WO2014068943A1 - 脂肪族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
脂肪族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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- WO2014068943A1 WO2014068943A1 PCT/JP2013/006365 JP2013006365W WO2014068943A1 WO 2014068943 A1 WO2014068943 A1 WO 2014068943A1 JP 2013006365 W JP2013006365 W JP 2013006365W WO 2014068943 A1 WO2014068943 A1 WO 2014068943A1
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- polyester resin
- aliphatic polyester
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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
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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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
- 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 an aliphatic polyester resin composition, and in particular, a polyester resin composition for applying a biodegradable polyester resin that is decomposed by the action of microorganisms as various industrial materials, and a molding composed thereof. It is about goods.
- 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.
- polyhydroxyalkanoate (hereinafter sometimes referred to as PHA) -based resins and also PHA-based resins.
- PHA polyhydroxyalkanoate
- PHA-based resins polyhydroxyalkanoate
- P3HB poly (3-hydroxybutyrate) homopolymer resin
- P3HB3HV poly (3-hydroxybutyrate-co-3-hydroxyvalerate) copolymer resin
- P3HB3HH poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) copolymer resin
- P3HB3HH poly (3-hydroxybutyrate-co-4-hydroxybutyrate
- the PHA-based resin is known to have a low crystallization rate. Therefore, it is necessary to lengthen the cooling time for solidification after heating and melting in the molding process, and the molding processability and productivity are improved. There is a problem that it is bad.
- Patent Document 1 discloses that crystallization of a PHA resin is promoted by mixing a compound having an amide bond with the PHA resin. However, further improvements are desired to improve productivity.
- the present invention improves the slow crystallization, which is a disadvantage of polyhydroxyalkanoates, and is particularly suitable for molding such as injection molding and sheet molding.
- An object of the present invention is to provide a resin composition that improves molding processability in processing and exhibits excellent productivity during molding or pellet production.
- the inventors of the present invention can promote crystallization of polyhydroxyalkanoate by blending a compound having an amide bond and pentaerythritol into polyhydroxyalkanoate that is slowly crystallized, and can be processed and processed. As a result, the present invention has been completed.
- the present invention contains a polyhydroxyalkanoate (A), a compound having an amide bond (B) and pentaerythritol (C),
- the compound (B) having the amide bond is represented by the following general formula: R 1 —C (O) N (R 2 ) 2 , R 1 —C (O) NH— (R 3 ) —NHC (O) —R 1 , R 1 —NHC (O) NH— (R 3 ) — NHC (O) NH—R 1 , R 1 —NHC (O) —R 2 , R 1 —NHC (O) — (R 3 ) —C (O) NH—R 1 , R 1 —C (O) NH — (R 3 ) —C (O) NH—R 1 , R 1 —NHC (O) NH— (R 3 ) —C (O) NH—R 1 , R 1 —NHC (O) NH— (R
- the compound (B) having an amide bond is at least one selected from lauric acid amide, myristic acid amide, stearic acid amide, behenic acid amide, and erucic acid amide.
- pentaerythritol (C) is 0.05 to 12 parts by weight with respect to 100 parts by weight of polyhydroxyalkanoate (A).
- the polyhydroxyalkanoate (A) is represented by the following general formula (1): [—CHR—CH 2 —CO—O—] (1) (In the formula, R is an alkyl group represented by C n H 2n + 1 , and n is an integer of 1 to 15, inclusive), The repeating unit shown by is included.
- the polyhydroxyalkanoate (A) is a poly (3-hydroxybutyrate) homopolymer resin, a poly (3-hydroxybutyrate-co-3-hydroxyvalerate) copolymer resin, a poly (3-hydroxybutyrate), Rate-co-3-hydroxyvalerate-co-3-hydroxyhexanoate) copolymer resin, poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) copolymer resin, and poly (3-hydroxy Butyrate-co-4-hydroxybutyrate) copolymer resin.
- the present invention also relates to a polyester resin molded article obtained by molding the aliphatic polyester resin composition.
- the crystallization slowness of the polyhydroxyalkanoate is improved, the moldability in the molding process such as injection molding and sheet formation is improved, and at the time of molding and pellet production Can improve productivity.
- the aliphatic polyester resin composition of the present invention contains PHA (A), a compound (B) having an amide bond, and pentaerythritol (C).
- PHA (A) is an aliphatic polyester resin containing a repeating unit represented by the general formula: [—CHR—CH 2 —CO—O—].
