KR20220091634A - Biodegradable polyester copolymer comprising anhydrosugar alcohol based polycarbonate diol and preparation method thereof, and molded article comprising the same - Google Patents

Abstract

The present invention relates to a biodegradable co-polyester resin comprising anhydrous sugar-alcohol-based polycarbonate diol, a preparation method thereof, and a molded article comprising the same, and more specifically, to a preparation method of a polyester resin which comprises: a repeating unit derived from a dicarboxylic component containing adipic acid or ester thereof; and a repeating unit derived from a diol component containing a specific content of anhydrous sugar alcohol-based polycarbonate diol in a specific content ratio to have significantly improved heat resistance and mechanical properties (for example, elongation) while maintaining excellent biodegradability compared to a conventional biodegradable polyester resin (for example, a PBAT resin), and a molded article comprising the same.

Description

Biodegradable co-polyester resin containing anhydrosugar alcohol-based polycarbonate diol, manufacturing method thereof, and molded article comprising the same

The present invention relates to a biodegradable co-polyester resin comprising anhydrosugar alcohol-based polycarbonate diol, a method for preparing the same, and a molded article comprising the same, and more particularly, to a dicarboxyl component comprising adipic acid or an ester thereof Comparison with conventional biodegradable polyester resins (eg, PBAT resins) by including a repeating unit derived from a specific content ratio of a repeating unit derived from a diol component containing a specific content of anhydrosugar alcohol-based polycarbonate diol Accordingly, it relates to a method for producing a polyester resin having significantly improved heat resistance and mechanical properties (eg, elongation) while maintaining excellent biodegradability, and a molded article including the same.

Hydrogenated sugar (also referred to as “sugar alcohol”) refers to a compound obtained by adding hydrogen to a reducing end group of a saccharide, generally HOCH ₂ (CHOH) _n CH ₂ OH (where n is an integer of 2 to 5) ), and is classified into tetritol, pentitol, hexitol, and heptitol (with 4, 5, 6 and 7 carbon atoms, respectively) according to the number of carbon atoms. Among them, hexitol having 6 carbon atoms includes sorbitol, mannitol, iditol, galactitol, and the like, and sorbitol and mannitol are particularly effective substances.

Anhydrosugar alcohol has the form of a diol having two hydroxyl groups in the molecule, and can be prepared by utilizing hexitol derived from starch (eg, Korean Patent No. 10-1079518, Korean Patent Application Laid-Open No. 10). -2012-0066904). Anhydrosugar alcohol is an eco-friendly material derived from renewable natural resources, and research on its manufacturing method has been in progress with a lot of interest from a long time ago. Among these anhydrosugar alcohols, isosorbide prepared from sorbitol has the widest industrial application range.

The use of anhydrosugar alcohol is very diverse, such as treatment of heart and blood vessel diseases, adhesives for patches, pharmaceuticals such as mouth fresheners, solvents for compositions in the cosmetic industry, and emulsifiers in the food industry. In addition, it can raise the glass transition temperature of polymer materials such as polyester, PET, polycarbonate, polyurethane, and epoxy resin, and has an effect of improving the strength of these materials. useful. In addition, it is known that it can be used as an eco-friendly solvent for adhesives, eco-friendly plasticizers, biodegradable polymers, and water-soluble lacquers.

As such, anhydrosugar alcohol has attracted a lot of attention due to its various application possibilities, and its use in actual industry is gradually increasing.

On the other hand, in order to respond to the depletion of fossil resources, the increase in carbon dioxide in the atmosphere due to the massive consumption of petroleum resources, and the global warming problem, efforts are being made to reduce the use of fossil resources. In this regard, interest in environmental circulating polymers is high, and studies on polyester resins using biomass raw materials such as anhydrosugar alcohol are being actively conducted. Aliphatic polyester resins using biomass raw materials are widely used in the fields of packaging materials, molded articles, and films, and are one of eco-friendly plastics that do not contain environmental hormones. In addition, as it has biodegradability, it is attracting attention as an eco-friendly material that can solve the environmental pollution problem caused by waste plastics, which has recently become an issue.

Recently, in polycarbonate mainly used for heat-resistant food containers, as the harmfulness of bisphenol A has been revealed, the need for an environmentally friendly, transparent and heat-resistant polyester resin is increasing.

In the case of the conventional homopolyester composed of terephthalic acid and ethylene glycol, mechanical properties and heat resistance can be improved to some extent through stretching crystallization and heat setting, but there is a limit in application use and heat resistance improvement. Accordingly, recently, a method for improving the heat resistance of a polyester resin has been developed by using isosorbide, a biomass-derived compound derived from starch, as a comonomer of the polyester resin. However, since isosorbide is a secondary alcohol, it is known that the reactivity is low and it is difficult to form a high-viscosity polyester resin used for the manufacture of sheets and bottles.

In addition, a typical PBAT (polybutylene adipate-co-terephthalate) resin of the biodegradable aliphatic polyester resin is a copolymer resin containing an aliphatic and an aromatic, and has various processability. However, since the unit price is high, it is a cause of greatly increasing the unit price of products such as packaging films manufactured by using it as a raw material, and has disadvantages in which heat resistance and mechanical properties are inferior.

Therefore, while maintaining excellent biodegradability, there is a need for development of a biodegradable polyester resin in which mechanical properties and heat resistance of conventional biodegradable polyester resins (eg, PBAT resins) are improved.

The present invention is to solve the problems of the prior art, and compared with the conventional biodegradable polyester resin (eg, PBAT resin), while maintaining excellent biodegradability, heat resistance and mechanical properties (eg, elongation) ) is a technical task to provide a significantly improved polyester resin and its manufacturing method, and a molded article including the same.

In order to achieve the above technical problem, the present invention, a repeating unit derived from a dicarboxyl component; and a repeating unit derived from a diol component, wherein the dicarboxyl component contains more than 20 mol% to less than 80 mol% of an aliphatic dicarboxyl compound and 20 mol% based on 100 mol% of the total dicarboxyl component. more than 80 mol% of an aromatic dicarboxyl compound, wherein the aliphatic dicarboxyl compound includes adipic acid or an ester thereof, and the diol component is 0.5 mol% based on 100 mol% of the total diol component A biodegradable polyester resin is provided comprising greater than to less than 35 mole % of anhydrosugar alcohol-based polycarbonate diol.

According to another aspect of the present invention, (1) an esterification reaction or a transesterification reaction of a dicarboxyl component and a diol component; and (2) subjecting the reaction product obtained in step (1) to a polycondensation reaction; in which the dicarboxyl component is more than 20 mol% to 80 mol% based on 100 mol% of the total dicarboxyl component. less than an aliphatic dicarboxyl compound and greater than 20 mol% to less than 80 mol% of an aromatic dicarboxyl compound, wherein the aliphatic dicarboxyl compound comprises adipic acid or an ester thereof, wherein the diol component comprises: A method for producing a biodegradable polyester resin is provided, comprising more than 0.5 mol% to less than 35 mol% of anhydrosugar alcohol-based polycarbonate diol based on 100 mol% of the total component.

According to another aspect of the present invention, there is provided a molded article comprising the biodegradable polyester resin according to the present invention.

