Polyester resin composition, preparation method thereof, and polyester film

Abstract

Provided are: a polyester resin composition comprising a polymer, which includes a repeating unit represented by chemical formula 1, and a furan dicarboxylic acid-based compound represented by chemical formula 2; a preparation method thereof; a polyester chip; and a polyester film. [Chemical formula 1] The definitions of chemical formula 1 and chemical formula 2 are as given in the specification.

Description

Polyester resin composition and method for producing the same, and polyester film

[0001] The present disclosure relates to a polyester resin composition, a method for producing the same, and a polyester film.

[0002] Polyester resin refers to a polymer resin that has an ester (RO-C(=O)-R') functional group in the main chain, and is used for various purposes in various industrial fields, such as packaging, display, and insulating materials.

[0003] A representative example is polyethylene terephthalate (PET) resin, which is manufactured by the reaction of terephthalic acid (TPA) and ethylene glycol (EG).

[0004] However, the main raw material for terephthalic acid is paraxylene, which is manufactured by refining crude oil. Therefore, the production and use of terephthalic acid contributes to the depletion of crude oil resources. Furthermore, the decomposition of terephthalic acid increases carbon dioxide emissions, contributing to environmental pollution and potentially contributing to climate change, including global warming.

[0005] In this regard, efforts are ongoing to replace terephthalic acid with 2,5-furan dicarboxylic acid (FDCA) in the production of polyester resins. FDCA, a biomass-derived material, can prevent the depletion of crude oil resources and, due to its biodegradability, minimize environmental pollution and climate change.

[0006] However, furan dicarboxylic acid is a compound with low thermal stability, and the process of esterifying it with a diol component causes thermal discoloration, such as yellowing and browning. To solve this problem, a method was devised to mix furan dicarboxylic acid with an aliphatic dicarboxylic acid and react it with the diol component, but the thermal discoloration problem has not yet been completely resolved.

[0007] According to one embodiment, a polyester resin composition having biodegradability while minimizing heat discoloration is provided.

[0008] According to another embodiment, a method for producing a polyester resin composition is provided, which can produce a polyester resin composition capable of minimizing the time of esterification reaction and minimizing thermal discoloration.

[0009] One embodiment provides a polyester resin composition comprising a polymer including a repeating unit represented by the following chemical formula 1, and a furan dicarboxylic acid compound represented by the following chemical formula 2:

[0010] [Chemical Formula 1]

[0011]

[0012] [Chemical Formula 2]

[0013]

[0014] In the above chemical formula 1 and chemical formula 2,

[0015] Above L 1 , L 2 , L 5 , and L 6 are each independently a single bond, or a substituted or unsubstituted alkylene having 1 to 10 carbon atoms,

[0016] Above L 3 and L 4 are each independently a substituted or unsubstituted alkylene having 1 to 10 carbon atoms,

[0017] above n 11is one of the integers between 50 and 200.

[0018] The content of the unreacted furan dicarboxylic acid compound in the above composition may be 0.1 ppm to 40 ppm.

[0019] The polymer including the repeating unit represented by the above chemical formula 1 may include a residue derived from a furan dicarboxylic acid compound and a residue derived from an alkylene glycol compound.

[0020] The molar ratio of the residue derived from the furan dicarboxylic acid compound and the residue derived from the alkylene glycol compound may be 1.2 to 1.5.

[0021] The composition may further include an oligomer, an aza-bicyclo catalyst, an imidazole additive, or a combination thereof.

[0022] The number average molecular weight (Mn) of the above oligomer may be 1,500 g / mol to 3,000 g / mol.

[0023] The above aza-bicyclo catalyst can be represented by one or more of the following chemical formulas 4 to 6:

[0024] [Chemical Formula 4]

[0025]

[0026] [Chemical Formula 5]

[0027]

[0028] [Chemical Formula 6]

[0029]

[0030] The above imidazole-based additive may be expressed by one or more of the following chemical formulas 7 to 9:

[0031] [Chemical Formula 7]

[0032]

[0033] [Chemical Formula 8]

[0034]

[0035] [Chemical Formula 9]

[0036]

[0037] The number average molecular weight (Mn) of the above polymer may be 20,000 g / mol to 40,000 g / mol.

[0038] Another embodiment provides a method for producing a polyester resin composition, comprising: an esterification reaction step of a reaction mixture including a furan dicarboxylic acid-based compound, an alkylene glycol-based compound, and an additive including an oligomer, an aza bicyclo-based catalyst, an imidazole-based additive, or a combination thereof; a polycondensation reaction step of an intermediate product obtained by the esterification reaction to obtain a polyester resin composition including a polymer and an unreacted furan dicarboxylic acid-based compound; wherein the content of the unreacted furan dicarboxylic acid-based compound in the polyester resin composition obtained by the polycondensation reaction is 0.1 ppm to 40 ppm.

[0039] The above oligomer may be included in an amount of 10 wt% to 50 wt% based on the total weight of the reaction mixture.

[0040] The number average molecular weight (Mn) of the above oligomer may be 1,500 g / mol to 3,000 g / mol.

[0041] Another embodiment provides a polyester film manufactured using the polyester resin composition described above.

[0042] The above polyester film may have a yellowness index of 1.48 or less as measured according to ASTM D1003-97.

[0043] The above polyester film may have a b* value of 1.41 or less according to the CIE1976 L*a*b* colorimetric system.

