Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones

Definitions

• the present invention relates to a resin composition for injection molding, an injection molded article, and a method for producing an injection molded article.
• Poly(3-hydroxyalkanoate) resins have excellent biodegradability in soil and seawater, and are materials that can solve the environmental problems caused by discarded plastics.
• the mechanical properties of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), a type of poly(3-hydroxyalkanoate) resin can be flexibly controlled by changing the composition ratio of 3-hydroxyhexanoate.
• a copolymer (A) of 3-hydroxybutyrate units and other hydroxyalkanoate units, the average content of which is 1 mol% to 6 mol%, and a copolymer (B) of 3-hydroxybutyrate units and other hydroxyalkanoate units, the average content of which is 24 mol% or more, have been proposed, which have good moldability and excellent impact resistance (see Patent Document 1).
• the poly(3-hydroxyalkanoate)-based resin component used in the production of this proposed injection molded article has a high viscosity, which makes it difficult to adjust the conditions during injection molding, and the molded article may be prone to warping due to residual stress, leaving room for improvement.
• the present invention aims to solve the above-mentioned problems in the past and achieve the following objectives. That is, the present invention aims to provide a resin composition for injection molding that can produce injection molded articles with excellent impact resistance and bending properties, and that has excellent injection moldability.
• the resin composition for injection molding of the present invention is a resin composition for injection molding containing a poly(3-hydroxyalkanoate)-based resin component
• the poly(3-hydroxyalkanoate)-based resin component is a copolymer (A) of 3-hydroxybutyrate units and other hydroxyalkanoate units having an average content of 5 mol% or more and less than 24 mol%, a copolymer (B) of 3-hydroxybutyrate units and other hydroxyalkanoate units having an average content of 24 mol% or more, and a copolymer (C) of 3-hydroxybutyrate units and other hydroxyalkanoate units having an average content of 1 mol% or more and less than 5 mol%.
• the copolymer (A) contains 5 parts by mass or more and 45 parts by mass or less with respect to 100 parts by mass of the total of the copolymer (A), the copolymer (B), and the copolymer (C), the content of the copolymer (B) is 35 parts by mass or more and 55 parts by mass or less with respect to 100 parts by mass of the total of the copolymer (A), the copolymer (B), and the copolymer (C), and the content of the copolymer (C) is 20 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the total of the copolymer (A), the copolymer (B), and the copolymer (C).
• the present invention can solve the above-mentioned problems and achieve the above-mentioned objectives, and can provide an injection molding resin composition that can produce injection molded articles with excellent impact resistance and bending properties and has excellent injection moldability.
• the resin composition for injection molding of the present invention contains a poly(3-hydroxyalkanoate)-based resin component, and further contains other components as required.
• the poly(3-hydroxyalkanoate)-based resin component is a mixture of at least three types of poly(3-hydroxyalkanoate)-based resins having different content ratios of constituent monomers, and contains copolymer (A), copolymer (B), and copolymer (C), and further contains other poly(3-hydroxyalkanoate)-based resins as necessary.
• Highly crystalline poly(3-hydroxyalkanoate) resins have excellent injection moldability but poor mechanical strength.
• low-crystalline poly(3-hydroxyalkanoate) resins have poor injection moldability but excellent mechanical strength. Therefore, by mixing a highly crystalline poly(3-hydroxyalkanoate) resin with a low-crystalline poly(3-hydroxyalkanoate) resin, the highly crystalline poly(3-hydroxyalkanoate) resin forms fine resin crystal layers, and the low-crystalline poly(3-hydroxyalkanoate) resin forms tie molecules that link the resin crystal layers together, which is expected to improve injection moldability and mechanical strength.
• a resin composition with a high viscosity is usually used, but in the case of injection molding, if the viscosity of the resin composition is high, there will be areas that are insufficiently filled with respect to the mold product shape during injection molding, and the molded article will be prone to warping.
• R represents an alkyl group represented by C p H 2p+1 , and p represents an integer of 1 to 15.
• R in the general formula (1) is not particularly limited as long as it is an alkyl group represented by C p H 2p+1 and can be appropriately selected depending on the purpose.
• R include linear or branched alkyl groups such as a methyl group, an ethyl group, a propyl group, a methylpropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, and a hexyl group.
• p is not particularly limited as long as it is an integer from 1 to 15 and can be appropriately selected depending on the purpose, with 1 to 10 being preferred, and 1 to 8 being more preferred.
• the poly(3-hydroxyalkanoate) resin is preferably a homopolymer or copolymer containing 3-hydroxybutyrate (hereinafter sometimes referred to as "3HB") units, more preferably a homopolymer or copolymer in which all the 3-hydroxybutyrate units are (R)-3-hydroxybutyrate units, and even more preferably a copolymer of 3-hydroxybutyrate units and other hydroxyalkanoate units.
• 3HB 3-hydroxybutyrate
• poly(3-hydroxyalkanoate) resins include poly(3-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxypropionate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (hereinafter sometimes referred to as "P3HB3HV”), poly(3-hydroxybutyrate-co-3-hydroxyvalerate-3-hydroxyhexanoate), and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (hereinafter sometimes referred to as "P3HB3HH").
• poly(3-hydroxybutyrate-co-3-hydroxyheptanoate), poly(3-hydroxybutyrate-co-3-hydroxyoctanoate), poly(3-hydroxybutyrate-co-3-hydroxynonanoate), poly(3-hydroxybutyrate-co-3-hydroxydecanoate), poly(3-hydroxybutyrate-co-3-hydroxyundecanoate), poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (hereinafter, sometimes referred to as "P3HB4HB”) may be mentioned. These may be used alone or in combination of two or more. Among these, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), poly(3-hydroxybutyrate-co-4-hydroxybutyrate), etc. are preferred from the viewpoint of the injection moldability and mechanical properties of the injection molded article obtained from the resin composition for injection molding.
