JP2022142501A - Aliphatic-aromatic polyester composition and method for producing aliphatic-aromatic polyester composition - Google Patents

Abstract

To provide an aliphatic-aromatic polyester composition having a high degree of crystallinity by improving deficiency of crystallization of conventional aliphatic-aromatic polyester.SOLUTION: Provided is an aliphatic-aromatic polyester composition comprising aliphatic-aromatic polyester and a nucleating agent. The aliphatic-aromatic polyester has an aliphatic diol unit, an aliphatic dicarboxylic acid unit, and an aromatic dicarboxylic acid unit. The nucleating agent comprises one or more compounds selected from the group consisting of fatty acid metal salts, phosphates, aromatic phosphonates, polyhydric alcohols, fatty amides, and copolymers of olefins and maleic acid. The composition comprises 0.01 to 100 pts.mass of the nucleating agent relative to 100 pts.mass of the aliphatic-aromatic polyester.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to an aliphatic-aromatic polyester composition containing an aliphatic-aromatic polyester and a specific nucleating agent, and a method for producing the same.

Various materials such as paper, plastic, aluminum foil, etc. are used for various applications such as packaging materials for various foods, medicines, miscellaneous liquids, powders, and solids, agricultural materials, and construction materials. . Among them, plastics are excellent in terms of strength, water resistance, moldability, transparency, cost, etc., and are therefore used in various applications such as bags and containers. Currently, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyethylene terephthalate, etc. are used for these applications. However, since these plastic products are difficult to decompose in the natural environment, they may remain in the ground when buried after use, or spoil the landscape when discarded. Moreover, even if it is incinerated, there are problems such as generation of harmful gas and damage to the incinerator.

Biodegradable resins are attracting attention as eco-friendly plastics that solve these problems. Films made of biodegradable resins are decomposed after use, and therefore can prevent global warming and environmental pollution. Therefore, in recent years, biodegradable resin films have been used for garbage bags, shopping bags, and the like.

As biodegradable resins, for example, aliphatic-aromatic polyesters such as polybutylene succinate terephthalate (PBST) and polybutylene succinate furanoate (PBSF) have been proposed. Aliphatic-aromatic polyesters can be produced by polycondensation reaction via esterification reaction and/or transesterification reaction (see Patent Document 1).

However, in general, copolymers including copolyesters tend to be inferior in crystallinity to corresponding homopolymers because they contain copolymer components in the main chain. Especially when polybutylene succinate (PBS) is copolymerized with a furandicarboxylic acid component as an aromatic dicarboxylic acid component, furandicarboxylic acid tends to have a greater effect on the thermophysical properties of the resin than terephthalic acid. It is known that the degree of crystallinity is greatly reduced only by polymerization (Non-Patent Document 1).

JP-A-2008-31457

N. Jacquel et al., Polymer 2015, 59, 234-242. “Bio-based alternatives in the synthesis of aliphatic-aromatic polyesters dedicated to biodegradable film applications.”

When the present inventors produced PBST by the method described in Patent Document 1, it was found that the polyester pellets were blocked due to insufficient crystallization of the obtained polyester. For this reason, even if PBST is used as a film or a molded product such as an inflation-molded bag, there is a concern that problems such as difficulty in cutting due to fusion between films and insufficient opening of the bag may occur. . It has also been found that increasing the crystallization time can result in a lengthy cooling process for the hot polymer, which can be a costly and inefficient process. Furthermore, it was expected that these problems would become more serious, particularly with PBSF in which furandicarboxylic acid is copolymerized with PBS.

In order to solve the problems of the prior art, the present invention aims to improve the lack of crystallization of conventional aliphatic-aromatic polyesters and to provide an aliphatic-aromatic polyester composition with a high degree of crystallinity and a method for producing the same. Make it an issue. Another object of the present invention is to provide a PBSF composition having excellent productivity and moldability, and a method for producing the same, even for PBSF, which has a particularly slow crystallization rate.

The present inventors have made intensive studies to solve the above problems. As a result, it was found that insufficient crystallization could be improved and the above problems could be solved by making an aliphatic-aromatic polyester composition containing an aliphatic-aromatic polyester such as PBSF and a specific nucleating agent, and the present invention was completed. let me
That is, the gist of the present invention resides in the following [1] to [7].

[1] An aliphatic-aromatic polyester composition containing an aliphatic-aromatic polyester and a nucleating agent, wherein the aliphatic-aromatic polyester has an aliphatic diol unit, an aliphatic dicarboxylic acid unit and an aromatic dicarboxylic acid unit and the nucleating agent is one or more selected from the group consisting of fatty acid metal salts, phosphates, aromatic phosphonates, polyhydric alcohols, fatty acid amides, and copolymers of olefins and maleic acid. An aliphatic-aromatic polyester composition containing 0.01 to 100 parts by mass of the nucleating agent based on 100 parts by mass of the aliphatic-aromatic polyester.

