Molding resin composition and molded article

Abstract

Provided are a resin composition that easily promotes the crystallization of polyhydroxyalkanoate and has excellent moldability, and a molded article obtained by molding the resin composition. [Solution] The present invention provides a molding resin composition used to produce molded articles, which contains a polyhydroxyalkanoate and a crystallization accelerator, and the crystallization accelerator includes a compound containing at least a unit derived from alkylene oxide. The molding resin composition of the present invention is easy to promote crystallization of the polyhydroxyalkanoate and has excellent moldability.

Description

[Technical Field]

[0001] The present invention relates to a molding resin composition and a molded article. [Background technology]

[0002] Plastics are highly processable and convenient, making them an indispensable material in human life. However, as large amounts of used plastics are discarded, the resulting environmental pollution and impact on ecosystems have come to the forefront, raising concerns that they may cause global warming and other significant environmental impacts. For this reason, biodegradable resins have recently been actively developed to solve the problem of plastic waste.

[0003] Aliphatic polyesters are known as representative biodegradable resins, such as polylactic acid and polyhydroxyalkanoates. A drawback of aliphatic polyesters is that they crystallize slowly, resulting in poorer moldability than other general-purpose resins and lower productivity. To address this issue, Patent Document 1, for example, proposes a polyhydroxyalkanoate composition containing erucic acid amide or the like as a crystallization accelerator and an aliphatic alcohol or fatty acid as a crystal nucleating agent. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special table number 2024-530559 Summary of the Invention [Problem to be solved by the invention]

[0005] However, in recent years, there has been an increasing demand for improving the molding cycle of polyhydroxyalkanoate resins to increase productivity. Therefore, it is necessary to establish a technology for further promoting the crystallization of polyhydroxyalkanoate resins. Therefore, it is extremely important to develop raw materials suitable for producing polyhydroxyalkanoate molded articles with excellent moldability.

[0006] The present invention has been made in view of the above, and aims to provide a resin composition that easily promotes crystallization of polyhydroxyalkanoate and has excellent moldability, and a molded article obtained by molding the resin composition. [Means for solving the problem]

[0007] As a result of extensive research to achieve the above object, the inventors discovered that the above object can be achieved by combining polyhydroxyalkanoate with a specific crystallization promoter, and thus completed the present invention.

[0008] That is, the present invention includes, for example, the subject matter described in the following sections. Item 1 A molding resin composition used to produce a molded body, Contains polyhydroxyalkanoate and a crystallization promoter, The crystallization accelerator comprises a compound containing at least a unit derived from alkylene oxide. Section 2 Item 2. The molding resin composition according to Item 1, wherein the alkylene oxide-derived unit is at least one selected from the group consisting of ethylene oxide-derived units and propylene oxide-derived units. Section 3 Item 3. The molding resin composition according to Item 2, wherein the crystallization accelerator is a compound having a unit derived from ethylene oxide. Section 4 Item 3. The molding resin composition according to Item 2, wherein the crystallization accelerator is a compound having a unit derived from propylene oxide. Section 5 Item 3. The molding resin composition according to Item 2, wherein the crystallization accelerator is an ethylene oxide and propylene oxide adduct. Section 6 Item 6. The molding resin composition according to any one of items 1 to 5, further comprising a fatty acid amide. Section 7 Item 7. The molding resin composition according to any one of items 1 to 6, which is for spinning. Section 8 Item 8. A molded article made from the molding resin composition according to any one of items 1 to 7. [Effects of the Invention]

[0009] The molding resin composition of the present invention is excellent in moldability because it is likely to promote crystallization of the polyhydroxyalkanoate. DETAILED DESCRIPTION OF THE INVENTION

[0010]

[0023] In the present specification, the terms "contain" and "comprise" include the concepts of "contain," "comprise," "consist essentially of," and "consist only of."

[0011] In the numerical ranges described in stages in this specification, the upper or lower limit of a certain numerical range can be arbitrarily combined with the upper or lower limit of another numerical range. In the numerical ranges described in this specification, the upper or lower limit of the numerical range may be replaced with a value shown in an example or a value that can be unambiguously derived from an example. In addition, in this specification, numerical values ​​connected with "to" mean a numerical range that includes the numbers before and after "to" as the lower and upper limits.

[0012] The molding resin composition of the present invention is used to produce a molded body and contains a polyhydroxyalkanoate and a crystallization promoter, and the crystallization promoter includes a compound containing at least a unit derived from an alkylene oxide.

[0013] The molding resin composition of the present invention is excellent in moldability because it easily promotes crystallization of the polyhydroxyalkanoate. Therefore, by using the molding resin composition of the present invention, molded articles can be easily obtained. In this specification, excellent moldability means that molded articles can be efficiently produced in a short molding cycle, and can include, for example, a phenomenon in which yarn breakage is less likely to occur in spinning.

[0014] (Polyhydroxyalkanoate) The molding resin composition of the present invention contains polyhydroxyalkanoate as an essential resin component.

[0015] Polyhydroxyalkanoates (hereinafter abbreviated as "PHAs") are a type of bioplastic, and are known to have a variety of structures. In the present invention, for example, a wide range of known PHAs can be used.

