin.
- Fatty acid such as barium acid Metal salt, liquid paraffin, olefin wax, stearylamide compound, etc. Power is not limited to these. If it is necessary to adjust the bubble diameter of the expanded particles, add a bubble regulator.
- the air conditioner include inorganic agents such as talc, silica, key acid lucium, calcium carbonate, acid aluminum, titanium oxide, diatomaceous earth, clay, baking soda, alumina, barium sulfate, acid aluminum, and bentonite. The amount used is preferably 0.005 to 2 parts by weight.
- the P3HA resin foamed particles of the present invention are obtained by first heat-melting and mixing P3HA resin and isocyanate compound using an extruder, ender, Banbury mixer, roll, etc.
- the weight per particle is preferably at least 0.1 mg, more preferably at least 0.5 mg.
- the upper limit is not particularly limited, but is preferably 10 mg or less. If it is less than 0.1 mg, it tends to be difficult to produce P3HA rosin particles.
- the P3HA resin particles thus obtained are preferably dispersed together with a dispersant in an aqueous dispersion medium in a closed container, and then a foaming agent is introduced into the closed container, so that the softening temperature of the P3HA resin particles is raised. And then, if necessary, after holding for a certain period of time near the foaming temperature, one end of the closed container is released, and the base resin and aqueous dispersion medium are kept at a pressure lower than the pressure in the closed container. Release into the atmosphere and foam the base resin to obtain P3HA foamed particles.
- Examples of the dispersant include inorganic substances such as tricalcium phosphate, calcium pyrophosphate, kaolin, basic magnesium carbonate, aluminum oxide, basic zinc carbonate, and the like, for example, sodium dodecylbenzenesulfonate, ⁇ - It is preferable to use a combination of a surfactant such as sodium olefin sulfonate and sodium normal sulfonate sulfonate.
- the amount of the inorganic substance used is preferably 0.1 to 3.0 parts by weight with respect to 100 parts by weight of ⁇ ⁇ 3 resin, and the amount of the surfactant used is 100 parts by weight of ⁇ ⁇ 3 resin. 0. 001-0. 5 parts by weight is preferred. 0. 001-0. 2 parts by weight is more preferred.
- aqueous dispersion medium economic points, handling points, and sexual points are usually preferred, but not limited thereto.
- the amount of the aqueous dispersion medium used is preferably 100 to 1000 parts by weight per 100 parts by weight of ⁇ ⁇ 3 resin.
- blowing agent examples include saturated hydrocarbons having 3 to 5 carbon atoms such as propane, normal butane, isobutane, normal pentane, isopentane, and neopentane, ethers such as dimethyl ether, jetyl ether, and methyl ethyl ether, and monochloromethane.
- saturated hydrocarbons having 3 to 5 carbon atoms such as propane, normal butane, isobutane, normal pentane, isopentane, and neopentane
- ethers such as dimethyl ether, jetyl ether, and methyl ethyl ether
- monochloromethane such as dichloromethane and dichlorodifluoroethane
- inorganic gases such as carbon dioxide, nitrogen and air, water, and the like.
- the amount of foaming agent added varies depending on the expansion ratio of the desired pre-foamed particles, the type of foaming agent, the type of polyester-based resin, the ratio of the resin particles to the dispersion medium, the space volume of the container, the impregnation or foaming temperature, etc. Usually, it is preferably 2 to: L0000 parts by weight, more preferably 5 to 5000 parts by weight, even more preferably 10 to L000 parts by weight with respect to 100 parts by weight of the resin particles. If the foaming agent is less than 2 parts by weight, there is a tendency that a sufficient expansion ratio cannot be obtained, and even if the foaming agent exceeds 10000 parts by weight, it is not possible to obtain an effect that is just added. Tend to be wasted.
- the foaming temperature of the P3HA resin particles is not particularly limited, but is preferably 100 to 150 ° C.
