WO2014188646A1 - ポリエステル樹脂組成物および該樹脂組成物を含む成形体 - Google Patents
ポリエステル樹脂組成物および該樹脂組成物を含む成形体 Download PDFInfo
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- WO2014188646A1 WO2014188646A1 PCT/JP2014/001751 JP2014001751W WO2014188646A1 WO 2014188646 A1 WO2014188646 A1 WO 2014188646A1 JP 2014001751 W JP2014001751 W JP 2014001751W WO 2014188646 A1 WO2014188646 A1 WO 2014188646A1
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- hydroxybutyrate
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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
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
Definitions
- the present invention relates to a polyester resin composition, and more particularly to a polyester resin composition for applying a biodegradable polyester resin that is decomposed by the action of microorganisms as various industrial materials, and a molded article composed thereof. Is.
- plastic waste has been able to solve the problems that have caused a great burden on the global environment, such as impact on the ecosystem, generation of harmful gases during combustion, global warming due to a large amount of combustion heat, Biodegradable plastics are actively developed.
- PHA polyhydroxyalkanoate
- Poly (3-hydroxybutyrate-co-4-hydroxybutyrate) copolymer resin, polylactic acid, and the like are attracting attention.
- the polyester resin has a low crystallization rate. Therefore, it is necessary to increase the cooling time for solidification after heating and melting in the molding process, and the molding processability and productivity are poor. There is a problem.
- the present invention improves the crystallization slowness of biodegradable polyester that is decomposed into water and carbon dioxide by the action of microorganisms, and improves the molding processability in molding processes such as injection molding and sheet molding. It aims at providing the resin composition which shows the productivity which was excellent at the time of pellet production.
- the present inventors can promote the crystallization of the polyester resin by blending the crystallization accelerator and pentaerythritol with the slow crystallization polyester resin, and improve the molding processability and productivity.
- the headline and the present invention were completed.
- the present invention relates to a polyester resin composition
- a polyester resin composition comprising a polyester resin (A), a crystallization accelerator (B), and pentaerythritol (C).
- the crystallization accelerator (B) is preferably a modified glycerin compound.
- the modified glycerin compound contains at least one selected from glycerin diacetomonolaurate, glycerin diacetomonooleate, glycerin monoacetomonostearate, glycerin diacetomonocaprylate, and glycerin diacetomonodecanoate.
- the crystallization accelerator (B) is preferably contained in an amount of 1 to 30 parts by weight with respect to 100 parts by weight of the polyester resin (A).
- the pentaerythritol (C) is preferably contained in an amount of 0.05 to 12 parts by weight based on 100 parts by weight of the polyester resin (A).
- the polyester resin (A) preferably contains at least one selected from polyhydroxyalkanoate, polyethylene succinate, polybutylene succinate, and polybutylene succinate adipate.
- the polyhydroxyalkanoate is poly (3-hydroxybutyrate), poly (3-hydroxybutyrate-co-3-hydroxyvalerate), poly (3-hydroxybutyrate-co-3-hydroxyvalerate-co -3-hydroxyhexanoate), poly (3-hydroxybutyrate-co-3-hydroxyhexanoate), poly (3-hydroxybutyrate-co-4-hydroxybutyrate) and polylactic acid It is preferable to contain at least one kind.
- the present invention also relates to a polyester resin molded product obtained by molding a polyester resin composition.
- the crystallization slowness of the biodegradable polyester is improved, and the molding processability in the molding process such as injection molding and sheet molding is improved. Productivity can be shown.
- the polyester resin composition of the present invention is characterized by containing a polyester resin (A), a crystallization accelerator (B), and pentaerythritol (C).
- the polyester resin (A) used in the present invention has a weight average molecular weight (hereinafter sometimes referred to as Mw) of 10,000 or more.
- Mw weight average molecular weight
- PHA is preferable because it is a bio-based material with a low environmental impact and biodegradability.
- PHA is poly (3-hydroxybutyrate), poly (3-hydroxybutyrate-co-3-hydroxyvale).
- the PHA used in the present invention has the formula (1): [—CHR—CH 2 —CO—O—] (wherein R is an alkyl group represented by C n H 2n + 1 , and n is an integer of 1 to 15) It is an aliphatic polyester containing a repeating unit represented by:
- the PHA is preferably a polymer resin composed of 80 mol% or more of 3-hydroxybutyrate, more preferably a polymer resin composed of 85 mol% or more, and is preferably produced by microorganisms.