[0016] PHA is a polymer compound having a structural unit represented by, for example, "-CHRCH2COO-". Here, R is a hydrocarbon group having 20 or less carbon atoms, preferably 15 or less, more preferably 10 or less, even more preferably 8 or less, particularly preferably 6 or less, and preferably 1 or more. Examples of R include alkyl groups, and specific examples include methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, pentyl, and hexyl groups.

[0017] Specific examples of PHA include polymers containing 3-hydroxyalkanoate structural units and / or 4-hydroxyalkanoate structural units. Specific examples of these structural units include 3-hydroxybutyrate structural units, 3-hydroxypropionate structural units, 3-hydroxypentanoate structural units, 3-hydroxyhexanoate structural units, 3-hydroxyheptanoate structural units, 3-hydroxyoctanoate structural units, 3-hydroxynonanoate structural units, 3-hydroxydecanoate structural units, 3-hydroxyundecanoate structural units, and 4-hydroxybutyrate structural units.

[0018] The PHA may contain 50 mol% or more of 3-hydroxyalkanoate constituent units, preferably 60 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, and particularly preferably 90 mol% or more.

[0019] Specific examples of PHA include: Poly(3-hydroxybutyrate) (abbreviation: PHB), Poly(3-hydroxybutyrate-co-3-hydroxypropionate), Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (abbreviation: P3HB3HV or PHBV), Poly(3-hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxyhexanoate) (abbreviation: P3HB3HV3HH), Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (abbreviated as P3HB3HH or PHBH), Poly(3-hydroxybutyrate-co-3-hydroxyheptanoate), poly(3-hydroxybutyrate-co-3-hydroxyoctanoate) (abbreviation: PHBO), Poly(3-hydroxybutyrate-co-3-hydroxynonanoate), Poly(3-hydroxybutyrate-co-3-hydroxydecanoate), Poly(3-hydroxybutyrate-co-3-hydroxyundecanoate), Examples include poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (abbreviation: P3HB4HB).

[0020] The weight-average molecular weight of the PHA is not particularly limited and can be set within an appropriate range depending on the method and application of the molded article, for example, within the same range as that of known PHAs. The weight-average molecular weight of the PHA is, for example, 100,000 to 1,000,000, preferably 200,000 to 900,000, and more preferably 300,000 to 800,000. The weight-average molecular weight of the PHA is measured from the polystyrene-equivalent molecular weight distribution using gel permeation chromatography (GPC) with a chloroform eluent. The column used in the GPC may be a column appropriate for measuring the molecular weight.

[0021] The method for producing PHA is not particularly limited, and for example, PHA can be obtained by a known production method, or it can also be obtained from a commercially available product.

[0022] The molding resin composition of the present invention can contain one or more PHAs.

[0023] (crystallization accelerator) The molding resin composition of the present invention contains a crystallization accelerator as an essential component. Such a crystallization accelerator is a component that has the effect of accelerating the crystallization of PHA.

[0024] As described above, the crystallization accelerator contains a compound containing at least a unit derived from alkylene oxide. The unit derived from alkylene oxide means a repeating structural unit formed by ring-opening of alkylene oxide, and for example, 1 -O-" (R 1 is an alkylene group).

[0025] The number of carbon atoms in the alkylene oxide is 20 or less, preferably 10 or less, more preferably 8 or less, even more preferably 6 or less, particularly preferably 4 or less, and preferably 1 or more, more preferably 2 or more. Therefore, examples of alkylene oxides include ethylene oxide, propylene oxide, and butylene oxide.

[0026] Among these, the alkylene oxide-derived unit is preferably at least one selected from the group consisting of ethylene oxide-derived units and propylene oxide-derived units, as this facilitates the promotion of crystallization of the PHA and improves moldability.

[0027] That is, the crystallization promoter may be a compound having units derived from ethylene oxide, or the crystallization promoter may be a compound having units derived from propylene oxide, or further, the crystallization promoter may be a compound containing both compounds having units derived from ethylene oxide and units derived from propylene oxide.

[0028] When the crystallization accelerator is a compound having units derived from ethylene oxide, the compound is a compound having a "-CH2CH2-O-" unit. When the crystallization accelerator is a compound having units derived from propylene oxide, the compound is a compound having a "-CH2CH(CH3)-O-" unit.

[0029] In the compound containing alkylene oxide-derived units, the content ratio of the alkylene oxide-derived units is not particularly limited. For example, in order to more easily promote the crystallization of PHA and to easily improve moldability, the content ratio of the alkylene oxide-derived units in the compound containing alkylene oxide-derived units is preferably 10 mol% or more, more preferably 15 mol% or more, even more preferably 20 mol% or more, even more preferably 25 mol% or more, and particularly preferably 30 mol% or more. Furthermore, the upper limit of the content ratio of the alkylene oxide-derived units in the compound containing alkylene oxide-derived units may be 100 mol% or may be 99 mol% or less.

[0030] The type of crystallization accelerator is not particularly limited as long as it contains a compound containing a unit derived from alkylene oxide.

[0031] Examples of the crystallization promoter include polyethylene glycol and polypropylene glycol.

[0032] Other examples of the crystallization promoter include compounds that contain a compound containing a unit derived from an alkylene oxide, and have a structure derived from an alcohol compound and a structure derived from a fatty acid.

