WO2024177051A1 - ポリ乳酸樹脂組成物 - Google Patents

ポリ乳酸樹脂組成物 Download PDF

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WO2024177051A1
WO2024177051A1 PCT/JP2024/005973 JP2024005973W WO2024177051A1 WO 2024177051 A1 WO2024177051 A1 WO 2024177051A1 JP 2024005973 W JP2024005973 W JP 2024005973W WO 2024177051 A1 WO2024177051 A1 WO 2024177051A1
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Prior art keywords
polylactic acid
acid resin
polyisoprene
resin composition
resin
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English (en)
French (fr)
Japanese (ja)
Inventor
浩 宇山
于懿 徐
章秀 菅原
舜介 近藤
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University of Osaka NUC
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Osaka University NUC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • 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
    • C08K5/14—Peroxides
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons

Definitions

  • the present invention relates to a polylactic acid resin composition, and more specifically to a polylactic acid resin composition with improved impact resistance.
  • Polylactic acid a type of bioplastic
  • polylactic acid has traditionally been widely used in a variety of fields, including medical and agricultural materials.
  • the applications of polylactic acid itself are limited due to its low impact resistance and flexibility, and there is a demand for improvements to its use as a resin composition in combination with additives.
  • thermoplastic properties for example, to be used in automobile parts and home appliance components, it is necessary for it to have thermoplastic properties in addition to improved impact resistance and flexibility.
  • Patent Documents 1 and 2 For example, a resin composition containing natural rubber, such as epoxidized natural rubber, and a carbodiimide compound for polylactic acid has been reported with the aim of improving the impact resistance of polylactic acid (Patent Documents 1 and 2). However, it is not suitable for industrial production due to reasons such as the poor working environment.
  • Patent Document 3 A method has also been proposed for increasing impact resistance by dynamically crosslinking natural rubber or eucommia elastomers using peroxides (Patent Document 3 and Non-Patent Document 1).
  • the presence of the peroxides can cause other physical properties of polylactic acid to deteriorate.
  • the polylactic acid resin composition obtained by dynamically crosslinking polylactic acid and eucommia elastomers in the presence of peroxides cannot be said to have a high degree of improvement in impact resistance, which only slightly exceeds that of ABS.
  • the present invention aims to solve the above problems, and has as its objective the provision of a polylactic acid resin composition that takes advantage of the biomass-derived characteristics of polylactic acid and can improve impact resistance.
  • the present invention relates to a polylactic acid resin composition
  • the present invention is constructed by dynamically crosslinking a resin mixture containing a polylactic acid resin and a cis-polyisoprene,
  • the polylactic acid resin composition has a polylactic acid resin content of 280 to 950 parts by mass per 100 parts by mass of the cis-polyisoprene.
  • the content of the polylactic acid resin is 290 to 570 parts by mass per 100 parts by mass of the cis-polyisoprene.
  • the resin mixture further comprises the following formula (I):
  • R 1 , R 2 , R 3 and R 4 are each independently a group selected from the group consisting of a hydrogen atom and an optionally branched alkyl group having 1 to 8 carbon atoms).
  • R 1 , R 2 and R 3 in the above formula (I) are n-butyl groups, and R 4 is a hydrogen atom.
  • the resin mixture further contains a crosslinking agent.
  • the crosslinking agent is selected from the group consisting of 2,5-dimethyl-2,5-di(t-butylperoxy)hexane and dicumyl peroxide.
  • the present invention also provides a method for producing a polylactic acid resin composition, comprising the steps of: A step of mixing a polylactic acid resin and a cis-polyisoprene to obtain a resin mixture; and a step of heating and kneading the resin mixture to dynamically crosslink the resin mixture; Inclusive of The content of the polylactic acid resin is 280 parts by mass to 950 parts by mass based on 100 parts by mass of the cis-polyisoprene.
  • the content of the polylactic acid resin is 290 to 720 parts by mass per 100 parts by mass of the cis-polyisoprene.
  • the present invention also relates to a resin molded product containing the above-mentioned polylactic acid resin composition.
  • the present invention can provide a resin composition that has improved impact resistance compared to polylactic acid.
  • the polylactic acid resin composition of the present invention also has thermoplasticity, making it possible to provide a wide range of resin molded products.
