JP7760771B1 - Molding resin composition and molded article - Google Patents

Abstract

The present invention provides 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.
[Selection diagram] None

Description

The present invention relates to a molding resin composition and a molded article.

Plastics are highly processable and convenient, making them an indispensable material in human life. However, as large amounts of used plastic are discarded, the resulting environmental pollution and impact on the ecosystem have come to the forefront, raising concerns that they could cause global warming and place a significant burden on the global environment. For this reason, there has been active research and development into biodegradable resins in recent years to solve the problem of plastic waste.

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.

Special table number 2024-530559

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 technology to further promote the crystallization of polyhydroxyalkanoate resins. Therefore, it is extremely important to develop raw materials suitable for producing polyhydroxyalkanoate molded articles with excellent moldability.

The present invention was made in consideration of the above, and aims to provide a resin composition that easily promotes crystallization of polyhydroxyalkanoate and has excellent moldability, as well as a molded article obtained by molding the resin composition.

As a result of extensive research to achieve the above objective, the inventors discovered that the above objective could be achieved by combining polyhydroxyalkanoate with a specific crystallization promoter, leading to the completion of the present invention.

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.
Item 5
Item 3. The molding resin composition according to Item 2, wherein the crystallization accelerator is an ethylene oxide and propylene oxide adduct.
Item 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.
Item 8
Item 8. A molded article of the molding resin composition according to any one of items 1 to 7.

The molding resin composition of the present invention easily promotes crystallization of the polyhydroxyalkanoate, resulting in excellent moldability.

Embodiments of the present invention are described in detail below. Note that, in this specification, the expressions "contain" and "comprise" include the concepts of "contain," "comprise," "consist essentially of," and "consist only of."

In the numerical ranges described in this specification in stages, 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 that numerical range may be replaced with a value shown in an example or a value that can be unambiguously derived from an example. Furthermore, in this specification, numerical values connected with "~" mean a numerical range that includes the numbers before and after "~" as the upper and lower limits.

The molding resin composition of the present invention is used to produce molded articles and contains polyhydroxyalkanoate and a crystallization accelerator, where the crystallization accelerator includes a compound containing at least units derived from alkylene oxide.

The molding resin composition of the present invention is excellent in moldability, as it readily promotes crystallization of the polyhydroxyalkanoate. Therefore, molded articles can be easily obtained using the molding resin composition of the present invention. In this specification, excellent moldability means that molded articles can be efficiently produced in a short molding cycle, and can include, for example, the phenomenon of less thread breakage in spinning.

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

Polyhydroxyalkanoates (hereinafter abbreviated as "PHA") 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.

PHA is, for example, a polymer compound having a structural unit represented by "-CHRCH ₂ COO-". 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.

Specific examples of PHAs 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.

PHA can contain 50 mol% or more of 3-hydroxyalkanoate structural 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.

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).

The weight-average molecular weight of the PHA is not particularly limited and can be set within an appropriate range depending on the use and application of the molded article. For example, it can be set to 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.

The method for producing PHA is not particularly limited; for example, PHA can be obtained by known production methods, or it can be obtained from commercially available products.

The molding resin composition of the present invention may contain one or more PHAs.

(Crystallization promoter)
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.

As described above, the crystallization accelerator contains a compound containing at least an alkylene oxide-derived unit. The alkylene oxide-derived unit refers to a repeating structural unit formed by ring-opening of an alkylene oxide, such as a group represented by "-R ¹ -O-" (R ¹ is an alkylene group).

The alkylene oxide has 20 or fewer carbon atoms, preferably 10 or fewer, more preferably 8 or fewer, even more preferably 6 or fewer, particularly preferably 4 or fewer, and preferably 1 or more, more preferably 2 or more. Therefore, examples of alkylene oxides include ethylene oxide, propylene oxide, and butylene oxide.

In particular, it is preferable that the alkylene oxide-derived unit be at least one selected from the group consisting of ethylene oxide-derived units and propylene oxide-derived units, as this facilitates the promotion of PHA crystallization and improves moldability.