[0033] Examples of the alcohol compound include various polyhydric alcohols, such as glycerin, erythritol, pentaerythritol, xylitol, sorbitol, mannitol, galactitol, maltitol, etc. Other examples of the alcohol compound include dehydrated condensates of alcohols such as sorbitan, mannitan, isosorbide, and isomannide.

[0034] Examples of fatty acids include a wide variety of known fatty acids, with fatty acids having 5 to 30 carbon atoms being preferred. The fatty acids may be either saturated or unsaturated. Specific examples of fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, linoleic acid, oleic acid, arachidic acid, behenic acid, tetracosanoic acid, cerotic acid, montanic acid, and melissic acid.

[0035] When the crystallization accelerator is a compound having a structure derived from an alcohol compound and a structure derived from a fatty acid, for example, an ester compound of an alkylene oxide adduct of a polyhydric alcohol and a fatty acid may be used. In such an ester compound, a hydroxyl group derived from the polyhydric alcohol or the alkylene oxide adduct may remain.

[0036] Examples of the ester compounds include polyoxyethylene glyceryl monostearate, polyoxyethylene sorbitol tetraoleate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene triisostearate hydrogenated castor oil, polyoxyethylene glycerin laurate, polyoxyethylene glycerin linoleate, polyoxyethylene glycerin stearate, polyoxyethylene glycerin isostearate, polyoxyethylene glycerin oleate, polyoxyethylene erythritol stearate, polyoxyethylene erythritol isostearate, polyoxyethylene sorbitol laurate, polyoxyethylene sorbitol linoleate, polyoxyethylene sorbitol stearate, polyoxyethylene sorbitol isostearate, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan cocoate, polyoxyethylene sorbitan myristylates, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan linoleate, and polyoxyethylene sorbitan laurate. Stearate, Polyoxyethylene sorbitan isostearate, Polyoxyethylene sorbitan-12-hydroxystearate, Polyoxyethylene sorbitan oleate, Polyoxyethylene sorbitan eicosanate, Polyoxyethylene sorbitan behenate, Polyoxyethylene sorbitan lignocerate, Polyoxyethylene isosorbide laurate, Polyoxyethylene isosorbide cocoate, Polyoxyethylene isosorbide myristate, Polyoxyethylene isosorbide palmitate, Polyoxyethylene isosorbide Polyoxyethylene isosorbide linoleate, polyoxyethylene isosorbide stearate, polyoxyethylene isosorbide isostearate, polyoxyethylene isosorbide-12-hydroxystearate, polyoxyethylene isosorbide oleate, polyoxyethylene isosorbide eicosanate, polyoxyethylene isosorbide behenate, polyoxyethylene isosorbide lignocerate, polyoxyethylene mannitol laurate, polyoxyethylene mannitol cocoate, polyoxyethylene mannitol myristylate,Polyoxyethylene mannitol palmitate, polyoxyethylene mannitol linoleate, polyoxyethylene mannitol stearate, polyoxyethylene mannitol isostearate, polyoxyethylene mannitol-12-hydroxystearate, polyoxyethylene mannitol oleate, polyoxyethylene mannitol eicosanate, polyoxyethylene mannitol behenate, polyoxyethylene mannitol lignocerate, polyoxyethylene mannitan laurate, polyoxyethylene mannitan cocoate, poly Oxyethylene mannitan myristate, polyoxyethylene mannitan palmitate, polyoxyethylene mannitan linoleate, polyoxyethylene mannitan stearate, polyoxyethylene mannitan isostearate, polyoxyethylene mannitan-12-hydroxystearate, polyoxyethylene mannitan oleate, polyoxyethylene mannitan eicosanate, polyoxyethylene mannitan behenate, polyoxyethylene mannitan lignocerate, polyoxyethylene isomannide laurate, polyoxyethylene mannitan Mannide cocoate, polyoxyethylene mannide myristylates, polyoxyethylene mannide palmitates, polyoxyethylene mannide linoleates, polyoxyethylene mannide stearate, polyoxyethylene mannide isostearate, polyoxyethylene mannide-12-hydroxystearate, polyoxyethylene mannide oleates, polyoxyethylene mannide laurates, polyoxyethylene mannide eicosanates, polyoxyethylene mannide behenates, polyoxyethylene mannide lignocerates, Polyoxyethylene xylitol laurate, polyoxyethylene xylitol cocoate, polyoxyethylene xylitol myristylate, polyoxyethylene xylitol palmitate, polyoxyethylene xylitol linoleate, polyoxyethylene xylitol stearate, polyoxyethylene xylitol isostearate, polyoxyethylene xylitol-12-hydroxystearate, polyoxyethylene xylitol oleate, polyoxyethylene xylitol eicosanate, polyoxyethylene xylitol behenate,Polyoxyethylene xylitol lignocerate, polyoxyethylene anhydroxylitol laurate, polyoxyethylene anhydroxylitol cocoate, polyoxyethylene anhydroxylitol myristylate, polyoxyethylene anhydroxylitol palmitate, polyoxyethylene anhydroxylitol linoleate, polyoxyethylene anhydroxylitol stearate, polyoxyethylene anhydroxylitol isostearate, polyoxyethylene anhydroxylitol-12-hydroxystearate, polyoxyethylene anhydroxylitol oleate, polyoxyethylene anhydroxylitol eicosanate, polyoxyethylene anhydroxylitol behenate, polyoxyethylene anhydroxylitol lignocerate, polyoxyethylene maltitol laurate, polyoxyethylene maltitol cocoate, polyoxyethylene maltitol myristylate, polyoxyethylene maltitol palmitate, polyoxyethylene maltitol linoleate, polyoxyethylene maltitol stearate, polyoxyethylene maltitol Polyoxyethylene anhydromaltitol isostearate, polyoxyethylene maltitol-12-hydroxystearate, polyoxyethylene maltitol oleate, polyoxyethylene maltitol eicosanate, polyoxyethylene maltitol behenate, polyoxyethylene maltitol lignocerate, polyoxyethylene anhydromaltitol laurate, polyoxyethylene anhydromaltitol cocoate, polyoxyethylene anhydromaltitol myristylate, polyoxyethylene anhydromaltitol palmitate, polyoxyethylene anhydromaltitol linoleate, polyoxyethylene anhydromaltitol stearate, polyoxyethylene anhydromaltitol isostearate, polyoxyethylene anhydromaltitol-12-hydroxystearate, polyoxyethylene anhydromaltitol oleate, polyoxyethylene anhydromaltitol eicosanate, polyoxyethylene anhydromaltitol behenate, polyoxyethylene anhydromaltitol lignocerate, polyoxyethylene galactitol laurate,Polyoxyethylene galactitol cocoate, polyoxyethylene galactitol myristylate, polyoxyethylene galactitol palmitate, polyoxyethylene galactitol linoleate, polyoxyethylene galactitol stearate, polyoxyethylene galactitol isostearate, polyoxyethylene galactitol-12-hydroxystearate, polyoxyethylene galactitol oleate, polyoxyethylene galactitol eicosanate, polyoxyethylene galactitol behenate, polyoxyethylene galactitol lignocerate, polyoxyethylene anhydrogalactitol laurate, polyoxyethylene anhydrogalactitol cocoate ester, polyoxyethylene anhydrogalactitol myristylates, polyoxyethylene anhydrogalactitol palmitates, polyoxyethylene anhydrogalactitol linoleates, polyoxyethylene anhydrogalactitol stearate, polyoxyethylene anhydrogalactitol isostearate, polyoxyethylene anhydrogalactitol-12-hydroxystearate, polyoxyethylene anhydrogalactitol oleates, polyoxyethylene anhydrogalactitol eicosanates, polyoxyethylene anhydrogalactitol behenates, polyoxyethylene anhydrogalactitol lignocerates, and the like.