- Specific examples include poly (3-hydroxybutyrate) homopolymer resin, poly (3-hydroxybutyrate-co-3-hydroxypropionate) copolymer resin, poly (3-hydroxybutyrate-co-3- Hydroxyvalerate) copolymer resin, poly (3-hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxyhexanoate) copolymer resin, poly (3-hydroxybutyrate-co-3-hydroxy) Hexanoate) copolymer resin, poly (3-hydroxybutyrate-co-3-hydroxyheptanoate) copolymer resin, poly (3-hydroxybutyrate-co-3-hydroxyoctanoate) copolymer resin, Poly (3-hydroxybutyrate-co-3-hydroxynonanoate) copolymer resin, poly (3-hydroxybut
- poly (3-hydroxybutyrate) homopolymer resin poly (3-hydroxybutyrate-co-3-hydroxyvalerate) copolymer resin, poly (3-hydroxy Butyrate-co-3-hydroxyvalerate-co-3-hydroxyhexanoate) copolymer resin, poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) copolymer resin, poly (3-hydroxy Butyrate-co-4-hydroxybutyrate) copolymer resin can be preferably used.
- 3-hydroxybutyrate hereinafter sometimes referred to as 3HB
- a copolymerized comonomer for example, 3-hydroxyvalerate (hereinafter sometimes referred to as 3HV), 3-hydroxyhexa
- 3HH 3-hydroxyvalerate
- 4-hydroxybutyrate ie, the monomer ratio in the copolymer resin
- Butyrate / comonomer 97/3 to 80/20 (mol% / mol%) is preferable, and 95/5 to 85/15 (mol% / mol%) is more preferable.
- the comonomer ratio is less than 3 mol%, the molding process temperature and the thermal decomposition temperature are close to each other, and it may be difficult to perform the molding process.
- the comonomer ratio exceeds 20 mol%, the crystallization of PHA is delayed, and thus productivity may be deteriorated.
- the said comonomer may be 1 type, 2 or more types can also be used for it. Even when two or more kinds of the comonomers are used, the preferred range of the monomer ratio (3-hydroxybutyrate / comonomer) in the copolymer resin is the same as described above.
- the ratio of each monomer in the PHA copolymer resin can be measured by gas chromatography as follows. To about 20 mg of dried PHA, 2 ml of a sulfuric acid / methanol mixture (15/85 (weight ratio)) and 2 ml of chloroform are added and sealed, and heated at 100 ° C. for 140 minutes to obtain the methyl ester of the PHA decomposition product. After cooling, 1.5 g of sodium hydrogen carbonate is added little by little to neutralize it, and the mixture is allowed to stand until the generation of carbon dioxide gas stops.
- the monomer unit composition of the PHA decomposition product in the supernatant is analyzed by capillary gas chromatography to determine the ratio of each monomer in the copolymer resin.
- GC-17A manufactured by Shimadzu Corporation was used, and “NEUTRA BOND-1” manufactured by GL Science Co., Ltd. (column length: 25 m, column inner diameter: 0.25 mm, liquid film thickness: 0.2 mm). 4 ⁇ m) is used. He is used as the carrier gas, the column inlet pressure is 100 kPa, and 1 ⁇ l of the sample is injected. As temperature conditions, the temperature is raised from an initial temperature of 100 ° C. to 200 ° C. at a rate of 8 ° C./min, and further from 200 to 290 ° C. at a rate of 30 ° C./min.
- the weight average molecular weight of the polyester resin (A) of the present invention is not particularly limited as long as it is 10,000 or more, but is preferably 100,000 to 2,500,000, more preferably 250,000 to 2,000,000 in terms of excellent processability and mechanical properties. More preferred is 300,000 to 1,000,000. If the weight average molecular weight is less than 100,000, the mechanical properties and the like may be inferior, and if it exceeds 2.5 million, molding may be difficult.
- the weight average molecular weight was measured using gel permeation chromatography (“Shodex GPC-101” manufactured by Showa Denko KK), using polystyrene gel (“Shodex K-804” manufactured by Showa Denko KK) as the column, and moving chloroform. It can be determined as the molecular weight when converted to polystyrene. At this time, a calibration curve is prepared using polystyrene having a weight average molecular weight of 31400, 197000, 668000, and 1920,000.