The anhydrosugar alcohol-based polycarbonate diol in the biodegradable polyester resin of the present invention can improve heat resistance by increasing the glass transition temperature (T _g ), and at the same time disturb the structural regularity of molecular chains in the biodegradable polyester resin. Biodegradability can be further improved. Therefore, according to the present invention, compared with conventional biodegradable polyester resins such as PBAT resins, heat resistance and mechanical properties (eg, elongation) of biodegradable polyester resins can be significantly improved, and biodegradability is further improved. can do it

Hereinafter, the present invention will be described in more detail.

The biodegradable polyester resin of the present invention includes a repeating unit derived from a dicarboxyl component; and repeating units derived from a diol component.

dicarboxyl component

The dicarboxyl component included as a repeating unit in the biodegradable polyester resin of the present invention includes an aliphatic dicarboxyl compound and an aromatic dicarboxyl compound.

The aliphatic dicarboxyl compound includes adipic acid or an ester thereof.

In one embodiment, the aliphatic dicarboxyl compound may include adipic acid or an ester thereof in an amount of 50 to 100 mol% based on 100 mol% of the total aliphatic dicarboxyl compound, more specifically 60 to 100 mol% or 80 to 100 mol% may be included in an amount, but is not limited thereto.

In one embodiment, the aliphatic dicarboxyl compound may further include an aliphatic dicarboxyl compound other than adipic acid or an ester thereof, and more specifically, an aliphatic dicarboxylic acid having 4 to 14 carbon atoms or an ester thereof. may further include. The aliphatic dicarboxyl compound other than adipic acid or an ester thereof may be included in an amount of, for example, 0 to 50 mol%, more specifically 0 to 40 mol%, based on 100 mol% of the total aliphatic dicarboxyl compound. % or may be included in an amount of 0 to 20 mol%, but is not limited thereto.

Also, in one embodiment, the aromatic dicarboxyl compound may include an aromatic dicarboxylic acid having 8 to 16 carbon atoms or an ester thereof.

More specifically, the aliphatic dicarboxylic compound other than adipic acid or its ester is cyclohexanedicarboxylic acid or its ester, sebacic acid or its ester, isodecylsuccinic acid or its ester, maleic acid or its ester, fumaric acid or its esters, succinic acid or its esters, glutaric acid or its esters, azelaic acid or its esters, itaconic acid or its esters, glutamic acid or its esters, 2,5-furandicarboxylic acid or its esters, tetrahydrofuran- 2,5-dicarboxylic acid or its ester, tetrahydrofuran-3,5-dicarboxylic acid or its ester, undecanedioic acid or its ester, dodecanedioic acid or its ester, tridecanedioic acid or its ester, tetra It may be selected from the group consisting of decanedioic acid or esters thereof, and combinations thereof.

In addition, more specifically, the aromatic dicarboxyl compound is phthalic acid or its ester, terephthalic acid or its ester, isophthalic acid or its ester, 1,5-naphthalenedicarboxylic acid or its ester, 2,6-naphthalenedicar acid or an ester thereof, diphenic acid or an ester thereof, p-phenylene diacetic acid or an ester thereof, o-phenylene diacetic acid or an ester thereof, and combinations thereof.

In one embodiment, the ester compound of the aliphatic dicarboxylic acid may be a monoester compound, a diester compound, or a mixture thereof, preferably a diester compound. For example, the ester compound of the aliphatic dicarboxylic acid may be a di(C1-C6)alkyl ester of an aliphatic dicarboxylic acid, such as dimethyl adipate, diethyl adipate, dimethyl succinate or diethyl succinate. have.

Further, in one embodiment, the ester compound of the aromatic dicarboxylic acid may be a monoester compound, a diester compound, or a mixture thereof, preferably a diester compound. For example, the ester compound of the aromatic dicarboxylic acid may be a di(C1-C6)alkyl ester of an aromatic dicarboxylic acid, such as dimethyl terephthalate, diethyl terephthalate, dimethyl isophthalate or diethyl isophthalate. can

The dicarboxyl component included as a repeating unit in the biodegradable polyester resin of the present invention is an amount of the aliphatic dicarboxyl compound in an amount of more than 20 mol% to less than 80 mol% based on 100 mol% of the total dicarboxyl component. include as If the content of the aliphatic dicarboxyl compound in 100 mol% of the total dicarboxyl component is 20 mol% or less, the biodegradability of the prepared biodegradable polyester resin is rapidly reduced, and mechanical properties (elongation) are very poor. Conversely, if the content of the aliphatic dicarboxyl compound in 100 mol% of the total dicarboxyl component is 80 mol% or more, the glass transition temperature of the prepared biodegradable polyester resin is lowered, the heat resistance is very poor, and the mechanical properties are also poor becomes

The dicarboxyl component included as a repeating unit in the biodegradable polyester resin of the present invention is based on 100 mol% of the total dicarboxyl component, in an amount of more than 20 mol% to less than 80 mol% of the aromatic dicarboxyl compound include as If the content of the aromatic dicarboxyl compound in 100 mol% of the total dicarboxyl component is 20 mol% or less, the glass transition temperature of the prepared biodegradable polyester resin is lowered, heat resistance is very poor, and mechanical properties are also poor. Conversely, if the content of the aromatic dicarboxyl compound in 100 mol% of the total dicarboxyl component is 80 mol% or more, the biodegradability of the prepared biodegradable polyester resin is rapidly reduced, and mechanical properties (elongation) are very poor.

In an embodiment, the content of the aliphatic dicarboxyl compound in the dicarboxyl component is greater than 20 mol%, 21 mol% or more, 23 mol% or more, 25 mol% or more, based on 100 mol% of the total dicarboxyl component, 27 mol% or more, 29 mol% or more, or 30 mol% or more, and also less than 80 mol%, 79 mol% or less, 77 mol% or less, 75 mol% or less, 73 mol% or less, 71 mol% or less, or 70 mol% or less It may be less than or equal to mol%, but is not limited thereto.

In one embodiment, the content of the aromatic dicarboxyl compound in the dicarboxyl component is more than 20 mol%, 21 mol% or more, 23 mol% or more, 25 mol% or more, based on 100 mol% of the total dicarboxyl component. , 27 mol% or more, 29 mol% or more, or 30 mol% or more, and also less than 80 mol%, 79 mol% or less, 77 mol% or less, 75 mol% or less, 73 mol% or less, 71 mol% or less, or It may be 70 mol% or less, but is not limited thereto.

diol ingredient

The diol component included as a repeating unit in the biodegradable polyester resin of the present invention includes anhydrosugar alcohol-based polycarbonate diol in an amount of more than 0.5 mol% to less than 35 mol% based on 100 mol% of the total diol component.

When the content of anhydrosugar alcohol-based polycarbonate diol in 100 mol% of the total diol component is 0.5 mol% or less, the glass transition temperature of the prepared biodegradable polyester resin is lowered, and heat resistance is poor. Conversely, if the content of anhydrosugar alcohol-based polycarbonate diol in 100 mol% of the total diol component is 35 mol% or more, a low molecular weight biodegradable polyester resin is generated due to reduced reactivity, and the intrinsic viscosity of the prepared biodegradable polyester resin and the glass transition temperature is lowered, heat resistance is very poor, and mechanical properties (elongation) are also poor.