[0037] Further examples of the crystallization accelerator include block polymers of two or more alkylene oxides, such as block polymers of ethylene oxide and propylene oxide. That is, the crystallization accelerator may be an ethylene oxide and propylene oxide adduct. Further examples of the crystallization accelerator include diester compounds of adipic acid and benzyl alcohol / diethylene glycol monomethyl ether.

[0038] The weight-average molecular weight of the crystallization accelerator is preferably 100 to 5,000. The weight-average molecular weight of the crystallization accelerator is measured from the polystyrene equivalent molecular weight distribution using gel permeation chromatography (GPC) with a chloroform eluent. As a column for the GPC, a column appropriate for measuring the molecular weight may be used.

[0039] The method for producing the crystallization accelerator is not particularly limited, and for example, the crystallization accelerator can be obtained by a known production method, or it is also possible to obtain the crystallization accelerator from a commercially available product.

[0040] The molding resin composition of the present invention may contain one or more crystallization accelerators.

[0041] In the molding resin composition of the present invention, the content of the crystallization accelerator is not particularly limited, and for example, relative to 100 parts by mass of PHA, the content of the crystallization accelerator can be 0.1 parts by mass or more, preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, even more preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, and particularly preferably 4 parts by mass or more. Also, the content of the crystallization accelerator can be 20 parts by mass or less, preferably 15 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 8 parts by mass or less, even more preferably 7 parts by mass or less, and particularly preferably 6 parts by mass or less.

[0042] (fatty acid amides) The molding resin composition of the present invention can contain a fatty acid amide as needed. When the molding resin composition of the present invention contains a fatty acid amide, the kneadability of the PHA and the crystallization accelerator is likely to be improved, and moldability is particularly likely to be improved. Specifically, when the molding resin composition of the present invention contains a fatty acid amide, the PHA is easily extruded when extruded. Therefore, the fatty acid amide is a component that functions as a so-called lubricant for the PHA.

[0043] The fatty acid amide is not particularly limited in type as long as it is an amide compound formed from a fatty acid and an amine compound, and for example, a wide range of known fatty amides can be used in the present invention. For example, the fatty acid amide can be a fatty acid amide having 8 to 24 carbon atoms, and among them, a bisamide compound obtained by reacting a fatty acid amide having 8 to 24 carbon atoms with a compound having two amino groups can be preferably mentioned.

[0044] The fatty acid amide may be a compound having a hydroxyl group or a compound having no hydroxyl group.