- the PHA (A) 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 1 or more and 15). It is preferably an aliphatic polyester containing a repeating unit represented by the following integer:
- a 3-hydroxybutyrate unit, a 3-hydroxyvalerate unit, a 3-hydroxyhexanoate unit, or a 4-hydroxybutyrate unit is preferably contained. .
- PHA (A) 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 a microorganism.
- 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
- 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, and poly (3- Hydroxybutyrate-co-4-hydroxybutyrate) copolymer resin can be preferably used.
- 3-hydroxybutyrate hereinafter sometimes referred to as 3HB
- 3-hydroxyvalerate hereinafter sometimes referred to as 3HV
- the composition ratio with a comonomer such as noate hereinafter sometimes referred to as 3HH
- 4-hydroxybutyrate hereinafter sometimes referred to as 4HB
- 3-hydroxybutyrate / comonomer 97/3 to 80/20 (mol% / mol%), 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 (A) is delayed, and thus productivity may be deteriorated.
- the ratio of each monomer in the copolymer resin of PHA (A) 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 (hereinafter sometimes referred to as Mw) of the PHA (A) of the present invention is preferably 200,000 to 2,500,000, more preferably 250,000 to 2,000,000, and further preferably 300,000 to 1,000,000.
- Mw weight average molecular weight
- mechanical properties and the like may be inferior, and when it exceeds 2.5 million, molding may be difficult.
- the weight average molecular weight was measured using gel permeation chromatography (GPC) (“Shodex GPC-101” manufactured by Showa Denko KK) and polystyrene gel (“Shodex K-804” manufactured by Showa Denko KK) as the column. It can be determined as the molecular weight when converted to polystyrene using chloroform as the mobile phase. 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 compound (B) having an amide bond used in the present invention has the following general formula: R 1 —C (O) N (R 2 ) 2 , R 1 —C (O) NH— (R 3 ) —NHC (O) —R 1 , R 1 —NHC (O) NH— (R 3 ) — NHC (O) NH—R 1 , R 1 —NHC (O) —R 2 , R 1 —NHC (O) — (R 3 ) —C (O) NH—R 1 , R 1 —C (O) NH — (R 3 ) —C (O) NH—R 1 , R 1 —NHC (O) NH— (R 3 ) —C (O) NH—R 1 , R 1 —NHC (O) NH— (R 3 ) —C (O) NH—R 1 , R 1 —NHC (O) NH— (R 3 ) —C (O
- Each R 1 is independently C 6 -C 30 alkyl, preferably C 12 -C 22 alkyl.
- Each R 2 is independently H or C 1 -C 20 alkyl, preferably H or C 1 -C 6 alkyl, more preferably H.
- Each R 3 is independently C 2 -C 10 alkylene, preferably C 2 -C 6 alkylene.
- the alkyl group or alkylene group may be saturated or unsaturated.
- a compound represented by R 1 —C (O) NH 2 is preferable.
- Specific examples include lauric acid amide, myristic acid amide, stearic acid amide, behenic acid amide, and erucic acid amide.
- the amount of the compound (B) having an amide bond used in the present invention is not particularly limited as long as crystallization of the polyhydroxyalkanoate (A) can be promoted.
- the lower limit of the content of the compound (B) having an amide bond is preferably 0 with respect to 100 parts by weight of the polyhydroxyalkanoate (A). 0.01 parts by weight, more preferably 0.05 parts by weight, still more preferably 0.1 parts by weight.
- the upper limit of the content of the compound (B) having an amide bond Is preferably 10 parts by weight, more preferably 7 parts by weight, and still more preferably 5 parts by weight with respect to 100 parts by weight of the polyhydroxyalkanoate (A).
- pentaerythritol (C) In the aliphatic polyester resin composition of the present invention, pentaerythritol (C) is used as a crystal nucleating agent for polyhydroxyalkanoate (A).
- Pentaerythritol (C) is the following formula (2)
- Pentaerythritol (C) 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 (C) used in the present invention is not particularly limited as long as it is generally available, and a reagent product or an industrial product can be used.
- reagent products include Wako Pure Chemical Industries, Ltd., Sigma-Aldrich, Tokyo Chemical Industry Co., and Merck.
- Guangei Chemical Co., Ltd. trade name: Pentalit
- 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 (C) as impurities.
- the oligomer has no effect on crystallization of polyhydroxyalkanoate (A), but does not inhibit the crystallization effect of pentaerythritol (C). Therefore, an oligomer may be included.