In one embodiment, the content of the anhydrosugar alcohol-based polycarbonate diol in the diol component is greater than 0.5 mol%, 0.6 mol% or more, 1 mol% or more, 1.5 mol% or more, based on 100 mol% of the total diol component, 2 mol% or more, 2.5 mol% or more, or 3 mol% or more, and also less than 35 mol%, 34 mol% or less, 32 mol% or less, 30 mol% or less, 28 mol% or less, 26 mol% or less, or 25 mol% or less % or less, but is not limited thereto.

In the present invention, "anhydrosugar alcohol" is generally called hydrogenated sugar or sugar alcohol, by removing one or more water molecules from a compound obtained by adding hydrogen to a reducing end group of saccharides. means any material obtained.

The anhydrosugar alcohol may be a mono-anhydrosugar alcohol, a dianhydrosugar alcohol, or a combination thereof.

The monoanhydrosugar alcohol is an anhydrosugar alcohol formed by removing one water molecule from the inside of a hydrogenated sugar, and has a tetraol form having four hydroxyl groups in the molecule. In the present invention, the type of mono-anhydrosugar alcohol is not particularly limited, but may preferably be mono-anhydrosugar hexitol, and more specifically 1,4-anhydrohexitol, 3,6-anhydrohexitol , 2,5-anhydrohexitol, 1,5-anhydrohexitol, 2,6-anhydrohexitol, or a mixture of two or more thereof.

The dianhydrosugar alcohol is an anhydrosugar alcohol formed by removing two water molecules from the inside of a hydrogenated sugar, has a diol form with two hydroxyl groups in the molecule, and can be prepared using hexitol derived from starch. . Since dianhydrosugar alcohol is an eco-friendly material derived from renewable natural resources, research on its manufacturing method has been in progress with a lot of interest from a long time ago. Among these dianhydrosugar alcohols, isosorbide prepared from sorbitol currently has the widest industrial application range. In the present invention, the type of the dianhydrosugar alcohol is not particularly limited, but preferably dianhydrosugar hexitol, and more specifically 1,4:3,6-dianhydrohexitol. The 1,4:3,6-dianhydrohexitol may be isosorbide, isomannide, isoidide, or a mixture of two or more thereof.

In a preferred embodiment of the present invention, the anhydrosugar alcohol is dianhydrosugar hexitol, more preferably isosorbide (1,4:3,6-dianhydrosorbitol), isomannide (1,4: 3,6-dianhydromannitol), isoidide (1,4:3,6-dianhydroiditol), or one selected from the group consisting of mixtures thereof, most preferably isosorbide can be used.

In one embodiment, the anhydrosugar alcohol-based polycarbonate diol includes (1) a repeating unit derived from an ether diol of anhydrosugar alcohol; and (2) a repeating unit derived from diester carbonate.

The ether diol of the anhydrosugar alcohol is an anhydrosugar alcohol-derived diol compound having an ether bond in the molecule, and is prepared by addition reaction of anhydrosugar alcohol and alkylene oxide, or anhydrosugar alcohol and alkylene carbonate (especially ethylene carbonate) It may be obtained by reacting, and is preferably prepared by addition reaction of anhydrosugar alcohol and alkylene oxide.

Specifically, the alkylene oxide may be a linear alkylene oxide having 2 to 20 carbon atoms or a branched alkylene oxide having 3 to 20 carbon atoms, and more specifically, a linear alkylene oxide having 2 to 10 carbon atoms or 3 to 10 carbon atoms. of a branched alkylene oxide, more specifically a linear alkylene oxide having 2 to 8 carbon atoms or a branched alkylene oxide having 3 to 8 carbon atoms, even more specifically a linear alkylene oxide having 2 to 4 carbon atoms or 3 carbon atoms to 4 branched alkylene oxides.

In one embodiment, the alkylene oxide may be ethylene oxide, propylene oxide, or a combination thereof.

In one embodiment, the ether diol of anhydrosugar alcohol obtained by reacting the anhydrosugar alcohol with alkylene oxide or alkylene carbonate (especially ethylene carbonate) may be a compound represented by the following formula (A):

[Formula A]

In the above formula (A),

R ₁ and R ₂ are each independently a linear alkylene group having 2 to 20 carbon atoms or a branched alkylene group having 3 to 20 carbon atoms, more specifically, a linear alkylene group having 2 to 10 carbon atoms or a branched alkylene group having 3 to 10 carbon atoms. , more specifically a linear alkylene group having 2 to 8 carbon atoms or a branched alkylene group having 3 to 8 carbon atoms, even more specifically a linear alkylene group having 2 to 4 carbon atoms or a branched alkylene group having 3 to 4 carbon atoms. ,

m and n each independently represent an integer of 0 to 15, provided that m+n represents an integer of 1 to 30.

More preferably, in Formula A,

R ₁ and R ₂ each independently represent an ethylene group, a propylene group or an isopropylene group, R ₁ and R ₂ may be the same as or different from each other, but preferably R ₁ and R ₂ are the same as each other,

m and n each independently represent an integer of 1 to 14, provided that m+n represents an integer of 2 to 15, preferably an integer of 3 to 15.

In one embodiment, as the ether diol of the anhydrosugar alcohol, the following isosorbide-propylene glycol, isosorbide-ethylene glycol, or a mixture thereof may be used.

[Isosorbide-Propylene Glycol]

In the above formula,

a and b are each independently an integer from 0 to 15, with the proviso that a+b is an integer from 1 to 30, preferably a and b are each independently an integer from 1 to 14, with the proviso that a+b is an integer from 2 to It may be an integer of 15 (preferably 3 to 15).

[Isosorbide-ethylene glycol]

In the above formula,

c and d are each independently an integer from 0 to 15, with the proviso that c+d is an integer from 1 to 30, preferably c and d are each independently an integer from 1 to 14, with the proviso that c+d is from 2 to It may be an integer of 15 (preferably 3 to 15).

The reaction of anhydrosugar alcohol and alkylene oxide is, for example, in the presence of an acid or alkali catalyst, at 100° C. to 150° C. for 3 hours to 8 hours, more specifically at 100° C. to 140° C. for 5 hours to 6 hours. may be performed, but is not particularly limited thereto.

The reaction of anhydrosugar alcohol with an alkylene carbonate (especially ethylene carbonate) is, for example, in the presence of an acid or alkali catalyst at 150° C. to 200° C. for 6 hours to 12 hours, more specifically at 150° C. to 180° C. 8 It may be carried out for hours to 10 hours, but is not particularly limited thereto.

In one embodiment, the content of the anhydrosugar alcohol ether diol-derived repeating unit in the anhydrosugar-alcohol-based polycarbonate diol is 15 to 80% by weight, based on 100% by weight of a total of repeating units in the anhydrosugar-alcohol-based polycarbonate diol. %, more specifically 20 to 70% by weight, more specifically 30 to 60% by weight, and even more specifically 40 to 55% by weight, but is not limited thereto. .

The type of the carbonic acid diester is not particularly limited, and for example, dialkyl carbonate, diaryl carbonate, alkylene carbonate, or a combination thereof may be used.