- the PHA is, for example, the Alcaligenes eutrophus AC32 strain in which the PHA synthase gene derived from Aeromonas caviae is introduced into Alcaligenes eutrophus (International deposit based on the Budapest Treaty, International Depositary Agency: National Institute of Advanced Industrial Science and Technology, Patent Organism Depositary) (Japan, Ibaraki Prefecture, Tsukuba City, 1-1-1 Higashi 1-Chuo 6), Date of original deposit: August 12, 1996, transferred on August 7, 1997, deposit number FERM BP-6038 (original deposit FERM P -15786))) (J. Bacteriol., 179, 4821 (1997)).
- the crystallization accelerator (B) of the present invention is a component that accelerates crystallization of the polyester resin (A) having a weight average molecular weight of less than 10,000, and is other than pentaerythritol.
- the crystallization accelerator (B) in the present invention is a compound that functions to promote the crystal nucleating agent effect of pentaerythritol (C) by blending, and accelerates the formation of crystals of the polyester resin containing pentaerythritol. Or a compound that can accelerate crystal growth.
- DSC differential scanning calorimetry
- a material that can increase the exothermic peak area that accompanies crystallization when cooling from a molten state at a constant cooling rate, a material that shifts the exothermic peak to a higher temperature side, or a molten state examples include materials that have the effect of increasing the crystal nucleus generation rate and the spherulite growth rate when cooling at an arbitrary temperature reduction rate.
- the take-up speed when extruding into a strand can be increased, the take-up speed can be increased during sheet / film molding, or the mold release time can be shortened during injection molding.
- the processability can be greatly improved.
- the amount of the crystallization accelerator (B) is 1 to 30 parts by weight, preferably 4 to 20 parts by weight, based on 100 parts by weight of the polyester resin (A). If the content is less than 1 part by weight, the effect of promoting crystallization may be small, and if it exceeds 30 parts by weight, the effect will not change and may cause bleeding out.
- the crystallization accelerator (B) a compound having an ester bond is preferable.
- Specific examples of the crystallization accelerator (B) include a modified glycerin compound, an adipate ester compound, a polyether ester compound, a benzoate ester compound, a phthalate ester compound, an isosorbide ester compound, In addition, polycaprolactone compounds can be used.
- the modified glycerin-based compound is a compound in which part or all of the hydroxyl groups of glycerin form an ester bond with a compound having a carboxyl group, for example.
- a glycerin ester compound is preferable.
- the glycerin ester-based compound any of monoester, diester or triester of glycerin can be used, but glycerin triester is preferable from the viewpoint of crystallization promoting action.
- glycerol triesters glycerol diacetate monoester is particularly preferable.
- glycerol diacetomonoester examples include glycerol diacetomonolaurate, glycerol diacetomonooleate, glycerol diacetomonostearate, glycerol diacetomonocaprylate, glycerol diacetomonodecanoate and the like.
- crystallization accelerator (B) glycerin diacetate monoester compound, adipic acid ester compound, polyether ester compound, benzoic acid ester compound, etc. are used because they have excellent affinity for resin components and are difficult to bleed. It can be preferably used. Diethylhexyl adipate, dioctyl adipate and diisononyl adipate can be preferably used as the adipic acid ester compound, and polyethylene glycol dibenzoate, polyethylene glycol dicaprylate and polyethylene glycol diisostearate can be preferably used as the polyether ester compound. .
- biomass-derived components such as epoxidized soybean oil, epoxidized fatty acid 2-ethylhexyl, and sebacic acid monoester can also be preferably used.
- modified glycerin compound examples include “Rikemar” (registered trademark) PL series manufactured by Riken Vitamin Co., Ltd.
- the crystallization accelerator (B) may be a mixture of not only one type but also two or more types, depending on the type of the polyester resin (A) and the crystal nucleating agent effect of the target pentaerythritol (C). The ratio can be adjusted as appropriate.
- the crystallization accelerator (B) is preferably glycerol diester, more preferably glycerol diacetomonoester, and further preferably glycerol diacetomonolaurate.
- pentaerythritol (C) is blended as a crystal nucleating agent for the polyester resin (A).
- pentaerythritol can further accelerate the crystallization of the polyester resin by the crystallization accelerator (B) in addition to increasing the crystallization speed of the polyester resin, and the molding processability and productivity are improved. Improved.