  • the polylactic acid resin composition of the present invention can utilize readily available biomass-derived materials as components, making it even more applicable to industrial production processes.
  • the polylactic acid resin composition of the present invention is prepared by dynamically crosslinking a resin mixture containing a polylactic acid resin and cis-polyisoprene.
  • the polylactic acid resin constituting the resin mixture is a general term for resins based on polylactic acid that are biodegradable (meaning that they can be decomposed, for example, by microorganisms, in various environments in nature, such as in soil, compost, fresh water, or seawater).
  • polylactic acid resins include polymers and copolymers containing L-lactic acid and/or D-lactic acid as monomer units, and copolymers of L-lactic acid and/or D-lactic acid as monomer units with other organic acids, such as glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, and 6-hydroxycaproic acid, and/or other alcohols, such as vinyl alcohol and butanediol, as other monomer units.
  • the polylactic acid resin contains the other monomer units, the other monomer units are preferably contained in a proportion of 50 mol% or less, more preferably 0.1 mol% to 50 mol%.
  • the polylactic acid resin is preferably poly(L-lactic acid), which is composed of L-lactic acid as a monomer unit, because it is versatile and easily available.
  • the weight-average molecular weight of the polylactic acid resin is preferably 10,000 to 1,000,000, and more preferably 50,000 to 500,000. If the weight-average molecular weight of the polylactic acid resin is below 10,000, the mechanical properties of the resulting polylactic acid resin composition may be reduced, compromising its versatility as a resin molded product. If the weight-average molecular weight of the polylactic acid resin is above 1,000,000, the moldability of the resulting polylactic acid resin composition may be reduced.
  • the polylactic acid resin may be obtained, for example, by ring-opening polymerization of lactide or dehydration condensation of L- and/or D-lactic acid, or by thermal polymerization of L- and/or D-lactic acid under reduced pressure in a specific organic solvent such as diphenyl ether.
  • the polylactic acid resin may be produced from biomass using a method known to those skilled in the art. Examples of biomass include, but are not limited to, plant materials such as corn, sweet potato, potato, and sugar cane, as well as combinations thereof.
  • the content of the polylactic acid resin is set, for example, based on the content of cis-polyisoprene described below.
  • the content of the polylactic acid resin is preferably 280 parts by mass to 950 parts by mass, more preferably 290 parts by mass to 720 parts by mass, and even more preferably 350 parts by mass to 570 parts by mass.
  • the content of the polylactic acid resin is less than 280 parts by mass, the amount of the polylactic acid resin contained in the obtained resin composition will be relatively reduced compared to the amount of other components, and there is a risk of departing from the objective of providing a polylactic acid resin composition that is derived from biomass and has excellent biodegradability, for example. If the content of the polylactic acid resin exceeds 950 parts by mass, the amount of the polylactic acid resin contained in the obtained resin composition will be relatively increased compared to the amount of other components, and there is a risk of the resin composition exhibiting undesirable properties of the polylactic acid resin (for example, reduced impact resistance and flexibility).
  • the cis-polyisoprene constituting the resin mixture may be, for example, derived from biomass, chemically synthesized, or a combination of these.
  • the cis-polyisoprene is obtained from a material derived from biomass, since it can be combined with the polylactic acid resin to provide an environmentally friendly resin composition.
  • such cis-polyisoprene may be appropriately chemically modified with maleic anhydride groups, maleimide groups, epoxy groups, etc.
  • Biomass containing cis-polyisoprene includes, for example, plant tissues consisting of the roots, stems (trunks), leaves, samaras (fruit skin and seeds), and bark of plants, as well as combinations thereof. Examples of plants that make up these include, but are not limited to, gutta percha (Palaquim gutta). Cis-polyisoprene can be obtained from the plants using methods known in the art.
  • the number average molecular weight (Mn) of the cis-polyisoprene is preferably 10,000 to 3,000,000, more preferably 15,000 to 1,000,000, and even more preferably 30,000 to 100,000.
  • the weight average molecular weight (Mw) of the cis-polyisoprene is preferably 10,000 to 3,000,000, more preferably 15,000 to 1,000,000, and even more preferably 30,000 to 100,000.