• the average content ratio of the other hydroxyalkanoate units in all monomer units constituting the poly(3-hydroxyalkanoate) resin component is not particularly limited and can be appropriately selected depending on the purpose, but from the viewpoint of productivity of the resin composition for injection molding, it is preferably 9 mol% or more and less than 16 mol%, more preferably 10 mol% or more and 15 mol% or less, and even more preferably 11 mol% or more and 14 mol% or less.
• the average content ratio of the other hydroxyalkanoate units in all monomer units constituting the poly(3-hydroxyalkanoate) resin component means the molar ratio of each monomer unit in all monomer units constituting the poly(3-hydroxyalkanoate) resin component, and when the poly(3-hydroxyalkanoate) resin component is a mixture of two or more poly(3-hydroxyalkanoate) resins, it means the molar ratio of each monomer unit contained in the entire mixture.
• the average content ratio of the other hydroxyalkanoate units in the total monomer units constituting the poly(3-hydroxyalkanoate) resin component can be adjusted by adjusting the blending ratio of the copolymer (A), the copolymer (B), and the copolymer (C).
• the copolymer (A) is a copolymer of 3-hydroxybutyrate units and other hydroxyalkanoate units, the average content of which is 5 mol % or more and less than 24 mol %.
• the copolymer (A) is the moderately crystalline poly(3-hydroxyalkanoate) resin.
• the "average content of other hydroxyalkanoate units" in the copolymer (A) refers to the molar ratio of the other hydroxyalkanoate units to the total monomer units constituting the copolymer (A).
• the average content of the other hydroxyalkanoate units in the copolymer (A) is 5 mol% or more and less than 24 mol%, preferably 5 mol% or more and 22 mol% or less, more preferably 5 mol% or more and 20 mol% or less, and even more preferably 5 mol% or more and 18 mol% or less.
• the other hydroxyalkanoate units in the copolymer (A) are not particularly limited and can be appropriately selected depending on the purpose. Examples include 3-hydroxyhexanoate units, 3-hydroxypropionate units, 3-hydroxyvalerate units, 3-hydroxyheptanoate units, 3-hydroxyoctanoate units, 3-hydroxyoctanoate units, 3-hydroxynanoate units, 3-hydroxydecanoate units, 3-hydroxyundecanoate units, and 4-hydroxybutyrate units. Only one of these may be contained in the copolymer (A), or two or more types may be contained. Among these, the 3-hydroxyhexanoate units are preferred as the other hydroxyalkanoate units in the copolymer (A) from the viewpoint of compatibility with other 3-hydroxyalkanoate resins.
• copolymer (A) examples include poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) and poly(3-hydroxybutyrate-co-4-hydroxybutyrate). These may be used alone or in combination of two or more. Among these, the copolymer (A) is preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate).
• the weight average molecular weight of the copolymer (A) is not particularly limited and can be appropriately selected depending on the purpose, but from the viewpoint of achieving both the impact resistance and bending elasticity of the injection molded body and the injection moldability, it is preferably 500,000 or less, more preferably 480,000 or less, and even more preferably 450,000 or less.
• the lower limit of the weight average molecular weight of the copolymer (A) is also not particularly limited and can be appropriately selected depending on the purpose, but from the viewpoint of the breaking strength of the material, it is preferably 200,000 or more, more preferably 250,000 or more, and even more preferably 300,000 or more.
• the upper and lower limits of the weight average molecular weight of the copolymer (A) can be appropriately combined, but it is preferably 200,000 or more and 500,000 or less, more preferably 250,000 or more and 480,000 or less, and even more preferably 300,000 or more and 450,000 or less.
• the weight average molecular weight of the copolymer (A) can be adjusted, for example, by hydrolyzing a high weight average molecular weight product to reduce its molecular weight.
• the content of the copolymer (A) is 5 parts by mass or more and 45 parts by mass or less, preferably 5 parts by mass or more and 35 parts by mass or less, and more preferably 5 parts by mass or more and 25 parts by mass or less, relative to 100 parts by mass of the total mass of the copolymer (A), the copolymer (B), and the copolymer (C). If the content of the copolymer (A) is less than 5 parts by mass relative to 100 parts by mass of the total mass of the copolymer (A), the copolymer (B), and the copolymer (C), the viscosity of the resin composition for injection molding increases, and the injection moldability deteriorates.
• the content of the copolymer (A) exceeds 45 parts by mass relative to 100 parts by mass of the total mass of the copolymer (A), the copolymer (B), and the copolymer (C), the mechanical strength of the obtained injection molded body decreases, and the impact resistance deteriorates.
• the copolymer (B) is a copolymer of 3-hydroxybutyrate units and other hydroxyalkanoate units, the average content of which is 24 mol % or more.
• the copolymer (B) is the low crystalline poly(3-hydroxyalkanoate) resin.
• the average content of the other hydroxyalkanoate units in the copolymer (B) is 24 mol% or more, preferably 24 mol% or more and 99 mol% or less, more preferably 24 mol% or more and 50 mol% or less, even more preferably 24 mol% or more and 35 mol% or less, and particularly preferably 24 mol% or more and 30 mol% or less.
• the "average content ratio of other hydroxyalkanoate units" in the copolymer (B) refers to the molar ratio of the other hydroxyalkanoate units to the total monomer units constituting the copolymer (B).
• the other hydroxyalkanoate units in the copolymer (B) are not particularly limited and can be appropriately selected depending on the purpose. Examples include 3-hydroxyhexanoate units, 3-hydroxypropionate units, 3-hydroxyvalerate units, 3-hydroxyheptanoate units, 3-hydroxyoctanoate units, 3-hydroxyoctanoate units, 3-hydroxynanoate units, 3-hydroxydecanoate units, 3-hydroxyundecanoate units, and 4-hydroxybutyrate units. Only one of these may be contained in the copolymer (B), or two or more types may be contained. Among these, the 3-hydroxyhexanoate units are preferred as the other hydroxyalkanoate units in the copolymer (B) from the viewpoint of compatibility with other 3-hydroxyalkanoate resins.
• the low-crystalline poly(3-hydroxyalkanoate) resin examples include poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) and poly(3-hydroxybutyrate-co-4-hydroxybutyrate). These may be used alone or in combination of two or more.