- Pentaerythritol is the following formula (2)
- Pentaerythritol is classified as a sugar alcohol, but is not derived from a natural product and can be synthesized by condensing acetaldehyde and formaldehyde in a basic environment.
- the pentaerythritol used in the present invention is not particularly limited as long as it is generally available, and reagent products or industrial products can be used.
- reagent products include Wako Pure Chemical Industries, Ltd., Sigma-Aldrich, Tokyo Chemical Industry Co., and Merck.
- reagent products include Wako Pure Chemical Industries, Ltd., Sigma-Aldrich, Tokyo Chemical Industry Co., and Merck.
- Guangei Chemical Co., Ltd. (trade name: Pentalit) and Toyo Chemicals Co., Ltd. can be mentioned, but is not limited thereto.
- Some commonly available reagent products and industrial products contain impurities such as dipentaerythritol and tripentaerythritol produced by dehydration condensation of pentaerythritol as impurities.
- the oligomer has no effect on the crystallization of the aliphatic polyester resin, but does not inhibit the crystallization effect of pentaerythritol. Therefore, the pentaerythritol used in the present invention may contain an oligomer.
- the amount of pentaerythritol used in the present invention is not particularly limited as long as crystallization of the polyester resin (A) can be promoted.
- the lower limit of the content of pentaerythritol is preferably 0.05 parts by weight with respect to 100 parts by weight of the polyester resin (A). Yes, more preferably 0.1 parts by weight, still more preferably 0.5 parts by weight.
- the upper limit of the content of pentaerythritol is 100% by weight of the polyester resin (A).
- the amount is preferably 12 parts by weight, more preferably 10 parts by weight, and still more preferably 8 parts by weight with respect to parts.
- the crystallization of the resin composition at the time of processing is stable under a wide range of processing conditions as compared to a polyester resin alone or a resin composition containing a polyester alcohol and a sugar alcohol compound other than pentaerythritol. Therefore, it has the following advantages.
- polyester resins poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) (hereinafter sometimes referred to as P (3HB-co-3HH)) and poly (3-hydroxybutyrate- When co-3-hydroxyvalerate (P (3HB-co-3HV)) is crystallized by cooling after heating and melting, the progress of crystallization is affected by the resin temperature at the time of melting, that is, at the time of melting.
- P (3HB-co-3HH) has a tendency that the resin temperature at the time of melting is about 170 ° C. from the melting point of the resin. The higher the resin temperature, the more difficult the crystallization of the resin during cooling tends to proceed, and when the resin temperature during melting is about 180 ° C.
- the resin temperature at the time of melting must be controlled within a temperature range of about 170 ° C. to 180 ° C. Since the temperature is not uniform, it is very difficult to control in the above temperature range.
- the crystallization of the polyester resin composition of the present invention proceeds stably over a wide temperature range when the resin is melted. That is, since the crystallization proceeds stably and quickly even when the resin temperature at the time of melting is higher than the melting point of the resin to about 190 ° C., the resin composition of the present invention is excellent for a wide range of processing conditions. It has processing characteristics. In addition, it is not preferable from the viewpoint of thermal degradation that the resin temperature during melting is 200 ° C. or higher.
- the progress of crystallization of polyhydroxyalkanoate also depends on the cooling temperature.
- P (3HB-co-3HH) has a tendency to proceed most when the cooling temperature after heating and melting is 50 to 70 ° C.
- the cooling temperature is lower than 50 ° C. or higher than 70 ° C.
- crystallization hardly progresses.
- the cooling water bath temperature, mold and cooling roll temperature correlate with the cooling temperature, and the cooling water temperature, mold and cooling roll temperature are within the above temperature range, that is, the range of 50 ° C to 70 ° C.
- the crystallization of the polyester resin composition of the present invention proceeds stably over a wide cooling temperature range of the resin after melting. That is, since the crystallization proceeds stably and quickly even when the cooling temperature after heating and melting is in the temperature range of 20 ° C. to 80 ° C., the resin composition of the present invention is excellent in processing over a wide range of processing conditions. It has characteristics.
- polyester resin composition of the present invention the following characteristics are manifested by the crystallization progressing stably and quickly.
- P (3HB-co-3HH) does not sufficiently crystallize at the time of molding, and gradually crystallizes after molding to grow spherulites. Therefore, the mechanical properties change over time, and the molded product becomes There was a tendency to gradually embrittle.