[0044] The above polyester film may have a haze of 1.0 or less.

[0045] A polyester resin composition according to one embodiment can exhibit biodegradability while minimizing heat discoloration.

[0046] In addition, a method for producing a polyester resin composition according to another embodiment can produce a polyester resin composition that can minimize the time of esterification reaction and minimize thermal discoloration.

[0047] The advantages and features of the technology described below, as well as the methods for achieving them, will become clearer with reference to the detailed implementation examples described below together with the attached drawings. However, the form of implementation may not be limited to the implementation examples disclosed below. Unless otherwise defined, all terms (including technical and scientific terms) used in this specification may be used in a meaning that can be commonly understood by those of ordinary skill in the relevant technical field. In addition, terms defined in commonly used dictionaries are not to be interpreted ideally or excessively unless explicitly and specifically defined.

[0048] When a part of this specification is said to "include" a certain component, this does not exclude other components, but rather includes other components, unless otherwise specifically stated. Furthermore, the singular includes the plural unless specifically stated otherwise.

[0049] In this specification, the term "moiety" refers to a certain part or unit derived from a specific compound when the specific compound participates in a chemical reaction and is included in the product of the chemical reaction. For example, a "moiety" derived from a furan dicarboxylic acid compound and a "moiety" derived from an alkylene glycol compound refer to a moiety derived from a furan dicarboxylic acid compound and a moiety derived from an alkylene glycol compound, respectively.

[0050] In this specification, the CIE1976 L*a*b* color space corresponds to a color space that is currently standardized worldwide, as defined by the CIE (International Commission on Illumination). In this CIE 1976 L*a*b* color space, the L* value represents brightness in color coordinates, and the range is 0 to 100, with 0 representing complete black and 100 representing complete white. a* represents whether it leans toward red or green. If this value is positive, that is, "+", it is red; if it is negative, that is, "-", it is green. b* represents whether it leans toward yellow or blue. If this value is positive, that is, "+", it is yellow; and if it is negative, that is, "-", it is blue.

[0051] Based on the above definitions, implementation examples of the present invention will be described in detail. However, these are presented as examples and are not intended to limit the present invention. The present invention is defined solely by the scope of the claims set forth below.

[0052]

[0053] polyester resin composition

[0054] One embodiment provides a polyester resin composition comprising a polymer including a repeating unit represented by the following chemical formula 1, and a furan dicarboxylic acid compound represented by the following chemical formula 2:

[0055] [Chemical Formula 1]

[0056]

[0057] [Chemical Formula 2]

[0058]

[0059] In the above chemical formula 1 and the above chemical formula 2, the L 1 , L 2 , L 5 , and L6 are each independently a single bond, or a substituted or unsubstituted alkylene having 1 to 10 carbon atoms, for example, a single bond, a methylene group, an ethylene group, or a combination thereof, and may be a single bond or a methylene group.

[0060] Above L 3 and L 4 are each independently a substituted or unsubstituted alkylene having 1 to 10 carbon atoms, for example, a single bond, a methylene group, an ethylene group, or a combination thereof, and may be a single bond or a methylene group.

[0061] above n 11 is an integer between 50 and 200, for example, n 11 The lower limit may be 50, 60, 70, 80, 90, 100, 110, 120, 130, 140 or 150, and the upper limit may be 200, 190, 180, 170 or 160.

[0062] The polymer including the repeating unit represented by the above chemical formula 1 may include a residue derived from a furan dicarboxylic acid compound and a residue derived from an alkylene glycol compound.

[0063] The above furan dicarboxylic acid compounds are derived from eco-friendly raw materials manufactured from biomass such as wood and corn, and can be completely decomposed (biodegraded) by microorganisms under certain conditions. Therefore, using furan dicarboxylic acid compounds instead of terephthalic acid as a raw material for polymers can prevent the depletion of crude oil resources. In addition, polymers manufactured using furan dicarboxylic acid compounds as raw materials exhibit biodegradability, which can contribute to the prevention of environmental pollution, climate change, etc. However, furan dicarboxylic acid compounds have low thermal stability, and polymers manufactured using them exhibit yellowing or browning and low brightness. Therefore, methods for minimizing thermal discoloration of resin compositions containing furan dicarboxylic acid compounds with low thermal stability, even when performing a high-temperature process using them as a reactant, have been studied. As a result, although the polyester resin composition according to one embodiment is manufactured using a furan dicarboxylic acid compound as a raw material, it contains a trace amount of unreacted furan dicarboxylic acid compound, and the content of the unreacted furan dicarboxylic acid compound must be minimized to minimize yellowing or browning of the resin composition and the resin film formed therefrom, and to implement high brightness.

[0064]

[0065] Furan dicarboxylic acid compounds

[0066] The above polymer contains a residue derived from a furan dicarboxylic acid compound (hereinafter, “furan dicarboxylic acid compound-derived residue”), and exhibits excellent biodegradability because it is derived from a furan dicarboxylic acid compound that can be represented by the following chemical formula 2.

[0067] [Chemical Formula 2]

[0068]

[0069] In the above chemical formula 2, L 5 and L 6 are each independently a single bond, or a substituted or unsubstituted alkylene having 1 to 10 carbon atoms.

[0070] For example, the furan dicarboxylic acid compound may be 2,5-furandicarboxylic acid, in which case L of the chemical formula 2 5 and L 6 can all be single bonds.