In one embodiment, examples of the dialkyl carbonate include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diisobutyl carbonate, ethylnormalbutyl carbonate and ethylisobutyl carbonate, and the di Examples of the lyl carbonate include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate and dim-cresyl carbonate, and examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 1,3-pentylene carbonate, 1,4 -pentylene carbonate, 1,5-pentylene carbonate, 2,3-pentylene carbonate, 2,4-pentylene carbonate, neopentylene carbonate, etc. are mentioned.

In one embodiment, the carbonic acid diester may be selected from dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, or a combination thereof, more preferably diphenyl carbonate.

In one embodiment, the content of the carbonic acid diester-derived repeating unit in the anhydrosugar alcohol-based polycarbonate diol is 10 to 50% by weight based on 100% by weight of the total repeating units in the anhydrosugar alcohol-based polycarbonate diol It may be, more specifically, may be 10 to 40% by weight, and more specifically may be 15 to 36% by weight, but is not limited thereto.

In one embodiment, the anhydrosugar alcohol-based polycarbonate diol may further include a repeating unit derived from an aliphatic diol.

The aliphatic diol may be a linear aliphatic diol having 2 to 10 carbon atoms or a branched aliphatic diol having 3 to 10 carbon atoms, more specifically, a linear aliphatic diol having 2 to 8 carbon atoms or a branched aliphatic diol having 3 to 8 carbon atoms, more More specifically, it may be a linear aliphatic diol having 2 to 6 carbon atoms or a branched aliphatic diol having 3 to 6 carbon atoms.

In one embodiment, the aliphatic diol is ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1 ,8-octanediol, 1,9-nonanediol, 1,10-decanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, 2-methyl-1,3-propanediol, 2-ethyl -1,3-propanediol, 2-butyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2,2 -diethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 3,3-dimethyl-1,5-pentanediol, 2,2,4,4-tetramethyl-1,5- Pentanediol, 2-ethyl-1,6-hexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-dihydroxyethylcyclohexane; norbornane-2,3-dimethanol or a combination thereof.

In one embodiment, when the aliphatic diol-derived repeating unit is present in the anhydrosugar-alcohol-based polycarbonate diol, the content thereof is 0.1 to 100% by weight of the total repeating units in the anhydrosugar-alcohol-based polycarbonate diol. It may be 35% by weight, more specifically 5 to 30% by weight, more specifically 15 to 25% by weight, but is not limited thereto.

In one embodiment, the anhydrosugar alcohol-based polycarbonate diol may include a repeating unit having the structure of Formula 1 below:

[Formula 1]

In Formula 1,

R ₁ and R ₂ are each independently a linear alkylene group having 2 to 20 carbon atoms (more specifically 2 to 10 carbon atoms, even more specifically 2 to 8 carbon atoms, even more specifically 2 to 4 carbon atoms) or 3 carbon atoms to 20 (more specifically, 3 to 10 carbon atoms, more specifically 3 to 8 carbon atoms, even more specifically 3 to 4 carbon atoms) is a branched alkylene group, and R ₁ and R ₂ may be the same as or different from each other. have.

In one embodiment, the repeating unit having the structure of Formula 1 may be derived from a reaction between an ether diol of anhydrosugar alcohol and a diester carbonate.

Also, in one embodiment, the anhydrosugar alcohol-based polycarbonate diol may further include a repeating unit having a structure of the following Chemical Formula 2:

[Formula 2]

In Formula 2,

R ₃ is a linear alkylene group having 2 to 10 carbon atoms (more specifically 2 to 8 carbon atoms, even more specifically 2 to 6 carbon atoms) or 3 to 10 carbon atoms (more specifically 3 to 8 carbon atoms, more specifically is a branched alkylene group having 3 to 6 carbon atoms.

In one embodiment, the repeating unit having the structure of Formula 2 may be derived from a reaction between an aliphatic diol and a carbonic acid diester.

The number average molecular weight (Mn) of the anhydrosugar alcohol-based polycarbonate diol may be adjusted according to the intended use, for example, the lower limit thereof may be 250 or more, 500 or more, 600 or more, 700 or more, or 1,000 or more, and , the upper limit may be 6,000 or less, 5,500 or less, 5,000 or less, 4,000 or less, or 3,000 or less, and preferably 600 to 5,500, but is not limited thereto.

The polydispersity index (PDI) of the anhydrosugar alcohol-based polycarbonate diol is not particularly limited, but its lower limit is 1.0 or more, 1.1 or more, or 1.2 or more, and its upper limit is 3.0 or less, 2.5 or less, or 2.0 or less. However, the present invention is not limited thereto. The polydispersity index is obtained by weight average molecular weight (Mw)/number average molecular weight (Mn), and can be generally obtained by measurement of gel permeation chromatography (GPC).

In one embodiment, the Gardner color number of the anhydrosugar alcohol-based polycarbonate diol may be 1 or less. The Gardner color number can be measured using a spectrophotometer capable of measuring Gardner color number (eg, CM-5 of Konica Minolta) according to ASTM D 1544, and the lower the Gardner color number, the closer to colorlessness do.

In the production of the anhydrosugar alcohol-based polycarbonate diol, an ether diol of anhydrosugar alcohol and optionally an aliphatic diol are used as a diol component, so anhydrosugar alcohol is essentially used to prepare a solid anhydrosugar alcohol-based polycarbonate diol. The reaction temperature can be lowered compared to the process of can keep

The content of phenols as a by-product contained in the anhydrosugar-alcohol-based polycarbonate diol is not particularly limited, but is preferably as small as possible, and the residual phenol amount in the anhydrosugar-alcohol-based polycarbonate diol may be 50 ppm or less, which is the detection limit.

The anhydrosugar alcohol-based polycarbonate diol may be prepared by reacting a mixture comprising an ether diol of anhydrosugar alcohol and a carbonic acid diester described above in the presence of a transesterification catalyst, wherein the mixture is optionally an aliphatic diol may include

The anhydrosugar alcohol-based polycarbonate diol used in the present invention is a method comprising reacting a mixture comprising (i) an ether diol of anhydrosugar alcohol and (ii) a carbonic acid diester in the presence of a transesterification catalyst. In this case, the mixture may optionally further include an aliphatic diol. The ether diols, diester carbonates, and aliphatic diols of anhydrosugar alcohol that can be used herein are the same as those described above.

In one embodiment, in the preparation of the anhydrosugar alcohol-based polycarbonate diol, anhydrosugar alcohol itself is not used as a diol component. That is, in one embodiment, the anhydrosugar alcohol-based polycarbonate diol does not include a repeating unit derived from the anhydrosugar alcohol itself.

The amount of the anhydrosugar alcohol ether diol used in the preparation of the anhydrosugar alcohol-based polycarbonate diol may be 30 to 95 wt%, more specifically 40 to 90 wt%, based on 100 wt% of the total reaction starting material mixture It may be, and more specifically, may be 50 to 85% by weight, and even more specifically, may be 55 to 80% by weight, but is not limited thereto.

