Polyester resin composition and preparation method for same

Abstract

The present invention relates to a polyester resin composition and a preparation method for same, the polyester resin composition undergoing esterification in the presence of a crystallization agent that can bond to the repeating units and / or terminal ends of the polyester resin, thereby stimulating the rate of crystallization as well as improving optical, mechanical, and processing properties.

Description

Polyester resin composition and method for producing the same

[0001] The present disclosure relates to a polyester resin composition and a method for producing the same, and more particularly, to a polyester resin composition and a method for producing the same, wherein the crystallization rate is promoted by promoting an esterification reaction by including a crystallizer that can be bonded to a repeating unit and / or terminal of the resin, while improving optical properties, mechanical properties, and processing properties.

[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 being made to replace terephthalic acid with 2,5-furan dicarboxylic acid (FDCA) in the manufacture of polyester resin compositions. Here, furan dicarboxylic acid, a biomass-derived material, can prevent the depletion of crude oil resources and, due to its biodegradability, minimize environmental pollution and climate change.

[0006] Accordingly, a polyfurandicarboxylate resin (PEF) can be manufactured by an esterification reaction of a diol compound and a furan dicarboxylic compound.

[0007] However, polyfurandicarboxylate resins have the disadvantage of a slow crystallization rate. To overcome this drawback, a method of polymerizing a diol compound with a long chain length that crystallizes quickly has been proposed. However, this method reduces the melting point of the polymer.

[0008] Additionally, crystallizers such as talc are known to accelerate crystallization rates. However, talc itself poses environmental concerns, leading to numerous regulations regarding its use.

[0009] According to one embodiment, a polyester resin composition is provided that promotes crystallization speed while improving optical properties, mechanical properties, and processing properties by promoting esterification reaction by including a crystallizer that can be bonded to repeating units and / or terminals of the resin.

[0010] According to another embodiment, a method for producing the polyester resin composition is provided.

[0011] A polyester resin composition according to one embodiment comprises a polymer including a repeating unit represented by the following chemical formula 1, and a crystallizer including a sodium salt of a polyhydric carboxylic acid or a sodium salt of a polyhydric alcohol, and has a yellow index of 0.9 or less as measured according to the ASTM E313 method using a CM-3600A measuring instrument from Minolta:

[0012] [Chemical Formula 1]

[0013]

[0014] In the above chemical formula 1, the above A 11 is a divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms, straight or branched chain, and the n 11is the number of repeating units, and is an integer in the range of 100 to 200.

[0015] In the above chemical formula 1, the above A 11 may contain a butylene group, a propylene group, an ethylene group, or a combination thereof.

[0016] The polymer may further include a terminal group represented by the following chemical formula 2-1:

[0017] [Chemical Formula 2-1]

[0018]

[0019] In the above chemical formula 2-1, the above A 21 is a divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms, straight or branched.

[0020] The polymer may further include a repeating unit represented by the following chemical formula 2-2, a repeating unit represented by the following chemical formula 2-3, or a combination thereof:

[0021] [Chemical Formula 2-2]

[0022]

[0023] [Chemical Formula 2-3]

[0024]

[0025] In the above chemical formulas 2-2 and 2-3, the above A 21 is a divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms, straight or branched chain, and the n 21 is the number of repeating units, and the above n 21 is an integer within the range of 100 to 200.

[0026] The crystallizing agent may include sodium 2,5-furandicarboxylate, monosodium citrate, monosodium glycerin, or a combination thereof.

[0027] The above crystallizer may be included in an amount of 0.005 wt% to 0.1 wt% based on 100 wt% of the polyester resin composition.

[0028] The above polyester resin composition may further include a titanium-based catalyst.

[0029] The above polyester resin composition may have a crystallinity of 28% or more calculated according to the following formula 1:

[0030] [Formula 1]

[0031] Crystallinity = T0 / T 100 100

[0032] In Equation 1, T0 is the crystallinity of the polyester resin composition in which only the polycondensation reaction is completed, and T 100 is the crystallinity of a polyester resin composition that is 100% crystallized.

[0033] The above polyester resin composition may have an L* of 57.5 or more as measured using a SA-400 colorimeter.

[0034] The above polyester resin composition may have a b* of 15 or less as measured using a SA-400 colorimeter.

[0035] A method for producing a polyester resin composition according to another embodiment comprises the steps of: subjecting a dicarboxylic acid compound including a diol compound and a furan dicarboxylic acid compound to an esterification reaction in the presence of a crystallizer; and subjecting the esterification reaction product to a polycondensation reaction to produce a polyester resin composition; wherein the crystallizer includes a sodium salt of a polyhydric carboxylic acid or a sodium salt of a polyhydric alcohol, and the polyester resin composition has a yellowness index (YI) of 0.9 or less as measured using a CM-3600A spectrophotometer.

[0036] The above diol compound may be a compound represented by the following chemical formula 3:

[0037] [Chemical Formula 3]

[0038]

[0039] In the above chemical formula 3, the above A 11 is a divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms, straight or branched.

[0040] The above furan dicarboxylic acid compound may be a compound represented by the following chemical formula 4:

[0041] [Chemical Formula 4]

[0042]

[0043] In the above chemical formula 4, the R 32 and R 33 are each independently a hydroxy group or an alkoxy group.