• the copolymer (B) is preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate).
• the weight average molecular weight of the copolymer (B) is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of achieving both the impact resistance and bending elasticity of the injection molded body and the injection moldability, it is preferably 2.5 million or less, more preferably 2.3 million or less, even more preferably 2 million or less, and particularly preferably 1 million or less.
• the lower limit of the weight average molecular weight of the copolymer (B) is also not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of material strength, it is preferably 200,000 or more, more preferably 250,000 or more, even more preferably 300,000 or more, and particularly preferably 500,000 or more.
• the upper and lower limits of the weight average molecular weight of the copolymer (B) can be appropriately combined, but it is preferably 200,000 or more and 2.5 million or less, more preferably 250,000 or more and 2.3 million or less, even more preferably 300,000 or more and 2 million or less, and particularly preferably 500,000 or more and 1 million or less.
• the weight average molecular weight of the copolymer (B) can be adjusted, for example, by hydrolyzing a high weight average molecular weight product to reduce its molecular weight.
• the content of the copolymer (B) is 35 parts by mass or more and 55 parts by mass or less, preferably 35 parts by mass or more and 50 parts by mass or less, and more preferably 35 parts by mass or more and 45 parts by mass or less, relative to 100 parts by mass of the total mass of the copolymer (A), the copolymer (B), and the copolymer (C). If the content of the copolymer (B) is less than 35 parts by mass relative to 100 parts by mass of the total mass of the copolymer (A), the copolymer (B), and the copolymer (C), the mechanical strength of the obtained injection molded body decreases and the impact resistance becomes poor.
• the content of the copolymer (B) exceeds 55 parts by mass relative to 100 parts by mass of the total mass of the copolymer (A), the copolymer (B), and the copolymer (C), the viscosity of the resin composition for injection molding increases and the injection moldability becomes poor.
• the copolymer (C) is a copolymer of 3-hydroxybutyrate units and other hydroxyalkanoate units, the average content of which is 1 mol % or more and less than 5 mol %.
• the copolymer (C) is the highly crystalline poly(3-hydroxyalkanoate) resin.
• the average content of the other hydroxyalkanoate units in the copolymer (C) is 1 mol% or more and less than 5 mol%, and preferably 2 mol% or more and 4 mol% or less.
• the "average content ratio of other hydroxyalkanoate units" in the copolymer (C) refers to the molar ratio of the other hydroxyalkanoate units to the total monomer units constituting the copolymer (C).
• the other hydroxyalkanoate units in the copolymer (C) are not particularly limited and may be appropriately selected depending on the purpose. Examples include 3-hydroxyhexanoate units, 3-hydroxypropionate units, 3-hydroxyvalerate units, 3-hydroxyheptanoate units, 3-hydroxyoctanoate units, 3-hydroxyoctanoate units, 3-hydroxynanoate units, 3-hydroxydecanoate units, 3-hydroxyundecanoate units, and 4-hydroxybutyrate units. Only one of these may be contained in the copolymer (C), or two or more types may be contained. Among these, the 3-hydroxyhexanoate units are preferred as the other hydroxyalkanoate units in the copolymer (C) from the viewpoint of compatibility with other 3-hydroxyalkanoate resins.
• copolymer (C) examples include poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) and poly(3-hydroxybutyrate-co-4-hydroxybutyrate). These may be used alone or in combination of two or more. Among these, the copolymer (C) is preferably poly(3-hydroxybutyrate-co-3-hydroxyhexanoate).
• the weight average molecular weight of the copolymer (C) is not particularly limited and can be appropriately selected depending on the purpose, but from the viewpoint of achieving both the impact resistance and bending elasticity of the injection molded body and the injection moldability, it is preferably 1 million or less, more preferably 800,000 or less, and even more preferably 700,000 or less.
• the lower limit of the weight average molecular weight of the copolymer (C) is also not particularly limited and can be appropriately selected depending on the purpose, but from the viewpoint of material strength, it is preferably 200,000 or more, more preferably 250,000 or more, and even more preferably 500,000 or more.
• the upper and lower limits of the weight average molecular weight of the copolymer (C) can be appropriately combined, but it is preferably 200,000 or more and 1 million or less, more preferably 250,000 or more and 800,000 or less, and even more preferably 500,000 or more and 700,000 or less.
• the weight average molecular weight of the copolymer (C) can be adjusted, for example, by hydrolyzing a high weight average molecular weight product to reduce its molecular weight.
• the content of the copolymer (C) is 20 parts by mass or more and 50 parts by mass or less, preferably 25 parts by mass or more and 45 parts by mass or less, and more preferably 30 parts by mass or more and 40 parts by mass or less, relative to 100 parts by mass of the total mass of the copolymer (A), the copolymer (B), and the copolymer (C). If the content of the copolymer (C) is less than 20 parts by mass relative to 100 parts by mass of the total mass of the copolymer (A), the copolymer (B), and the copolymer (C), the flexural modulus becomes low and the injection moldability becomes poor. Also, if the content of the copolymer (C) exceeds 50 parts by mass relative to 100 parts by mass of the total mass of the copolymer (A), the copolymer (B), and the copolymer (C), the impact resistance becomes poor.
• the other poly(3-hydroxyalkanoate)-based resins other than the copolymer (A), the copolymer (B), and the copolymer (C) are not particularly limited as long as they do not impair the effects of the present invention, and can be appropriately selected depending on the purpose, and examples thereof include homopolymers consisting of only 3-hydroxyalkanoate units, copolymers of 3-hydroxyalkanoate units other than 3-hydroxybutyrate and the other hydroxyalkanoate units, copolymers of 3-hydroxybutyrate units and the other hydroxyalkanoate units, in which the average content ratio of the other hydroxyalkanoate units is different from that of the copolymer (A), the copolymer (B), and the copolymer (C), and the like. These may be used alone or in combination of two or more.
• a GC-17A manufactured by Shimadzu Corporation
• a NEUTRA BOND-1 column inner diameter: 0.25 mm, liquid film thickness: 0.4 ⁇ m, manufactured by GL Science Co., Ltd.