[0045] Examples of fatty acid amides having no hydroxyl group include fatty acid monoamides such as erucic acid amide, caprylic acid amide, capric acid amide, myristic acid amide, palmitic acid amide, lauric acid amide, stearic acid amide, arachidinamide, behenic acid amide, lignoceric acid amide, stearic acid monoethanolamide, oleic acid amide, linoleic acid amide, and arachidonic acid amide; N,N'-ethylenebiscaprylic acid amide, butylenebiscaprylic acid amide, and hexamethylenebiscaprylamide; Acid amide, m-xylylene biscaprylic acid amide, N,N'-ethylene biscapric acid amide, butylene biscapric acid amide, hexamethylene biscapric acid amide, m-xylylene biscapric acid amide, N,N'-ethylene bislauric acid amide, butylene bislauric acid amide, hexamethylene bislauric acid amide, m-xylylene bislauric acid amide, N,N'-ethylene bisstearic acid amide, butylene bisstearic acid amide, hexamethylene bisstearic acid amide , m-xylylene bisstearic acid amide, ethylene bisarachidic acid amide, butylene bisarachidic acid amide, hexamethylene bisarachidic acid amide, m-xylylene bisarachidic acid amide, ethylene bisbehenic acid amide, butylene bisbehenic acid amide, hexamethylene bisbehenic acid amide, m-xylylene bisbehenic acid amide, ethylene bislignoceric acid amide, butylene bisoleic acid amide, hexamethylene bislignoceric acid amide, m-xylylene bislignoceric acid Examples of the amide include carboxylic acid amide, ethylene bisoleic acid amide, butylene bisoleic acid amide, hexamethylene bisoleic acid amide, m-xylylene bisoleic acid amide, ethylene bislinoleic acid amide, butylene bislinoleic acid amide, hexamethylene bislinoleic acid amide, m-xylylene bislinoleic acid amide, ethylene bisarachidonic acid amide, butylene bisarachidonic acid amide, hexamethylene bisarachidonic acid amide, and m-xylylene bisarachidonic acid amide.

[0046] Examples of fatty acid amides having a hydroxyl group include 8-hydroxycaprylic acid amide, 10-hydroxylauric acid amide, 10-hydroxycapric acid amide, 11-hydroxymyristic acid amide, 16-hydroxypalmitic acid amide, 12-hydroxystearic acid amide, 2-hydroxyarachidic acid amide, 2-hydroxybehenic acid amide, 2-hydroxylignoceric acid amide, 12-hydroxystearic acid monoethanolamide, 12-hydroxyoleic acid amide, 11-hydroxylinoleic acid amide, 2-hydroxyarachidic ... Hydroxyl group-containing fatty acid monoamides such as chidonamide, N,N'-ethylenebis-8-hydroxycapric acid amide, N,N'-butylenebis-8-hydroxycapric acid amide, N,N'-hexamethylenebis-8-hydroxycapric acid amide, N,N'-m-xylylenebis-8-hydroxycapric acid amide, N,N'-ethylenebis-10-hydroxylauric acid amide, N,N'-butylenebis-10-hydroxylauric acid amide, N,N'-hexamethylenebis-10-hydroxylauric acid amide, N,N'-m-xylylenebis-8-hydroxycapric acid amide, N,N'-ethylenebis-11-hydroxymyristate amide, N,N'-butylenebis-11-hydroxymyristate amide, N,N'-hexamethylenebis-11-hydroxymyristate amide, N,N'-m-xylylenebis-11-hydroxymyristate amide, N,N'-ethylenebis-16-hydroxypalmitic acid amide, N,N'-butylenebis-16-hydroxypalmitic acid amide, N,N'-hexamethylenebis-16-hydroxypalmitic acid amide, N,N '-m-Xylylenebis-16-hydroxypalmitic acid amide, N,N'-ethylenebis-12-hydroxystearic acid amide, N,N'-butylenebis-12-hydroxystearic acid amide, N,N'-hexamethylenebis-12-stearic acid amide, N,N'-m-xylylenebis-12-hydroxystearic acid amide, N,N'-ethylenebis-2-hydroxyarachidic acid amide, N,N'-butylenebis-2-hydroxyarachidic acid amide, N,N'-m-Xylylenebis-2-hydroxyarachidic acid amide, N,N'-ethylenebis-2-hydroxybehenic acid amide, N,N'-butylenebis-2-hydroxybehenic acid amide, N,N'-hexamethylenebis-2-hydroxybehenic acid amide, N,N'-m-xylylenebis-2-hydroxybehenic acid amide, N,N'-ethylenebis-2-hydroxylignoceric acid amide, N,N'-butylenebis-2-hydroxylignoceric acid amide, N,N'-hexamethylenebis-2-hydroxylignoceric acid amide, N,N'-m-xylylenebis-2-hydroxylignoceric acid amide, N,N'-ethylenebis-12-hydroxyoleic acid amide, N,N'-butylenebis-12-hydroxyoleic acid amide, N,N Examples of hydroxyl group-containing fatty acid bisamides include N,N'-hexamethylenebis-12-hydroxyoleic acid amide, N,N'-m-xylylenebis-12-hydroxyoleic acid amide, N,N'-ethylenebis-11-hydroxylinoleic acid amide, N,N'-butylenebis-11-hydroxylinoleic acid amide, N,N'-hexamethylenebis-11-hydroxylinoleic acid amide, N,N'-m-xylylenebis-11-hydroxylinoleic acid amide, N,N'-ethylenebis-11-hydroxyarachidonic acid amide, N,N'-butylenebis-11-hydroxyarachidonic acid amide, N,N'-hexamethylenebis-11-hydroxyarachidonic acid amide, and N,N'-m-xylylenebis-11-hydroxyarachidonic acid amide.