- the polyester resin composition of the present invention produces a large number of microcrystals immediately after molding, spherulites hardly grow after molding, and the embrittlement of the molded product is also suppressed, so that the product quality stability Is excellent in terms of.
- polyhydroxyalkanoate has a slow crystallization progress and needs to be designed so that, for example, the cooling process takes a long time during pelletization.
- the take-off speed at the time of T-die film molding is not reduced, the releasability from the cooling roll is bad, and there is a possibility that the productivity and the shape of the film are deteriorated, or the balloon becomes unstable at the time of inflation film molding. there's a possibility that.
- burrs that are formed when the resin enters are adhered to the molded product. Since polyhydroxyalkanoate is slow in crystallization and has a long time for the resin to have fluidity, burrs are likely to occur, and a large amount of labor is required for the post-treatment of the molded product. On the other hand, since the polyester resin composition of the present invention is rapidly crystallized, the above-mentioned problems are hardly caused.
- the polyester resin composition according to the present invention can be easily produced by a known melt kneader as long as it can be heated and kneaded to a temperature equal to or higher than the melting point of the polyester resin.
- a method in which a polyester resin, a crystallization accelerator, pentaerythritol, and, if necessary, other components are melt-kneaded with an extruder, a roll mill, a Banbury mixer, etc.
- pentaerythritol A method of preparing a high-concentration master batch in advance, melt-kneading the polyhydroxyalkanoate and the graft copolymer in a desired ratio, and using them for molding can be used. Pentaerythritol, crystallization accelerator and polyhydroxyalkanoate may be added to the kneader at the same time, or pentaerythritol may be added after the polyhydroxyalkanoate and graft copolymer have been melted first. .
- the polyester resin composition in the present invention may contain various additives as long as the effects of the present invention are not impaired.
- the additives include, for example, lubricants, crystal nucleating agents other than pentaerythritol, plasticizers, hydrolysis inhibitors, antioxidants, mold release agents, ultraviolet absorbers, dyes, pigments and other colorants, and inorganic fillers.
- these additives have biodegradability.
- additives include inorganic fibers such as carbon fibers and organic fibers such as human hair and wool.
- natural fibers such as bamboo fiber, pulp fiber, kenaf fiber, other similar plant substitute species, Mallow family annual plant, linden annual plant plant and the like can also be used. From the viewpoint of reducing carbon dioxide, plant-derived natural fibers are preferable, and kenaf fibers are particularly preferable.
- a polyester resin composition is prepared by melt-kneading the polyester resin, the crystallization accelerator and pentaerythritol, and if necessary, the various additives using an extruder, kneader, Banbury mixer, roll, etc. It is extruded after being extruded into a strand shape, and then cut to obtain pellets made of a polyester resin composition having a particle shape such as a cylindrical shape, an elliptical column shape, a spherical shape, a cubic shape, or a rectangular parallelepiped shape.
- the temperature at which the polyester resin and the crystallization accelerator are melt-kneaded depends on the melting point, melt viscosity, etc. of the polyester resin used and the melt viscosity of the graft copolymer.
- the resin temperature at the die outlet of the melt-kneaded product is preferably 140 to 200 ° C, more preferably 150 to 195 ° C, and further preferably 160 to 190 ° C. If the resin temperature of the melt-kneaded product is less than 140 ° C, the kneading may be insufficient, and if it exceeds 200 ° C, the polyhydroxyalkanoate may be thermally decomposed.
- the pellets produced by the above method are sufficiently dried at 40 to 80 ° C. to remove moisture, and then molded by a known molding method, whereby an arbitrary molded body can be obtained.
- the molding method include film molding, sheet molding, injection molding, blow molding, blow molding, fiber spinning, extrusion foaming, and bead foaming.
- Examples of the method for producing a film molded body include T-die extrusion molding, calendar molding, roll molding, and inflation molding.
- the film forming method is not limited to these.
- the molding temperature during film molding is preferably 140 to 190 ° C.
- the film obtained from the polyester resin composition of the present invention can be thermoformed by heating, vacuum formed, and press formed.
- an injection molding method such as an injection molding method, a gas assist molding method, or an injection compression molding method that is generally employed when molding a thermoplastic resin
- an in-mold molding method, a gas press molding method, a two-color molding method, a sandwich molding method, PUSH-PULL, SCORIM, or the like can also be employed according to other purposes.
- the injection molding method is not limited to these.