• He was used as the carrier gas, the column inlet pressure was 100 kPa, and 1 ⁇ L of sample was injected.
• the temperature conditions were as follows: the initial temperature was raised from 100° C. to 200° C. at a rate of 8° C./min, and then the temperature was raised further from 200° C. to 290° C. at a rate of 30° C./min.
• the weight average molecular weight of the poly(3-hydroxyalkanoate) resin components as a whole is not particularly limited and can be selected as appropriate depending on the purpose, but from the viewpoint of achieving both the impact resistance and bending elasticity of the injection molded body and the injection moldability, it is preferably 2 million or less, more preferably 1.5 million or less, and even more preferably 1 million or less.
• the lower limit of the weight average molecular weight of the poly(3-hydroxyalkanoate) resin components as a whole is also not particularly limited and can be selected as appropriate depending on the purpose, but from the viewpoint of material strength, it is preferably 200,000 or more, more preferably 250,000 or more, and even more preferably 300,000 or more.
• the upper and lower limits of the weight average molecular weight of the poly(3-hydroxyalkanoate) resin components as a whole can be combined as appropriate, but it is preferably 200,000 or more and 2 million or less, more preferably 250,000 or more and 1.5 million or less, and even more preferably 300,000 or more and 1 million or less.
• the weight average molecular weight of the copolymer (A), the copolymer (B), the copolymer (C), or the poly(3-hydroxyalkanoate)-based resin component can be measured in terms of polystyrene by gel permeation chromatography (GPC) using a chloroform solution.
• GPC gel permeation chromatography
• a column suitable for measuring the weight average molecular weight may be used.
• a specific example of the method includes a method in which a gel permeation chromatography system (e.g., Shodex (registered trademark) GPC-101, manufactured by Showa Denko K.K.) is used in which two columns (e.g., Shodex (registered trademark) KM-806M, manufactured by Showa Denko K.K.) are connected together, chloroform is used as a mobile phase, and the weight average molecular weight is measured in terms of a polystyrene standard.
• a gel permeation chromatography system e.g., Shodex (registered trademark) GPC-101, manufactured by Showa Denko K.K.
• two columns e.g., Shodex (registered trademark) KM-806M, manufactured by Showa Denko K.K.
• chloroform is used as a mobile phase
• the weight average molecular weight is measured in terms of a polystyrene standard.
• the poly(3-hydroxyalkanoate) resin component is preferably one that has not been crosslinked using a crosslinking agent such as an organic peroxide.
• the poly(3-hydroxyalkanoate) resin component is preferably a resin component that does not have a crosslinked structure.
• the method for producing the poly(3-hydroxyalkanoate) resin is not particularly limited and may be appropriately selected depending on the purpose, and may be a production method by chemical synthesis or a production method using a microorganism.
• the production method for the poly(3-hydroxyalkanoate) resin is preferably a production method using a microorganism, since a poly(3-hydroxyalkanoate) resin having an (R)-3-hydroxyalkanoate unit can be efficiently obtained.
• the poly(3-hydroxyalkanoate) resin can be produced by any known method using a microorganism.
• the following microorganisms are known to produce copolymers of 3-hydroxybutyrate and other hydroxyalkanoates:
• Examples of producers of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (P3HB3HV) and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (P3HB3HH) include Aeromonas caviae and Cupriavidus necator into which genes of the P3HA synthase group have been introduced (see T. Fukui, Y. Doi, J. Bateriol., 179, p4821-4830 (1997), International Publication No.
• P3HB4HB poly(3-hydroxybutyrate-co-4-hydroxybutyrate)
• Alcaligenes eutrophus is known.
• the P3HB3HH producing bacteria Alcaligenes eutrophus AC32 strain (FERM BP-6038) into which the genes of the P3HA synthase group have been introduced in order to improve the productivity of P3HB3HH (see T. Fukui, Y. Doi, J. Bateriol., 179, pp. 4821-4830 (1997)) and Cupriavidus necator into which the genes of the P3HA synthase group have been introduced (see International Publication No. WO 2019/142845) are preferred.
• these microorganisms can be cultured under appropriate conditions to accumulate poly(3-hydroxyalkanoate) resins such as P3HB3HH within the cells, and microbial cells can be used.
• poly(3-hydroxyalkanoate) resins such as P3HB3HH
• microbial cells can be used.
• genetically modified microorganisms into which various poly(3-hydroxyalkanoate) resin synthesis-related genes have been introduced may be used according to the poly(3-hydroxyalkanoate) resin to be produced, and the culture conditions, including the type of substrate, may be optimized.
• the method for obtaining a mixture of three or more poly(3-hydroxyalkanoate) resins namely, copolymer (A), copolymer (B), copolymer (C), and, if necessary, other poly(3-hydroxyalkanoate) resins, is not particularly limited and can be appropriately selected depending on the purpose, and may be a method for obtaining the mixture using the microorganisms, or a method for obtaining the mixture by chemical synthesis.
• the mixture may be obtained by melt-kneading three or more resins using an extruder, kneader, Banbury mixer, roll, or the like, or the mixture may be obtained by dissolving three or more resins in a solvent, mixing, and drying.
• the other components in the resin composition for injection molding are not particularly limited as long as they do not impair the effects of the present invention and can be appropriately selected depending on the purpose, and examples thereof include other resins other than the poly(3-hydroxyalkanoate)-based resin component, inorganic fillers, various other additives, etc. These may be used alone or in combination of two or more.
• the other resins are not particularly limited as long as they do not impair the effects of the present invention, and examples thereof include aliphatic polyester resins such as polybutylene succinate adipate, polybutylene succinate, polycaprolactone, and polylactic acid; aliphatic aromatic polyester resins such as polybutylene adipate terephthalate, polybutylene sebacate terephthalate, and polybutylene azelate terephthalate. These may be used alone or in combination of two or more.