[0047] The method for producing the fatty acid amide is not particularly limited, and for example, the fatty acid amide can be obtained by a known production method, or it is also possible to obtain the fatty acid amide from a commercially available product.

[0048] The molding resin composition of the present invention can contain one or more fatty acid amides.

[0049] In the molding resin composition of the present invention, the content of fatty acid amide is not particularly limited, and for example, relative to 100 parts by mass of PHA, the content of fatty acid amide is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, even more preferably 0.3 parts by mass or more, even more preferably 0.5 parts by mass or more, and particularly preferably 0.7 parts by mass or more. The content of crystallization accelerator is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, even more preferably 2 parts by mass or less, and particularly preferably 1.5 parts by mass or less.

[0050] (Molding resin composition) The molding resin composition of the present invention contains a PHA (polyhydroxyalkanoate) and a crystallization accelerator as essential components, and optionally contains the fatty acid amide. The molding resin composition of the present invention may contain other components as long as the effects of the present invention are not impaired. Examples of other components include various components contained in PHA molded articles, such as inorganic fillers, flame retardants, antioxidants, impact resistance improvers, antistatic agents, hydrolysis inhibitors, antifogging agents, light stabilizers, UV absorbers, pigments, colorants, mildew inhibitors, antibacterial agents, and foaming agents.

[0051] In the molding resin composition of the present invention, the total mass of the PHA and crystallization accelerator is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more. The molding resin composition of the present invention may consist only of the PHA and the crystallization accelerator. In another embodiment of the molding resin composition of the present invention, the total mass of the PHA, crystallization accelerator, and fatty acid amide is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more. The molding resin composition of the present invention may consist only of the PHA, the crystallization accelerator, and the fatty acid amide.

[0052] The method for preparing the molding resin composition of the present invention is not particularly limited, and various methods can be adopted. For example, the molding resin composition of the present invention can be prepared by mixing the PHA, the crystallization accelerator, and the fatty acid amide added as needed in desired amounts.

[0053] As an example of a method for preparing the molding resin composition of the present invention, a mixture of PHA, a crystallization accelerator, and optionally a fatty acid amide is prepared, and the mixture is melt-treated by an appropriate method and then discharged to prepare the molding resin composition of the present invention. The melting temperature can be, for example, 140 to 200°C, more preferably 140 to 200°C, more preferably 150 to 195°C, and particularly preferably 160 to 190°C, in that good dispersibility can be obtained while suppressing thermal decomposition. The melt-treatment method is not particularly limited, and an extruder, Banbury mixer, kneader, heated roll, etc. can be used.

[0054] The form of the molding resin composition of the present invention is not particularly limited, and examples thereof include various forms such as powder, pellets, granules, liquid, paste, solution, and dispersion.

[0055] The molding resin composition of the present invention can be molded into a desired shape. The molding method is not particularly limited, and for example, known molding methods can be widely adopted in the present invention. Examples of molding methods include cast molding, injection molding, blow molding, and extrusion molding. In addition, the molding resin composition of the present invention can be molded into a fibrous form by spinning. The spinning method (spinning treatment) is also not particularly limited, and for example, known spinning conditions can be widely adopted in the present invention.

[0056] The type of molded article obtained from the molding resin composition of the present invention is not particularly limited, and examples thereof include fiber, sheet, block, film, and rod shapes, and these molded articles can also be further processed into desired shapes.

[0057] The molded article is obtained using the molding resin composition of the present invention, and for example, crystallization of the PHA is likely to be accelerated during molding, thereby shortening the molding cycle, i.e., improving moldability and increasing production efficiency.

[0058] When the molding resin composition of the present invention is subjected to a spinning process, thread breakage is unlikely to occur during the spinning process, and therefore the molding resin composition of the present invention is suitable for spinning.

[0059] When the molding resin composition of the present invention is molded using a mold, the mold retention time can be shortened and the molded article can be easily removed from the mold without deformation.

[0060] Furthermore, when the molding resin composition of the present invention contains a fatty acid amide in addition to a PHA and a crystallization accelerator, the kneadability of the PHA is excellent. Specifically, the melt-kneaded PHA becomes easier to extrude, and for example, the extrusion efficiency can be improved by about 10% compared to PHA alone.

[0061] In specifying the inventions included in the present disclosure, the components (properties, structures, functions, etc.) described in the embodiments of the present disclosure may be combined in any manner. In other words, the present disclosure includes all subject matter consisting of all combinations of the components that can be combined as described in this specification. [Example]

[0062] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.

[0063] Appropriate raw materials were selected from the raw materials shown below to prepare molding resin compositions.