- the temperature at which the base resin is heated is not particularly limited as long as it is equal to or higher than the softening temperature of the base resin, but it is usually preferably 100 to 150 ° C.
- the low-pressure atmosphere for releasing the base resin and the aqueous dispersion medium is not particularly limited as long as the pressure is lower than the pressure of the sealed container, but is preferably atmospheric pressure. .
- the foamed P3HA resin particles of the present invention can be used as is for packaging materials, tableware materials, architecture, civil engineering, agriculture, horticultural materials, automobile interior materials, adsorption, carrier'filter materials, etc.
- it is heat-molded by pressurizing and aging with pressurized air, filling foamed particles with foaming ability and filling the mold that can be closed but cannot be sealed, and then introducing water vapor into the mold.
- a foamed molded product of P3HA resin particles is produced.
- PHBH poly (3-hydroxybutyrate-to-co-3-hydroxyhexanoate)
- the surface of the molded body was visually observed and evaluated according to the following criteria.
- Foaming factor VZ (WZ / 0)
- Each compact sample was cut into 15 cm x 3 cm, treated for 24 hours at 60 ° C and 80% relative humidity, and the measured force, volume change rate of length, width, and thickness before and after treatment were calculated.
- the P3HA resin foam particles of the example were buried in soil with a depth of 10 cm, and after 6 months, the shape change was observed to evaluate the degradability.
- Moldable water vapor pressure range is 0. IMPa (gauge) or more
- Moldable water vapor pressure range is 0. OlMPa (gauge) or more 0. IMPa (gauge) less
- Moldable water vapor pressure range is less than 0. OlMPa (gauge)
- Alcaligenes eutrophus AC32 with PHA synthase gene derived from Aeromonas caviae introduced into Alcaligenes eutrophus as microorganism (Accession number FERM BP— 6038 (transferred from original deposit (FERM P— 15786) deposited on August 12, 1996)) (flat August 7, 1997, National Institute of Advanced Industrial Science and Technology, Patent Biological Deposit Center, addressed to: 1-chome, Tsukuba 1-chome, 1-chome, Ibaraki, Japan 6)) adjusted PHBH produced by (HH rate 12 mol 0/0) 100 parts by weight of polyisobutylene Xia sulfonate compound (Nippon polyurethane industry Co., Ltd., Millionate MR- 200 (Isoshianeto group from 2.7 to 2.8 equivalents of Z Mole)) After hand blending 2 parts by weight, it is melt-kneaded at a cylinder temperature of 145 ° C with a ⁇ 35mm single-scre
- the PHBH foamed resin particles B are filled in a 300 X 400 X 30mm mold, and 0.2 to 0.3 to 5 MPa (gauge) of water vapor is introduced into the mold. B were heated and fused together to obtain a PHBH resin foam molded article C with good surface smoothness with a foaming ratio of 25 times and a closed cell ratio of 91%. Although the heating width at the time of molding was evaluated according to the above criteria, a good molded product with a wide molding heating width was obtained. The PHBH foamed molded product C was strong, with almost no thermal deformation under high temperature and high humidity without shrinkage after fabrication. Moreover, the biodegradability of this resin was good. The results are shown in Table 1.
- Example 2 The same procedure as in Example 1 was carried out except that PHBH of PHBH rosin particles A was PHBH having an HH ratio of 7 mol% and the temperature in the container at the time of foaming was 126 ° C. As a result, the foaming ratio was 12 times, the closed cell ratio was 96%, and the PHBH had a crystal structure showing two melting points (153 ° C (Tml), 122 ° C (Tm2)) in the DSC curve by differential scanning calorimetry. Resin foam particles B were obtained. Furthermore, 0.17 to 0.30 MPa (gauge) of water vapor is introduced and heated and fused.