[0044] The above dicarboxylic acid compound further includes an aromatic dicarboxylic acid compound, an aliphatic dicarboxylic acid compound, or a mixture thereof, and the aromatic dicarboxylic acid compound may include isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, diphenyl dicarboxylic acid, 4,4'-stilbenedicarboxylic acid, 2,5-thiophenedicarboxylic acid, or a mixture thereof, and the aliphatic dicarboxylic acid compound may include malonic acid, succinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, fumaric acid, 2,2-dimethylglutaric acid, suberic acid, maleic acid, itaconic acid, maleic acid, or a mixture thereof.

[0045] The above esterification reaction step is carried out at a temperature of 160°C to 260°C for 1 to 8 hours. The above polycondensation reaction can be carried out at a temperature of 220°C to 300°C for 1 to 7 hours.

[0046] A polyester resin composition according to one embodiment includes a crystallizer that can be bonded to a repeating unit and / or terminal of a polyester resin to promote an esterification reaction, thereby promoting a crystallization rate while simultaneously improving optical properties, mechanical properties, and processing properties.

[0047] Hereinafter, embodiments of the present disclosure will be described in detail so that those skilled in the art can easily implement the present disclosure. However, the present disclosure may be implemented in various different forms and is not limited to the embodiments described herein.

[0048] Throughout this specification, whenever a part is referred to as "comprising" a certain component, this does not exclude other components, but rather includes other components, unless otherwise stated. Furthermore, the singular includes the plural unless specifically stated otherwise.

[0049] The term "alkyl" as used herein, unless otherwise stated, refers to saturated monovalent aliphatic hydrocarbon radicals, including straight and branched chains, having a specific number of carbon atoms. An alkyl group typically has from 1 to 20 carbon atoms ("C1-C 20 alkyl"), preferably having 1 to 12 carbon atoms ("C1-C 12Alkyl"), more preferably containing 1 to 8 carbon atoms ("C1-C8 alkyl"), or 1 to 6 carbon atoms ("C1-C6 alkyl"), or 1 to 4 carbon atoms ("C1-C4 alkyl"). Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, and the like. The alkyl group may be substituted or unsubstituted. In particular, unless otherwise specified, the alkyl group may be substituted with one or more halogens, up to the total number of hydrogen atoms present on the alkyl moiety. Thus, C1-C4 alkyl may be a halogenated alkyl group, for example, a fluorinated alkyl group having 1 to 4 carbon atoms, such as trifluoromethyl (-CF3) or difluoroethyl (-CH2CHF2). Includes.

[0050] An alkyl group described herein as optionally substituted may be substituted with one or more substituents, which substituents are independently selected unless otherwise stated. The total number of substituents is equal to the total number of hydrogen atoms on the alkyl moiety, to the extent that such substitution makes chemical sense. An optionally substituted alkyl group typically contains from 1 to 6 optional substituents, often from 1 to 5 optional substituents, preferably from 1 to 4 optional substituents, and more preferably from 1 to 3 optional substituents.

[0051] Optional substituents suitable for the alkyl group include, but are not limited to, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, 3- to 12-membered heterocyclyl, C6-C 12 Aryl and 5- to 12-membered heteroaryl, halo, =O(oxo), =S(thiono), =N-CN, =N-OR x , =NR x , -CN, -C(O)R x , -CO2R x, -C(O)NR x R y , -SR x , -SOR x , -SO2R x , -SO2NR x R y , -NO2, -NR x R y , -NR x C(O)R y , -NR x C(O)NR x R y , -NR x C(O)OR x , -NR x SO2R y , -NR x SO2NR x R y , -OR x , -OC(O)R x and -OC(O)NR x R y , and each R x and R y is independently hydrogen (H), C1-C8 alkyl, C1-C8 acyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, 3- to 12-membered heterocyclyl, C6-C 12 Aryl or 5 to 12 membered heteroaryl, or R x and R y can form a 3- to 12-membered heterocyclyl or 5- to 12-membered heteroaryl ring together with the N atom to which they are attached, each optionally selected from O, N and S(O) q (wherein q is 0 to 2) may contain 1, 2 or 3 additional heteroatoms selected from, and each R x and R yis optionally substituted with 1 to 3 substituents independently selected from the group consisting of halo, =O, =S, =N-CN, =N-OR', =NR', -CN, -C(O)R', -CO2R', -C(O)NR'2, -SOR', -SO2R', -SO2NR'2, -NO2, -NR'2, -NR'C(O)R', -NR'C(O)NR'2, -NR'C(O)OR', -NR'SO2R', -NR'SO2NR'2, -OR', -OC(O)R' and -OC(O)NR'2, wherein each R' is independently hydrogen (H), C1-C8 alkyl, C1-C8 acyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, 3- to 12-membered heterocyclyl, C6-C 12 Aryl or C5-C 12 Heteroaryl, and each C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, 3- to 12-membered heterocyclyl, C6-C 12 Aryl and 5- to 12-membered heteroaryl may be optionally substituted as further defined herein.