[2] The aliphatic-aromatic polyester composition according to [1], wherein the molar ratio of the aliphatic dicarboxylic acid unit to the aromatic dicarboxylic acid unit in the aliphatic-aromatic polyester is 20:80 to 80:20. thing.

[3] The aliphatic-aromatic polyester composition according to [1] or [2], wherein the aliphatic-aromatic polyester is polybutylene succinate furanoate.

[4] the nucleating agent is sodium montanate, magnesium stearate, aluminum=bis(4,4′,6,6′-tetra-tert-butyl-2,2′-methylenediphenyl=phosphate)=hydroxide; One or more selected from the group consisting of calcium phosphate, pentaerythritol, hexamethylenebishydroxystearate amide, ethylenebishydroxystearate amide, zinc phenylphosphonate, and copolymers of α-olefins and maleic anhydride The aliphatic-aromatic polyester composition according to any one of [1] to [3], comprising a compound.

[5] A method for producing an aliphatic-aromatic polyester and an aliphatic-aromatic polyester composition containing a nucleating agent, comprising esterifying an aliphatic diol component with an aliphatic dicarboxylic acid component and an aromatic dicarboxylic acid component, or esterifying a step of conducting an exchange reaction followed by a polycondensation reaction; and a step of adding a nucleating agent to the resulting molten resin, wherein the nucleating agent is a fatty acid metal salt, a phosphate, an aromatic phosphonate, A method for producing an aliphatic-aromatic polyester composition comprising one or more compounds selected from the group consisting of polyhydric alcohols, fatty acid amides, and copolymers of olefins and maleic acid.

[6] A method for producing an aliphatic-aromatic polyester composition containing an aliphatic-aromatic polyester and a nucleating agent, wherein the aliphatic-aromatic polyester comprises an aliphatic diol unit, an aliphatic dicarboxylic acid unit and an aromatic dicarboxylic acid from the group consisting of fatty acid metal salts, phosphates, aromatic phosphonates, polyhydric alcohols, fatty acid amides, and copolymers of olefins and maleic acid in the molten aliphatic-aromatic polyester having units; A method for producing an aliphatic-aromatic polyester composition, comprising a step of kneading one or more selected compounds.

[7] A method for producing an aliphatic-aromatic polyester composition according to [5] or [6], further comprising a step of melt-kneading a resin other than the aliphatic-aromatic polyester. A method of making the composition.

According to the present invention, by allowing a specific nucleating agent to exist in an aliphatic-aromatic polyester such as PBSF, the lack of crystallization can be improved, and the problem of blocking between resin pellets and fusion between films can be eliminated. Aromatic polyester compositions can be produced and are expected to be used to provide high quality molded articles.

BEST MODE FOR CARRYING OUT THE INVENTION Below, embodiments of the present invention will be described in detail. The description of the constituent elements described below is an example (representative example) of embodiments of the present invention, and the present invention is not limited to these contents unless it exceeds the gist thereof.

In the present invention, the term "dicarboxylic acid component" refers to a compound that serves as a raw material for polyester, such as dicarboxylic acid and dicarboxylic acid derivatives such as dicarboxylic acid alkyl esters. In the present invention, the "diol component" refers to a diol compound that is used as a raw material for polyester.
In the present invention, the "dicarboxylic acid unit" refers to a structural unit of an aliphatic aromatic polyester derived from a polyester raw material such as dicarboxylic acid and dicarboxylic acid derivatives such as dicarboxylic acid alkyl esters. In the present invention, the "diol unit" refers to a structural unit of an aliphatic-aromatic polyester derived from a diol component that is a polyester raw material.
In the present invention, the “aromatic dicarboxylic acid” may be any dicarboxylic acid having aromaticity, and includes “heteroaromatic dicarboxylic acid”.
In the present invention, the nucleating agent includes those capable of becoming crystal nuclei and so-called crystallization accelerators.

[Aliphatic-aromatic polyester composition]
The aliphatic-aromatic polyester composition of the present invention comprises an aliphatic-aromatic polyester (hereinafter sometimes referred to as "aliphatic-aromatic polyester according to the present invention" or simply "aliphatic-aromatic polyester") and a nucleating agent. (Hereinafter, it may be referred to as "nucleating agent according to the present invention" or simply "nucleating agent".). The aliphatic-aromatic polyester of the present invention has aliphatic diol units, aliphatic dicarboxylic acid units and aromatic dicarboxylic acid units.