- Tml 153 ° C
- Tm2 122 ° C
- Example 2 The same operation as in Example 2 was conducted except that the temperature in the container at the time of foaming was 125 ° C. As a result, the expansion ratio is 8 times, the closed cell ratio is 97%, and the differential scanning calorimetry DSC curve shows two crystalline melting points (151 ° C (Tml), 124 ° C (Tm2)). Expanded particles B were obtained. Furthermore, 0.17 to 0.30 MPa (gauge) of water vapor was introduced and heated and fused to obtain PHBH resin foam foam C with good surface smoothness of 10 times the expansion ratio and 93% closed cell ratio. Obtained. The heating width at the time of molding was evaluated according to the above criteria, but the molding heating width was wide and a good molded body was obtained. The PHBH foamed molded product C was strong with almost no thermal deformation under high temperature and high humidity without shrinkage after fabrication. The biodegradability of this resin was good. The results are shown in Table 1.
- Example 2 The same operation as in Example 2 was conducted except that the temperature in the container at the time of foaming was 123 ° C. and 1 part by weight of the polyisocyanate compound was used. As a result, a foaming ratio of 10 times and a closed cell ratio of 92%, a PHBH resin having a crystal structure showing two melting points (149 ° C (Tml), 121 ° C (Tm2)) in the DSC curve by differential scanning calorimetry. Expanded particles B were obtained. Furthermore, 0.17 to 0.30 MPa (gauge) of water vapor was introduced and heated and fused to obtain PHBH resin foam molded article C having a foaming ratio of 12 times and an independent cell ratio of 90%.
- Tml 149 ° C
- Tm2 121 ° C
- Expanded particles B were obtained.
- 0.17 to 0.30 MPa (gauge) of water vapor was introduced and heated and fused to obtain PHBH resin foam molded article C having a foaming ratio of 12 times and an
- Example 2 The same procedure as in Example 1 was conducted except that the temperature in the container at the time of foaming was 121 ° C. and that 1 part by weight of the polyisocyanate compound was used. As a result, the expansion ratio is 15 times and the closed cell ratio is 91%. Then, PHBH resin foamed particles B having a crystal structure showing two melting points (144 ° C (Tml), 114 ° C (Tm2)) in the DSC curve by differential scanning calorimetry were obtained. Furthermore, 0.23 to 0.35 MPa (gauge) of water vapor was introduced and heated and fused to obtain PHBH resin foam molded product C having an expansion ratio of 18 times and an independent cell ratio of 90%.
- Tml melting points
- Tm2 114 ° C
- 0.23 to 0.35 MPa (gauge) of water vapor was introduced and heated and fused to obtain PHBH resin foam molded product C having an expansion ratio of 18 times and an independent cell ratio of 90%.
- Example 2 The same operation as in Example 1 was conducted except that the temperature in the container at the time of foaming was 128 ° C. and 4 parts by weight of the polyisocyanate compound was used.
- PHBH ⁇ has a crystal structure with two expansion points (154 ° C (Tml), 121 ° C (Tm 2)) in the DSC curve by differential scanning calorimetry with a foaming ratio of 20 times and a closed cell ratio of 98%. Lipofoam particles B were obtained.
- 0.23 to 0.35 MPa (gauge) of water vapor was introduced and heated and fused to obtain PHBH resin foam molded product C having an expansion ratio of 22 times and an closed cell ratio of 94%.
- PHBH ⁇ has a crystal structure with a foaming ratio of 13 times and a closed cell ratio of 53% and two melting points (145 ° C (Tml) and 113 ° C (Tm2)) in the DSC curve by differential scanning calorimetry.
- Lipofoam particles B were obtained. Further, it was heated by introducing steam of 0.02 MPa (gauge), but PHBH resin expanded foam B contracted greatly, and it was not possible to obtain good PHBH resin expanded foam C. The biodegradability of this resin was good. The results are shown in Table 1.