[0052] As used herein, unless otherwise stated, the term "divalent aliphatic hydrocarbon (i.e., alkylene)" refers to a divalent hydrocarbyl group having a specified number of carbon atoms capable of linking two other groups together. Often, alkylene is represented by the group -(CH2) n-(wherein n is 1 to 8, preferably n is 1 to 4). If specified, alkylene may also be substituted with other groups and may include at least 1 degree of unsubstitution (i.e., an alkenylene or alkynylene moiety) or a ring. The open valencies of the alkylene need not be at opposite ends of the chain. Thus, branched alkylene groups such as -CH(Me)-, -CH2CH(Me)-, and -C(Me)2- are also included within the scope of the term "alkylene", as are cyclic groups such as cyclopropane-1,1-diyl and unsaturated groups such as ethylene (-CH=CH-) or propylene (-CH2-CH=CH-). The alkylene groups are optionally substituted by the same groups as described herein as suitable for alkyl.

[0053] As used herein, the term “halo” or “halogen” refers to fluorine (F), chlorine (Cl), bromine (Br), or iodine (I), unless otherwise stated.

[0054] The term “hydroxy” as used herein, unless otherwise stated, refers to an —OH group.

[0055] The term "alkoxy" as used herein, unless otherwise stated, refers to a monovalent -O-alkyl group wherein the alkyl moiety has the specified number of carbon atoms. Alkoxy groups typically have from 1 to 8 carbon atoms ("C1-C8 alkoxy"), or from 1 to 6 carbon atoms ("C1-C6 alkoxy"), or from 1 to 4 carbon atoms ("C1-C4 alkoxy"). For example, C1-C4 alkoxy includes methoxy (-OCH3), ethoxy (-OCH2CH3), isopropoxy (-OCH(CH3)2), tert-butyloxy (-OC(CH3)3), and the like. The alkoxy group is optionally substituted on the alkyl moiety by the same groups described herein as appropriate for alkyl. In particular, the alkoxy group may be optionally substituted with one or more halo atoms, particularly one or more fluoro atoms, up to the total number of hydrogen atoms present on the alkyl moiety. Such groups are referred to as "haloalkoxy" groups having a specific number of carbon atoms and substituted with one or more halo substituents, e.g., when fluorinated, more specifically as "fluoroalkoxy" groups, typically containing from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, often 1 or 2 carbon atoms, and 1, 2 or 3 halo atoms (i.e., "C1-C6 haloalkoxy", "C1-C4 haloalkoxy" or "C1-C2 haloalkoxy"). More specifically, fluorinated alkyl groups can be specifically referred to as fluoroalkoxy groups, typically substituted with 1, 2 or 3 fluoro atoms, e.g., C1-C6, C1-C4 or C1-C2 fluoroalkoxy groups. Therefore, C1-C4 fluoroalkoxy includes trifluoromethyloxy (-OCF3), difluoromethyloxy (-OCF2H), fluoromethyloxy (-OCFH2), difluoroethyloxy (-OCH2CF2H), etc.

[0056] As used herein, the terms "optionally substituted" and "substituted or unsubstituted" are used interchangeably to indicate that the particular group being described may have no non-hydrogen substituents (i.e., unsubstituted), or that the group may have one or more non-hydrogen substituents (i.e., substituted). Unless otherwise specified, the total number of substituents that may be present is equal to the number of H atoms present on the unsubstituted form of the group being described. When an optional substituent is attached via a double bond (e.g., an oxo (=O) substituent), the group occupies an available valence, so that the total number of other substituents included is reduced by two. When an optional substituent is independently selected from a list of alternatives, the selected groups may be the same or different. It will be understood that throughout this specification, the number and nature of optional substituents will be limited to the extent that such substitution makes chemical sense.

[0057] In this specification, * indicated at both ends of a chemical formula indicates that it is connected to another adjacent chemical formula.

[0058]

[0059] 1. Polyester resin composition

[0060] A polyester resin composition according to one embodiment comprises a polymer including a repeating unit represented by the following chemical formula 1, and a crystallizer including a sodium salt of a polyhydric carboxylic acid or a sodium salt of a polyhydric alcohol, and has a yellow index of 0.9 or less as measured according to the ASTM E313 method using a CM-3600A measuring instrument from Minolta.

[0061] [Chemical Formula 1]

[0062]

[0063] In the above chemical formula 1,

[0064] A above 11is a divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms, straight or branched chain, and the n 11 is the number of repeating units.

[0065] above n 11 is an integer within a given range. For example, the above n 11 The lower limit may be about 100, 110, 120, 130, 140 or 150, and the upper limit may be about 200, 190, 180, 170 or 160.

[0066] above n 11 may have a range that is greater than or equal to any one of the lower limits described above; less than or equal to any one of the upper limits described above; or greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0067] When a known sodium salt nucleating agent that cannot be bonded to a polyester resin is added, the degree of crystallinity may increase, but there is a problem that discoloration occurs due to thermal decomposition. However, in the case of a polyester resin composition containing the crystallizing agent, the degree of crystallinity is high, and the yellowness value is within a predetermined range, so that discoloration can be prevented. The specific method for measuring the yellowness index is as described in the test example section.