• the content of the other resins in the resin composition for injection molding is not particularly limited as long as it does not impair the effects of the present invention and can be appropriately selected depending on the purpose, but is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less, per 100 parts by mass of the poly(3-hydroxyalkanoate)-based resin components in total. There is no particular lower limit for the content of the other resins, and it may be 0 parts by mass.
• the resin composition for injection molding may contain an inorganic filler from the viewpoint of improving the mechanical strength of the resulting injection molded article.
• the inorganic filler is not particularly limited as long as it does not impair the effects of the present invention, and examples thereof include silica-based inorganic fillers, alumina, zircon, iron oxide, zinc oxide, titanium oxide, silicon nitride, boron nitride, aluminum nitride, silicon carbide, glass, silicone rubber, silicone resin, titanium oxide, carbon fiber, mica, graphite, carbon black, ferrite, graphite, diatomaceous earth, white clay, clay, talc, calcium carbonate, manganese carbonate, magnesium carbonate, barium sulfate, and silver powder.
• silica-based inorganic fillers alumina, zircon, iron oxide, zinc oxide, titanium oxide, silicon nitride, boron nitride, aluminum nitride, silicon carbide, glass, silicone rubber, silicone resin, titanium oxide, carbon fiber, mica, graphite, carbon black, ferrite, graphite, diatomaceous earth, white clay, clay,
• silica-based inorganic fillers examples include quartz, fumed silica, silicic acid anhydride, fused silica, crystalline silica, noncrystalline silica, amorphous silica, fillers obtained by condensing alkoxysilanes, and ultrafine amorphous silica. These inorganic fillers may be used alone or in combination of two or more.
• the inorganic filler is preferably a silica-based inorganic filler, since it can provide an effect of improving the mechanical properties of the injection molded article obtained from the resin composition for injection molding.
• the type of the silica-based inorganic filler is not particularly limited, and from the viewpoint of versatility, synthetic amorphous silica produced by a dry method or a wet method can be used.
• any of those that have been subjected to hydrophobic treatment or non-hydrophobic treatment can be used. These may be used alone or in combination of two or more types.
• the inorganic filler may be surface-treated to improve dispersibility in the resin material.
• the treating agent used for the surface treatment is not particularly limited and may be appropriately selected from known treating agents, such as higher fatty acids, silane coupling agents, titanate coupling agents, sol-gel coating agents, and resin coating agents. These may be used alone or in combination of two or more.
• the moisture content of the inorganic filler is not particularly limited and can be appropriately selected from known treatment agents. From the viewpoint of easily suppressing hydrolysis of the poly(3-hydroxyalkanoate)-based resin, the moisture content is preferably 0.01% by mass to 10% by mass, more preferably 0.01% by mass to 5% by mass, and even more preferably 0.01% by mass to 1% by mass.
• the moisture content of the inorganic filler can be determined in accordance with JIS-K5101-15-1:2004 (Pigment testing methods - Part 15: Heat loss).
• the volume average particle size of the inorganic filler is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of excellent mechanical properties and injection moldability of an injection molded article obtained from the resin composition for injection molding, the volume average particle size is preferably 0.1 ⁇ m to 100 ⁇ m, and more preferably 0.1 ⁇ m to 50 ⁇ m.
• the volume average particle size of the inorganic filler can be measured using a laser diffraction/scattering device (for example, Microtrac MT3100II, manufactured by Nikkiso Co., Ltd.).
• the content of the inorganic filler in the resin composition for injection molding is not particularly limited as long as it does not impair the effects of the present invention, and can be appropriately selected depending on the purpose, but is preferably 40 parts by mass or less, more preferably 35 parts by mass or less, and even more preferably 30 parts by mass or less, relative to 100 parts by mass of the poly(3-hydroxyalkanoate)-based resin component.
• the inorganic filler does not have to be blended into the resin composition for injection molding, but blending the inorganic filler has the advantage of improving the strength of the injection molded article obtained from the resin composition for injection molding.
• the lower limit of the content of the inorganic filler in the resin composition for injection molding is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, relative to 100 parts by mass of the poly(3-hydroxyalkanoate)-based resin component.
• the upper and lower limits of the content of the inorganic filler in the resin composition for injection molding can be appropriately combined, but is preferably 1 part by mass or more and 40 parts by mass or less, more preferably 5 parts by mass or more and 35 parts by mass or less, and even more preferably 10 parts by mass or more and 30 parts by mass or less, relative to 100 parts by mass of the poly(3-hydroxyalkanoate)-based resin component.
• a dispersing aid in combination with the silica.
• the dispersing aid is not particularly limited as long as it does not impair the effects of the present invention, and examples thereof include glycerin ester compounds, adipic acid ester compounds, polyether ester compounds, phthalic acid ester compounds, isosorbide ester compounds, polycaprolactone compounds, etc. These may be used alone or in combination of two or more.
• the dispersion aid is preferably a modified glycerin-based compound such as glycerin diacetomonolaurate, glycerin diacetomonocaprylate, or glycerin diacetomonodecanoate, since these have excellent affinity with poly(3-hydroxyalkanoate)-based resin components and are less likely to bleed; an adipate-based compound such as diethylhexyl adipate, dioctyl adipate, or diisononyl adipate; or a polyether ester-based compound such as polyethylene glycol dibenzoate, polyethylene glycol dicaprylate, or polyethylene glycol diisostearate; and more preferably one containing a large amount of biomass-derived components, since this can increase the biomass content of the entire resin composition for injection molding.
• a modified glycerin-based compound such as glycerin diacetomonolaurate, glycerin diacetomonocapry
• dispersion aids examples include the "Rikemal” (registered trademark) PL series from Riken Vitamin Co., Ltd. and the Polysorb series from ROQUETTE.
• the content of the dispersing aid in the resin composition for injection molding is not particularly limited as long as it does not impair the effects of the present invention, and can be appropriately selected depending on the purpose, but it is preferably 0.1 to 20 parts by mass per 100 parts by mass of the poly(3-hydroxyalkanoate)-based resin components in total.
• the dispersing aid does not have to be mixed into the resin composition for injection molding.