In addition, the amount of the diester carbonate used in preparing the anhydrosugar alcohol-based polycarbonate diol may be 5 to 70% by weight, more specifically 10 to 60% by weight, based on 100% by weight of the total reaction starting material mixture. may be, and more specifically, may be 15 to 50% by weight, and even more specifically may be 20 to 45% by weight, but is not limited thereto.

In addition, when an aliphatic diol is additionally used as an optional component in the preparation of the anhydrosugar alcohol-based polycarbonate diol, the amount used may be 0.1 to 30% by weight based on 100% by weight of the total reaction starting material mixture, and more Specifically, it may be 0.5 to 25% by weight, more specifically 1 to 20% by weight, and even more specifically 5 to 18% by weight, but is not limited thereto.

As the transesterification catalyst, a metal generally considered to have transesterification ability or a compound such as a hydroxide or salt thereof may be used without limitation.

Examples of the catalyst metal include Group 1 metals such as lithium, sodium, potassium, rubidium, and cesium; Group 2 metals, such as magnesium, calcium, strontium, and barium; Group 4 metals, such as titanium and zirconium; Group 5 metals, such as hafnium; Group 9 metals, such as cobalt; Group 12 metals, such as zinc; Group 13 metals, such as aluminum; Group 14 metals, such as germanium, tin, and lead; Group 15 metals, such as antimony and bismuth; and lanthanide-based metals such as lanthanum, cerium, europium, and ytterbium. Among these, from the viewpoint of increasing the transesterification reaction rate, a Group 1 metal or a Group 2 metal is preferable, and a Group 2 metal is particularly preferable.

Examples of the use of the salt compound of the catalyst metal include halide salts such as chloride, bromide, and iodide; carboxylates such as acetate, formate and benzoate; sulfonic acid salts such as methanesulfonic acid, toluenesulfonic acid, and trifluoromethanesulfonic acid; phosphorus-containing salts such as phosphate, hydrogen phosphate, and dihydrogen phosphate; and acetylacetonate salts. The catalyst metal may also be used as an alkoxide such as methoxide or ethoxide.

The said catalyst metal, the hydroxide of a catalyst metal, and the salt compound of a catalyst metal may be used individually by 1 type, and may mix and use 2 or more types.

In one embodiment, when a compound containing a Group 1 metal is used as the transesterification catalyst, examples thereof include sodium hydroxide, potassium hydroxide; cesium hydroxide; lithium hydroxide; sodium bicarbonate; sodium carbonate; potassium carbonate; cesium carbonate; lithium carbonate; sodium acetate; potassium acetate; cesium acetate; lithium acetate; sodium stearate; potassium stearate; cesium stearate; lithium stearate; sodium borohydride; sodium borophenylide; sodium benzoate; potassium benzoate; cesium benzoate; lithium benzoate; disodium hydrogen phosphate; dipotassium hydrogen phosphate; lithium hydrogen phosphate; disodium phenylphosphate; disodium salt, dipotassium salt, isesium salt or ilithium salt of bisphenol A; and a sodium salt, potassium salt, cesium salt or lithium salt of phenol.

In one embodiment, when a compound containing a Group 2 metal is used as the transesterification catalyst, examples thereof include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium hydrogen carbonate, calcium hydrogen carbonate, strontium hydrogen carbonate, barium hydrogen carbonate. , magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, or magnesium phenyl phosphate.

In the production of anhydrosugar alcohol-based polycarbonate diol, the amount of the transesterification catalyst used is 0.01 to 500 ppm, more specifically 0.1 to 100 ppm, even more specifically 1 as a metal conversion weight ratio to the weight of the raw material diol. It may be ~50 ppm, but is not limited thereto.

In the method for producing anhydrosugar alcohol-based polycarbonate diol, in the reaction of a mixture containing an ether diol of anhydrosugar alcohol, a diester carbonate, and optionally an aliphatic diol, the reaction temperature is not particularly limited, but usually 70° C. or higher, 100 It may be ℃ or more, or 130 ℃ or more, and usually 250 ℃ or less, 230 ℃ or less, 200 ℃ or less, 180 ℃ or less, 170 ℃ or less, or 165 ℃ or less. The reaction may be carried out under normal or reduced pressure conditions (eg, 10 kPa or less, 5 kPa or less, or 1 kPa or less), and may be usually carried out for 1 to 50 hours, 1 to 20 hours, or 1 to 10 hours, However, the present invention is not limited thereto.

In one embodiment, the diol component included as a repeating unit in the biodegradable polyester resin of the present invention may further include an aliphatic diol (“additional aliphatic diol”) other than the above-described anhydrosugar alcohol-based polycarbonate diol.

In one embodiment, the additional aliphatic diol may be an aliphatic diol having 2 to 15 carbon atoms, more specifically, an aliphatic diol having 2 to 10 carbon atoms.

In one embodiment, the content of the additional aliphatic diol in the diol component may be greater than 65 mol% and less than 99.5 mol%, based on 100 mol% of the total diol component. When the content of the additional aliphatic diol in the diol component is less than the above level, a low molecular weight biodegradable polyester resin is produced due to reduced reactivity, and the intrinsic viscosity and glass transition temperature of the prepared biodegradable polyester resin are reduced, and heat resistance This becomes very poor, and the mechanical properties (elongation) may also be poor, and conversely, if it is higher than the above level, the glass transition temperature of the prepared biodegradable polyester resin may be lowered, and heat resistance may be poor.

In one embodiment, the content of the additional aliphatic diol in the diol component is greater than 65 mol%, 66 mol% or more, 68 mol% or more, 70 mol% or more, 72 mol% or more, based on 100 mol% of the total diol component; 74 mol% or more or 75 mol% or more, and also less than 99.5 mol% 99.4 mol% or less, 99 mol% or less, 98.5 mol% or less, 98 mol% or less, 97.5 mol% or less, or 97 mol% or less, However, the present invention is not limited thereto.

In one embodiment, the additional aliphatic diol is, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propane diol, 1,3-propane diol, 1,2-butane diol, 1,3 -Butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,3- Hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, neopentyl glycol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexane Diol, 1,2-cyclohexane dimethanol, 1,3-cyclohexane dimethanol, 1,4-cyclohexane dimethanol, tetramethylcyclobutane diol, tricyclodecanedimethanol, adamantanediol, 2,2- dimethyl-1,3-propane diol, 2-ethyl-2-t-butyl-1,3-propane diol, 2,2,4-trimethyl-1,6-hexane diol, or combinations thereof and may preferably be butane diol, but is not limited thereto.

The intrinsic viscosity (IV) of the biodegradable polyester resin of the present invention is obtained by dissolving the biodegradable polyester resin in a mixture of phenol and tetrachloroethane (weight ratio = 50:50) to prepare a 0.5 wt% solution, then Uberod It can be measured at 35° C. using a viscometer, and the intrinsic viscosity value can be greater than 0.8, greater than 0.85, or greater than 0.9, and less than 1.3, less than or equal to 1.25, or less than or equal to 1.2, for example greater than 0.8 to less than 1.3, 0.85 to 1.25. or 0.9 to 1.2. If the intrinsic viscosity value is 0.8 or less, heat resistance and mechanical properties may be poor, and if the intrinsic viscosity value is 1.3 or more, the color may be poor.