[0071] The above furan dicarboxylic acid compound-derived residue can be represented by the following chemical formula 2-1:

[0072] [Chemical Formula 2-1]

[0073]

[0074] In the above chemical formula 2-1, L 7 and L 8 are each independently a single bond, or a substituted or unsubstituted alkylene having 1 to 10 carbon atoms; * indicates a bonding position.

[0075] For example, when the furan dicarboxylic acid compound is 2,5-furandicarboxylic acid, L of the chemical formula 2-1 7 and L 8 All of them can be single bonds.

[0076]

[0077] alkylene glycol compounds

[0078] The polymer includes a residue derived from an alkylene glycol compound (hereinafter referred to as “alkylene glycol compound-derived residue”), and exhibits excellent compatibility and elongation properties due to the residue derived from the alkylene glycol compound.

[0079] The above alkylene glycol compound can be represented by the following chemical formula 3:

[0080] [Chemical Formula 3]

[0081]

[0082] In the above chemical formula 3, L 9 and L 10are each independently a substituted or unsubstituted alkylene having 1 to 10 carbon atoms. For example, the alkylene glycol compound may be ethylene glycol. In this case, L of the chemical formula 3 9 is C1 alkylene (i.e., methylene), and L 10 may be a C1 alkylene (i.e., methylene).

[0083] The residue derived from the above alkylene glycol compound can be represented by the following chemical formula 3-1:

[0084] [Chemical Formula 3-1]

[0085]

[0086] In the above chemical formula 3-1, L 11 and L 12 are each independently a substituted or unsubstituted alkylene having 1 to 10 carbon atoms; * indicates a bonding position. For example, when the alkylene glycol compound is ethylene glycol, L of the chemical formula 3-1 11 is C1 alkylene (i.e., methylene), and L 12 may be C1 alkylene (i.e., methylene).

[0087] The molar ratio of the furan dicarboxylic acid-based compound-derived residue and the alkylene glycol-based compound-derived residue in the polymer is 1.0 to 1.5, for example, 1.1 to 1.5, for example, 1.2 to 1.5, but is not limited thereto. Since the molar ratio of the furan dicarboxylic acid-based compound-derived residue and the alkylene glycol-based compound-derived residue in the polymer satisfies the above range, the content of unreacted furan dicarboxylic acid-based compound in the composition according to one embodiment can be minimized, thereby minimizing thermal discoloration of the composition.

[0088] The number average molecular weight (Mn) of the polymer may be 20,000 g / mol to 40,000 g / mol, for example, 22,000 g / mol to 38,000 g / mol, 23,000 g / mol to 37,000 g / mol, 24,000 g / mol to 36,000 g / mol, or 24,000 g / mol to 35,000 g / mol, but is not limited thereto. When the number average molecular weight (Mn) of the polymer satisfies the above range, film processing is possible, so that the processed film can be used as a packaging material, and a desired modulus can be achieved. In addition, the viscosity of the composition can be optimized to improve productivity and yield.

[0089] The ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) of the polymer, i.e., molecular weight distribution (MWD), may be from 1.1 to 3.0, for example, from 1.4 to 2.7, from 1.6 to 2.5, or from 1.79 to 2.4, but is not limited thereto.

[0090]

[0091] unreacted furan dicarboxylic acid compound

[0092] A polyester resin composition according to one embodiment can minimize heat discoloration of the composition by including an unreacted furan dicarboxylic acid compound represented by the following chemical formula 2. The unreacted furan dicarboxylic acid compound refers to a furan dicarboxylic acid compound that has not formed a polymer after polymerization reaction between the furan dicarboxylic acid compound and the alkylene glycol compound, i.e., has not reacted:

[0093] [Chemical Formula 2]

[0094]

[0095] In the above chemical formula 2, L 5 and L 6 are each independently a single bond, or a substituted or unsubstituted alkylene having 1 to 10 carbon atoms.

[0096] Since the unreacted furan dicarboxylic acid compound has low thermal stability, even if a composition containing the unreacted furan dicarboxylic acid compound is post-treated at high temperature or in a vacuum, the unreacted furan dicarboxylic acid compound is not removed and may remain in the composition or a polyester chip or film formed from the composition, which may cause yellowing and discoloration.

[0097] The content of the unreacted furan dicarboxylic acid compound in the composition is 40 ppm or less, for example, 0.1 ppm to 40 ppm, 0.1 ppm to 35 ppm, 0.1 ppm to 31 ppm, 0.1 ppm to 30 ppm, 0.1 ppm to 25 ppm, 0.1 ppm to 20 ppm, and is not limited thereto. When the unreacted furan dicarboxylic acid compound is included in an amount greater than the above range, carbonization may occur when the excessive unreacted furan dicarboxylic acid compound is exposed to high temperature, and the b* value of the resin composition and the polyester film formed therefrom may increase and cause thermal discoloration to yellow. That is, by including the unreacted furan dicarboxylic acid compound in the composition in the above range, thermal discoloration of the composition can be minimized. In addition, since the composition satisfies the standards for food packaging raw materials according to the regulations of the U.S. Food and Drug Administration (FDA), the composition can be applied when manufacturing food packaging films, etc.

[0098]

[0099] A polyester resin composition according to one embodiment may further include an oligomer, an aza-bicyclo catalyst, an imidazole additive, or a combination thereof.