Nucleating agents contained in the aliphatic-aromatic polyester composition of the present invention include fatty acid metal salts, phosphates, aromatic phosphonates, polyhydric alcohols, fatty acid amides, and copolymers of olefins and maleic acid. is a compound of any one of The total amount of the nucleating agent contained in the aliphatic-aromatic polyester composition of the present invention is 0.01 to 100 parts by weight per 100 parts by weight of the aliphatic-aromatic polyester.

[Aliphatic-aromatic polyester]
<Diol unit>
The aliphatic diol units of the aliphatic-aromatic polyester according to the present invention are not particularly limited, and have units derived from diol compounds that are commonly used as starting materials for polyesters.
Specific examples of aliphatic diol units include units derived from the following diol compounds.
That is, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8 - alkylene diols such as octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, neopentyl glycol; diethylene glycol, oxyalkylene diols such as polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol; Examples include units derived from aliphatic diol compounds such as alkylene diols.
The number of carbon atoms in the aliphatic diol compound is preferably 2 to 13, more preferably 4 or more, more preferably 10 or less, still more preferably 6 or less, and particularly preferably 4.

As the aliphatic diol compound, from the viewpoint of the physical properties of the aliphatic aromatic polyester, alkylene diols and cycloalkylene diols are preferable, alkylene diols and cycloalkylene diols having 10 or less carbon atoms are more preferable, and alkylene diols having 6 or less carbon atoms and Cycloalkylenediols are more preferred, and 1,4-butanediol is particularly preferred.

The aliphatic-aromatic polyester according to the present invention may have only one type of aliphatic diol unit, or may have two or more types.

In the aliphatic-aromatic polyester according to the present invention, the total amount (molar ratio) of aliphatic diol units is preferably the highest among all diol units, and 50 mol% or more of all diol units are aliphatic diol units. This ratio is more preferably 60 mol % or more, particularly preferably 70 mol % or more, and most preferably 90 mol % or more. The upper limit of the proportion of the aliphatic diol in the diol units is 100 mol %.

When having a 1,4-butanediol unit as an aliphatic diol unit, the ratio of the 1,4-butanediol unit is the melting point (heat resistance) of the aliphatic aromatic polyester, biodegradability, from the viewpoint of mechanical properties. It is preferably 50 mol % or more, more preferably 60 mol % or more, even more preferably 70 mol % or more, particularly preferably 90 mol % or more, relative to the group diol units. The upper limit of this ratio is 100 mol %.

Of the aliphatic diol units, ethylene glycol units, 1,3-propanediol units and 1,4-butanediol units are preferably units derived from biomass (plant raw materials) from the viewpoint of reducing environmental load.

<Dicarboxylic acid unit>
Aliphatic dicarboxylic acid units and aromatic dicarboxylic acid units possessed by the aliphatic-aromatic polyester according to the present invention are not particularly limited, and units derived from aliphatic dicarboxylic acid compounds that are usually used as raw materials for polyesters and aromatic dicarboxylic acid compounds It has units of origin.

The dicarboxylic acid unit is preferably a biomass (plant raw material)-derived unit, and more preferably a biomass (plant raw material)-derived unit, from the viewpoint of reducing the environmental load. As dicarboxylic acid units derived from biomass (plant raw materials), units derived from succinic acid, succinic anhydride, adipic acid, sebacic acid and the like are particularly preferred.

Specific examples of aliphatic dicarboxylic acid units include units derived from dicarboxylic acid compounds such as the following dicarboxylic acids and alkyl esters of dicarboxylic acids. Thus, for example, aliphatic acids such as oxalic acid, malonic acid, succinic acid, succinic anhydride, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecadicarboxylic acid, dodecadicarboxylic acid, dimer acid, etc. A unit derived from dicarboxylic acid and the like are included. Among these, units derived from aliphatic dicarboxylic acids such as succinic acid, succinic anhydride, adipic acid and sebacic acid or derivatives thereof such as alkyl esters are preferred from the viewpoint of the physical properties of the aliphatic aromatic polyester.

Main chain carbon number constituting the aliphatic dicarboxylic acid unit is preferably 2 to 50, the upper limit is more preferably 18 or less, more preferably 13 or less, even more preferably 10 or less, particularly preferably 9 or less, 8 The following are particularly preferred. On the other hand, the lower limit of the number of main chain carbon atoms constituting the aliphatic dicarboxylic acid unit is more preferably 3 or more. The number of carbon atoms is most preferably 4. In particular, succinic acid is most preferable as the aliphatic dicarboxylic acid because it tends to increase the crystallinity of the aliphatic-aromatic polyester.

The aliphatic-aromatic polyester according to the present invention may have only one type of aliphatic dicarboxylic acid unit, or may have two or more types.