In addition, the biodegradable polyester resin of the present invention has a low intrinsic viscosity change rate and is excellent in heat resistance. Intrinsic viscosity change rate, for example, after preparing a biodegradable polyester resin in the form of a pellet, 1 g of biodegradable polyester pellets are placed on an aluminum plate, left in an oven at 65 ° C. for 72 hours, and then taken out again and the heat history at room temperature After removal, the intrinsic viscosity can be measured to calculate the rate of change compared to the initial intrinsic viscosity, and the rate of change in intrinsic viscosity of the biodegradable polyester resin of the present invention may be less than 30%, preferably less than 20%. As the intrinsic viscosity change rate of the biodegradable polyester resin is lower, it means less denaturation by heat, ie, excellent heat resistance.

In addition, the biodegradable polyester resin of the present invention has high elongation and excellent mechanical properties. The elongation of the biodegradable polyester resin may be measured according to ASTM D638. The elongation of the biodegradable polyester resin of the present invention may be, for example, 500% or more, and more preferably 600% or more or 700% or more.

According to another aspect of the present invention, (1) an esterification reaction or a transesterification reaction of a dicarboxyl component and a diol component; and (2) subjecting the reaction product obtained in step (1) to a polycondensation reaction; in which the dicarboxyl component is more than 20 mol% to 80 mol% based on 100 mol% of the total dicarboxyl component. less than an aliphatic dicarboxyl compound and greater than 20 mol% to less than 80 mol% of an aromatic dicarboxyl compound, wherein the aliphatic dicarboxyl compound comprises adipic acid or an ester thereof, wherein the diol component comprises: A method for producing a biodegradable polyester resin is provided, comprising more than 0.5 mol% to less than 35 mol% of anhydrosugar alcohol-based polycarbonate diol based on 100 mol% of the total component.

The dicarboxyl component used in the biodegradable polyester resin manufacturing method of the present invention and the diol component including anhydrosugar alcohol-based polycarbonate diol are the same as described above.

In addition, the diol component may further include an aliphatic diol (“additional aliphatic diol”) other than anhydrosugar alcohol-based polycarbonate diol, and the additional aliphatic diol is as described above.

According to one embodiment, in step (1), the reaction molar ratio of the diol component to the dicarboxyl component (total number of moles of diol component/total number of moles of dicarboxyl component) is 1.0 to 1.5, and then 150 to 250°C, preferably 200 to 250°C, more preferably 200 to 240°C, and 0.1 to 3.0 kgf/cm 2 , preferably 0.2 to 2.0 kgf/cm 2 pressure conditions (reduced pressure conditions) Alternatively, transesterification may be carried out.

Here, when the reaction molar ratio of the diol component to the dicarboxyl component (total number of moles of diol component/total number of moles of dicarboxyl component) is less than 1, unreacted dicarboxyl component remains during the polymerization reaction, so that the There is a fear that mechanical properties and color may decrease, and when it exceeds 1.5, the polymerization reaction rate is too slow, and there is a risk that the productivity of the polyester resin may be reduced.

The esterification reaction time or transesterification reaction time is usually 1 to 5 hours, preferably 3 to 4 hours, and may vary depending on the reaction temperature and pressure, and the reaction molar ratio of the dicarboxyl component to the diol component.

A catalyst is not required in step (1), but in one embodiment, a catalyst may be used to shorten the reaction time. The esterification reaction or transesterification reaction of step (1) may be performed in a batch or continuous manner, and each reaction raw material may be separately input.

According to one embodiment, in step (2), before the start of the polycondensation reaction, a polycondensation catalyst and a stabilizer may be added to the reaction product of the esterification reaction or the transesterification reaction. As the polycondensation catalyst, a polycondensation catalyst commonly used in this field may be used without limitation, for example, a titanium-based compound, a germanium-based compound, an antimony-based compound, an aluminum-based compound, and a tin-based compound. One type or a mixture of two or more types may be used. As the stabilizer added to the polycondensation reaction, a phosphorus-based compound may be generally used, and for example, phosphoric acid, trimethyl phosphate, triethyl phosphate, or a mixture thereof may be used.

The polycondensation reaction is carried out at a temperature of 200 to 280 °C, preferably 210 to 260 °C, more preferably 220 to 240 °C, and a reduced pressure of 500 to 0.1 mmHg. The reduced pressure condition is for removing by-products of the polycondensation reaction.

In one embodiment, (a) (i) a dicarboxyl component comprising adipic acid and dimethyl terephthalate and an aliphatic dicarboxyl compound other than adipic acid; and (ii) anhydrosugar alcohol-based polycarbonate diol and, if necessary, a polymerization reaction product comprising a diol component including another aliphatic diol, at a pressure of 0.1 to 3.0 kgf/cm 2 and a temperature of 150 to 250° C. The esterification reaction or the transesterification reaction was carried out for an average residence time of 5 hours. (b) Next, the esterification or transesterification reaction product is subjected to a polycondensation reaction under a reduced pressure condition of 500 to 0.1 mmHg and a temperature of 200 to 280° C. for an average residence time of 1 to 10 hours, and the polycondensation reaction according to the present invention An ester resin can be prepared. Preferably, the final vacuum degree of the polycondensation reaction is 1.0 mmHg or less, and the esterification or transesterification reaction may be performed under an inert gas atmosphere.

The biodegradable polyester resin according to the present invention, compared with conventional biodegradable polyester resins such as PBAT resin, not only significantly improves heat resistance and mechanical properties (eg, elongation), but also further improves biodegradability, so it is molded Therefore, it can be usefully used in various articles.

Therefore, according to another aspect of the present invention, there is provided a molded article comprising the biodegradable polyester resin according to the present invention. In the present invention, 'molded article' means a molded article by extrusion, injection, or other known processing.

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples. However, the scope of the present invention is not limited by these examples.

[Example]

<Preparation of anhydrous sugar alcohol-alkylene glycol>

Preparation Example A1: Preparation of isosorbide-ethylene glycol (5 mol adduct of ethylene oxide of isosorbide)

1,460 g of isosorbide and 3.0 g of potassium hydroxide were placed in a reactor capable of pressurization and heating, and the inside of the reactor was substituted using nitrogen and heated to 100° C., and moisture in the reactor was removed through vacuum pressure reduction. Thereafter, 2,200 g of ethylene oxide was slowly added and the reaction was carried out at 100° C. to 140° C. for 5 hours to 6 hours. At this time, the reaction temperature was controlled not to exceed 140 °C. When the reaction was completed, the reaction product was cooled to 50° C., 40 g of a metal adsorbent (AMBOSOL MP20) was added, and heated again to remove residual metal ions by stirring at 100° C. to 120° C. for 1 hour to 5 hours (at this time, nitrogen was added or vacuum decompression was performed). After confirming that no metal ions are detected, the temperature is cooled to 60°C to 90°C, and residual by-products are removed through filtration. 3,500 g of isosorbide-ethylene glycol (5 mol adduct of ethylene oxide of isosorbide) was obtained.

Preparation A2: Preparation of isosorbide-propylene glycol (5 mol adduct of propylene oxide of isosorbide)

In the same manner as in Preparation Example A1, except that 2,900 g of propylene oxide was used instead of ethylene oxide, a transparent liquid isosorbide-propylene in which the hydrogens of the hydroxy groups at both ends of isosorbide are substituted with hydroxypropyl groups 4,200 g of glycol (5 mol adduct of propylene oxide of isosorbide) were obtained.