[0100] The above oligomer is an oligomer derived from the reaction of a furan dicarboxylic acid-based compound and an alkylene glycol-based compound, and refers to a compound having a similar structural unit type constituting the oligomer to a polymer including a furan dicarboxylic acid-based compound-derived residue and an alkylene glycol-based compound-derived residue, but having a smaller molecular weight. By further including the oligomer in the composition, the content of unreacted furan dicarboxylic acid-based compound in the composition can be within the above range, and thermal discoloration of the composition can be minimized.

[0101] The number average molecular weight (Mn) of the above oligomer is 1,500 g / mol to 3,000 g / mol, for example, 1,600 g / mol to 2,900 g / mol, 1,700 g / mol to 2,800 g / mol, but is not limited thereto.

[0102] The above composition may further comprise a catalyst or additive, which is described in detail in the method for producing a polyester resin composition below.

[0103]

[0104] Method for producing a polyester resin composition

[0105] Another embodiment provides a method for producing a polyester resin composition, comprising: an esterification reaction step of a reaction mixture comprising a furan dicarboxylic acid-based compound, an alkylene glycol-based compound, and an additive comprising an oligomer, an aza-bicyclo-based catalyst, an imidazole-based additive, or a combination thereof; and a polycondensation reaction step of an intermediate product obtained by the esterification reaction to obtain a polyester resin composition comprising a polymer and unreacted furan dicarboxylic acid-based compound.

[0106] Hereinafter, descriptions that overlap with the above contents will be omitted, and each step of the above manufacturing method will be described in detail.

[0107] A method for manufacturing a polyester resin composition according to one embodiment includes a reaction of esterifying a reaction mixture including a furan dicarboxylic acid-based compound, an alkylene glycol-based compound, and an additive including an oligomer, an aza bicyclo-based catalyst, an imidazole-based additive, or a combination thereof. As described above, since the reaction mixture includes an additive including an oligomer, an aza bicyclo-based catalyst, an imidazole-based additive, or a combination thereof, the content of unreacted furan dicarboxylic acid-based compound in the composition can be minimized, and thermal discoloration of the composition can be minimized. In addition, the esterification reaction time can be minimized, thereby improving process efficiency.

[0108] In the above esterification reaction, the molar ratio of the furan dicarboxylic acid-based compound and the alkylene glycol-based compound is 1.0 to 1.5, for example, 1.1 to 1.5, for example, 1.2 to 1.5, but is not limited thereto. Since the molar ratio of the furan dicarboxylic acid-based compound and the alkylene glycol-based compound in the polymer satisfies the above range, the content of unreacted furan dicarboxylic acid-based compound in the composition according to one embodiment can be minimized, thereby minimizing thermal discoloration of the composition.

[0109] In the above esterification reaction, the reaction mixture contains 10 wt% to 50 wt% of the oligomer based on the total weight, for example, 15 wt% to 50 wt%, 20 wt% to 50 wt%, 25 wt% to 50 wt%, 30 wt% to 50 wt%, but is not limited thereto. By containing the oligomer in the above content range in the reaction mixture, the content of unreacted furan dicarboxylic acid-based compounds in the polyester resin composition can be minimized, thereby minimizing thermal discoloration of the composition.

[0110] In the above esterification reaction, the reaction mixture may include an aza-bicyclo catalyst, an imidazole-based additive, or a combination thereof. For example, the aza-bicyclo catalyst refers to a compound that includes a nitrogen-containing ring within the compound and includes another ring that shares at least two carbon atoms among the nitrogen-containing rings or at least one carbon atom with the nitrogen atom. For example, the aza-bicyclo catalyst may be represented by one or more of the following chemical formulae 4 to 6, but is not limited thereto:

[0111] [Chemical Formula 4]

[0112]

[0113] [Chemical Formula 5]

[0114]

[0115] [Chemical Formula 6]

[0116]

[0117] Meanwhile, in addition to the aza-bicyclo catalyst, the catalyst used in the esterification reaction may further include a catalyst such as a titanium (Ti)-based compound, a tin (Sn)-based compound, or an antimony (Sb)-based compound. By including the catalyst, the reaction rate of the esterification reaction can be improved from the initial stage of the reaction, and the time for which the polyester resin composition is exposed to heat can be shortened. The esterification reaction catalyst can be used in an amount of 1 ppm to 100 ppm based on the central atom in the synthesized polyester. When the content of the esterification reaction catalyst is within the above range, there is an advantage in that the appearance properties of the manufactured polyester can be improved, and at the same time, the efficiency of the esterification reaction can be greatly improved.

[0118] For example, an imidazole-based additive is a compound containing an imidazolium cation, wherein the two nitrogens of the imidazolium may be substituted with a substituted or unsubstituted C1 to C10 alkyl group. In addition, an anion for matching the charge with the imidazolium cation may be included, and any monovalent anion may be included regardless of type. For example, the imidazole-based additive may be expressed by any one or more of the following chemical formulae 7 to 9:

[0119] [Chemical Formula 7]

[0120]

[0121] [Chemical Formula 8]

[0122]

[0123] [Chemical Formula 9]

[0124]

[0125] The esterification reaction may be performed under a nitrogen (N2) atmosphere, a temperature range of 180°C to 250°C, and a pressure of 1 to 5.5 atm for 1 to 5 hours. For example, the esterification reaction may be performed at a temperature range of 180°C or higher, 182°C or higher, 184°C or higher, or 185°C or higher, and 220°C or lower, 210°C or lower, 200°C or lower, or 195°C or lower. In addition, the esterification reaction may be performed at 1 atm or higher, 5.5 atm or lower, 5 atm or lower, 3 atm or lower, or 1.5 atm or lower, and may be performed for 1 hour or longer, 1.5 hours or longer, or 2 hours or longer, 5 hours or shorter, 4 hours or shorter, or 3 hours or shorter. When the temperature, pressure, reaction time, etc. of the above esterification reaction are within the above range, the reaction yield is high, the reaction proceeds sufficiently, and the properties of the final polyester manufactured are improved, while the possibility of the appearance of the manufactured polyester turning yellow is reduced, which has the advantage of being advantageous.