When the aliphatic dicarboxylic acid unit is a succinic acid unit, the ratio of the succinic acid unit to the total aliphatic dicarboxylic acid unit from the viewpoint of the melting point (heat resistance), biodegradability, and mechanical properties of the aliphatic aromatic polyester is preferably 50 mol % or more, more preferably 70 mol % or more, and even more preferably 90 mol % or more. In addition, this upper limit is 100 mol%.

Specific examples of aromatic dicarboxylic acid units include units derived from dicarboxylic acid compounds such as the following dicarboxylic acids and alkyl esters of dicarboxylic acids. That is, for example, dicarboxylic acid units derived from terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, furandicarboxylic acid, derivatives thereof such as alkyl esters, and the like can be mentioned. Terephthalic acid, isophthalic acid, and furandicarboxylic acid are preferable, and terephthalic acid and furandicarboxylic acid are particularly preferable, from the viewpoint of physical properties of the aliphatic-aromatic polyester.

The aliphatic-aromatic polyester according to the present invention may have only one type of aromatic dicarboxylic acid unit, or may have two or more types.

The aromatic dicarboxylic acid unit is preferably a unit derived from biomass (plant raw material)-derived dicarboxylic acid, and particularly preferably a unit derived from biomass-derived furandicarboxylic acid or terephthalic acid.

When the aromatic dicarboxylic acid unit is a furandicarboxylic acid unit, the ratio of the furandicarboxylic acid unit is the highest among all aromatic dicarboxylic acid units from the viewpoint of the melting point (heat resistance) and mechanical properties of the aliphatic aromatic polyester. more preferably 50 mol % or more, still more preferably 60 mol % or more, particularly preferably 80 mol % or more, based on the total aromatic dicarboxylic acid units. In addition, this upper limit is 100 mol%.

PBSF is preferable because it is easy to achieve a high bio-degree. However, PBSF has a slow crystallization rate. Therefore, PBSF is particularly preferable for the aliphatic-aromatic polyester according to the present invention in that the effect of promoting crystallization by the nucleating agent is easily exhibited.

The molar ratio of the aliphatic dicarboxylic acid unit to the aromatic dicarboxylic acid unit in the dicarboxylic acid unit of the aliphatic-aromatic polyester according to the present invention is the heat resistance, biodegradability, mechanical properties, and moldability of the aliphatic-aromatic polyester. From the viewpoint of, aliphatic dicarboxylic acid unit: aromatic dicarboxylic acid unit = preferably 20: 80 to 80: 20, more preferably 30: 70 to 70: 30, 30: 70 to 60: 40 more preferably 40:60 to 60:40, particularly preferably 50:50 to 60:40.

<Other copolymer units>
The aliphatic-aromatic polyester according to the present invention may have constitutional units other than the aliphatic diol unit, the aliphatic dicarboxylic acid unit and the aromatic dicarboxylic acid unit. Such other copolymerized units include lactic acid, glycolic acid, hydroxybutyric acid, hydroxycaproic acid, 2-hydroxy-3,3-dimethylbutyric acid, 2-hydroxy-3-methylbutyric acid, 2-hydroxyisocaproic acid, Oxycarboxylic acids such as malic acid, maleic acid, citric acid, and fumaric acid, esters and lactones of these oxycarboxylic acids, oxycarboxylic acid polymers, etc., or tri- or more functional polycarboxylic acids such as glycerin, trimethylolpropane, and pentaerythritol. Units derived from tri- or more functional polyvalent carboxylic acids such as hydric alcohols, propanetricarboxylic acid, pyromellitic acid, benzophenonetetracarboxylic trimellitic acid, and anhydrides thereof, and the like, and the like.

Among these, the presence of a small amount of units derived from a tri- or more functional oxycarboxylic acid, a tri- or more functional alcohol, a tri- or more functional carboxylic acid, etc. tends to increase the viscosity of the polyester. Among them, units derived from oxycarboxylic acids such as malic acid, citric acid and fumaric acid or polyhydric alcohols such as glycerin, trimethylolpropane and pentaerythritol are preferable, and units derived from trimethylolpropane are particularly preferable.

When the aliphatic-aromatic polyester according to the present invention has units derived from a trifunctional or higher polyfunctional compound, the proportion tends to increase the viscosity of the aliphatic-aromatic polyester when it is large, and on the other hand, when it is small, the fat Gel (unmelted matter) is less likely to form in the aromatic polyester. Therefore, the ratio of units derived from tri- or higher polyfunctional compounds is preferably 0.001 to 5 mol%, preferably 0.05 to 0.5 mol%, relative to the total dicarboxylic acid units. more preferred.