  • the resin mixture may further contain trans-polyisoprene in addition to the cis-polyisoprene.
  • Trans-polyisoprene may be, for example, derived from biomass, chemically synthesized, or a combination of these.
  • trans-polyisoprene is preferably obtained from a material derived from biomass, since it can be combined with the polylactic acid resin to provide an environmentally friendly resin composition.
  • such trans-polyisoprene may also be appropriately chemically modified with maleic anhydride groups, maleimide groups, epoxy groups, etc.
  • Trans-polyisoprene is found in large amounts in plant tissues such as the roots, stems (trunks), leaves, samaras (fruit skin and seeds), and bark of plants such as Eucommia ulmoides Oliver and Mimusops balata, and can be obtained from these plants using methods known in the art.
  • the number average molecular weight (Mn) of the trans-polyisoprene is preferably 10,000 to 1,500,000, more preferably 50,000 to 1,500,000, and even more preferably 100,000 to 1,500,000.
  • the weight average molecular weight (Mw) of the trans-polyisoprene is preferably 1 ⁇ 10 3 to 5 ⁇ 10 6 , more preferably 1 ⁇ 10 4 to 5 ⁇ 10 6 , and even more preferably 1 ⁇ 10 5 to 5 ⁇ 10 6 .
  • the amount of trans-polyisoprene is not particularly limited, but is preferably 10 to 1,000 parts by mass, and more preferably 25 to 400 parts by mass, assuming that the amount of cis-polyisoprene is 100 parts by mass. By including trans-polyisoprene in such a range, it is also possible to reduce the amount of cis-polyisoprene in the polylactic acid resin composition of the present invention (although within the above range).
  • Both cis-polyisoprene and trans-polyisoprene preferably have a particulate form and exist in a state of forming a finely dispersed sea-island structure in the matrix of the polylactic acid resin.
  • the average particle size of the cis- and/or trans-polyisoprene having such a particulate form is preferably 0.1 ⁇ m to 100 ⁇ m, more preferably 0.1 ⁇ m to 10 ⁇ m.
  • the average particle size of the cis- and/or trans-polyisoprene can be calculated, for example, by etching the cross section of a sample piece composed of the obtained polylactic acid resin composition with a solvent such as n-hexane to remove the polyisoprene particles present on the cross section, surface-treating the pores thus revealed (corresponding to the particle size of the cis- and/or trans-polyisoprene contained in the polyresin composition) using a sputtering method such as gold deposition, and then measuring the radius of the surface-treated pores through the viewing angle of an electron microscope photograph.
  • a solvent such as n-hexane
  • the resin mixture further contains the following formula (I) as an auxiliary agent:
  • R 1 , R 2 , R 3 and R 4 are each independently a group selected from the group consisting of a hydrogen atom and an optionally branched alkyl group having 1 to 8 carbon atoms).
  • the compound represented by formula (I) is, for example, a compound having a boiling point of 120°C to 250°C, preferably 125°C to 230°C, at 1 atmosphere (1 mmbar).
  • Specific examples of compounds represented by formula (I) include triethyl citrate (TEC), tributyl citrate (TBC), tributyl o-acetyl citrate (ATBC), tris(2-ethylhexyl) o-acetyl citrate (ATEHC), and combinations thereof.
  • TEC triethyl citrate
  • TBC tributyl citrate
  • ATBC tributyl o-acetyl citrate
  • ATEHC tris(2-ethylhexyl) o-acetyl citrate
  • the auxiliary contains tributyl citrate (TBC) because it is easily available and provides the resulting resin composition with even better impact resistance.
  • TBC tributyl citrate
  • the content of the auxiliary agent is preferably 3% to 30% by mass, more preferably 5% to 20% by mass, based on the total polylactic acid resin composition. If the content of the auxiliary agent is less than 3% by mass, the resulting resin composition may not have sufficient impact resistance. If the content of the auxiliary agent exceeds 30% by mass, the impact resistance of the resulting resin composition will hardly change, and productivity may be poor.
  • dynamic crosslinking of a resin mixture containing a polylactic acid resin and cis-polyisoprene is carried out, for example, by adding a suitable crosslinking agent to the resin mixture.