[0126] The above esterification exchange reaction can be performed in a batch or continuous manner, and each raw material can be introduced separately, but as an example, it can be introduced in the form of a slurry in which the alkylene glycol is mixed with a furan-based dicarboxylic acid.

[0127] A method for manufacturing a polyester resin composition according to one embodiment includes a process of subjecting an intermediate product obtained by an esterification reaction to a polycondensation reaction after an esterification reaction.

[0128] The above polycondensation reaction can be carried out at a temperature range of 240 to 300°C and under a pressure of 1 torr or less or 0.4 to 0.8 torr or less for 2 to 6 hours. When the temperature, pressure, reaction time, etc. during the polycondensation are within the above ranges, there is an advantage in that glycol, a by-product of the polycondensation reaction, is effectively removed, so that the final reaction product exhibits an appropriate intrinsic viscosity, and the appearance of the polyester produced is less likely to turn yellow.

[0129] During the above condensation, a polycondensation reaction catalyst may be used. The polycondensation catalyst may be added to the product of the esterification reaction before the initiation of the polycondensation reaction, may be added before the esterification reaction, or may be added during the esterification reaction step. The polycondensation catalyst may be a titanium-based compound, a germanium-based compound, an antimony-based compound, an aluminum-based compound, a tin-based compound, or a mixture thereof. Examples of the titanium compounds include tetraethyl titanate, acetyltripropyl titanate, tetrapropyl titanate, tetrabutyl titanate, polybutyl titanate, 2-ethylhexyl titanate, octylene glycol titanate, lactate titanate, triethanolamine titanate, acetylacetonate titanate, ethyl acetoacetic ester titanate, isostearyl titanate, titanium dioxide, titanium dioxide / silicon dioxide copolymer, titanium dioxide / zirconium dioxide copolymer, etc. Examples of the germanium compounds include germanium dioxide (GeO2), germanium tetrachloride (GeCl4), germanium ethyleneglycoxide, germanium acetate, copolymers using these, mixtures thereof, etc.

[0130] Another embodiment provides a polyester chip and a polyester film comprising the polyester resin composition.

[0131] The above polyester film has a yellowness measured based on the ASTM D1003-97 standard of 1.48 or less, for example, 1.47 or less, 1.46 or less, 1.20 or less, 1.10 or less, 1.0 or less, for example, 1.2 or more, 1.25 or more, 1.30 or more, but is not limited thereto.

[0132] The above polyester film has a b* value according to the CIE1976 L*a*b* colorimetric system of 1.41 or less, for example, 1.40 or less, 1.39 or less, 1.38 or less, for example, 1.20 or more, 1.25 or more, 1.30 or more, but is not limited thereto.

[0133] The haze of the above polyester film is 1.0 or less, for example, 0.9 or less, 0.8 or less, for example, 0.1 or more, 0.2 or more, but is not limited thereto.

[0134] Hereinafter, examples and comparative examples of the present invention are described. The following examples are merely illustrative of the present invention, and the present invention is not limited to the following examples.

[0135]

[0136] Preparation of polyester resin composition

[0137] Example 1

[0138] 771.2 g of 2,5-furandicarboxylic acid (hereinafter referred to as FDCA), 368.0 g of ethylene glycol (hereinafter referred to as EG), and 106.8 g (10 wt%) of polyethylene pranoate oligomer are charged into a 2 L autoclave reactor, and an esterification reaction of FDCA and EG is performed at a temperature of 210° C. and in a nitrogen atmosphere for 2 hours.

[0139] After the esterification reaction is completed, a titanium-based catalyst (AC436) is added as a polycondensation catalyst so that the concentration is 10 ppm, stirred for 30 minutes, and the internal temperature of the reactor is increased for 1 hour. The reaction is carried out for 2 to 6 hours at a temperature of 260°C under a vacuum of 0.8 torr or less, and when the load transmitted to the torque meter of the autoclave reaches the desired load, the composition is discharged to obtain a polyester resin composition. The concentration of unreacted 2,5-furandicarboxylic acid in the obtained polyester resin composition is 19 ppm.

[0140]

[0141] Example 2

[0142] A polyester resin composition was prepared in the same manner as in Example 1, except that 599.8 g of 2,5-furandicarboxylic acid, 286.2 g of ethylene glycol, and 320.44 g (30 wt%) of polyethylene pranoate oligomer were used. The concentration of unreacted 2,5-furandicarboxylic acid in the obtained polyester resin composition was 15 ppm.