<Intrinsic viscosity of aliphatic-aromatic polyester>
When the intrinsic viscosity (IV) of the aliphatic-aromatic polyester of the present invention is high, it is easy to obtain a molded article with high mechanical strength, and when it is low, the melt viscosity is low and molding is easy. The intrinsic viscosity of the aliphatic-aromatic polyester of the present invention is preferably 1.0 dL/g or more, more preferably 1.2 dL/g or more. On the other hand, it is preferably 2.5 dL/g or less, more preferably 2.2 dL/g or less, and even more preferably 2.0 dL/g or less. In addition, the intrinsic viscosity is measured by the method used in Examples described later.

[Nucleating agent]
The aliphatic-aromatic polyester composition of the present invention comprises at least one nucleus selected from fatty acid metal salts, phosphates, aromatic phosphonates, polyhydric alcohols, fatty acid amides, and copolymers of olefins and maleic acid. containing agents.

Fatty acid metal salts include lithium stearate, barium stearate, zinc stearate, sodium stearate, calcium stearate, magnesium stearate, aluminum stearate, calcium 12-hydroxystearate, zinc 12-hydroxystearate, 12-hydroxystearate. magnesium montanate, aluminum 12-hydroxystearate, barium 12-hydroxystearate, lithium 12-hydroxystearate, sodium 12-hydroxystearate, sodium montanate, calcium montanate, lithium montanate, zinc montanate, magnesium montanate , Aluminum Montanate, Calcium Laurate, Barium Laurate, Zinc Laurate, Lithium Laurate, Sodium Laurate Calcium Ricinoleate, Barium Ricinoleate, Zinc Ricinoleate, Potassium Caprylate, Sodium Caprylate, Calcium Caprylate, Magnesium Caprylate , aluminum octylate, zinc myristate, zinc palmitate, dimethyl sodium sulfoisophthalate, and the like.
Among these fatty acid metal salts, 12-hydroxystearate, stearate and montanate are preferred, and magnesium stearate and sodium montanate are particularly preferred, from the viewpoint of high fat solubility and easy compatibility with polyester.

Phosphates include sodium phosphate, potassium phosphate, calcium phosphate, magnesium phosphate, zinc phosphate, aluminum phosphate, iron phosphate, ammonium phosphate and the like. Among these, sodium phosphate and calcium phosphate are preferred.
Aromatic phosphonates include zinc phenylphosphonate, 2-hydroxy-2-oxo-4,6,10,12-tetra-tert-butyl-1,3,2-dibenzo[d,g]perhydrodi Compositions containing the Na salt of oxaphosphalosine, aluminum = bis(4,4',6,6'-tetra-tert-butyl-2,2'-methylenediphenyl = phosphate) = hydroxide, and the like.

Polyhydric alcohols include trimethylolpropane, inositol and pentaerythritol. Among these, pentaerythritol is preferred.
The polyhydric alcohol used as the nucleating agent is already produced and added to the aliphatic aromatic polyester, and the polyhydric alcohol contained as polyhydric alcohol units in the aliphatic aromatic polyester as the above-mentioned copolymerization component. It is clearly distinguished from the hydric alcohol.

Examples of fatty acid amides include N-stearyloleic acid amide, N-stearyl erucic acid amide, N-oleyl stearic acid amide, lauric acid amide, N-stearyl stearic acid amide, palmitic acid amide, stearic acid amide, hydroxystearic acid amide, N-methylolstearic acid amide, hexamethylenebisoleic acid amide, N,N'-dioleyladipic acid amide, ethylenebisoleic acid amide, ethylenebiserucic acid amide, hexamethylenebishydroxystearic acid amide, hexamethylenebisstearic acid Amide, N,N'-distearyladipamide, methylenebisstearic acid amide, hexamethylenebisbehenic acid amide, ethylenebisstearic acid amide, ethylenebishydroxystearic acid amide, ethylenebislauric acid amide, ethylenebiscapric acid amide , erucamide and the like. Among these, N-oleylstearic acid amide, hydroxystearic acid amide, hexamethylenebishydroxystearic acid amide, ethylenebishydroxystearic acid amide, and erucic acid amide are preferred, and hexamethylenebishydroxystearic acid amide is particularly preferred. , ethylene bishydroxystearic acid amide.

Copolymers of olefins and maleic acid include copolymers of olefins and maleic anhydride, copolymers of styrene and maleic anhydride, and the like. A copolymer of olefin and maleic anhydride is preferred.
From the point of view of safety, nucleating agents are listed as compounds on the positive list of food utensils, containers and packaging based on the Food Sanitation Law, and are classified as food additives in the Food Additive Petition of the US Food and Drug Administration. Compounds approved as food contact materials and products certified by the European Regulation (EC) No. 1935/2004 are preferred. That is, fatty acid metal salts, sodium phosphate, potassium phosphate, calcium phosphate, magnesium phosphate, aluminum phosphate, iron phosphate, ammonium phosphate, pentaerythritol and hexamethylenebishydroxystearic acid amide are highly safe, preferable.