[0068] In another example, the lower limit of the Yellow Index may be about 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, or 0.75, and the upper limit may be about 0.88, 0.86, 0.84, 0.82, 0.8, 0.78, 0.76, 0.74, 0.72, 0.7, 0.68, 0.66, 0.64, 0.62, 0.6, 0.58, or 0.56.

[0069] The yellow index of the polyester resin composition may have a range that is, in addition to the above-described range, lower than or equal to any one of the upper limits described above; or higher than or exceeding any one of the lower limits described above, but lower than or equal to any one of the upper limits described above.

[0070] In the above chemical formula 1, the above A 11 may contain a butylene group, a propylene group, an ethylene group, or a combination thereof.

[0071] The polyester resin composition includes a crystallizer comprising a sodium salt of a polyhydric carboxylic acid or a sodium salt of a polyhydric alcohol, which may remain without participating in the esterification reaction.

[0072] The above crystallizing agent can participate in a reaction during the manufacture of a polyester resin and be bonded to the polyester resin.

[0073] The above crystallizer may be bonded to the repeating unit and / or terminal of the polyester resin.

[0074] For example, the polymer may further include a terminal group represented by the following chemical formula 2-1.

[0075] [Chemical Formula 2-1]

[0076]

[0077] In the above chemical formula 2-1, the above A 21 is a divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms, straight or branched.

[0078] Additionally, the polymer may further include a repeating unit represented by the following chemical formula 2-2, a repeating unit represented by the following chemical formula 2-3, or a combination thereof.

[0079] [Chemical Formula 2-2]

[0080]

[0081] [Chemical Formula 2-3]

[0082]

[0083] In the above chemical formulas 2-2 and 2-3, the above A 21 is a divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms, straight or branched chain, and the n 21 is the number of repeating units.

[0084] above n 21 is an integer within a given range. For example, the above n 21 The lower limit may be about 100, 110, 120, 130, 140 or 150, and the upper limit may be about 200, 190, 180, 170 or 160.

[0085] above n 21 may have a range that is greater than or equal to any one of the lower limits described above; less than or equal to any one of the upper limits described above; or greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0086] The above polymer may be included within a predetermined range relative to 100 wt% of the polyester resin composition.

[0087] For example, the lower limit of the polymer relative to 100 wt% of the polyester resin composition may be about 99.9 wt%, 99.95 wt%, or 100 wt%, and the upper limit may be about 100 wt% or 99.995%.

[0088] The polymer may have a range of less than or equal to any one of the upper limits described above, or greater than or equal to any one of the lower limits described above, and less than or equal to any one of the upper limits described above, based on 100 wt% of the polyester resin composition.

[0089] The polyester resin composition may include a crystallizer that can be bonded to repeating units and / or terminal groups of the polyester resin.

[0090] For example, the crystallizing agent may include sodium 2,5-furandicarboxylate, monosodium citrate, monosodium glycerin, or a combination thereof.

[0091] The crystallizer included in the polyester resin composition may be an unreacted residue, and the content of the crystallizer may be adjusted within an appropriate range with respect to 100 wt% of the polyester resin composition.

[0092] The lower limit of the content of the crystallizer relative to 100 wt% of the polyester resin composition may be about 0.005 wt%, 0.006 wt%, 0.007 wt%, 0.008 wt%, 0.009 wt%, 0.01 wt%, 0.015 wt%, or 0.02 wt%, and the upper limit may be about 0.1 wt%, 0.09 wt%, 0.08 wt%, 0.07 wt%, 0.06 wt%, 0.05 wt%, 0.04 wt%, or 0.03 wt%.

[0093] The crystallizer may have a range of at least or exceeding any one of the lower limits described above, or less than or equal to any one of the upper limits described above, or more than or exceeding any one of the lower limits described above and less than or equal to any one of the upper limits described above, based on 100 wt% of the polyester resin composition.

[0094] That is, the crystallizer does not react and remains mostly as residue, but mostly reacts and can be bonded to the repeating units and / or terminal groups of the polyester resin.

[0095] The above polyester resin composition may further include a titanium-based catalyst.

[0096] The type of the above titanium-based catalyst is not limited as long as it is a titanium-based catalyst added during the production of polyester resin.

[0097] The above titanium-based catalyst can be included within a predetermined range based on 1 kg of the above polymer.

[0098] For example, based on 1 kg of the polymer, the lower limit of the content of the titanium-based catalyst may be about 5 ppm, 6 ppm, 7 ppm, 8 ppm, 9 ppm or 10 ppm, and the upper limit may be about 50 ppm, 40 ppm, 30 ppm, 20 ppm or 10 ppm.

[0099] The content of the titanium-based catalyst may be, based on 1 kg of polymer, greater than or equal to any one of the lower limits described above; less than or equal to any one of the upper limits described above; or greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0100] For example, the titanium-based catalyst may include tetraethyl titanate, acetyltripropyl titanate, tetrapropyl titanate, tetrabutyl titanate, polybutyl titanate, 2-ethylhexyl titanate, octylene glycol titanate, lactate titanate, triethanolamine titanate, acetyl acetonate titanate, ethyl acetoacetic ester titanate, isostearyl titanate, titanium dioxide, titanium isopropoxide, titanium chelate, titanium dioxide / silicon dioxide copolymer, titanium dioxide / zirconium dioxide copolymer, or a combination thereof.