- the molding temperature at the time of injection molding is preferably 140 to 190 ° C.
- the mold temperature is preferably 20 to 80 ° C., and more preferably 30 to 70 ° C.
- the molded article of the present invention can be suitably used in agriculture, fishery, forestry, horticulture, medicine, hygiene, food industry, clothing, non-clothing, packaging, automobiles, building materials, and other fields.
- KNK-005 strain (see US Pat. No. 7,384,766) was used for culture production.
- Tanehaha medium 1w / v% Meat-extract, 1w / v% Bacto-Tryptone, 0.2w / v% Yeast-extract, 0.9w / v% Na 2 HPO 4 ⁇ 12H 2 O, 0.15w / V% KH 2 PO 4 (pH 6.8).
- the composition of the preculture medium is 1.1 w / v% Na 2 HPO 4 ⁇ 12H 2 O, 0.19 w / v% KH 2 PO 4 , 1.29 w / v% (NH 4 ) 2 SO 4 , 0.1 w / v% MgSO 4 ⁇ 7H 2 O , 0.5v / v% trace metal salt solution (1.6 w in 0.1N HCl / v% FeCl 3 ⁇ 6H 2 O, 1w / v% CaCl 2 ⁇ 2H 2 O, 0 0.02 w / v% CoCl 2 .6H 2 O, 0.016 w / v% CuSO 4 .5H 2 O, 0.012 w / v% NiCl 2 .6H 2 O).
- palm oil was added at a concentration of 10 g / L.
- the composition of the PHA production medium is 0.385 w / v% Na 2 HPO 4 ⁇ 12H 2 O, 0.067 w / v% KH 2 PO 4 , 0.291 w / v% (NH 4 ) 2 SO 4 , 0.1 w / v% MgSO 4 .7H 2 O, 0.5 v / v% trace metal salt solution (1.6 W / v% FeCl 3 .6H 2 O in 0.1N hydrochloric acid, 1 w / v% CaCl 2 .2H 2 O, 0 0.02 w / v% CoCl 2 ⁇ 6H 2 O, 0.016 w / v% CuSO 4 ⁇ 5H 2 O, 0.012 w / v% NiCl 2 ⁇ 6H 2 O), 0.05 w / v% BIOSPUREX 200K (Antifoamer: manufactured by Cognis Japan).
- a glycerol stock (50 ⁇ l) of the KNK-005 strain was inoculated into a seed medium (10 ml) and cultured for 24 hours to perform seed culture.
- 1.0 v / v% of the seed mother culture solution was inoculated into a 3 L jar fermenter (MDL-300 type, manufactured by Maruhishi Bioengine) containing 1.8 L of a preculture medium.
- the operating conditions were a culture temperature of 33 ° C., a stirring speed of 500 rpm, an aeration rate of 1.8 L / min, and the culture was performed for 28 hours while controlling the pH between 6.7 and 6.8.
- a 14% aqueous ammonium hydroxide solution was used for pH control.
- 1.0 V / v% of the preculture solution was inoculated into a 10 L jar fermenter (MDS-1000, manufactured by Maruhishi Bioengine) containing 6 L of production medium.
- the operating conditions were a culture temperature of 28 ° C., a stirring speed of 400 rpm, an aeration rate of 6.0 L / min, and a pH controlled between 6.7 and 6.8.
- a 14% aqueous ammonium hydroxide solution was used for pH control. Palm oil was used as the carbon source.
- Culturing was performed for 64 hours, and after completion of the cultivation, the cells were collected by centrifugation, washed with methanol, freeze-dried, and the weight of the dried cells was measured.
- He was used as the carrier gas
- the column inlet pressure was 100 kPa
- 1 ⁇ l of the sample was injected.
- the temperature was raised from an initial temperature of 100 to 200 ° C. at a rate of 8 ° C./min, and further from 200 to 290 ° C. at a rate of 30 ° C./min.
- PHA poly (3-hydroxybutyrate-co-3-hydroxyhexanoate)
- the weight average molecular weight Mw measured by GPC was 600,000.
- the 3-hydroxyhexanoate (3HH) composition was 5.6 mol%.
- Examples 1 to 7 Manufacture of polyester resin composition
- Pellets of the polyester resin composition were mixed using the same direction meshing type twin screw extruder (manufactured by Nippon Steel Co., Ltd .: TEX30) at the mixing ratio shown in Table 1. Manufactured and evaluated for pellet productivity.