[0064] (PHA) ·PHB:PB3000 manufactured by Beijing Microstructure Factory Biological Technology Co., Ltd. ·PHBV: PV3000 manufactured by Beijing Microstructure Factory Biotechnology Co., Ltd. (contains 3mol% of 3HV (3-hydroxyvalerate)) ·PHBH: BP350-PD manufactured by Beijing Blue Crystal Microbial Technology Co., Ltd. (contains 11 mol% of 3HH (3-hydroxyhexanoate))

[0065] (crystallization accelerator) Crystallization accelerator 1: Polyethylene glycol (PEG-600 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Crystallization accelerator 2: Polypropylene glycol (PPG manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Crystallization accelerator 3: EO / PO block polymer (Dai-ichi Kogyo Seiyaku Co., Ltd. "Epane U-105" (registered trademark)) Crystallization accelerator 4: Polyoxyethylene triisostearate hydrogenated castor oil (Japan Emulsion Co., Ltd. "EMALEX RWIS-320" (registered trademark)) Crystallization accelerator 5: Polyoxyethylene glyceryl monostearate (Japan Emulsion Co., Ltd. "EMALEX GM-20" (registered trademark)) Crystallization accelerator 6: Polyoxyethylene sorbitol tetraoleate (Kao Corporation "Rheodol 430V" (registered trademark)) Crystallization accelerator 7: Polyoxyethylene sorbitan monostearate (Dai-ichi Kogyo Seiyaku Co., Ltd. "Solgen TW-60" (registered trademark)) Crystallization accelerator 8: Polyoxyethylene sorbitan tristearate (Dai-ichi Kogyo Seiyaku Co., Ltd. "Solgen TW-65" (registered trademark)) Crystallization accelerator 9: Daihachi Chemical Industry Co., Ltd. "DAIFATTY-101" (registered trademark, a diester compound of adipic acid and a 1 / 1 mixture of benzyl alcohol and diethylene glycol monomethyl ether)

[0066] (fatty acid amides) Fatty acid amide 1: Erucic acid amide (Kao Corporation's "Fatty acid amide E") Fatty acid amide 2: N,N'-ethylene-bisstearylamide (Dai-ichi Kogyo Seiyaku Co., Ltd. "EBA") Fatty acid amide 3: N,N'-ethylenebis-12-hydroxystearylamide (ITOHWAX J-530, Ito Oil Mills)

[0067] (Other ingredients) Glycerin monostearate (Kao Corporation "Excel S-95" (registered trademark)) Sorbitol (Tokyo Chemical Industry Co., Ltd.) Sorbitan monostearate (Kao Corporation "SP-S10V" (registered trademark)) Sorbitan tristearate (Kao Corporation "SP-S30V" (registered trademark)) Pentaerythritol (Tokyo Chemical Industry Co., Ltd.) Myo-inositol (Tokyo Chemical Industry Co., Ltd.) Galactitol (Tokyo Chemical Industry Co., Ltd.)

[0068] (inorganic filler) Talc (Talc MS from Nippon Talc Co., Ltd.) Boron nitride (Denka "BN SP-3") Zinc phenylphosphonate (Nissan Chemical "Ecopromote") Copper phthalocyanine (Tokyo Chemical Industry Co., Ltd.)

[0069] Example 1A A molding resin composition was prepared by selecting the raw materials shown in Example 1A in the recipe of Table 1. Specifically, a mixture obtained by mixing 100 parts by mass of PHB and 5 parts by mass of crystallization accelerator 1 was heated and kneaded using a twin-screw extruder (manufactured by Technovel Co., Ltd., KZW20-30MG) at a cylinder temperature of 180 to 190°C, to obtain a pelletized molding resin composition.

[0070] (Examples 2A to 9A) Pellets of molding resin compositions were obtained in the same manner as in Example 1A, except that the raw materials and their blending amounts were changed as shown in Table 1.

[0071] Example 10A A molding resin composition was prepared by selecting the raw materials shown in Example 10A in the recipe of Table 2. Specifically, a mixture obtained by mixing 100 parts by mass of PHB, 5 parts by mass of crystallization accelerator 1, and 1 part by mass of fatty acid amide 1 (erucic acid amide) was heated and kneaded using a twin-screw extruder (manufactured by Technovel Co., Ltd., KZW20-30MG) at a cylinder temperature of 180 to 190°C, to obtain a pelletized molding resin composition.

[0072] (Examples 11A to 18A) Pellets of molding resin compositions were obtained in the same manner as in Example 1A, except that the raw materials and their blending amounts were changed as shown in Table 2.

[0073] (Comparative Examples 1A to 6A) Pellets of molding resin compositions were obtained in the same manner as in Example 1A, except that the raw materials and their blending amounts were changed as shown in Table 3.

[0074] (Comparative Examples 7A to 12A) Pellets of molding resin compositions were obtained in the same manner as in Example 1A, except that the raw materials and their blending amounts were changed as shown in Table 4.

[0075] Examples 1B to 9B Pellets of molding resin compositions were obtained in the same manner as in Example 1A, except that the raw materials and their blending amounts were changed as shown in Table 5.

[0076] (Examples 10B to 18B) Pellets of molding resin compositions were obtained in the same manner as in Example 1A, except that the raw materials and their blending amounts were changed as shown in Table 6.

[0077] (Comparative Examples 1B to 6B) Pellets of molding resin compositions were obtained in the same manner as in Example 1A, except that the raw materials and their blending amounts were changed as shown in Table 7.

[0078] (Comparative Examples 7B to 12B) Pellets of molding resin compositions were obtained in the same manner as in Example 1A, except that the raw materials and their blending amounts were changed as shown in Table 8.

[0079] Examples 1C to 8C Pellets of molding resin compositions were obtained in the same manner as in Example 1A, except that the raw materials and their blending amounts were changed as shown in Table 9 and the cylinder temperature was set to 150 to 160°C.

[0080] (Examples 9C to 15C) Pellets of molding resin compositions were obtained in the same manner as in Example 1A, except that the raw materials and their blending amounts were changed as shown in Table 10.