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

When the crystallization accelerator is a compound having a unit derived from ethylene oxide, the compound is a compound having a "-CH ₂ CH ₂ -O-" unit. When the crystallization accelerator is a compound having a unit derived from propylene oxide, the compound is a compound having a "-CH ₂ CH(CH ₃ )-O-" unit.

In a compound containing alkylene oxide-derived units, the content of the alkylene oxide-derived units is not particularly limited. For example, in order to more easily promote crystallization of the PHA and improve moldability, the content of the alkylene oxide-derived units in a 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 of the alkylene oxide-derived units in a compound containing alkylene oxide-derived units may be 100 mol% or may be 99 mol% or less.

The type of crystallization promoter is not particularly limited, as long as it contains a compound containing units derived from alkylene oxide.

Examples of crystallization promoters include polyethylene glycol, polypropylene glycol, etc.

Other examples of crystallization promoters include compounds that contain units derived from alkylene oxides and have a structure derived from an alcohol compound and a structure derived from a fatty acid.

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

Fatty acids include a wide variety of known fatty acids, with fatty acids having 5 to 30 carbon atoms being preferred. 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.

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

Examples of the above 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 myristylate, and polyoxyethylene sorbitan palmitate. mitate, polyoxyethylene sorbitan linoleate, polyoxyethylene sorbitan 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 myristylate, polyoxyethylene isosorbide palmitate, 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 myristylates, 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, polyoxyethylene mannitan myristylates, polyoxyethylene mannitan palmitate, polyoxyethylene mannitan linoleate, polyoxyethylene mannitan stearate, polyoxyethylene mannitan isostearate, polyoxyethylene mannitan-12 -hydroxystearate, polyoxyethylene mannite oleate, polyoxyethylene mannite eicosanate, polyoxyethylene mannite behenate, polyoxyethylene mannite lignocerate, polyoxyethylene isomannide laurate, polyoxyethylene mannite cocoate, polyoxyethylene mannite myristylates, polyoxyethylene mannite palmitates, polyoxyethylene mannite linoleate, polyoxyethylene mannite stearate, polyoxyethylene mannite isostearate, polyoxyethylene mannite-12-hydroxystearate, polyoxyethylene mannite oleate, polyoxyethylene mannite laurate, polyoxyethylene mannite eicosanate, polyoxyethylene mannite behenate, polyoxyethylene mannite lignocerate, polyoxyethylene xylitol laurate, polyoxyethylene xylitol cocoate, polyoxyethylene xylitol myristylates, 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 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 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 Examples of such hydroxypropyl esters include galactitol oleate, polyoxyethylene galactitol eicosanate, polyoxyethylene galactitol behenate, polyoxyethylene galactitol lignocerate, polyoxyethylene anhydrogalactitol laurate, polyoxyethylene anhydrogalactitol cocoate, polyoxyethylene anhydrogalactitol myristylate, polyoxyethylene anhydrogalactitol palmitate, polyoxyethylene anhydrogalactitol linoleate, polyoxyethylene anhydrogalactitol stearate, polyoxyethylene anhydrogalactitol isostearate, polyoxyethylene anhydrogalactitol-12-hydroxystearate, polyoxyethylene anhydrogalactitol oleate, polyoxyethylene anhydrogalactitol eicosanate, polyoxyethylene anhydrogalactitol behenate, and polyoxyethylene anhydrogalactitol lignocerate.

Another example of a crystallization accelerator is a block polymer of two or more alkylene oxides, such as a block polymer of ethylene oxide and propylene oxide. That is, the crystallization accelerator may be an ethylene oxide and propylene oxide adduct. Another example of a crystallization accelerator is a diester compound of adipic acid and benzyl alcohol/diethylene glycol monomethyl ether.

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

The method for producing the crystallization promoter is not particularly limited. For example, the crystallization promoter can be obtained by a known production method, or it can be obtained as a commercially available product.

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

In the molding resin composition of the present invention, the content of the crystallization accelerator is not particularly limited. For example, per 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. Furthermore, 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.

(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.

There are no particular limitations on the type of fatty acid amide, as long as it is an amide compound formed from a fatty acid and an amine compound. For example, a wide variety of known fatty amides can be used in the present invention. For example, fatty acid amides can include fatty acid amides having 8 to 24 carbon atoms. Of these, preferred examples include bisamide compounds obtained by reacting a fatty acid amide having 8 to 24 carbon atoms with a compound having two amino groups.