[0143]

[0144] Example 3

[0145] A polyester resin composition was prepared in the same manner as in Example 1, except that 428.4 g of 2,5-furandicarboxylic acid, 204.4 g of ethylene glycol, and 534.07 g (50 wt%) of polyethylene pranoate oligomer were used. The concentration of unreacted 2,5-furandicarboxylic acid in the obtained polyester resin composition was 12 ppm.

[0146]

[0147] Example 4

[0148] 856.9 g of 2,5-furandicarboxylic acid (FDCA) and 408.9 g of ethylene glycol (EG) are charged into a 2 L autoclave reactor, and 50 ppm of 2-Azabicyclo[2.2.1]hept-5-en-3-one (ABH) is used as a catalyst for the esterification reaction, and the esterification reaction of FDCA and EG is performed at 210°C in a nitrogen atmosphere for 2 hours.

[0149] After the esterification reaction is completed, a titanium-based catalyst (AC436) is added as a polycondensation catalyst so that the concentration is 10 ppm, stirred for 30 minutes, and the internal temperature of the reactor is increased for 1 hour. The reaction is carried out for 2 to 6 hours at a temperature of 260°C under a vacuum of 0.8 torr or less, and when the load transmitted to the torque meter of the autoclave reaches the desired load, the composition is discharged to obtain a polyester resin composition. The concentration of unreacted 2,5-furandicarboxylic acid in the obtained polyester resin composition is 19 ppm.

[0150]

[0151] Example 5

[0152] A polyester resin composition was prepared in the same manner as in Example 4, except that 50 ppm of 1,5-Diazabicyclo[4.3.0]-5-nonene (hereinafter, DAC) was used instead of 50 ppm of ABH as a catalyst for the esterification reaction. The concentration of unreacted 2,5-furandicarboxylic acid in the obtained polyester resin composition was 18 ppm.

[0153]

[0154] Example 6

[0155] A polyester resin composition was prepared in the same manner as in Example 4, except that 50 ppm of 2-(2-Azabicyclo[2.2.1]hept-2-yl)ethanol (hereinafter, ABHE) was used instead of 50 ppm of ABH as a catalyst for the esterification reaction. The concentration of unreacted 2,5-furandicarboxylic acid in the obtained polyester resin composition was 17 ppm.

[0156]

[0157] Example 7

[0158] 856.9 g of 2,5-furandicarboxylic acid (FDCA) and 408.9 g of ethylene glycol (EG) are added to a 2 L autoclave reactor, and 50 ppm of 1-Butyl-3-methylimidazolium methanesulfonate (BMIMS) is used as an additive, and an esterification reaction of FDCA and EG is performed at 210°C in a nitrogen atmosphere for 2 hours.

[0159] After the esterification reaction is completed, a titanium-based catalyst (AC436) is added as a polycondensation catalyst so that the concentration is 10 ppm, stirred for 30 minutes, and the internal temperature of the reactor is increased for 1 hour. The reaction is carried out for 2 to 6 hours at a temperature of 260°C and a vacuum state of 0.8 torr or less, and when the load transmitted to the torque meter of the autoclave reaches the desired load, the composition is discharged to obtain a polyester resin composition. The concentration of unreacted 2,5-furandicarboxylic acid in the obtained polyester resin composition is 15 ppm.

[0160]

[0161] Example 8

[0162] A polyester resin composition was prepared in the same manner as in Example 7, except that 50 ppm of 1-Butyl-3-methylimidazolium Tribromide (hereinafter, BMITB) was used instead of 50 ppm of BMIMS as an additive. The concentration of unreacted 2,5-furandicarboxylic acid in the obtained polyester resin composition was 14 ppm.

[0163]

[0164] Example 9

[0165] A polyester resin composition was prepared in the same manner as in Example 7, except that 50 ppm of 1-Butyl-3-methylimidazolium Trifluoro(trifluoromethyl)borate (hereinafter, BMITTB) was used instead of 50 ppm of BMIMS as an additive. The concentration of unreacted 2,5-furandicarboxylic acid in the obtained polyester resin composition was 13 ppm.

[0166]

[0167] Comparative Example 1

[0168] A polyester resin composition was prepared in the same manner as in Example 1, except that 856.9 g of 2,5-furandicarboxylic acid (FDCA; hereinafter referred to as FDCA) was used, 408.9 g of ethylene glycol was used, and no oligomer was used. The concentration of unreacted 2,5-furandicarboxylic acid in the obtained polyester resin composition was 51 ppm.

[0169]

[0170] Comparative Example 2

[0171] A polyester resin composition was prepared in the same manner as in Comparative Example 1, except that the catalyst concentration for the polycondensation reaction was 50 ppm. The concentration of unreacted 2,5-furandicarboxylic acid in the obtained polyester resin composition was 53 ppm.

[0172]

[0173] Comparative Example 3

[0174] A polyester resin composition was prepared in the same manner as in Comparative Example 1, except that 5 ppm of phosphoric acid (PA) was added as an additive to the reaction mixture. The concentration of unreacted 2,5-furandicarboxylic acid in the obtained polyester resin composition was 54 ppm.

[0175]

[0176] Comparative Example 4

[0177] A polyester resin composition was prepared in the same manner as in Comparative Example 1, except that 443.0 ethylene glycol was used. The concentration of unreacted 2,5-furandicarboxylic acid in the obtained polyester resin composition was 35 ppm.