  • the polylactic acid resin and cis-polyisoprene are inherently incompatible with each other even when the two components are simply blended.
  • the polylactic acid resin and cis-polyisoprene, which have such properties, can be made compatible with each other by dynamically crosslinking them in the presence of an appropriate crosslinking agent.
  • the crosslinking agent that can be used in the polylactic acid resin composition of the present invention is premixed in the resin mixture together with the polylactic acid resin and cis-polyisoprene. By dynamically crosslinking such a resin mixture, it is possible to provide the resulting resin composition with superior physical properties (e.g., impact resistance) compared to uncrosslinked compositions.
  • crosslinking agents include organic peroxides (e.g., 2,5-dimethyl-2,5-di(t-butylperoxy)hexane and dicumyl peroxide, and combinations thereof); sulfur; organic sulfur compounds; organic nitroso compounds (e.g., aromatic nitroso compounds); oxime compounds; metal oxides (e.g., zinc oxide and magnesium oxide, and combinations thereof); polyamines; semimetals and their compounds (e.g., semimetals such as selenium and tellurium and their compounds, and combinations thereof); resin crosslinking agents (e.g., alkylphenol formaldehyde resins and brominated alkylphenol formaldehyde resins, and combinations thereof); organic organosiloxane compounds having two or more SiH groups in the molecule; and combinations thereof.
  • organic peroxides e.g., 2,5-dimethyl-2,5-di(t-butylperoxy)hexane and dicumyl peroxide, and
  • organic peroxides as crosslinking agents because they prevent the deterioration of the mechanical properties of the resin composition itself due to the decomposition of polylactic acid resins and cis-polyisoprene during crosslinking; they do not require large-scale equipment for crosslinking; and they are easily available as reagents and materials for industrial production.
  • the content of the crosslinking agent can be preferably set based on the content of the cis-polyisoprene.
  • the content of the crosslinking agent is preferably 0.3 parts by mass to 50 parts by mass, more preferably 2.8 parts by mass to 48 parts by mass, and even more preferably 4 parts by mass to 45 parts by mass. If the content of the crosslinking agent is less than 0.3 parts by mass, it may be difficult to perform appropriate dynamic crosslinking in the obtained resin composition, and satisfactory impact resistance may not be provided. If the content of the crosslinking agent exceeds 50 parts by mass, the dynamic crosslinking formed in the obtained resin composition becomes so-called over-crosslinking, which tightly binds each constituent molecule, and may deteriorate the moldability of the resin composition itself.
  • the polylactic acid resin composition of the present invention may further contain other additive materials as necessary.
  • additive materials include fillers, crystal nucleating agents, plasticizers, vulcanization accelerators, antioxidants, and flexibility agents, as well as combinations thereof.
  • fillers include, but are not limited to, cellulose powder, carbon black, silica, talc, and titanium dioxide, and combinations thereof.
  • the crystal nucleating agent is not particularly limited as long as it can promote the crystallization of the polylactic acid resin, and either inorganic or organic crystal nucleating agents can be used.
  • the crystal nucleating agent is preferably organic, and more preferred examples include homopolymers containing, as monomer units, lactic acid (units) with a different chirality from the polylactic acid resin, and copolymers containing the lactic acid units and other monomer units (for example, polysaccharides such as starch and glucomannan, monosaccharides such as glucose, disaccharides such as sucrose and maltose, and oligosaccharides such as cyclodextrin).
  • the plasticizer, vulcanization accelerator, and antioxidant are not particularly limited, and for example, commercially available products may be used.
  • a softening agent is, but is not limited to, polycaprolactone.
  • the amount of other additive materials is not particularly limited, and can be selected by a person skilled in the art in any amount taking into consideration the amount of polylactic acid resin, polyisoprene, and auxiliary agents.
  • the polylactic acid resin composition of the present invention is produced by dynamically crosslinking a resin mixture containing a polylactic acid resin, cis-polyisoprene, and optionally trans-polyisoprene, an auxiliary agent, a crosslinking agent, and/or other additive materials.
  • dynamic crosslinking refers to the formation of a crosslinked structure of cis-polyisoprene obtained by kneading a resin mixture, specifically, the crosslinked cis-polyisoprene obtained by the reaction of cis-polyisoprene with a crosslinking agent being finely dispersed in the resin composition due to the shear force during kneading.