<Production of anhydrous sugar alcohol-based polycarbonate diol>

Preparation B1: Preparation of anhydrosugar alcohol-based polycarbonate diol using isosorbide-ethylene glycol

500 g of isosorbide-ethylene glycol and 117.5 g of diphenyl carbonate obtained in Preparation Example A1 were put in a 5-neck flask with a nitrogen gas pipe and a vacuum pump installed with a trap for removing by-products connected and containing a stirrer, a thermometer and a heater. , heated to 100° C. under a nitrogen atmosphere, and then, when melting of the reaction raw material was confirmed, 5.0 mg of magnesium acetate tetrahydrate was added and stirring was started. A nitrogen atmosphere was maintained until the reaction temperature reached 120 ° C. After that, the reaction system was heated to 155 ° C while maintaining the closed system (at this time, if nitrogen atmosphere is continuously maintained, the ratio changes due to sublimation of the reaction raw material, and the desired molecular weight Note that it is impossible to reach ). When the set temperature is reached, the reaction proceeds while maintaining the temperature for 1 hour, and after confirming that phenol, a by-product, is refluxed through the reactor wall, the pressure is reduced to 100 Torr to 120 Torr within 30 minutes using a vacuum pump, and the generated phenol The reaction proceeded for about 1 to 2 hours while removing the. When the amount of phenol generated reached 70 to 80% of the theoretical amount, the pressure was reduced to 5 Torr to 10 Torr, and then the reaction was further carried out for 1 hour to 2 hours. After that, when about 95% of the phenol is removed, nitrogen is bubbled into the reaction product for 1 to 2 hours while maintaining the reduced pressure to completely remove the remaining residual phenol. Through this, about 498 g of anhydrosugar alcohol-based polycarbonate diol was obtained.

The obtained anhydrosugar alcohol-based polycarbonate diol was a transparent liquid having a Gardner color number of 1 or less, and had a hydroxyl value of 185.9. The number average molecular weight converted from the hydroxyl value was 603.5, the measured PDI was 1.64, and the amount of residual phenol was measured to be less than the detection limit of 50 ppm.

Preparation B2: Preparation of anhydrosugar alcohol-based polycarbonate diol using isosorbide-propylene glycol

Isosorbide obtained in Preparation Example A1 Instead of ethylene glycol, isosorbide obtained in Preparation Example A2 500g of propylene glycol was used, and the content of diphenyl carbonate was changed from 117.5g to 70g except that, About 423 g of anhydrosugar alcohol-based polycarbonate diol was obtained in the same manner as in Preparation Example B1.

The obtained polycarbonate diol was a transparent liquid having a Gardner color number of 1 or less, and had a hydroxyl value of 180.6. The number average molecular weight converted from the hydroxyl value was 621.1, the measured PDI was 1.66, and the amount of residual phenol was measured to be 50 ppm or less, the detection limit.

<Production of biodegradable polyester resin>

Examples 1 to 9 and Comparative Examples 1 to 7

Put the reactants of the composition shown in Table 1 below in a 15 L melt-condensation reactor, add 550 ppm of a titanium-based catalyst based on an acid component (dimethyl terephthalate, DMT), and then esterify while raising the temperature to 210 ° C. The reaction was carried out, and alcohol produced as a by-product was removed. When more than 80% of the theoretical amount of alcohol flows out of the system, 750 ppm of a titanium-based catalyst and antioxidant based on the acid component (DMT) is added, and the pressure of the reaction system is increased to 1 mmHg while raising the temperature to 245°C. By gradually reducing the pressure, biodegradable polyester resins of Examples 1 to 9 and Comparative Examples 1 to 7 were prepared.

<Evaluation of physical properties>

The physical properties of the biodegradable polyester resins of Examples 1 to 9 and Comparative Examples 1 to 7 were measured by the following method, and the results are shown in Table 1 below.

(1) Intrinsic Viscosity (IV): A 0.5 wt% solution was prepared by dissolving a biodegradable polyester resin in a mixture of phenol and tetrachloroethane (weight ratio = 50:50), and then using an Uberod viscometer at 35 ° C. The viscosity was measured.

(2) Melting point: Using a thermal differential scanning calorimeter (DSC), the temperature was raised at a temperature increase rate of 10° C./min, cooled to remove the thermal history, and the temperature was increased again to measure the melting point.

(3) Glass transition temperature: The glass transition temperature (Tg) when the biodegradable polyester resin is heated at a temperature increase rate of 10°C/min and then cooled to room temperature and then scanned again at a temperature increase rate of 10°C/min is measured did.

(4) Intrinsic viscosity change rate (heat resistance evaluation item): After preparing a biodegradable polyester resin in the form of a pellet, 1 g of the biodegradable polyester pellet is placed on an aluminum plate, left in an oven at 65° C. for 72 hours, and then taken out again at room temperature After removing the thermal history from the intrinsic viscosity, the rate of change compared to the initial intrinsic viscosity was calculated.

(5) Elongation: Elongation was measured according to ASTM D638.

(6) Biodegradability: After freezing and pulverizing biodegradable polyester resin chips, the frozen and pulverized resin chips are placed in compost maintained at a temperature of 30-40 ° C and humidity of 55-60% to measure biodegradation under compost conditions. After embedding, biodegradability was measured at regular time intervals (after 1 month, after 2 months, and after 3 months). The standard soil and landfill conditions used were in accordance with ASTM D 5338-92.

<Ingredient Description>

- ISB-EO carbonate diol: anhydrosugar alcohol-based polycarbonate diol obtained in Preparation Example B1

- ISB-PO carbonate diol: anhydrosugar alcohol-based polycarbonate diol obtained in Preparation B2

- DMT: dimethyl terephthalate

As shown in Table 1, in the case of Examples 1 to 9 according to the present invention, by including anhydrosugar alcohol-based polycarbonate diol in a specific content range, the resin has a high glass transition temperature and excellent heat resistance (change in intrinsic viscosity) and excellent mechanical properties (elongation) and biodegradability were maintained.

On the other hand, in the case of a conventional biodegradable polyester resin (PBAT) resin in which anhydrosugar alcohol-based polycarbonate diol is not used (Comparative Example 1), the glass transition temperature is lowered, and the intrinsic viscosity change rate is 30% or more to less than 50% high, and the heat resistance was poor.

In addition, in the case of the biodegradable polyester resin in which the anhydrosugar alcohol-based polycarbonate diol was used in excess of the range specified in the present invention (Comparative Examples 2 and 3), a low molecular weight biodegradable polyester resin was obtained due to reduced reactivity. , the intrinsic viscosity and glass transition temperature were lowered, the intrinsic viscosity change rate was 50% to 100%, so the heat resistance was very poor, the mechanical properties were also poor because the elongation was less than 600%, and the anhydrosugar alcohol-based polycarbonate diol was In the case of the biodegradable polyester resin used in less than the range specified in the present invention (Comparative Examples 4 and 5), the glass transition temperature is lowered, and the intrinsic viscosity change rate is 30% or more to less than 50%, and the heat resistance is poor. there was.