• additives include nucleating agents, lubricants, plasticizers, antistatic agents, flame retardants, conductive agents, heat insulating agents, crosslinking agents, antioxidants, ultraviolet absorbers, colorants, inorganic fillers, organic fillers, and hydrolysis inhibitors. These may be used alone or in combination of two or more. Among these, the additives are preferably biodegradable additives.
• the crystal nucleating agent is not particularly limited as long as it does not impair the effects of the present invention, and may be appropriately selected depending on the purpose, and examples thereof include pentaerythritol, orotic acid, aspartame, cyanuric acid, glycine, zinc phenylphosphonate, boron nitride, etc. These may be used alone or in combination of two or more.
• the crystal nucleating agent is preferably pentaerythritol, since it is particularly effective in promoting the crystallization of the poly(3-hydroxyalkanoate)-based resin component.
• the content of the crystal nucleating agent in the resin composition for injection molding is not particularly limited as long as it does not impair the effects of the present invention and can be appropriately selected depending on the purpose, but is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass, and even more preferably 0.7 to 1.5 parts by mass, relative to a total of 100 parts by mass of the poly(3-hydroxyalkanoate)-based resin components.
• the lubricant is not particularly limited as long as it does not impair the effects of the present invention, and can be appropriately selected depending on the purpose.
• the lubricant include behenic acid amide, oleic acid amide, erucic acid amide, stearic acid amide, palmitic acid amide, N-stearyl behenic acid amide, N-stearyl erucic acid amide, ethylene bisstearic acid amide, ethylene bisoleic acid amide, ethylene biserucic acid amide, ethylene bislauric acid amide, ethylene biscapric acid amide, p-phenylene bisstearic acid amide, and polycondensates of ethylenediamine, stearic acid, and sebacic acid. These may be used alone or in combination of two or more. Among these, behenic acid amide and erucic acid amide are preferred because they have a particularly excellent lubricant effect on the poly(3-hydroxyalkanoate
• the amount of the lubricant contained in the resin composition for injection molding is not particularly limited as long as it does not impair the effects of the present invention and can be appropriately selected depending on the purpose, but is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and even more preferably 0.1 to 1.5 parts by mass, relative to a total of 100 parts by mass of the poly(3-hydroxyalkanoate)-based resin components.
• the plasticizer is not particularly limited as long as it does not impair the effects of the present invention, and may be appropriately selected depending on the purpose.
• the plasticizer include glycerin ester compounds, citrate ester compounds, sebacic acid ester compounds, adipate ester compounds, polyether ester compounds, benzoic acid ester compounds, phthalic acid ester compounds, isosorbide ester compounds, polycaprolactone compounds, and dibasic acid ester compounds. These may be used alone or in combination of two or more.
• the plasticizer is preferably a glycerin ester compound, a citrate ester compound, a sebacic acid ester compound, or a dibasic acid ester compound, in that it has a particularly excellent plasticizing effect on the poly(3-hydroxyalkanoate) resin component.
• the glycerin ester compound is not particularly limited, and examples thereof include glycerin diacetomonolaurate.
• the citrate ester compound is not particularly limited, and examples thereof include tributyl acetyl citrate.
• the sebacic acid ester compound is not particularly limited, and examples thereof include dibutyl sebacate.
• the dibasic acid ester compound is not particularly limited, and examples thereof include benzyl methyl diethylene glycol adipate.
• the content of the plasticizer in the resin composition for injection molding is not particularly limited as long as it does not impair the effects of the present invention and can be appropriately selected depending on the purpose, but is preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass, and even more preferably 3 to 10 parts by mass, per 100 parts by mass of the poly(3-hydroxyalkanoate)-based resin components in total.
• the melt viscosity of the resin composition for injection molding is not particularly limited and may be appropriately selected depending on the purpose, but the melt viscosity measured at 165° C. and a shear rate of 608/s is preferably 400 Pa ⁇ s or more and 500 Pa ⁇ s or less, more preferably 410 Pa ⁇ s or more and 480 Pa ⁇ s or less, and even more preferably 420 Pa ⁇ s or more and 470 Pa ⁇ s or less.
• the melt viscosity of the resin composition for injection molding is 400 Pa ⁇ s or more, it is easy to reduce flash during molding, and when it is 500 Pa ⁇ s or less, injection moldability is improved.
• the melt viscosity of the resin composition for injection molding is measured by the following method.
• a capillograph e.g., 1D PMD-C, manufactured by Toyo Seiki Seisakusho Co., Ltd.
• an orifice having a diameter of 1 mm, a length of 10 mm, and an inlet angle of 45° and heated to 165° C.
• a piston is lowered at a rate of 50 mm/min (shear rate of 608/s), and the melt viscosity at a shear rate of 608/s is calculated from the stress applied to the piston when the molten resin is extruded from the orifice.
• the resin composition for injection molding of the present invention can produce injection molded articles with excellent impact resistance and bending properties, and has excellent injection moldability, so it is suitable for use in the production of injection molded articles, and is particularly suitable for use in the production method of injection molded articles of the present invention described below.
• An injection molded article according to one embodiment of the present invention contains the resin composition for injection molding according to the present invention.
• An injection molded article according to another embodiment of the present invention is an injection molded article containing a poly(3-hydroxyalkanoate)-based resin component, and has a Charpy impact strength of 10 kJ/m2 or more and a flexural modulus of 520 MPa or more.
• the injection molded article of the present invention is excellent in impact resistance and bending properties.
• the injection molded article according to the embodiment contains the resin composition for injection molding of the present invention, and further contains other components as necessary.
• the injection molded article according to the embodiment may be made of the resin composition for injection molding of the present invention.
• the impact resistance and flexural modulus of the injection molded body according to the above embodiment are not particularly limited and can be appropriately selected depending on the properties of the resin composition for injection molding, but it is preferable that they are in the same numerical range as the impact resistance and flexural modulus of the injection molded body according to another embodiment described below.
• An injection molded article according to another embodiment of the present invention is an injection molded article containing a poly(3-hydroxyalkanoate)-based resin component, and has a Charpy impact strength of 10 kJ/m2 or more and a flexural modulus of 520 MPa or more.