- the amount of pentaerythritol (C) used in the present invention is not particularly limited as long as crystallization of polyhydroxyalkanoate (A) can be promoted.
- the lower limit of the content of pentaerythritol (C) is 100 parts by weight of polyhydroxyalkanoate (A).
- it is 0.05 weight part, More preferably, it is 0.1 weight part, More preferably, it is 0.5 weight part.
- the amount of pentaerythritol (C) is too large, the viscosity at the time of melt processing may decrease, making it difficult to process.
- the upper limit of the content of pentaerythritol (C) is polyhydroxyalkanoate.
- it is 12 weight part with respect to 100 weight part of content of (A), More preferably, it is 10 weight part, More preferably, it is 8 weight part.
- the aliphatic polyester resin composition of the present invention is a polyhydroxyalkanoate alone, a resin composition containing a polyhydroxyalkanoate and an amide compound, or a resin composition containing a polyhydroxyalkanoate and a sugar alcohol compound other than pentaerythritol.
- a resin composition containing a polyhydroxyalkanoate and a sugar alcohol compound other than pentaerythritol is excellent in that it proceeds stably under a wide range of processing conditions, it has the following advantages.
- polyhydroxyalkanoates poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) (P3HB3HH), poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (P3HB3HV), etc.
- the progress of crystallization is affected by the resin temperature at the time of melting. That is, the higher the resin temperature during melting, the more difficult the crystallization proceeds.
- the resin temperature at the time of melting is about 170 ° C. from the melting point of the resin, the crystallization of the resin at the time of cooling tends to become difficult as the resin temperature at the time of melting increases.
- the resin temperature at the time of 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.
- the resin temperature at the time of melting is not uniform. It is very difficult to control in the above temperature range.
- the crystallization of the aliphatic 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 (A) depends on the cooling temperature.
- crystallization of P3HB3HH tends to proceed most when the cooling temperature after heating and melting is 50 to 70 ° C., and when the cooling temperature is lower than 50 ° C. or higher than 70 ° C., crystallization is less likely to proceed.
- the mold temperature correlates with the cooling temperature, and the mold temperature must be controlled within the above temperature range, that is, in the range of 50 ° C to 70 ° C. In order to control the mold temperature uniformly. However, it is necessary to precisely design the mold structure and shape, which is very difficult.
- the crystallization of the aliphatic 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.
- the aliphatic polyester resin composition of the present invention is a conventional polyhydroxyalkanoate alone, a resin composition containing a polyhydroxyalkanoate and an amide compound, or a resin composition containing a sugar alcohol compound other than polyhydroxyalkanoate and pentaerythritol. Since it has the above-mentioned advantages that cannot be obtained with a product, it has excellent processing characteristics in that a wide range of resin temperatures at the time of melting and cooling temperatures of molds can be set.
- the following characteristics are manifested by the crystallization progressing stably and quickly.
- P3HB3HH has a tendency that crystallization does not proceed sufficiently at the time of molding, so that crystallization gradually progresses after molding and spherulites grow, so that mechanical properties change with time and the molded product gradually becomes brittle. was there.
- the aliphatic polyester resin composition of the present invention produces a large number of microcrystals immediately after molding, the spherulites are difficult to grow after molding, and the embrittlement of the molded product is also suppressed. Excellent in terms of stability.
- the cavity part for example, parting line part, insert part, slide core sliding part, etc.
- the resin melted in the gap at the time of injection molding
- the “burrs” that are formed by the adhering to adhere 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.
- the aliphatic polyester resin composition of the present invention is preferable in practical use because it is difficult to be burred because it is rapidly crystallized and the post-treatment effort of the molded product can be reduced.
- the aliphatic 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 polyhydroxyalkanoate (A).
- a polyhydroxyalkanoate (A), a compound (B) having an amide bond, pentaerythritol (C), and, if necessary, other components are melt-kneaded by an extruder, a roll mill, a Banbury mixer, etc.
- a master batch having a high concentration of the compound (B) having an amide bond and pentaerythritol (C) is prepared in advance, and this is added to the polyhydroxyalkanoate (A) in a desired ratio.
- a method of melting and kneading and using for molding can be used.
- Pentaerythritol (C), polyhydroxyalkanoate (A) and compound (B) having an amide bond may be added to the kneader at the same time or after the polyhydroxyalkanoate (A) has been melted first. You may add the compound (B) which has an amide bond, and a pentaerythritol (C).
- the aliphatic polyester resin composition in the present invention may contain various additives as long as the effects of the present invention are not impaired.