[0101] In addition to having a yellowness within the above-described range, the above polyester resin composition may have crystallinity, optical properties, mechanical properties and / or processing properties described below.

[0102] The polyester resin composition may have excellent crystallinity. For example, the polyester resin composition may have a crystallinity within a predetermined range, as calculated by Equation 1 below. A specific method for measuring the crystallinity is as described in the Test Examples section.

[0103] [Formula 1]

[0104] Crystallinity = T0 / T 100 100

[0105] In Equation 1, T0 is the crystallinity of the polyester resin composition in which only the polycondensation reaction is completed, and T 100 is the crystallinity of a polyester resin composition that is 100% crystallized.

[0106] The lower limit of the crystallinity may be about 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54% or 55%, and the upper limit is not limited, but may be, for example, about 65%, 60%, 50%, 45%, 40%, 35% or 30%.

[0107] The crystallinity of the polyester resin composition may be higher than or equal to any one of the lower limits described above; or may be higher than or equal to any one of the lower limits described above and lower than or equal to any one of the upper limits described above.

[0108] The polyester resin composition may have L* and b* values ​​within a predetermined range as measured using an SA-400 colorimeter. The L* value represents brightness in color coordinates and ranges from 0 to 100, with 0 representing complete black and 100 representing complete white. The b* represents whether the color is biased toward yellow or blue. If the value is a positive value, "+", it is yellow, and if it is a negative value, "-", it is blue. The specific measuring method for the L* and b* is as described in the Test Example section.

[0109] The lower limit of the above L* may be about 57.5, 58, 58.5, 59, 59.5, 60, 60.5, 61, 61.5, 62 or 62.5, and the upper limit may be about 100, 95, 90, 85, 80, 75, 70, 65, 60 or 55.

[0110] The above L* may have a range that is equal to or greater than any one of the lower limits described above; or equal to or greater than any one of the lower limits described above, and equal to or less than any one of the upper limits described above.

[0111] Additionally, the lower limit of the above b* may be about 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14, and the upper limit may be about 15, 14.5, 14, 13.5, 13, 12.5, or 12.

[0112] The above b* may have a range that is less than or equal to any one of the upper limits described above; or is greater than or equal to any one of the lower limits described above, but less than or equal to any one of the upper limits described above.

[0113] The above polyester resin composition may have a glass transition temperature within a predetermined range. A specific method for measuring the glass transition temperature is as described in the Test Examples section.

[0114] The lower limit of the glass transition temperature of the polyester resin composition may be about 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C or 85°C, and the upper limit may be about 150°C, 145°C, 140°C, 135°C, 130°C, 125°C, 120°C, 115°C, 110°C, 105°C, 100°C, 95°C, 90°C or 85°C.

[0115] The glass transition temperature may be greater than or equal to any one of the lower limits described above; less than or equal to any one of the upper limits described above; or greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0116] Since the above polyester resin composition has a glass transition temperature within the above range, a polyester having excellent processability can be obtained.

[0117] The intrinsic viscosity (IV) of the above polyester resin composition measured at 25°C may have a value within a predetermined range. The specific method for measuring the intrinsic viscosity is as described in the test example section.

[0118] The lower limit of the intrinsic viscosity measured at 25°C may be about 0.4 dl / g, 0.45 dl / g, 0.5 dl / g, 0.55 dl / g, 0.6 dl / g or 0.65 dl / g, and the upper limit may be about 1 dl / g, 0.95 dl / g, 0.9 dl / g, 0.85 dl / g, 0.8 dl / g, 0.75 dl / g, 0.7 dl / g or 0.65 dl / g.

[0119] The intrinsic viscosity of the polyester resin composition measured at 25°C may have a range of greater than or equal to any one of the lower limits described above; less than or equal to any one of the upper limits described above; or greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0120] The above polyester resin composition may have a transmittance within a predetermined range. The method for measuring the transmittance is as described in the test example section.

[0121] The lower limit of the above transmittance may be about 70%, 75%, 80%, 85% or 90%, and the upper limit may be, but is not limited to, about 100%, 99%, 98%, 97%, 96%, 95%, 94%, 93%, 92%, 91%, 90% or 89%.

[0122] The transmittance of the polyester resin composition may have a range of greater than or equal to any one of the lower limits described above; less than or equal to any one of the upper limits described above; or greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0123] The polyester resin composition may have an excellent elastic modulus by including the crystallizer. For example, the polyester resin composition may have an elastic modulus within a predetermined range. The specific method for measuring the elastic modulus is as described in the Test Examples section.

[0124] The lower limit of the elastic modulus may be about 2.2 GPa, 2.3 GPa, 2.4 GPa, 2.5 GPa, 2.6 GPa, 2.7 GPa, 2.8 GPa or 2.9 GPa, and the upper limit may be about 3.5 GPa, 3.4 GPa, 3.3 GPa, 3.2 GPa, 3.1 GPa, 3 GPa, 2.9 GPa, 2.8 GPa, 2.7 GPa, 2.6 GPa, 2.5 GPa, 2.4 GPa or 2.3 GPa.