• the poly(3-hydroxyalkanoate)-based resin component is not particularly limited and can be appropriately selected depending on the purpose, but suitable examples include those described in the section ⁇ Poly(3-hydroxyalkanoate)-based resin component> in the above (Resin composition for injection molding).
• the Charpy impact strength of the injection molded article according to the another embodiment is 10 kJ/m 2 or more, preferably 25 kJ/m 2 or more, more preferably 30 kJ/m 2 or more.
• the Charpy impact strength of the injection molded article according to the other embodiment can be adjusted by adjusting the blending ratio of the high crystalline poly(3-hydroxyalkanoate) resin, the medium crystalline poly(3-hydroxyalkanoate) resin, and the low crystalline poly(3-hydroxyalkanoate) resin, and when the injection molded article according to the other embodiment contains the injection molding resin composition of the present invention, it can be adjusted by adjusting the blending ratio of the copolymer (A), the copolymer (B), and the copolymer (C).
• the Charpy impact strength can be measured in accordance with the notched Charpy impact test described in JIS-K 7111-1:2012 (Plastics-Determination of Charpy impact properties-Part 1: Non-instrumented impact test). Specifically, first, a test piece (length 80 mm, width 10 mm, thickness 4 mm) for measuring the Charpy impact value is prepared from the injection molded article according to the other embodiment.
• the test piece for measuring the Charpy impact value can be prepared, for example, using an automatic notch processing machine (for example, manufactured by Yasuda Seiki Co., Ltd.).
• the test piece for measuring the Charpy impact value is a test piece that is used two weeks after the preparation of the test piece.
• a Charpy impact tester manufactured by Yasuda Seiki Co., Ltd.
• the measurement atmosphere is 23°C and 50% RH.
• the flexural modulus of the injection molded body according to the other embodiment is 520 MPa or more, preferably 650 MPa or more, more preferably 700 MPa or more, and even more preferably 850 MPa or more.
• the upper limit of the flexural modulus of the injection molded body according to the other embodiment is not particularly limited and can be appropriately selected according to the purpose, but from the viewpoint of impact resistance, it is preferably 1,200 MPa or less, more preferably 1,100 MPa or more, and even more preferably 1,000 MPa or more. If the flexural modulus of the injection molded body according to the other embodiment is less than 520 MPa, the injection molded body may become soft and difficult to handle.
• the upper and lower limits of the flexural modulus of the injection molded body according to the other embodiment can be appropriately combined, but is 520 MPa or more, but is preferably 650 MPa or more to 1,200 MPa or less, more preferably 700 MPa or more to 1,100 MPa or more, and even more preferably 850 MPa or more to 1,000 MPa or more.
• the flexural modulus of the injection molded article according to the other embodiment can be adjusted by adjusting the blending ratio of the highly crystalline poly(3-hydroxyalkanoate) resin, the medium crystalline poly(3-hydroxyalkanoate) resin, and the low crystalline poly(3-hydroxyalkanoate) resin, and when the injection molded article according to the other embodiment contains the injection molding resin composition of the present invention, it can be adjusted by adjusting the blending ratio of the copolymer (A), the copolymer (B), and the copolymer (C).
• the flexural modulus can be measured in accordance with JIS-K 7171:2016 (Plastics-Determination of flexural properties). Specifically, a three-point bending tester (Autograph AG-X500N, manufactured by Shimadzu Corporation) is used to measure in accordance with JIS-K 7171:2016 (Plastics - Determination of bending properties).
• the test conditions are a test speed of 2 mm/min, a distance between the support stands of 64 mm, and a radius of the indenter and the support stand of 5.0 mm.
• the measurement atmosphere is 23°C and 50% RH.
• the measurement sample is a sample two weeks after molding.
• injection molded article of the present invention are not particularly limited, but because it has excellent impact resistance and bending properties, it can be suitably used, for example, for bottles, containers, cases for beverages, liquid foods, liquid detergents, etc., toys, entertainment products, tableware, agricultural materials, office automation parts, home appliance parts, body parts for ships and aircraft structures, automobile parts, daily necessities, stationery products, entertainment products, etc.
• the method for producing an injection molded article of the present invention includes a step of injection molding the resin composition for injection molding of the present invention to obtain an injection molded article (hereinafter, sometimes referred to as the "injection molding step"), and may further include other steps as necessary.
• the method for producing an injection molded article of the present invention uses the resin composition for injection molding of the present invention, which has excellent injection moldability, and therefore is excellent in production efficiency and can produce an injection molded article that has excellent impact resistance and bending properties.
• the injection molding step is a step of obtaining an injection molded article by injection molding the resin composition for injection molding of the present invention.
• the method for injection molding the resin composition for injection molding is not particularly limited and can be appropriately selected from known methods.
• injection molding methods such as gas-assisted molding and injection compression molding can be mentioned.
• In-mold molding, gas press molding, two-color molding, sandwich molding, PUSH-PULL, SCORIM, etc. can also be used.
• Specific examples of methods for injection molding the resin composition for injection molding include a method in which the resin composition for injection molding that has been heated and melted is injected into a mold, the resin composition for injection molding is cooled and solidified in the mold, the mold is opened, and the molded article is released to obtain an injection molded article.
• the other steps are not particularly limited and can be appropriately selected depending on the purpose.
• Examples of the other steps include a poly(3-hydroxyalkanoate)-based resin component preparation step and a resin composition for injection molding preparation step.
• the poly(3-hydroxyalkanoate)-based resin component preparation step is a step of preparing the poly(3-hydroxyalkanoate)-based resin component, which is a raw material of the resin composition for injection molding.
• the poly(3-hydroxyalkanoate)-based resin component preparation step can be suitably carried out by the method described in the section "-Production method of poly(3-hydroxyalkanoate)-based resin-" in the above (Resin composition for injection molding).
• the step of preparing a resin composition for injection molding is a step of preparing the resin composition for injection molding to be used in the injection molding step. More specifically, the step of preparing a resin composition for injection molding is This is a process in which the poly(3-hydroxyalkanoate) resin component, which is the raw material of the molding resin composition, and, if necessary, other components are melted and kneaded.