- the polyhydroxyalkanoate raw material A1 was obtained in Production Example 1, the polyhydroxyalkanoate raw material A2 was obtained in Production Example 2, and the polyhydroxyalkanoate raw material A3 was produced in Production Example 3. What was obtained in (1) was used.
- polyhydroxyalkanoate raw material A4 poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (3-hydroxyvalerate (3HV) composition is 5.0 mol%) manufactured by Sigma-Aldrich It was.
- the weight average molecular weight Mw was 650,000.
- crystallization accelerator raw material B1 glycerin diacetomonolaurate (manufactured by Riken Vitamin Co., Ltd., “Riquemar (registered trademark)” PL012), and as crystallization accelerator raw material B2, glycerin diacetomonoester: (CH 3 CO) — O—CH 2 —CH—O— (COCH 3 ) CH 2 —O— (COC n H2 n + 1 ) (manufactured by Riken Vitamin Co., Ltd., “Riquemar®” PL019) was used.
- pentaerythritol raw material C pentaerythritol (manufactured by Guangei Perstorp, “Pentalit T (registered trademark)”) was used.
- Pellet productivity was evaluated as follows. At a set temperature of the extruder of 120 to 140 ° C., the screw rotation speed was gradually increased from 100 rpm to increase the discharge amount. The strand-shaped molten resin coming out of the die of the extruder passes through a 1.5 m long hot bath filled with 60 ° C water, crystallizes and solidifies, and is cut into pellets by a pelletizer. The In order to increase the resin discharge rate and increase the pellet productivity, it is necessary to increase the screw rotation speed of the extruder to increase the linear velocity of the strand. When the screw rotation speed is increased, the resin temperature increases due to shear heat generation, and the residence time in the hot tub decreases as the linear velocity increases.
- polyester resin composition was obtained by melt-kneading at a set temperature of 120 to 140 ° C. and a screw rotation speed of 100 rpm using a same direction meshing type twin screw extruder (manufactured by Nippon Steel Co., Ltd .: TEX30). The polyester resin composition was drawn from a die in a strand shape and cut into a pellet shape.
- the molded sheet When the resin is sufficiently crystallized, the molded sheet is released from the cooling roll and wound up. However, if the linear velocity of the sheet is increased, the time of contact with the cooling roll is shortened, so that it does not crystallize. Therefore, it cannot be released from the roll.
- the maximum sheet linear velocity at which a sheet can be released is defined as sheet productivity. The higher the linear velocity value, the better the sheet productivity.
- the resin temperature was measured by bringing the molten resin coming out of the T die into direct contact with a K-type thermocouple.