[0081] (Comparative examples 1C to 9C) Pellets of molding resin compositions were obtained in the same manner as in Example 1A, except that the raw materials and their blending amounts were changed as shown in Table 11.

[0082] The molding resin compositions obtained in the examples and comparative examples were evaluated for crystallinity, prevention performance, and kneading performance by the following methods.

[0083] (Relative crystallinity) The relative crystallinity was measured by differential scanning calorimetry (DSC). Specifically, the molding resin compositions obtained in each Example and Comparative Example were heated from room temperature to 200°C at a rate of 10°C / min, then cooled to -30°C at a rate of 50°C / min, and then heated a second time to 200°C at a rate of 10°C / min. From the obtained DSC curve, the crystallization enthalpy (ΔHc) and melting enthalpy (ΔHm) were measured, and the crystallinity was calculated. The relative crystallinity was calculated using the following formula based on the values ​​of the crystallization enthalpy (ΔHc) and melting enthalpy (ΔHm) during the second heating in the DSC. Relative crystallinity (%) = {(ΔHm-ΔHc) / ΔHm} × 100 In the case of molding resin compositions containing PHB and PHBV, the relative crystallinity was determined according to the following criterion 1, and in the case of molding resin compositions containing PHBH, the relative crystallinity was determined according to the following criterion 2. ≪Judgment Criteria 1≫ A: The relative crystallinity is 90% or more, and the crystallinity is extremely high. B: The relative crystallinity is 70% or more and less than 90%, and the crystallinity is high. C: The relative crystallinity is less than 70%, and the crystallinity is low. ≪Judgment Criteria 2≫ A: The relative crystallinity is 70% or more, and the crystallinity is extremely high. B: The relative crystallinity is 50% or more and less than 70%, and the crystallinity is high. C: The relative crystallinity is less than 50%, and the crystallinity is low.

[0084] (Spinning performance) The pellets (molding resin compositions) prepared in each of the Examples and Comparative Examples were melted in a single-screw extruder with a screw diameter of 25 mm, and the resin was extruded from a spinning die with a 0.3 mm diameter spindle at a melt spinning temperature of 180° C. The resin was then taken up with a suction gun, and the state of the fiber was observed and evaluated according to the following criteria. ≪Judgment criteria≫ A: No thread breakage occurs, no sticking to the suction gun, and excellent spinning performance. B: The yarn breaks and cannot be spun, or the yarn sticks to the suction gun.

[0085] (Mixing performance) The mixture obtained by mixing the PHA and the crystallization accelerator was heated and kneaded using a twin-screw extruder (KZW20-30MG, manufactured by Technovel Co., Ltd.) at a cylinder temperature of 180 to 190°C, and then extruded to obtain a pelletized molding resin composition. The kneading performance was evaluated based on the extrusion amount using the following criteria. ≪Judgment criteria≫ A: The discharge amount was 10% or more higher than when PHA was discharged alone, and the kneading performance was extremely excellent. B: The discharge amount was about the same as when PHA was discharged alone, and the kneading performance was not impaired. C: The discharge amount was reduced by 10% or more compared to when PHA was discharged alone, and the kneading performance was poor.

[0086] The blending compositions and evaluation results of the molding resin compositions obtained in each Example and Comparative Example are shown in Tables 1 to 11. In Tables 1 to 11, blank cells indicate that the corresponding raw material was not used.

[0087] From the tables, it can be seen that molding resin compositions containing PHA (PHB, PHBV, or PHBH) and a specified crystallization accelerator tend to promote PHA crystallization and have excellent moldability, specifically, excellent spinnability. Furthermore, molding resin compositions containing fatty acid amides allow the melt-kneaded PHA to be more easily extruded, and in this respect also have excellent moldability. From the above, it was demonstrated that the molding resin compositions obtained in the examples shorten the molding cycle.

[0088] [Table 1]

[0089] [Table 2]

[0090] [Table 3]

[0091] [Table 4]

[0092] [Table 5]

[0093] [Table 6]

[0094]

Table 7

[0095]

Table 8

[0096]

Table 9

[0097]

Table 10

[0098]

Table 11

Claims

1. A molding resin composition used to produce a molded body, Contains polyhydroxyalkanoate (excluding polylactic acid), a crystallization promoter, and a fatty acid amide, The crystallization accelerator comprises a compound containing at least a unit derived from alkylene oxide.

2. The molding resin composition according to claim 1, wherein the polyhydroxyalkanoate (excluding polylactic acid) has a structural unit represented by -CHRCH 2 COO- (R is a hydrocarbon group having 20 or less carbon atoms).

3. 2. The molding resin composition according to claim 1, wherein the alkylene oxide-derived unit is at least one selected from the group consisting of ethylene oxide-derived units and propylene oxide-derived units.

4. The molding resin composition according to claim 3 , wherein the crystallization accelerator is a compound having a unit derived from ethylene oxide.

5. The molding resin composition according to claim 3 , wherein the crystallization accelerator is a compound having a unit derived from propylene oxide.

6. 4. The molding resin composition according to claim 3, wherein the crystallization accelerator is an ethylene oxide and propylene oxide adduct.

7. The molding resin composition according to claim 1, which is for spinning.

8. A molded article made from the molding resin composition according to any one of claims 1 to 7.

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