[0125] The elastic modulus of the polyester resin composition may be equal to or greater than any one of the lower limits described above; or may be equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0126] The polyester resin composition described above can have excellent tensile strength by including the crystallizer. For example, the polyester resin composition can have a tensile strength within a predetermined range. The specific method for measuring the tensile strength is as described in the Test Examples section.

[0127] The lower limit of the tensile strength may be about 100 MPa, 101 MPa, 102 MPa, 103 MPa, 104 MPa, 105 MPa, 106 MPa, 107 MPa, 108 MPa, 109 MPa, 110 MPa, 111 MPa, 112 MPa, 113 MPa, 114 MPa or 115 MPa, and the upper limit may be about 120 MPa, 119 MPa, 118 MPa, 117 MPa, 116 MPa, 115 MPa, 114 MPa, 113 MPa, 112 MPa, 111 MPa, 110 MPa, 109 MPa, 108 MPa, 107 MPa, 106 MPa, 105 MPa, It could be around 104 MPa, 103 MPa or 102 MPa.

[0128] The tensile strength of the polyester resin composition may be higher than or equal to any one of the lower limits described above; or may be higher than or equal to any one of the lower limits described above and lower than or equal to any one of the upper limits described above.

[0129] The polyester resin composition described above can have excellent elongation by including the crystallizer. For example, the polyester resin composition can have an elongation within a predetermined range. The specific method for measuring the elongation is as described in the Test Examples section.

[0130] The lower limit of the elongation of the polyester resin composition may be about 25%, 26%, 27%, 28%, 29%, or 30%, and the upper limit may be about 50%, 45%, 40%, or 35%.

[0131] The elongation of the polyester resin composition may be equal to or greater than any one of the lower limits described above; or may be equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0132] The above polyester resin composition can satisfy the above-described characteristics by including a crystallizer that can be bonded to the repeating unit and / or terminal group of the polyester resin, thereby accelerating the crystallization speed and simultaneously improving the optical properties, mechanical properties, and processing properties.

[0133] The polyester resin composition may have a number average molecular weight (Mn) within a predetermined range.

[0134] For example, the lower limit of the number average molecular weight (Mn) of the polyester resin composition may be about 10,000 g / mol, 15,000 g / mol, 20,000 g / mol, 24,000 g / mol, or 25,000 g / mol, and the upper limit may be about 40,000 g / mol, 35,000 g / mol, 30,000 g / mol, 25,000 g / mol, or 24,500 g / mol.

[0135] The polyester resin composition may have a number average molecular weight (Mn) that is equal to or greater than any one of the lower limits described above; equal to or less than any one of the upper limits described above; or equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0136] When the number average molecular weight of the polyester resin composition satisfies the above range, the mechanical properties and processing characteristics can be improved.

[0137] The polyester resin composition may have a ratio of weight average molecular weight (Mw) / number average molecular weight (Mn), i.e., a molecular weight distribution (MWD), within a predetermined range.

[0138] For example, the lower limit of the molecular weight distribution may be about 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, or 2.1, and the upper limit may be about 2.4, 2.3, 2.2, 2.1, 2.0, or 1.95.

[0139] The polyester resin composition may have a molecular weight distribution that is greater than or equal to any one of the lower limits described above; less than or equal to any one of the upper limits described above; or greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0140] When the molecular weight distribution of the polyester resin composition satisfies the above range, the defect rate can be reduced and the process cost can be reduced.

[0141]

[0142] 2. Method for producing polyester resin composition

[0143] A method for producing a polyester resin composition according to one embodiment comprises the steps of: subjecting a dicarboxylic acid compound including a diol compound and a furan dicarboxylic acid compound to an esterification reaction in the presence of a crystallizer; and subjecting the esterification reaction product to a polycondensation reaction to produce a polyester resin composition; wherein the crystallizer includes a sodium salt of a polyhydric carboxylic acid or a sodium salt of a polyhydric alcohol, and the polyester resin composition has a yellow index of 0.9 or less measured according to the ASTM E313 method using a CM-3600A measuring instrument from Minolta.

[0144] The specific method for measuring the above yellowness is as described in the test example section, and the lower and upper limits of the above yellowness are as described in “1. Polyester resin composition.”

[0145] A method for manufacturing a polyester resin composition according to one embodiment can accelerate the crystallization rate by introducing a crystallizer, and at the same time, improve optical properties, mechanical properties, and / or processing properties.

[0146] In the above esterification reaction (ES) step, a dicarboxylic acid compound including a diol compound and a furan dicarboxylic acid compound is reacted in the presence of a crystallizer.

[0147] The above diol compound may be an aliphatic diol compound. The above aliphatic diol compound may be a compound represented by the following chemical formula 3.

[0148] [Chemical Formula 3]

[0149]

[0150] In chemical formula 3, A 11 is a divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms, straight or branched.

[0151] For example, the diol compound may include an aliphatic diol compound having 2 to 20 carbon atoms, for example, 2 to 12 carbon atoms, or a combination thereof. Examples of such aliphatic diol compounds include linear, branched, or cyclic aliphatic diol components such as ethylene glycol, diethylene glycol, triethylene glycol, propanediol (e.g., 1,2-propanediol, 1,3-propanediol), 1,4-butanediol, pentanediol, hexanediol (e.g., 1,6-hexanediol), neopentyl glycol (2,2-dimethyl-1,3-propanediol), 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and tetramethylcyclobutanediol.