- the additive includes, for example, a lubricant, pentaerythritol (C), and a crystal nucleating agent other than the compound (B) having an amide bond, a plasticizer, a hydrolysis inhibitor, an antioxidant, a release agent, and an ultraviolet absorber.
- Colorants such as dyes and pigments, inorganic fillers and the like can be used depending on the purpose, but these additives are preferably biodegradable.
- 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.
- PHA a compound having an amide bond
- B a compound having an amide bond
- C pentaerythritol
- the various additives are melt-kneaded using an extruder, kneader, Banbury mixer, roll, etc.
- An aliphatic polyester resin composition that is extruded into a strand shape and then cut to form an aliphatic 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 PHA (A) is melt-kneaded cannot be unconditionally defined because of the melting point, melt viscosity, etc. of PHA (A) used, but the resin temperature at the die outlet of the melt-kneaded product is 140-200 ° C.
- the temperature is 150 to 195 ° C, more preferably 160 to 190 ° C. If the resin temperature of the melt-kneaded product is less than 140 ° C, kneading may be insufficient, and if it exceeds 200 ° C, PHA (A) 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 sheet molded body include T-die extrusion molding, calendar molding, and roll molding.
- the sheet forming method is not limited to these.
- the molding temperature during sheet molding is preferably 140 to 190 ° C.
- the sheet obtained from the aliphatic polyester resin composition of the present invention can be subjected to thermoforming by heating, vacuum forming, press molding, and sheet blow molding.
- 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.
- Polyhydroxyalkanoate raw material A1 The one obtained in Production Example 1 was used.
- 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, 0.5v / 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, 0.02w / V% CoCl 2 ⁇ 6H 2 O, 0.016 w / v% CuSO 4 ⁇ 5H 2 O, 0.012 w / v% NiCl 2 ⁇ 6H 2 O dissolved in), 0.05 w / v% BIOSPUREX 200K (antifoaming agent: 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) (PHBH) as shown in chemical formula (1).
- the composition of 3-hydroxyhexanoate (3HH) was 5.6 mol% (3HB composition was 94.4 mol%).
- PHBH was obtained from the culture solution by the method described in International Publication No. 2010/066753.
- the weight average molecular weight Mw measured by GPC was 600,000.
- Polyhydroxyalkanoate raw material A2 The one obtained in Production Example 2 was used.
- Polyhydroxyalkanoate raw material A3 The one obtained in Production Example 3 was used.
- Polyhydroxyalkanoate raw material A4 Poly (3-hydroxybutyrate-co-3-hydroxyvalerate) manufactured by Sigma-Aldrich Co. (3-hydroxyvalerate (3HV) composition is 5 mol%, 3HB composition Is 95 mol%).
- Examples 1 to 7> Polyhydroxyalkanoate raw material A1, compound raw material B1 or B2 having an amide bond and pentaerythritol (manufactured by Wako Pure Chemical Industries, Ltd.) are shown in Table 1 (hereinafter, the mixing ratio in the table indicates parts by weight). In the same direction, the mixture was melt kneaded at a set temperature of 120 to 140 ° C. and a screw rotation speed of 100 rpm using a same direction meshing twin screw extruder (manufactured by Nippon Steel Co., Ltd .: TEX30) to obtain an aliphatic polyester resin composition. .
- the aliphatic polyester resin composition was drawn from a die in a strand shape and cut into a pellet shape. At this time, the resin temperature at the die outlet was 165 to 190 ° C., although it varied depending on the compounding amount of the compound having an amide bond and pentaerythritol.
- an injection molding machine manufactured by Nissei Plastic Industrial Co., Ltd .: FN1000
- the molding machine has a cylinder set temperature of 130 to 160 ° C. and a mold set temperature of 50 ° C., 150 mm ⁇ 150 mm ⁇ 2 mm.
- a thick flat test piece was molded.
- the resin temperature at the time of injection was measured by bringing the injected molten resin into contact, and the mold temperature was measured by bringing the mold surface into direct contact with a K-type thermocouple.
- the mold release time A shorter release time indicates faster crystallization and better moldability.
- Examples 8 to 14> (Production of aliphatic polyester resin composition) With the compounding ratios shown in Table 2, pellets of the aliphatic polyester resin composition were produced using the same direction meshing type twin screw extruder (manufactured by Nippon Steel Co., Ltd .: TEX30), and the pellet productivity was evaluated.
- 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.