- Example 3 The same procedure as in Example 3 was conducted except that a polyisocyanate compound was used for the PHBH resin particles A. As a result, the expansion ratio was 10 times and the closed cell ratio was 90%. According to the DSC curve, PHBH resin foam expanded particles B having a crystal structure showing two melting points (149 ° C. (Tml), 123 ° C. (Tm 2)) were obtained. Furthermore, 0.15 MPa (gauge) water vapor was introduced and heated, but it was not possible to obtain a good PHBH resin foam foam C with large shrinkage of the compact. Moreover, the biodegradability of this resin was good. The results are shown in Table 1.
- Polylactic acid having a D-form ratio of 10%, a number average molecular weight of 100,000, a weight average molecular weight of 210,000, and a residual lactide of 0.2% using a twin screw extruder (TEX35B manufactured by Toshiba Machine Co., Ltd., LZD 35) Socionate compound (manufactured by Nippon Polyurethane Industry Co., Ltd., Millionate MR-200 (isocyanate group 2.7 to 2.8 equivalents Z mol)) Melt and knead together with 2 parts by weight, and use an underwater cutter to make approximately lmm ⁇ A beaded rosin composition was obtained. The beaded rosin composition was aged in 42 ° C warm water for 15 hours and secondary crosslinked, then dehydrated, dried and impregnated with foaming gas.
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Abstract
Description
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2006800116073A CN101193956B (zh) | 2005-04-14 | 2006-04-10 | 聚羟基链烷酸酯树脂发泡粒子及其成形体、和该树脂发泡粒子的制造方法 |
US11/911,552 US8076381B2 (en) | 2005-04-14 | 2006-04-10 | Polyhydroxyalkanoate-based resin foamed particle, molded article comprising the same and process for producing the same |
JP2007521191A JP5014127B2 (ja) | 2005-04-14 | 2006-04-10 | ポリヒドロキシアルカノエート樹脂発泡粒子、およびその成形体と該樹脂発泡粒子の製造方法 |
EP06731496.3A EP1873195B1 (en) | 2005-04-14 | 2006-04-10 | Method of producing a molded product |
Applications Claiming Priority (2)
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JP2005-116975 | 2005-04-14 | ||
JP2005116975 | 2005-04-14 |
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WO2006112287A1 true WO2006112287A1 (ja) | 2006-10-26 |
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PCT/JP2006/307549 WO2006112287A1 (ja) | 2005-04-14 | 2006-04-10 | ポリヒドロキシアルカノエート樹脂発泡粒子、およびその成形体と該樹脂発泡粒子の製造方法 |
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US (1) | US8076381B2 (ja) |
EP (1) | EP1873195B1 (ja) |
JP (1) | JP5014127B2 (ja) |
CN (1) | CN101193956B (ja) |
WO (1) | WO2006112287A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009001525A1 (ja) * | 2007-06-27 | 2008-12-31 | Kaneka Corporation | 生分解性脂肪族ポリエステル系発泡粒子及びその成形体 |
WO2019146555A1 (ja) * | 2018-01-26 | 2019-08-01 | 株式会社カネカ | ポリ(3-ヒドロキシアルカノエート)系発泡粒子およびポリ(3-ヒドロキシアルカノエート)系発泡成形体 |
Families Citing this family (25)
Publication number | Priority date | Publication date | Assignee | Title |
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JPWO2019146555A1 (ja) * | 2018-01-26 | 2021-01-07 | 株式会社カネカ | ポリ(3−ヒドロキシアルカノエート)系発泡粒子およびポリ(3−ヒドロキシアルカノエート)系発泡成形体 |
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Also Published As
Publication number | Publication date |
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JPWO2006112287A1 (ja) | 2008-12-11 |
EP1873195A4 (en) | 2011-05-25 |
EP1873195B1 (en) | 2013-09-11 |
CN101193956A (zh) | 2008-06-04 |
US8076381B2 (en) | 2011-12-13 |
CN101193956B (zh) | 2011-02-09 |
US20090149560A1 (en) | 2009-06-11 |
EP1873195A1 (en) | 2008-01-02 |
JP5014127B2 (ja) | 2012-08-29 |
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