• the method for melting and kneading the raw materials of the resin composition for injection molding is not particularly limited and can be appropriately selected from known methods, such as a method of melting and kneading using an extruder, kneader, Banbury mixer, roll, or other device.
• the temperature at which the raw materials for the resin composition for injection molding are melted and kneaded cannot be generally defined as it depends on the melting point and melt viscosity of the poly(3-hydroxyalkanoate) resin component and other resins used, but the resin temperature at the die outlet of the molten kneaded product is preferably 150°C to 200°C, more preferably 155°C to 195°C, and even more preferably 160°C to 190°C.
• the poly(3-hydroxyalkanoate) resin component can be suitably melted, and if it is 200°C or lower, the poly(3-hydroxyalkanoate) resin component can be prevented from thermally decomposing.
• the resin composition for use in injection molding obtained by melting and kneading the raw materials for the resin composition for use in injection molding may be further formed into resin pellets of a desired shape.
• Specific examples of the method for producing the resin pellets include a method in which the raw materials of the resin composition for injection molding are melted and kneaded to obtain a resin composition for injection molding, which is extruded into a strand shape using an extruder, and then cut into resin pellets having particle shapes such as a cylindrical shape, an elliptical cylindrical shape, a spherical shape, a cubic shape, a rectangular parallelepiped shape, etc.
• the resin pellets are preferably thoroughly dried at 40°C to 80°C to remove moisture before being subjected to the injection molding process.
• P3HB3HH-3(B): P3HB3HH (average content: 3HB / 3HH 73.6 / 26.4 (mol% / mol%), weight average molecular weight (Mw): 660,000 g / mol), produced in accordance with the method of Example 9 of WO 2019/142845.
• P3HB3HH-4(C): P3HB3HH (average content ratio: 3HB / 3HH 97.9 / 2.1 (mol% / mol%), weight average molecular weight (Mw): 660,000 g / mol, produced in accordance with the method of Example 2 of WO 2019/142845.
• Additive 1 Pentaerythritol (Neuraizer P, manufactured by Mitsubishi Chemical Corporation)
• Additive 2 Behenic acid amide (BNT-22H, manufactured by Nippon Fine Chemicals Co., Ltd.)
• Example 1 Preparation of poly(3-hydroxyalkanoate)-based resin component>
• the total mass of the polyhydroxyalkanoate resin (P3HA) was 100 parts by mass, and various P3HAs were mixed based on the compositions and blending amounts shown in the following Table 1. Note that the unit of blending amount of each component in Table 1 is "parts by mass,” and 100 parts by mass is 10 kg.
• Examples 2 to 4 and Comparative Examples 1 to 3 In the preparation of the poly(3-hydroxyalkanoate)-based resin component of Example 1, except that the composition and blending amounts were changed to the respective compositions and blending amounts shown in Table 1 below, the preparation of the poly(3-hydroxyalkanoate)-based resin component, compounding, and production of the injection molded article were carried out in the same manner as in Example 1, thereby obtaining the injection molded articles of Examples 2 to 4 and Comparative Examples 1 to 3, respectively.
• test pieces Using the obtained test pieces, a test was performed in accordance with the notched Charpy impact test described in JIS-K 7111-1:2012 (Plastics - Determination of Charpy impact properties - Part 1: Non-instrumented impact test) using a Charpy impact tester (manufactured by Yasuda Seiki Co., Ltd.). The measurement atmosphere was 23°C and 50% RH. The test pieces for measuring the Charpy impact value were used after 2 weeks from the preparation of the test pieces.
• a resin composition for injection molding containing a poly(3-hydroxyalkanoate)-based resin component is A copolymer (A) of 3-hydroxybutyrate units and other hydroxyalkanoate units having an average content of 5 mol % or more and less than 24 mol %; A copolymer (B) of 3-hydroxybutyrate units and other hydroxyalkanoate units having an average content of 24 mol% or more, and a copolymer (C) of 3-hydroxybutyrate units and other hydroxyalkanoate units having an average content of 1 mol% or more and less than 5 mol%, Contains the content of the copolymer (A) is 5 parts by mass or more and 45 parts by mass or less with respect to 100 parts by mass of the total mass of the copolymer (A), the copolymer (B), and the copolymer (C); the content of the copolymer
• ⁇ 2> The resin composition for injection molding according to ⁇ 1>, wherein the copolymer (A) has a weight average molecular weight of 500,000 or less.
• ⁇ 3> The resin composition for injection molding according to ⁇ 1> or ⁇ 2>, wherein an average content ratio of the other hydroxyalkanoate units in all monomer units constituting the poly(3-hydroxyalkanoate)-based resin component is 9 mol % or more and less than 16 mol %.
• ⁇ 4> The resin composition for injection molding according to any one of ⁇ 1> to ⁇ 3>, wherein the other hydroxyalkanoate unit is a 3-hydroxyhexanoate unit.
• ⁇ 5> The resin composition for injection molding according to any one of ⁇ 1> to ⁇ 4>, wherein the melt viscosity measured at 165° C. and a shear rate of 608/s is 400 Pa ⁇ s or more and 500 Pa ⁇ s or less.
• An injection-molded article comprising the resin composition for injection molding according to any one of ⁇ 1> to ⁇ 5>.
• ⁇ 7> The injection molded article according to ⁇ 6>, having a Charpy impact strength of 10 kJ/m2 or more .
• ⁇ 8> The injection-molded article according to ⁇ 6> or ⁇ 7>, wherein the injection-molded article has a flexural modulus of 520 MPa or more.
• An injection-molded article containing a poly(3-hydroxyalkanoate)-based resin component is characterized by having a Charpy impact strength of 10 kJ/m2 or more and a flexural modulus of elasticity of 520 MPa or more.
• a method for producing an injection-molded article comprising the step of injection molding the resin composition for injection molding according to any one of ⁇ 1> to ⁇ 5> to obtain an injection-molded article.

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