- Examples 15 to 18> (Production of polyester resin composition) Using an in-direction meshing twin screw extruder (manufactured by Nippon Steel Co., Ltd .: TEX30), melt-kneading was performed at a set temperature of 120 to 140 ° C. and a screw rotation speed of 100 rpm to obtain an aliphatic polyester resin composition.
- the aliphatic 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
前記アミド結合を有する化合物(B)が、下記一般式:
R1-C(O)N(R2)2、R1-C(O)NH-(R3)-NHC(O)-R1、R1-NHC(O)NH-(R3)-NHC(O)NH-R1、R1-NHC(O)-R2、R1-NHC(O)-(R3)-C(O)NH-R1、R1-C(O)NH-(R3)-C(O)NH-R1、R1-NHC(O)NH-(R3)-C(O)NH-R1、若しくはR1-NHC(O)NH-(R3)-NHC(O)-R1で表される化合物であるか、又はそれらの組み合わせであり、
式中、各R1は、独立してC6~C30アルキルであり、
各R2は、独立してH又はC1~C20アルキルであり、及び
各R3は、独立してC2~C10アルキレンであることを特徴とする、
脂肪族ポリエステル樹脂組成物に関する。
[-CHR-CH2-CO-O-] (1)
(式中、RはCnH2n+1で表されるアルキル基で、nは1以上15以下の整数である。)、
で示される繰り返し単位を含む。
本発明において、PHA(A)は、一般式 :[-CHR-CH2-CO-O-]で示される繰り返し単位を含む脂肪族ポリエステル樹脂である。
本発明に用いるアミド結合を有する化合物(B)は、下記一般式:
R1-C(O)N(R2)2、R1-C(O)NH-(R3)-NHC(O)-R1、R1-NHC(O)NH-(R3)-NHC(O)NH-R1、R1-NHC(O)-R2、R1-NHC(O)-(R3)-C(O)NH-R1、R1-C(O)NH-(R3)-C(O)NH-R1、R1-NHC(O)NH-(R3)-C(O)NH-R1、R1-NHC(O)NH-(R3)-NHC(O)-R1のいずれかで表される化合物である。これらの化合物は単独で用いても良く、組み合わせて使用してもよい。
本発明の脂肪族ポリエステル樹脂組成物ではポリヒドロキシアルカノエート(A)の結晶核剤としてペンタエリスリトール(C)が用いられる。
本発明の脂肪族ポリエステル樹脂組成物は、ポリヒドロキシアルカノエート単独、ポリヒドロキシアルカノエートとアミド化合物を含む樹脂組成物、あるいは、ポリヒドロキシアルカノエートとペンタエリスリトール以外の糖アルコール化合物を含む樹脂組成物に比べて、加工時の樹脂組成物の結晶化が幅広い加工条件で安定して進行する点で優れているので以下に示すような利点がある。
本発明の脂肪族ポリエステル樹脂組成物からなる成形体の製造方法を以下に例示する。
培養生産にはKNK-005株(米国特許第7384766号明細書を参照)を用いた。
MgSO4・7H2O、0.5v/v% 微量金属塩溶液(0.1N 塩酸に1.6w/v% FeCl3・6H2O、1w/v% CaCl2・2H2O、0.02w/v%
CoCl2・6H2O、0.016w/v% CuSO4・5H2O、0.012w/v% NiCl2・6H2Oを溶かしたもの)、0.05w/v% BIOSPUREX200K(消泡剤:コグニスジャパン社製)とした。
KNK-005株の代わりにKNK-631株(国際公開第2009/145164号参照)を用いた他は、製造例1と同様にしてポリヒドロキシアルカノエート原料A2、PHBHを得た。重量平均分子量Mwは62万、3HH組成は7.8モル%(3HB組成は、92.2モル%)であった。
KNK-631株および炭素源としてパーム核油を用いた以外は、製造例1と同様の方法でポリヒドロキシアルカノエート原料A3、PHBHを得た。重量平均分子量Mwは65万、3HH組成は11.4モル%(3HB組成は、88.6モル%)であった。
・原料B1:日本精化社製 BNT22H(ベヘン酸アミド)
・原料B2:日本精化社製 ニュートロン-2(ステアリン酸アミド)
(脂肪族ポリエステル樹脂組成物の製造)
ポリヒドロキシアルカノエート原料A1、アミド結合を有する化合物原料B1またはB2およびペンタエリスリトール(和光純薬工業株式会社製)を、表1に示した配合比率(以下、表中の配合比は、重量部を示す)で、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、脂肪族ポリエステル樹脂組成物を得た。当該脂肪族ポリエステル樹脂組成物を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。このとき、ダイス出口での樹脂温は、アミド結合を有する化合物やペンタエリスリトールの配合量によって異なるが、165~190℃であった。
得られたペレットを原料として、射出成形機(日精樹脂工業社製:FN1000)を用い、成形機のシリンダー設定温度は130~160℃、金型の設定温度は50℃で、150mm×150mm×2mm厚の平板状の試験片を成形した。射出時の樹脂温度は射出した溶融樹脂を、また、金型温度は金型の表面を、K型熱電対で直接接触させて測定した。