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Abstract
Description
結晶化促進剤(B)としては、エステル結合を有する化合物が好ましい。結晶化促進剤(B)として、具体的には、変性グリセリン系化合物、アジピン酸エステル系化合物、ポリエーテルエステル系化合物、安息香酸エステル系化合物、フタル酸エステル系化合物、イソソルバイドエステル系化合物、およびポリカプロラクトン系化合物などを用いることができる。
で示される化合物である。多価アルコール類の一種であり、融点260.5℃の白色結晶の有機化合物である。ペンタエリスリトールは糖アルコールに分類されるが、天然物由来ではなく、アセトアルデヒドとホルムアルデヒドを塩基性環境下で縮合して合成することができる。
ペレット生産性は次のようにして評価した。押出機の設定温度120~140℃で、スクリュー回転数を100rpmから徐々に高め吐出量をあげた。押出機のダイスから出てくるストランド状の溶融樹脂は設定60℃の水で満たされた1.5m長の温浴槽内を通過して結晶化、固化して、ペレタイザーにてペレット状にカットされる。樹脂吐出量をあげてペレット生産性を上げるためには、押出機のスクリュー回転数をあげてストランドの線速をあげる必要がある。スクリュー回転数を上げると剪断発熱によって樹脂温度が高まり、かつ線速が上がるに従い温浴槽での滞留時間が短くなる。樹脂温度が高まると結晶化し難くなり、また、60℃温浴槽での滞留時間が短くなると、樹脂は結晶化しきれずに軟化したままになる。すなわち、樹脂温度が高まり温浴槽での滞留時間が短くなるとペレタイザーでカットできなくなる。ペレット化できる最大のストランド線速をペレット生産性と定義した。線速値が高いほどペレット生産性は優れることを意味する。線速を上げる際は押出機のスクリュー回転数も上げてストランド直径(長径と短径の平均)が3mm±0.2mmとなるように調整した。尚、樹脂温度は押出機のダイスから出てくる溶融樹脂をK型熱電対で直接接触させて測定した。結果は表1に示した。
実施例1~7と同様の方法で、ポリエステル樹脂組成物のペレット生産性を評価し、結果を表1に示した。
(ポリエステル樹脂組成物の製造)
同方向噛合型2軸押出機(日本製鋼社製:TEX30)を用いて、設定温度120~140℃、スクリュー回転数100rpmで溶融混錬し、ポリエステル樹脂組成物を得た。当該ポリエステル樹脂組成物はダイスからストランド状に引き取り、ペレット状にカットした。
シート生産性は次のように評価した。得られたペレットを原料として、Tダイシート成形機(東洋精機製作所社製:ラボプラストミル)を用い、ダイスリップ厚=250μm、ダイスリップ幅=150mm、シリンダー設定温度=120~140℃、ダイス設定温度=140~150℃、冷却ロール設定温度60℃にて、100mm幅のシートを成形した。Tダイからシート状にでてきた溶融樹脂は冷却ロールに接触することで結晶化し、厚さ100μmのシートに成形される。樹脂が十分に結晶化した場合は、成形されたシートは冷却ロールから離型され、巻き取られるが、シートの線速が早まると冷却ロールに接触している時間が短くなるので結晶化せずに十分に固化しないのでロールから離型できなくなる。シートが離型できる最大のシート線速をシート生産性と定義した。線速値が高いほどシート生産性は優れることを意味する。なお、樹脂温度はTダイから出てくる溶融樹脂をK型熱電対で直接接触させて測定した。
実施例8~13と同様の方法で、ポリエステル樹脂組成物のシート生産性を評価し、結果を表2に示した。
Claims (8)
- ポリエステル樹脂(A)、結晶化促進剤(B)およびペンタエリスリトール(C)を含有することを特徴とするポリエステル樹脂組成物。
- 前記結晶化促進剤(B)が変性グリセリン系化合物であることを特徴とする請求項1に記載のポリエステル樹脂組成物。
- 前記変性グリセリン系化合物が、グリセリンジアセトモノラウレート、グリセリンジアセトモノオレート、グリセリンモノアセトモノステアレート、グリセリンジアセトモノカプリレート、グリセリンジアセトモノデカノエートから選ばれる少なくとも1種を含有することを特徴とする請求項2に記載のポリエステル樹脂組成物。
- 前記結晶化促進剤(B)をポリエステル樹脂(A)100重量部に対して1~30重量部含有していることを特徴とする、請求項1から3の何れかに記載のポリエステル樹脂組成物。
- 前記ペンタエリスリトール(C)をポリエステル樹脂(A)100重量部に対して0.05~12重量部含有していることを特徴とする、請求項1から4の何れかに記載のポリエステル樹脂組成物。
- ポリエステル樹脂(A)が、ポリヒドロキシアルカノエート、ポリエチレンサクシネート、ポリブチレンサクシネート、およびポリブチレンサクシネート・アジペートから選択される少なくとも1種を含有する樹脂であることを特徴とする請求項1から5の何れかに記載のポリエステル樹脂組成物。
- 前記ポリヒドロキシアルカノエートが、ポリ(3-ヒドロキシブチレート)、ポリ(3-ヒドロキシブチレート-コ-3-ヒドロキシバレレート)、ポリ(3-ヒドロキシブチレート-コ-3-ヒドロキシバレレート-コ-3-ヒドロキシヘキサノエート)、ポリ(3-ヒドロキシブチレート-コ-3-ヒドロキシヘキサノエート)、ポリ(3-ヒドロキシブチレート-コ-4-ヒドロキシブチレート)およびポリ乳酸から選択される少なくとも1種を含有することを特徴とする、請求項1から6の何れかに記載のポリエステル樹脂組成物。
- 請求項1から7の何れかに記載のポリエステル樹脂組成物を成形してなるポリエステル樹脂成形体。
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WO2020040093A1 (ja) * | 2018-08-20 | 2020-02-27 | 株式会社カネカ | ポリ(3-ヒドロキシブチレート)系樹脂チューブ及びその製造方法 |
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