  • Such dynamic crosslinking in a resin composition can be easily altered by a person skilled in the art, for example, by varying the conditions in the kneading step described below.
  • the polylactic acid resin composition of the present invention has an island-sea structure in which cis-polyisoprene is finely dispersed in the matrix of polylactic acid resin, and has improved impact resistance compared to polylactic acid resin alone.
  • the polylactic acid resin composition of the present invention can be used in a variety of resin molded products (e.g., molded products for automobiles, electrical appliances, agricultural materials, office supplies, and daily necessities) that were previously considered difficult to produce using conventional polylactic acid resin alone due to the lack of impact resistance, etc.
  • Method for producing polylactic acid resin composition In producing the polylactic acid resin composition of the present invention, first, the above-mentioned polylactic acid resin and cis-polyisoprene, and, if necessary, trans-polyisoprene, an auxiliary, a crosslinking agent and/or other additives are mixed to form a resin mixture.
  • the polylactic acid resin, cis-polyisoprene, trans-polyisoprene, auxiliary agent, cross-linking agent, and other additive materials may be mixed in various orders.
  • the polylactic acid resin and cis-polyisoprene are mixed in advance and kneaded at a predetermined temperature, and then the cross-linking agent is added to this kneaded mixture to form the resin mixture (note that in this case, other additive materials may be added after kneading with the kneading device described below).
  • the polylactic acid resin, cis-polyisoprene, and the cross-linking agent, etc. may be directly charged into a kneading device as described below, or may be mixed once in a separate container to form the resin mixture.
  • the resin mixture is then kneaded under heat.
  • kneading devices can be used for this kneading.
  • kneading devices include, but are not limited to, a segment mixer, a Banbury mixer, a Brabender mixer, a pressure kneader, a single-screw extruder, a twin-screw extruder, and an open roll.
  • the temperature required for kneading can be set at any temperature by those skilled in the art, taking into consideration the melting point of the polylactic acid resin used and/or the decomposition onset temperature of cis-polyisoprene.
  • the temperature applied to the kneading is preferably 140°C to 250°C, more preferably 150°C to 220°C, and even more preferably 160°C to 200°C. If the temperature applied to the kneading is less than 140°C, it may be difficult to knead the resin mixture uniformly. If the temperature applied to the kneading is more than 250°C, the molecular weight of the polylactic acid resin and/or cis-polyisoprene may decrease, and the mechanical properties of the resulting resin composition may deteriorate.
  • the time required for kneading is not necessarily limited because it can vary depending on the total amount of the resin mixture used, the ratio of the contents of the polylactic acid resin, cis-polyisoprene, and trans-polyisoprene, auxiliary, crosslinking agent, and other additive materials that make up the resin mixture, and can be set at any time by a person skilled in the art.
  • the time required for kneading is preferably 3 to 60 minutes, more preferably 5 to 30 minutes. If the time required for kneading is less than 3 minutes, the dynamic crosslinking in the resin mixture will be insufficient, and the impact resistance of the resulting resin composition may not be significantly improved compared to that of the polylactic acid resin alone.
  • the molecular chains of the polylactic acid resin and/or cis-polyisoprene in the resin mixture may be broken, resulting in a decrease in the mechanical properties of the resulting resin composition.
  • the resin mixture is dynamically crosslinked, and a resin composition having an island structure consisting of a polyisoprene component dispersed phase composed of cis-polyisoprene and optionally trans-polyisoprene, and a polylactic acid component matrix phase can be obtained.
  • the polylactic acid resin composition of the present invention is characterized in that, although the polyisoprene component is crosslinked, it has thermoplastic properties due to the polylactic acid resin that is a constituent component. Therefore, the polylactic acid resin composition of the present invention can be molded into any resin molded product using known thermoplastic resin molding methods such as extrusion molding, injection molding, blow molding, compression molding, etc., and molding devices that use these methods. Furthermore, the resin molded products thus obtained can also be further remolded.