表1に示した配合比で、実施例1~7と同様の方法で、脂肪族ポリエステル樹脂組成物のペレットを作製し、射出成形の離型時間を測定した。結果は表1に示した。
(脂肪族ポリエステル樹脂組成物の製造)
表2に示した配合比で、同方向噛合型2軸押出機(日本製鋼社製:TEX30)を用いて脂肪族ポリエステル樹脂組成物のペレットを製造し、ペレット生産性を評価した。
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。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2に示した。
実施例8~14と同様の方法で、脂肪族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2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、脂肪族ポリエステル樹脂組成物を得た。当該脂肪族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=150~160℃、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15~18と同様の方法で、脂肪族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3に示した。
Claims (6)
- ポリヒドロキシアルカノエート(A)、アミド結合を有する化合物(B)およびペンタエリスリトール(C)を含有し、
前記アミド結合を有する化合物(B)が、下記一般式:
R1-C(O)N(R2)2、R1-C(O)NH-(R3)-NHC(O)-R1、R1-NHC(O)NH-(R3)-NHC(O)NH-R1、R1-NHC(O)-R2、R1-NHC(O)-(R3)-C(O)NH-R1、R1-C(O)NH-(R3)-C(O)NH-R1、R1-NHC(O)NH-(R3)-C(O)NH-R1、若しくはR1-NHC(O)NH-(R3)-NHC(O)-R1で表される化合物であるか、又はそれらの組み合わせであり、
式中、各R1は、独立してC6~C30アルキルであり、
各R2は、独立してH又はC1~C20アルキルであり、及び
各R3は、独立してC2~C10アルキレンであることを特徴とする、
脂肪族ポリエステル樹脂組成物。 - 前記アミド結合を有する化合物(B)が、ラウリン酸アミド、ミリスチン酸アミド、ステアリン酸アミド、ベヘン酸アミド、及びエルカ酸アミドから選ばれる1種以上であることを特徴とする請求項1に記載の脂肪族ポリエステル樹脂組成物。
- ポリヒドロキシアルカノエート(A)100重量部に対して、ペンタエリスリトール(C)が0.05~12重量部であることを特徴とする、請求項1または2に記載の脂肪族ポリエステル樹脂組成物。
- ポリヒドロキシアルカノエート(A)が、下記一般式(1)
[-CHR-CH2-CO-O-] (1)
(式中、RはCnH2n+1で表されるアルキル基で、nは1以上15以下の整数である。)、
で示される繰り返し単位を含むことを特徴とする請求項1~3の何れかに記載の脂肪族ポリエステル樹脂組成物。 - ポリヒドロキシアルカノエート(A)が、ポリ(3-ヒドロキシブチレート)単独重合樹脂、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)共重合樹脂、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)共重合樹脂、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)共重合樹脂、及びポリ(3-ヒドロキシブチレート-コ-4-ヒドロキシブチレート)共重合樹脂から選択される1種以上であることを特徴とする請求項1~4の何れかに記載の脂肪族ポリエステル樹脂組成物。
- 請求項1~5の何れかに記載の脂肪族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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| US14/439,512 US9340659B2 (en) | 2012-10-29 | 2013-10-28 | Aliphatic polyester resin composition and molded article containing this resin composition |
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| JP2024530559A (ja) * | 2022-08-12 | 2024-08-23 | 上海藍晶微生物科技有限公司 | 結晶化促進剤を含むポリヒドロキシアルカノエート組成物及び成形体 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2913360A4 (en) | 2016-05-18 |
| EP2913360B1 (en) | 2017-04-12 |
| US20150291771A1 (en) | 2015-10-15 |
| US9340659B2 (en) | 2016-05-17 |
| JPWO2014068943A1 (ja) | 2016-09-08 |
| EP2913360A1 (en) | 2015-09-02 |
| JP6368245B2 (ja) | 2018-08-01 |
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