The fatty acid amide may be a compound having a hydroxyl group or a compound not having a hydroxyl group.

Examples of fatty acid amides without hydroxyl groups 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, as well as 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 amide, m-xylylenebisstearic acid amide, ethylenebisarachidic acid amide, butylenebisarachidic acid amide, hexamethylenebisarachidic acid amide, m-xylylenebisarachidic acid amide, ethylenebisbehenic acid amide, butylenebisbehenic acid amide, hexamethylenebisbehenic acid amide, m-xylylenebisbehenic acid amide, ethylenebislignoceric acid amide, butylenebisoleic acid amide, hexamethylenebislignoceric acid amide, m-xylylenebislignoceric acid Examples of suitable amides include 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.

Examples of fatty acid amides having a hydroxyl group include hydroxyl group-containing fatty acid monoamides such as 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, and 2-hydroxyarachidonic acid amide; 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, and N,N'-ethylenebis-10-hydroxylauric acid. acid amide, N,N'-butylenebis-10-hydroxylauric acid amide, N,N'-hexamethylenebis-10-hydroxylauric acid amide, N,N'-m-xylylenebis-10-hydroxylauric acid amide, N,N'-ethylenebis-11-hydroxymyristic acid amide, N,N'-butylenebis-11-hydroxymyristic acid amide, N,N'-hexamethylenebis-11-hydroxymyristic acid amide, N,N'-m-xylylenebis 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'-hexamethylenebis-2-hydroxyarachidic acid amide, N,N'-m-xylylenebis-2-hydroxyarachidic acid amide, N,N'-ethylenebis-2-hydroxybenzamide lignoceramide, N,N'-butylenebis-2-hydroxybehenamide, N,N'-hexamethylenebis-2-hydroxybehenamide, N,N'-m-xylylenebis-2-hydroxybehenamide, N,N'-ethylenebis-2-hydroxylignoceramide, N,N'-butylenebis-2-hydroxylignoceramide, N,N'-hexamethylenebis-2-hydroxylignoceramide, N,N'-m-xylylenebis-2-hydroxybehenamide Hydroxylignoceric acid amide, N,N'-ethylene bis-12-hydroxyoleic acid amide, N,N'-butylene bis-12-hydroxyoleic acid amide, N,N'-hexamethylene bis-12-hydroxyoleic acid amide, N,N'-m-xylylene bis-12-hydroxyoleic acid amide, N,N'-ethylene bis-11-hydroxylinoleic acid amide, N,N'-butylene bis-11-hydroxylinoleic acid amide, N,N'-hexamethylene bis-12-hydroxyoleic acid amide Examples include hydroxyl group-containing fatty acid bisamides such as methylene bis-11-hydroxylinoleic acid amide, N,N'-m-xylylene bis-11-hydroxylinoleic acid amide, N,N'-ethylene bis-11-hydroxyarachidonic acid amide, N,N'-butylene bis-11-hydroxyarachidonic acid amide, N,N'-hexamethylene bis-11-hydroxyarachidonic acid amide, and N,N'-m-xylylene bis-11-hydroxyarachidonic acid amide.

The method for producing fatty acid amides is not particularly limited. For example, fatty acid amides can be obtained by known production methods, or they can be obtained as commercially available products.

The molding resin composition of the present invention may contain one or more fatty acid amides.

In the molding resin composition of the present invention, the content of fatty acid amide is not particularly limited. For example, per 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. Furthermore, the content of the 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.

(Resin composition for molding)
The molding resin composition of the present invention contains 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.

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 solely 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 solely of the PHA, crystallization accelerator, and fatty acid amide.

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

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-processed 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. 140 to 200°C is more preferred, 150 to 195°C is even more preferred, and 160 to 190°C is particularly preferred, as this tends to suppress thermal decomposition while achieving good dispersibility. There are no particular limitations on the melt-processing method, and an extruder, Banbury mixer, kneader, heated roll, etc. can be used.