The aliphatic-aromatic polyester composition of the present invention may contain only one of these nucleating agents, or may contain two or more.

The amount of the nucleating agent contained in the aliphatic-aromatic polyester composition of the present invention is preferably large in that the aliphatic-aromatic polyester is likely to be crystallized, but on the other hand, the nucleating agent is dispersed. From the point of view of ease of Therefore, the aliphatic-aromatic polyester composition of the present invention contains a total of 0.01 to 100 parts by mass of a nucleating agent per 100 parts by mass of the aliphatic-aromatic polyester. The content of the nucleating agent is preferably 0.01 to 25 parts by mass, more preferably 0.01 to 10 parts by mass, even more preferably 0.01 to 1 part by mass, particularly preferably 0.01 to 10 parts by mass. 02 to 0.5 parts by mass, most preferably 0.05 to 0.3 parts by mass.

<Other ingredients>
The aliphatic-aromatic polyester composition of the present invention may contain, in addition to the aliphatic-aromatic polyester and the nucleating agent, an aliphatic polyester, an aliphatic oxycarboxylic acid-based polyester, and the like. Furthermore, carbodiimide compounds, fillers, plasticizers, biodegradable resins other than those mentioned above, such as polycaprolactone, polyamide, polyvinyl alcohol, cellulose ester, etc., starch, cellulose, paper, wood flour, chitin/chitosan, coconut It may contain fine powders of animal/plant material such as shell powder, walnut shell powder, or mixtures thereof. In addition, it contains heat stabilizers, plasticizers, lubricants, antiblocking agents, nucleating agents other than the above nucleating agents, inorganic fillers, coloring agents, pigments, ultraviolet absorbers, light stabilizers, modifiers, cross-linking agents, etc. may be

[Physical properties of the aliphatic-aromatic polyester composition]
<Melting enthalpy ratio>
The effect of promoting crystallization by containing a specific nucleating agent in the aliphatic-aromatic polyester composition of the present invention can be evaluated by the melting enthalpy ratio compared with a composition produced without using a nucleating agent. . That is, it can be seen that crystallization is sufficiently promoted due to the high melting enthalpy ratio. The melting enthalpy ratio of the aliphatic-aromatic polyester composition of the present invention is preferably 1.2 or more, more preferably 2 or more, further preferably 2.5 or more, and 3 or more. is particularly preferred, 5 or more is particularly preferred, and 7 or more is most preferred. There is no particular upper limit for the melting enthalpy ratio.
In the present invention, the melting enthalpy can be measured by the method described in Examples below.

[Method for producing an aliphatic-aromatic polyester composition]
The aliphatic-aromatic polyester composition containing the aliphatic-aromatic polyester of the present invention and a nucleating agent is polycondensed after subjecting a diol component and a dicarboxylic acid component, which are raw materials of the aliphatic-aromatic polyester, to an esterification or transesterification reaction. It has a step of reacting and a step of adding a nucleating agent to the resulting molten resin. Moreover, it has a step of adding the above-described nucleating agent according to the present invention during the production of this polyester or to the polyester produced by this method.

The step of subjecting the diol component and the dicarboxylic acid component to an esterification or transesterification reaction, followed by a polycondensation reaction can be carried out by a known polyester production method. Moreover, the reaction between the diol component and the dicarboxylic acid component is preferably an esterification reaction because alcohol is not by-produced and the safety is high.

The diol component and dicarboxylic acid component that are raw materials are preferably compounds that form the above-described diol units and dicarboxylic acid units. Additives and the like used in polyester production are the same as other components that may be contained in the above-mentioned aliphatic-aromatic polyester.

The method for producing the aliphatic-aromatic polyester composition of the present invention (hereinafter sometimes referred to as "the method for producing the aliphatic-aromatic polyester composition of the present invention" or "the method for producing the polyester composition of the present invention"). ), the nucleating agent may be added during the production of the polyester, or the nucleating agent may be added to the produced polyester.

The method of adding the nucleating agent to the polyester is not particularly limited, and whether the nucleating agent is present in the esterification or transesterification reaction system or in the polycondensation reaction system, the nucleating agent may be added in a molten state by an extruder. It may be mixed with the resin. Addition of the nucleating agent to the polyester is preferably carried out by kneading the nucleating agent with the aliphatic aromatic polyester in a molten state. It is preferable to have a step of kneading the nucleating agent with the aliphatic-aromatic polyester.