In addition, in the case of the biodegradable polyester resin in which the aromatic dicarboxyl compound is used in excess of the range specified in the present invention (Comparative Example 6), the biodegradability is sharply reduced, the mechanical properties (elongation) are very poor, and the aliphatic dicarbonate In the case of the biodegradable polyester resin in which the carboxyl compound is used in excess of the range specified in the present invention (Comparative Example 7), the glass transition temperature is lowered, and the intrinsic viscosity change rate is very high, from 50% to 100%, and the heat resistance is very high. It became poor, and the mechanical properties (elongation) also deteriorated.

Claims (16)

repeating units derived from a dicarboxyl component; and a repeating unit derived from a diol component;
The dicarboxyl component contains more than 20 mol% to less than 80 mol% of an aliphatic dicarboxyl compound and more than 20 mol% to less than 80 mol% of an aromatic dicarboxyl compound, based on 100 mol% of the total dicarboxyl component including,
The aliphatic dicarboxyl compound comprises adipic acid or an ester thereof,
The diol component, based on 100 mol% of the total diol component, contains more than 0.5 mol% to less than 35 mol% of anhydrosugar alcohol-based polycarbonate diol,
Biodegradable polyester resin. According to claim 1,
The aliphatic dicarboxyl compound further comprises an aliphatic dicarboxylic acid having 4 to 14 carbon atoms or an ester thereof as an aliphatic dicarboxyl compound other than adipic acid or an ester thereof,
The aromatic dicarboxyl compound comprises an aromatic dicarboxylic acid having 8 to 16 carbon atoms or an ester thereof,
Biodegradable polyester resin. 3. The method of claim 2,
An aliphatic dicarboxyl compound other than adipic acid or its ester is cyclohexanedicarboxylic acid or its ester, sebacic acid or its ester, isodecylsuccinic or its ester, maleic acid or its ester, fumaric acid or its ester, succinic acid or Esters thereof, glutaric acid or its esters, azelaic acid or its esters, itaconic acid or its esters, glutamic acid or its esters, 2,5-furandicarboxylic acid or its esters, tetrahydrofuran-2,5-dicarboxylic acid or its esters acid or its ester, tetrahydrofuran-3,5-dicarboxylic acid or its ester, undecanedioic acid or its ester, dodecanedioic acid or its ester, tridecanedioic acid or its ester, tetradecanedioic acid or its ester, and combinations thereof,
Aromatic dicarboxyl compound is phthalic acid or its ester, terephthalic acid or its ester, isophthalic acid or its ester, 1,5-naphthalenedicarboxylic acid or its ester, 2,6-naphthalenedicarboxylic acid or its ester, diphenic acid or esters thereof, p-phenylene diacetic acid or esters thereof, o-phenylene diacetic acid or esters thereof, and combinations thereof,
Biodegradable polyester resin. The method according to claim 1, wherein the anhydrosugar alcohol-based polycarbonate diol comprises: (1) a repeating unit derived from an ether diol of anhydrosugar alcohol; And (2) a repeating unit derived from diester carbonate; containing, biodegradable polyester resin. The biodegradable polyester resin according to claim 4, wherein the ether diol of anhydrosugar alcohol is prepared by addition reaction of anhydrosugar alcohol and alkylene oxide. 6. The method according to claim 5, wherein the anhydrosugar alcohol is selected from the group consisting of isosorbide, isomannide, isoidide or mixtures thereof, and the alkylene oxide is a linear or branched alkyl having 2 to 20 carbon atoms or a branched alkyl having 3 to 20 carbon atoms. Which is selected from the group consisting of ren oxide, biodegradable polyester resin. 5. The biodegradable polyester resin of claim 4, wherein the carbonic acid diester is selected from dialkyl carbonates, diaryl carbonates, alkylene carbonates, or combinations thereof. The biodegradable polyester resin according to claim 4, wherein the anhydrosugar alcohol-based polycarbonate diol further comprises a repeating unit derived from an aliphatic diol. The biodegradable polyester resin according to claim 4, wherein the anhydrosugar alcohol-based polycarbonate diol comprises a repeating unit having a structure of the following formula (1):
[Formula 1]

In Formula 1, R ₁ and R ₂ are each independently a linear alkylene group having 2 to 20 carbon atoms or a branched alkylene group having 3 to 20 carbon atoms, and R ₁ and R ₂ may be the same as or different from each other. The biodegradable polyester resin according to claim 8, wherein the anhydrosugar alcohol-based polycarbonate diol further comprises a repeating unit having a structure of the following formula (2):
[Formula 2]

In Formula 2, R ₃ is a linear alkylene group having 2 to 10 carbon atoms or a branched alkylene group having 3 to 10 carbon atoms. According to claim 1, wherein the diol component further comprises an aliphatic diol other than the anhydrosugar-alcohol-based polycarbonate diol, and the content of the aliphatic diol other than the anhydrosugar-alcohol-based polycarbonate diol is based on 100 mol% of the total of the diol component , which is greater than 65 mol% and less than 99.5 mol%, biodegradable polyester resin. 12. The method of claim 11, wherein the aliphatic diol other than anhydrosugar alcohol-based polycarbonate diol is ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propane diol, 1,3-propane diol, 1,2-butane diol; 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1 ,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, neopentyl glycol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4 -Cyclohexanediol, 1,2-cyclohexane dimethanol, 1,3-cyclohexane dimethanol, 1,4-cyclohexane dimethanol, tetramethylcyclobutanediol, tricyclodecanedimethanol, adamantanediol, 2 ,2-dimethyl-1,3-propane diol, 2-ethyl-2-t-butyl-1,3-propane diol, 2,2,4-trimethyl-1,6-hexane diol, or a combination thereof selected from, biodegradable polyester resins. (1) subjecting the dicarboxyl component and the diol component to an esterification reaction or a transesterification reaction; and
(2) subjecting the reaction product obtained in step (1) to a polycondensation reaction;
The dicarboxyl component contains more than 20 mol% to less than 80 mol% of an aliphatic dicarboxyl compound and more than 20 mol% to less than 80 mol% of an aromatic dicarboxyl compound, based on 100 mol% of the total dicarboxyl component including,
The aliphatic dicarboxyl compound comprises adipic acid or an ester thereof,
The diol component, based on 100 mol% of the total diol component, contains more than 0.5 mol% to less than 35 mol% of anhydrosugar alcohol-based polycarbonate diol,
A method for producing a biodegradable polyester resin. The method according to claim 13, wherein the diol component further comprises an aliphatic diol other than the anhydrosugar-alcohol-based polycarbonate diol, and the content of the aliphatic diol other than the anhydrosugar-alcohol-based polycarbonate diol is based on 100 mol% of the total of the diol component. As a method for producing a biodegradable polyester resin, more than 65 mol% to less than 99.5 mol%. The biodegradable polyester resin according to claim 13, wherein in step (1), the reaction molar ratio of the diol component to the dicarboxyl component (total number of moles of diol component/total number of moles of dicarboxyl component) is 1.0 to 1.5. Way. A molded article comprising the biodegradable polyester resin according to any one of claims 1 to 12.