The form of the molding resin composition of the present invention is not particularly limited, and may be in various forms, such as powder, pellets, granules, liquid, paste, solution, dispersion, etc.

The molding resin composition of the present invention can be molded into a desired shape. There are no particular limitations on the molding method, and for example, a wide range of known molding methods can be used in the present invention. 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 fibers by a spinning process. There are also no particular limitations on the spinning process (spinning treatment), and for example, a wide range of known spinning conditions can be used in the present invention.

The type of molded article obtained from the molding resin composition of the present invention is not particularly limited, and examples include fibers, sheets, blocks, films, rods, etc., and these molded articles can also be further processed into desired shapes.

The molded article is obtained using the molding resin composition of the present invention, and, for example, crystallization of the PHA is easily promoted during molding. This shortens the molding cycle, i.e., results in excellent moldability and increases manufacturing efficiency.

When the molding resin composition of the present invention is spun into fibers, thread breakage during the spinning process is less likely to occur. Therefore, the molding resin composition of the present invention is suitable for spinning.

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

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

When specifying the inventions encompassed by this disclosure, the components (properties, structures, functions, etc.) described in each embodiment of this disclosure may be combined in any way. In other words, this disclosure encompasses all subject matter consisting of any and all combinations of the components that can be combined as described herein.

The present invention will be explained in more detail below using examples, but the present invention is not limited to these examples.

Appropriate raw materials were selected from the raw materials listed below to prepare a molding resin composition.

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

(Crystallization promoter)
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 ("EMALEX RWIS-320" (registered trademark) from Nippon Emulsion Co., Ltd.)
Crystallization accelerator 5: polyoxyethylene glyceryl monostearate ("EMALEX GM-20" (registered trademark) from Nippon Emulsion Co., Ltd.)
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)

(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 ("EBA" manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Fatty acid amide 3: N,N'-ethylenebis-12-hydroxystearylamide (ITOHWAX J-530, manufactured by Ito Oil Mills, Ltd.)

(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.)

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

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.

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.

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.

(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.

(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.

(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.

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.

(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.

(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.

(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.

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.

(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.

(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.

The crystallinity, prevention performance, and kneading performance of the molding resin compositions obtained in each example and comparative example were evaluated using the following methods.

(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 based on the values of the crystallization enthalpy (ΔHc) and melting enthalpy (ΔHm) during the second heating in DSC, using the following formula: 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.

(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 having 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 yarn breakage occurs, no sticking to the suction gun, and excellent spinning performance.
B: Yarn breakage occurs and spinning is not possible, or the yarn sticks to the suction gun.

(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. Based on the extrusion amount, the kneading performance was evaluated according to 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 amount of discharge was approximately 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.

Tables 1 to 11 show the formulations and evaluation results of the molding resin compositions obtained in each example and comparative example. Note that in Tables 1 to 11, blank cells indicate that the corresponding raw material was not used.

From each table, it can be seen that molding resin compositions containing PHA (PHB, PHBV, or PHBH) and a specified crystallization accelerator tended to promote PHA crystallization and had excellent moldability, specifically, excellent spinnability. Furthermore, molding resin compositions containing fatty acid amides made it easier to extrude the melt-kneaded PHA, and in this respect also had excellent moldability. From the above, it was demonstrated that the molding resin compositions obtained in the examples shorten the molding cycle.

Claims (8)

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. The polyhydroxyalkanoate (excluding polylactic acid) is -CHRCH ₂ 2. The molding resin composition according to claim 1, which has a structural unit represented by COO-- (R is a hydrocarbon group having 20 or less carbon atoms). The molding resin composition according to claim 1, wherein the alkylene oxide-derived units are at least one selected from the group consisting of ethylene oxide-derived units and propylene oxide-derived units. The molding resin composition according to claim 3 , wherein the crystallization accelerator is a compound having a unit derived from ethylene oxide. The molding resin composition according to claim 3 , wherein the crystallization accelerator is a compound having a unit derived from propylene oxide. 4. The molding resin composition according to claim 3 , wherein the crystallization accelerator is an ethylene oxide and propylene oxide adduct. The molding resin composition according to claim 1, which is for spinning. A molded article made from the molding resin composition according to any one of claims 1 to 7 .