When adding a nucleating agent to a molten aliphatic-aromatic polyester using an extruder, a kneader such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a roll mixer, a Brabender plastograph, or a kneader blender is used. A method of mixing by kneading may be mentioned. The nucleating agent may be added at once or may be added to the resin in two or more portions.

Further, the aliphatic-aromatic polyester composition of the present invention may be melt-kneaded with a resin other than the aliphatic-aromatic polyester of the present invention. That is, the method for producing the aliphatic-aromatic polyester composition of the present invention may further include a step of melt-kneading a resin other than the aliphatic-aromatic polyester of the present invention.

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

Methods for measuring physical properties and evaluation items employed in the following examples are as follows.

<Intrinsic viscosity (IV) (dL/g)>
Using an Ubbelohde viscometer, it was determined in the following manner. Using a mixed solvent of phenol / tetrachloroethane (mass ratio 1/1), at 30 ° C., the polyester composition solution with a concentration of 0.5 g / dL and the number of seconds for the solvent alone were measured, and the following formula (1) Intrinsic viscosity was obtained.
IV=((1+4K _H η _SP ) ^0.5 −1)/(2K _H C) (1)
However, η _SP = η/η ₀ −1, where η is the number of seconds the sample solution falls, η ₀ is the number of seconds the solvent falls, C is the concentration of the sample solution (g/dL), and K _H is Huggins constant. is. _KH adopted 0.33.

<Melting enthalpy ratio>
Measurement was performed using DSC7020 (manufactured by Hitachi High-Tech Science), after the temperature was raised from room temperature (25 ° C.) to 200 ° C. at a rate of 10 ° C./min, from 200 ° C. to -50 ° C. at a rate of 10 ° C./min. and then heated from -50°C to 200°C at a rate of 10°C/min.
DSC measurements were performed by this method on the aliphatic-aromatic polyester composition and the polyester from which the nucleating agent was removed. Here, the area of the endothermic peak corresponding to the melting of the sample resin in the second heating process is defined as the melting enthalpy (ΔHm and ΔHm ₀ , respectively). At this time, the value obtained by dividing ΔHm by ΔHm ₀ (ΔHm/ΔHm ₀ ) was defined as the melting enthalpy ratio and used for evaluation.

[Example]
Compositions were prepared using the following nucleating agents and PBSF. Both the nucleating agent and PBSF were dried at 60° C. for 15 hours using a vacuum dryer “DP33” manufactured by Yamato Scientific Co., Ltd. and used.

<Nucleating agent>
In the examples, the following nucleating agents N-1 to N-9 were used.
N-1: sodium montanate "NS-8" manufactured by Nitto Kasei Kogyo Co., Ltd.
N-2: Magnesium stearate manufactured by Tokyo Kasei Kogyo Co., Ltd. N-3: Aluminum = bis (4,4',6,6'-tetra-tert-butyl-2,2'- manufactured by ADEKA Co., Ltd.) methylene diphenyl phosphate) = mixture of hydroxide and organic compound "NA-21"
N-4: Calcium phosphate manufactured by Fujifilm Wako Pure Chemical Co., Ltd. N-5: Pentaerythritol manufactured by Tokyo Chemical Industry Co., Ltd. N-6: Hexamethylene bishydroxystearate amide manufactured by Mitsubishi Chemical Corporation "Sripax ZHH"
N-7: Ethylenebishydroxystearate amide "Slipax H" manufactured by Mitsubishi Chemical Corporation
N-8: Copolymer of α-olefin and maleic anhydride manufactured by Mitsubishi Chemical Corporation "Diacarna 30"
N-9: Zinc phenylphosphonate "Eco Promote" manufactured by Nissan Chemical Industries, Ltd.
In Comparative Examples 2 and 3, the following nucleating agents n-1 to n-2 were used.
n-1: Talc (hydrous magnesium silicate (Mg ₃ Si ₄ O ₁₀ (OH) ₂ )) “Nano Ace D600” manufactured by Nippon Talc Co., Ltd.
n- _{2: talc (hydrous magnesium silicate (Mg Si O 10 ( OH) 2 )} ) manufactured by Nippon Talc Co., Ltd. "MS-KY"