  • Example 1 Preparation and testing of dynamically crosslinked resin sample (E1) 36.0 g of pellets of polylactic acid (PLA) (Terramac TE-2000, manufactured by Unitika Ltd.) as a polylactic acid-based resin and 4.0 g of cis-polyisoprene (CPI) (manufactured by Sigma-Aldrich) as a rubber component were added to a Labo Plastomill (4C150-01, manufactured by Toyo Seiki Co., Ltd.) equipped with a segment mixer whose temperature was adjusted to 180 ⁇ 10°C, and melt-kneaded for 1 minute under conditions of 180°C and 25 rpm, and then cooled to 150°C and further melt-kneaded for 3 minutes under conditions of 150°C and 25 rpm to obtain a kneaded product, which was further kneaded for 20 minutes under conditions of 160°C and 25 rpm to obtain a resin sample (E1) in which the kneaded product was dynamically crosslinked.
  • the resin sample (E1) obtained above was molded into a film having a thickness of 500 ⁇ 100 ⁇ m and a width of 4 mm, and a tensile test was performed on this film according to JIS K 6251 using a small tabletop testing machine (EZ-Graph, manufactured by Shimadzu Corporation) with a load cell of 500 N.
  • the test conditions were a crosshead speed of 10 mm/min and a test piece length of 20 mm. From the obtained stress-strain curve, the maximum stress (MPa) and Young's modulus (GPa) were obtained.
  • the toughness was calculated from the integral value of the stress-strain curve of the above tensile test. The results are shown in Table 2.
  • the resin sample (E1) obtained above was cut into small pieces, and a small injection molding machine (manufactured by Thermo Fisher Scientific/model: HAAKE MiniJet Pro) was used to mold strips (80 x 10 x 4 mm) for Charpy impact testing.
  • the test pieces were subjected to single notching using a notching tool (manufactured by INSTRON).
  • the Charpy impact test was performed using an impact tester (manufactured by Ueshima Seisakusho Co., Ltd.) in accordance with JIS K 7111-1.
  • the obtained impact strengths are shown in Table 2.
  • Example 2 Preparation and testing of dynamically crosslinked resin sample (E2) 36.0 g of pellets of polylactic acid (PLA) (Terramac TE-2000, manufactured by Unitika Ltd.) as a polylactic acid-based resin and 4.0 g of cis-polyisoprene (CPI) (manufactured by Sigma-Aldrich) as a rubber component were added to a Labo Plastomill (4C150-01, manufactured by Toyo Seiki Co., Ltd.) equipped with a segment mixer whose temperature was adjusted to 180 ⁇ 10°C, and the mixture was melt-kneaded for 1 minute under conditions of 180°C and 25 rpm, and then cooled to 150°C and further melt-kneaded for 3 minutes under conditions of 150°C and 25 rpm to obtain a kneaded product.
  • PVA polylactic acid
  • CPI cis-polyisoprene
  • Examples 3 and 4 Preparation and testing of dynamically crosslinked resin samples (E3) and (E4))
  • Resin samples (E3) and (E4) were obtained by dynamic crosslinking in the same manner as in Example 2, except that the contents of PLA, CPI, crosslinking agent, and antioxidant used were changed as shown in Table 2.
  • the obtained resin samples (E3) and (E4) were tested in the same manner as in Example 1. The results are shown in Table 2.
  • Example 5 Preparation and testing of dynamically crosslinked resin sample (E5) A dynamically crosslinked resin sample (E5) was obtained in the same manner as in Example 1, except that the contents of PLA and CPI used were changed as shown in Table 2. The obtained resin sample (E5) was tested in the same manner as in Example 1. The results are shown in Table 2.
  • Example 6 and 7 Preparation and testing of dynamically crosslinked resin samples (E6) and (E7)
  • Resin samples (E6) and (E7) were obtained by dynamic crosslinking in the same manner as in Example 2, except that the contents of PLA, CPI, crosslinking agent, and antioxidant used were changed as shown in Table 2.
  • the obtained resin samples (E6) and (E7) were tested in the same manner as in Example 1. The results are shown in Table 2.