[0152] In particular, the aliphatic diol compound may be ethylene glycol or 1,4-butanediol. In this case, in chemical formula 5, A 11 may be C2 alkylene (i.e., ethylene) or C4 alkylene (i.e., butylene).

[0153] The above furan dicarboxylic acid compound may be a bio-derived material, and the polyester resin composition may be biodegradable due to the furan dicarboxylic acid compound.

[0154] The furan dicarboxylic acid compound may be a compound represented by the following chemical formula 4.

[0155] [Chemical Formula 4]

[0156]

[0157] In chemical formula 4, R 32 and R 33 are each independently a hydroxy group or an alkoxy group.

[0158] For example, the furan dicarboxylic acid compound may be 2,5-furandicarboxylic acid or an ester thereof, in which case in formula 3, R 32 and R 33 may be a hydroxyl group or an alkoxy group.

[0159] The dicarboxylic acid compound may further include an additional dicarboxylic acid component in addition to the furan dicarboxylic acid compound.

[0160] The above dicarboxylic acid compound may further include an aromatic dicarboxylic acid compound, an aliphatic dicarboxylic acid compound, or a mixture thereof.

[0161] The above aromatic dicarboxylic acid may be an aromatic dicarboxylic acid having 8 to 20 carbon atoms, for example, 8 to 14 carbon atoms, or a mixture thereof, and may be a naphthalenedicarboxylic acid such as isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl dicarboxylic acid, 4,4'-stilbenedicarboxylic acid, or 2,5-thiophenedicarboxylic acid. The terephthalic acid includes a dicarboxylic acid such as terephthalic acid, an alkyl ester thereof (a lower alkyl ester having 1 to 4 carbon atoms such as monomethyl, monoethyl, dimethyl, diethyl or dibutyl ester) and / or an acid anhydride thereof, and may react with a diol component to form a dicarboxylic acid moiety such as a terephthaloyl moiety.

[0162] Aliphatic dicarboxylic acid compounds can impart thermochromic properties to polyester resins.

[0163] The aliphatic dicarboxylic acid compound may be a compound represented by the following chemical formula 5.

[0164] [Chemical Formula 5]

[0165]

[0166] In chemical formula 5, A 21 is a divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms, straight or branched chain, and R 42 and R 43 are each independently a hydroxy group or an alkoxy group.

[0167] For example, the aliphatic dicarboxylic acid compound may be malonic acid, succinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, fumaric acid, 2,2-dimethylglutaric acid, suberic acid, maleic acid, itaconic acid, or maleic acid.

[0168] In particular, the aliphatic dicarboxylic acid compound may be succinic acid or adipic acid. In this case, in chemical formula 5, R 42 and R 43 is a hydroxyl group, and A 21 may be C2 alkylene (i.e., ethylene) or C4 alkylene (i.e., butylene).

[0169] The above crystallizer is as described in the “1. Polyester resin composition” section.

[0170] The above crystallizer can be added during the esterification reaction.

[0171] The amount of the above crystallizer may be within a predetermined range based on 1 kg of polymer.

[0172] For example, the lower limit of the input amount of the crystallizer may be about 50 ppm, 60 ppm, 70 ppm, 80 ppm, 90 ppm, 100 ppm, 110 ppm, 120 ppm, 130 ppm, 140 ppm, 150 ppm, 160 ppm, 170 ppm, 180 ppm, 190 ppm, 200 ppm, 300 ppm, 400 ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 900 ppm or 1000 ppm, and the upper limit may be about 2000 ppm, 1900 ppm, 1800 ppm, 1700 ppm, 1600 ppm, 1500 ppm, 1400 ppm, It can be 1300 ppm, 1200 ppm, 1100 ppm, 1000 ppm, 900 ppm, 800 ppm, 700 ppm, 600 ppm, 500 ppm, 400 ppm, 300 ppm, 200 ppm, 100 ppm, or 50 ppm.

[0173] The amount of the crystallizer added may be, based on 1 kg of polymer, more than or exceeding any one of the lower limits described above; less than or equal to any one of the upper limits described above; or more than or exceeding any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0174] By adjusting the amount of the crystallizing agent added within the above-mentioned range, the crystallization rate can be promoted while at the same time improving the optical properties, mechanical properties and / or processing properties.

[0175] The esterification reaction can be carried out by simultaneously introducing a diol compound and a furan dicarboxylic acid compound.

[0176] The esterification reaction step can be performed for a predetermined time at a temperature within a predetermined range in a nitrogen (N2) atmosphere.

[0177] For example, the lower limit of the temperature may be about 160°C, 170°C, 180°C, 190°C, 200°C, or 210°C, and the upper limit may be about 260°C, 250°C, 240°C, 230°C, 220°C, or 210°C.

[0178] Additionally, the lower limit of the above time may be about 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours or 3.5 hours, and the upper limit may be about 8 hours, 7 hours, 6 hours, 5 hours or 4 hours.

[0179] The temperature and time may each have a range that is greater than or equal to any one of the lower limits described above; less than or equal to any one of the upper limits described above; or greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0180] The esterification reaction step can be performed batchwise or continuously.