[0178]

[0179] Comparative Example 5

[0180] A polyester resin composition was prepared in the same manner as in Comparative Example 4, except that 511.1 g of ethylene glycol was used. The concentration of unreacted 2,5-furandicarboxylic acid in the obtained polyester resin composition was 31 ppm.

[0181]

[0182] The materials and their contents used in the production of the polyester resin compositions according to Examples 1 to 9 and Comparative Examples 1 to 5 are summarized in Table 1 below.

[0183]

[0184]

[0185] Evaluation 1: Physical property evaluation of polyester chips

[0186] For each polyester resin composition manufactured in Examples 1 to 9 and Comparative Examples 1 to 5, the polyester polymer manufactured through the above process was discharged through the lower nozzle of the reactor, cooled by passing through a cooling water bath, and cut into pellets using a rotary cutter. The cut pellets were dehydrated using a blower to manufacture polyester polymer chips. Polyester chips were manufactured by the method described above, and the physical properties of each manufactured polyester chip were evaluated by the following method, which are shown in Table 2 below.

[0187]

[0188] Evaluation 1-1: Measurement of unreacted FDCA content

[0189] A 10 ml vial is prepared by adding a certain amount of methanol solvent and FDCA (Sigma Aldrch) to the concentrations of 0 ppm, 100 ppm, 200 ppm, and 500 ppm. A calibration curve is drawn for each content using this solution according to the measuring device and measurement conditions below. The reliability of the calibration curve for each content must be 99.95% or higher. The polyester chips prepared in Examples 1 to 9 and Comparative Examples 1 to 5 are placed in a grinder and ground into powder. 0.2 g of the powder and 2 g of MeOH are added to a 10 ml vial to dilute to 10 wt%, and then unreacted FDCA is dissolved using a magnetic stirrer for 24 hours. After filtering this solution, the Retation Time and Peak Area of ​​unreacted FDCA are calculated according to the measuring device and measurement conditions below. The unreacted FDCA content in the polyester resin composition was measured using this area and the above content-specific calibration curve.

[0190] Analytical equipment and conditions

[0191] - Analysis method: High Performance Liquid Chromatography (HLPC)

[0192] - Analysis instrument: Agilent 1260 Infinity Ⅱ

[0193] - Detector: Agilent 1100 series G1318A

[0194] - Mobile phase / eluent: Acetonitrile / Ammonium acetate 20mM aqueous solution = 20 / 80

[0195] - Column (maker, model no.): C18 (Hector) (250mm × 4.6mm, 5μm particle size)

[0196] - Temperature: 25 ℃

[0197] - Flow rate: 0.7 mL / min

[0198] - Injection volume, sample concentration: 1 μl, 0.1% MeOH, DMSO solution

[0199] - Quantitative wavelength: 265 nm

[0200]

[0201] Evaluation 1-2: Color Evaluation

[0202] To prevent deviation in color difference values, more than half (80 g or more) of the capacity of a container dedicated to chip measurement was filled with polyester chips according to Examples 1 to 9 and Comparative Examples 1 to 5 manufactured above, leaving the remainder as air, and using a Chip colorimeter from Nippon Denshoku (sa-4000), L* and b* values ​​were measured.

[0203]

[0204] Evaluation 1-3: Intrinsic Viscosity Evaluation

[0205] 0.5 g of the polyester chips prepared in Examples 1 to 9 and Comparative Examples 1 to 5 were added to a 20 ml vial together with 10 ml of a 1:1 solution of Phenol:Tetrachloroethane, and completely dissolved in a 100°C oil bath. Then, the intrinsic viscosity (IV) was measured at 25°C using an Ostwald viscometer.

[0206]

[0207] Evaluation 1-4: Molecular Weight Evaluation

[0208] The number average molecular weight (Mn) of the polyester resin composition manufactured according to the above oligomer, examples and comparative examples is measured by gel chromatography under the following conditions.

[0209] - Measuring instrument: EcoSEC HLC-8320 GPC

[0210] - Column (maker, model no.): TSKgel guardcolumn SuperAW-H + 2 x TSKgel SuperAWM-H

[0211] - Eluent: Hexafluoroisopropanol (HFIP) + 0.01 N Sodium trifluoroacetate (NaTFA)

[0212] - Temperature: 40 ℃

[0213] - Flow rate: 0.3 mL / min

[0214] - Injection volume, sample concentration: 15 ㎕, 3 mg / mL

[0215] - Standard sample: Polymethyl methacrylate (PMMA)

[0216] - Detector: Refractive Index (RI) detector

[0217]

[0218] Evaluation 2: Physical property evaluation of polyester resin film

[0219] Each polyester resin composition manufactured in Examples 1 to 9 and Comparative Examples 1 to 5 was melted at a temperature of 180°C to 260°C. The melt was extruded through a die, formed into a sheet, and rapidly cooled. The sheet thus obtained was stretched 3.0 times in the machine direction (MD) and then 3.7 times in the transverse direction (TD). To impart dimensional stability to the stretched film, a biaxially stretched film was obtained by heat-setting at 120°C to 160°C under tension. The physical properties of each polyester resin film manufactured above were evaluated by the following method and are shown in Table 2 below.