  • Example 8 Preparation and testing of dynamically crosslinked resin sample (E8) 36.0 g of pellets of polylactic acid (PLA) (Terramac TE-2000, manufactured by Unitika Ltd.) as a polylactic acid-based resin, 4.0 g of cis-polyisoprene (CPI) (manufactured by Sigma-Aldrich) as a rubber component, and 4.0 g of tributyl citrate (TBC) as an auxiliary were added to a Labo Plastomill (4C150-01, manufactured by Toyo Seiki Co., Ltd.) equipped with a segment mixer whose temperature was adjusted to 180 ⁇ 10°C, and melt-kneaded for 1 minute under conditions of 180°C and 25 rpm, then cooled to 150°C, and further melt-kneaded for 3 minutes under conditions of 150°C and 25 rpm to obtain a kneaded product.
  • PVA polylactic acid
  • CPI cis-polyisoprene
  • the resin sample (E8) obtained in Example 8 had significantly improved toughness and impact strength compared to the resin sample (E6) obtained in Example 6, which did not contain the auxiliary TBC.
  • Example 9 Preparation and testing of dynamically crosslinked resin sample (E9) 32.0 g of pellets of polylactic acid (PLA) (Terramac TE-2000, manufactured by Unitika Ltd.) as a polylactic acid-based resin and 8.0 g of cis-polyisoprene (CPI) (manufactured by Sigma-Aldrich) as a rubber component were added to a Labo Plastomill (4C150-01, manufactured by Toyo Seiki Co., Ltd.) equipped with a segment mixer whose temperature was adjusted to 180 ⁇ 10°C, and melt-kneaded for 1 minute under conditions of 180°C and 25 rpm, and then cooled to 150°C and further melt-kneaded for 3 minutes under conditions of 150°C and 25 rpm to obtain a kneaded product.
  • PVA polylactic acid
  • CPI cis-polyisoprene
  • this resin sample (E9) was freeze-fractured to prepare a thin section for observation, and the surface condition of this section was observed using a scanning electron microscope (SEM) (SU-3500, manufactured by Hitachi High-Technologies Corporation). The obtained SEM photograph is shown in Figure 1.
  • SEM scanning electron microscope
  • Example 10 Preparation and testing of dynamically crosslinked resin sample (E10) A dynamically crosslinked resin sample (E10) was obtained in the same manner as in Example 9, except that the contents of PLA, CPI, crosslinking agent, and antioxidant used were changed as shown in Table 4. The obtained resin sample (E10) was tested in the same manner as in Example 1. The results are shown in Table 4. Furthermore, an SEM photograph was obtained for the obtained resin sample (E10) in the same manner as in Example 9. The obtained SEM photograph is shown in FIG.
  • the present invention is useful for a variety of resin molded products (e.g., molded products for automobiles, electrical appliances, agricultural materials, office supplies, and daily necessities) that were previously difficult to produce using conventional polylactic acid resins alone.
  • resin molded products e.g., molded products for automobiles, electrical appliances, agricultural materials, office supplies, and daily necessities

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000095898A (ja) * 1998-09-24 2000-04-04 Jsr Corp 生分解性材料の改質剤、およびそれを用いた生分解性材料組成物
JP2004057016A (ja) * 2002-07-25 2004-02-26 Unitika Ltd 生分解性農業用マルチ
JP2013523981A (ja) * 2010-04-13 2013-06-17 フテロ ソシエテ アノニム 再生可能な資源に由来するポリマーの組成物
KR20130109707A (ko) * 2012-03-28 2013-10-08 (주)월드트렌드 생분해성 플라스틱 조성물
WO2017110164A1 (ja) * 2015-12-24 2017-06-29 日立造船株式会社 ポリ乳酸樹脂組成物およびその製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000095898A (ja) * 1998-09-24 2000-04-04 Jsr Corp 生分解性材料の改質剤、およびそれを用いた生分解性材料組成物
JP2004057016A (ja) * 2002-07-25 2004-02-26 Unitika Ltd 生分解性農業用マルチ
JP2013523981A (ja) * 2010-04-13 2013-06-17 フテロ ソシエテ アノニム 再生可能な資源に由来するポリマーの組成物
KR20130109707A (ko) * 2012-03-28 2013-10-08 (주)월드트렌드 생분해성 플라스틱 조성물
WO2017110164A1 (ja) * 2015-12-24 2017-06-29 日立造船株式会社 ポリ乳酸樹脂組成物およびその製造方法

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