<Production of polyester>
PBSF was prepared with a 1,4-butanediol unit:succinic acid unit:2,5-furandicarboxylic acid unit (molar ratio) of 50:20:30.
24.2 parts by mass of succinic acid, 48.0 parts by mass of 2,5-furandicarboxylic acid and 1,4-butane as raw materials were placed in a reaction vessel equipped with a stirring device, a nitrogen inlet, a heating device, a thermometer and a pressure reducing port. 92.4 parts by mass of diol and 0.138 parts by mass of trimethylolpropane were added. To this, it was added so that 30 mass ppm as titanium atoms per polyester to obtain tetra-n-butyl titanate. Nitrogen gas was introduced while stirring the inside of the vessel, and the inside of the system was made into a nitrogen atmosphere by vacuum replacement. Next, while stirring the inside of the system, the temperature was raised from 180° C. to 195° C. over 1 hour, and the reaction was carried out at 195° C. for 2 hours. After that, an amount of 70 mass ppm as titanium atoms per polyester to obtain tetra-n-butyl titanate is added, and the temperature is raised to 240° C. over 1.5 hours so that the temperature becomes 0.07×10 ³ Pa or less. The pressure was reduced, and the polycondensation was continued while the heating and pressure reduction state was maintained. After 1.5 hours, the polymerization was terminated to obtain an aliphatic-aromatic polyester. The intrinsic viscosity of the resulting aliphatic-aromatic polyester was 1.361 dL/g.

<Production of polyester composition>
PBSF and each nucleating agent were kneaded according to the following procedure using a desktop kneading tester Labo Plastomill "KF-6V" (manufactured by Toyo Seiki Seisakusho Co., Ltd.). After raising the temperature of the kneading unit to 180° C., rotating the blade at 10 rpm, 5.5 g of PBSF was added to the sample inlet, and then 0.055 g of the nucleating agent shown in Table 1 (per 100 parts by mass of PBSF 1 part by mass) was added (no nucleating agent was added in Comparative Example 1). The mixture was kneaded for 3 minutes at a blade rotation speed of 300 rpm to obtain a kneaded product of PBSF and a nucleating agent. Kneading was performed in the atmosphere. The melting enthalpy ratio of the resulting composition was measured, and the results are summarized in Table 1 below.

Table 1 confirms that the crystallization of the aliphatic-aromatic polyester composition of the present invention was promoted by containing a specific nucleating agent.

Claims (7)

An aliphatic-aromatic polyester composition containing an aliphatic-aromatic polyester and a nucleating agent,
The aliphatic-aromatic polyester has an aliphatic diol unit, an aliphatic dicarboxylic acid unit and an aromatic dicarboxylic acid unit,
The nucleating agent is one or more compounds selected from the group consisting of fatty acid metal salts, phosphates, aromatic phosphonates, polyhydric alcohols, fatty acid amides, and copolymers of olefins and maleic acid. become,
An aliphatic-aromatic polyester composition containing 0.01 to 100 parts by mass of the nucleating agent per 100 parts by mass of the aliphatic-aromatic polyester. 2. The aliphatic-aromatic polyester composition according to claim 1, wherein the molar ratio of said aliphatic dicarboxylic acid units: said aromatic dicarboxylic acid units in said aliphatic-aromatic polyester is from 20:80 to 80:20. 3. The aliphatic-aromatic polyester composition according to claim 1 or 2, wherein the aliphatic-aromatic polyester is polybutylene succinate furanoate. The nucleating agent is sodium montanate, magnesium stearate, aluminum = bis(4,4',6,6'-tetra-tert-butyl-2,2'-methylenediphenyl = phosphate) = hydroxide, calcium phosphate, penta Composed of one or more compounds selected from the group consisting of erythritol, hexamethylenebishydroxystearic acid amide, ethylenebishydroxystearic acid amide, zinc phenylphosphonate, and copolymers of α-olefins and maleic anhydride The aliphatic-aromatic polyester composition according to any one of claims 1 to 3. A method for producing an aliphatic-aromatic polyester composition containing an aliphatic-aromatic polyester and a nucleating agent, comprising subjecting an aliphatic diol component, an aliphatic dicarboxylic acid component, and an aromatic dicarboxylic acid component to an esterification or transesterification reaction. and adding a nucleating agent to the resulting molten resin, wherein the nucleating agent is a fatty acid metal salt, a phosphate, an aromatic phosphonate, or a polyhydric alcohol , fatty acid amides, and copolymers of olefins and maleic acid. A method for producing an aliphatic-aromatic polyester composition containing an aliphatic-aromatic polyester and a nucleating agent, wherein the aliphatic-aromatic polyester has an aliphatic diol unit, an aliphatic dicarboxylic acid unit and an aromatic dicarboxylic acid unit. 1 selected from the group consisting of fatty acid metal salts, phosphates, aromatic phosphonates, polyhydric alcohols, fatty acid amides, and copolymers of olefins and maleic acid in the molten aliphatic-aromatic polyester; A method for producing an aliphatic-aromatic polyester composition, comprising a step of kneading seeds or two or more compounds. A method for producing an aliphatic-aromatic polyester composition according to claim 5 or 6, further comprising the step of melt-kneading a resin other than the aliphatic-aromatic polyester. .