[0220]

[0221] Evaluation 2-1: Y transmittance, yellow index, b* evaluation

[0222] The polyester films manufactured from the polyester resin compositions according to Examples 1 to 9 and Comparative Examples 1 to 5 were cut into a size of 10 cm X 10 cm (longitudinal length X transverse length) to prepare specimens. The parallel transmittance, diffuse transmittance, yellow index, and b* value of the specimens were measured using a Minolta CM-3600A spectrophotometer according to the ASTM D1003-97 measurement method. The Y transmittance is defined as the sum of the parallel transmittance and the diffuse transmittance. Therefore, the transmittance was obtained from the Y parallel transmittance and the diffuse transmittance of the specimens.

[0223]

[0224] Evaluation 2-2: Haze Evaluation

[0225] The haze of the polyester biaxially stretched films according to Examples 1 to 9 and Comparative Examples 1 to 5 was measured using a Haze Meter, a Murakami Color Reseach Lab. (HM-150) facility.

[0226]

[0227]

[0228] Referring to Table 2 above, the polyester resin composition according to the comparative example had an unreacted FDCA content exceeding 50 ppm, whereas the polyester resin composition according to the example had an unreacted FDCA content of 30 ppm or less. It can be seen that the polyester resin film manufactured from the polyester resin composition according to the example has a lower yellowness and a lower b* value than the polyester resin film according to the comparative example. That is, the polyester resin film according to the example did not exhibit thermal discoloration compared to the comparative example. In addition, it can be seen that the polyester resin film manufactured from the polyester resin composition according to the example has a higher Y transmittance and a lower haze value than the polyester resin film according to the comparative example. That is, it was confirmed that the polyester resin film according to the example can implement higher transparency than the comparative example.

[0229] Although the preferred embodiments have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements made by those skilled in the art using the basic concepts defined in the following claims also fall within the scope of the present invention.

Claims

1. A polymer comprising a repeating unit represented by the following chemical formula 1, and A polyester resin composition comprising a furan dicarboxylic acid compound represented by the following chemical formula 2: [Chemical Formula 1] [Chemical formula 2] In the above chemical formula 1 and the above chemical formula 2, Above L 1 , L 2 , L 5 , and L 6 are each independently a single bond, or a substituted or unsubstituted alkylene having 1 to 10 carbon atoms, Above L 3 and L 4 are each independently a substituted or unsubstituted alkylene having 1 to 10 carbon atoms, above n 11 is one of the integers between 50 and 200.

2. A polyester resin composition in claim 1, wherein the content of the furan dicarboxylic acid compound in the composition is 0.1 ppm to 40 ppm.

3. In the first paragraph, the polymer including the repeating unit represented by the chemical formula 1 is a polyester resin composition including a residue derived from a furan dicarboxylic acid compound and a residue derived from an alkylene glycol compound.

4. A polyester resin composition in claim 1, wherein the molar ratio of the furan dicarboxylic acid-based compound-derived residue and the alkylene glycol-based compound-derived residue is 1.2 to 1.

5.

5. A polyester resin composition according to claim 1, further comprising an oligomer, an aza-bicyclo catalyst, an imidazole additive, or a combination thereof.

6. A polyester resin composition in claim 5, wherein the number average molecular weight (Mn) of the oligomer is 1,500 g / mol to 3,000 g / mol.

7. In the fifth paragraph, the aza-bicyclo catalyst is a polyester resin composition represented by at least one of the following chemical formulae 4 to 6: [Chemical Formula 4] [Chemical Formula 5] [Chemical formula 6] 8. In paragraph 5, the imidazole-based additive is a polyester resin composition represented by at least one of the following chemical formulas 7 to 9: [Chemical formula 7] [Chemical formula 8] [Chemical formula 9] 9. A polyester resin composition according to claim 1, wherein the number average molecular weight (Mn) of the polymer is 20,000 g / mol to 40,000 g / mol.

10. An esterification reaction step of a reaction mixture comprising a furan dicarboxylic acid compound, an alkylene glycol compound, and an additive including an oligomer, an aza bicyclo catalyst, an imidazole additive, or a combination thereof; A step of obtaining a polyester resin composition including a polymer and an unreacted furan dicarboxylic acid compound by subjecting the intermediate product obtained through the above esterification reaction to a polycondensation reaction; A method for producing a polyester resin composition, wherein the content of the unreacted furan dicarboxylic acid compound in the polyester resin composition obtained by the above polycondensation reaction is 0.1 ppm to 40 ppm.

11. A method for producing a polyester resin composition in claim 10, wherein the molar ratio of the furan dicarboxylic acid compound and the alkylene glycol compound is 1.2 to 1.5, the oligomer is contained in an amount of 10 to 50 wt% based on the total weight of the reaction mixture, and the number average molecular weight (Mn) of the oligomer is 1,500 g / mol to 3,000 g / mol.

12. In the 10th paragraph, the aza-bicyclo catalyst is represented by at least one of the following chemical formulas 4 to 6, and the imidazole-based additive is represented by at least one of the following chemical formulas 7 to 9, a method for producing a polyester resin composition: [Chemical Formula 4] [Chemical Formula 5] [Chemical formula 6] [Chemical formula 7] [Chemical formula 8] [Chemical formula 9] 13. A polyester film manufactured using a polyester resin composition according to any one of claims 1 to 9.

14. In the 13th paragraph, the polyester film is a polyester film having a yellowness of 1.48 or less as measured according to the ASTM D1003-97 standard.

15. In the 13th paragraph, the polyester film is a polyester film having a b* value of 1.41 or less according to the CIE1976 L*a*b* colorimetric system and a haze of 1.0 or less.

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