[0181] Meanwhile, the esterification reaction step may be performed in the presence of a titanium-based catalyst. In particular, the titanium-based catalyst can be added to the esterification reaction step to improve the reaction rate from the beginning and shorten the time the polyester resin is exposed to heat.

[0182] The type of the above titanium-based catalyst is the same as that described in the “1. Polyester resin composition” section.

[0183] The above titanium catalyst can be added within a predetermined range based on 1 kg of polymer.

[0184] The lower limit of the amount of the titanium catalyst to be added may be about 5 ppm, 6 ppm, 7 ppm, 8 ppm, 9 ppm or 10 ppm, and the upper limit may be about 50 ppm, 40 ppm, 30 ppm, 20 ppm or 10 ppm.

[0185] The amount of the titanium-based catalyst to be added may be, based on 1 kg of polymer, more than or exceeding any one of the lower limits described above; less than or equal to any one of the upper limits described above; or more than or exceeding any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0186] The above polycondensation reaction (PC) step can be performed for a predetermined time at a temperature within a predetermined range in a vacuum atmosphere.

[0187] For example, the lower limit of the temperature may be about 220°C, 230°C, 240°C, 250°C, or 260°C, and the upper limit may be about 300°C, 290°C, 280°C, 270°C, or 260°C.

[0188] Additionally, the lower limit of the above time may be about 1 hour, 2 hours, 3 hours, 4 hours, 4.5 hours or 5 hours, and the upper limit may be about 7 hours, 6.5 hours, 6 hours, 5.5 hours or 5 hours.

[0189] The temperature and time may each have a range that is greater than or equal to any one of the lower limits described above; less than or equal to any one of the upper limits described above; or greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0190] The polycondensation reaction step can be carried out under a vacuum slightly higher than 0 atm. The vacuum is measured using a vacuum gauge, and polymerization is usually carried out in the range of 0.4 torr to 0.8 torr.

[0191] During the polycondensation reaction, a polycondensation reaction catalyst can be used.

[0192] The polycondensation catalyst may be added to the product of the esterification reaction before the start of the polycondensation reaction, may be added to the mixture including the diol component and the dicarboxylic acid component before the esterification reaction, or may be added during the esterification reaction step.

[0193] As a polycondensation catalyst, a titanium compound, a germanium compound, an antimony compound, an aluminum compound, a tin compound, or a mixture thereof can be used.

[0194] As for titanium compounds, the same as those exemplified as titanium catalysts in the “1. Polyester resin composition” section.

[0195] Germanium compounds include germanium dioxide (GeO2), germanium tetrachloride (GeCl4), germanium ethyleneglycoxide, germanium acetate, copolymers using these, and mixtures thereof.

[0196] Optionally, the method for producing a polyester resin composition may further include, after the polymerization step, a step of introducing a chain extender to produce a chain-extended polyester resin composition.

[0197] A polyester resin composition having desired properties can be manufactured by increasing the molecular weight through a chain extension reaction.

[0198] As chain extenders, polyvalent isocyanate compounds, aromatic amine compounds, etc. can be used. Polyvalent isocyanate compounds may include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, hexamethylene diisocyanate, triphenylmethane triisocyanate, or mixtures thereof, and as aromatic amine compounds, in particular, Lonza's DETDA80 product, which is a mixture of 3,5-diethyl-2,4-diaminotoluene and 3,5-diethyl-2,6-diaminotoluene in a weight ratio of 20:80, can be used.

[0199] Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement them. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein.

[0200]

[0201] [Manufacture of crystallizer]

[0202] Manufacturing Example 1. Manufacturing of crystallizer (A)

[0203] In an autoclave (capacity 5 L), 1700 g of water, 1 mol of 2,5-furandicarboxylic acid (156.09 g), and 1 mol of sodium hydroxide (39.997 g) were added and the reaction was carried out so that the solid content became 10%.

[0204] After purging the above autoclave 5 times with N2, the reaction was carried out at 100 rpm under a pressure of 2 bar of nitrogen, and after raising the temperature to 80°C for 30 minutes, the reaction was carried out until all 2,5-furandicarboxylic acid was dissolved in water.

[0205] After all 2,5-furandicarboxylic acid was dissolved in water, the reaction was continued for an additional hour, then the reaction was terminated, cooled to room temperature, and impurities that were not dissolved in water were removed through a filter process, and then all water was removed using a freeze dryer.

[0206] As a result, 169.2 g of sodium 2,5-polydicarboxylic acid was obtained as a crystallizer (A), and the yield was approximately 95%.

[0207]

[0208] Manufacturing Example 2. Manufacturing of crystallizer (B)

[0209] A crystallizer (B) was prepared in the same manner as in Manufacturing Example 1, except that water was added from 1700 g to 2050 g and 1 mol of citric acid (192.124 g) was added instead of 1 mol of 2,5-furandicarboxylic acid (156.09 g).

[0210] As the manufactured crystallizer (B), 196.99 g of monosodium citrate was obtained, and the yield was approximately 92%.

[0211]

[0212] Manufacturing Example 3. Manufacturing of crystallizer (C)

[0213] A crystallizer (C) was prepared in the same manner as in Manufacturing Example 1, except that water was added from 1700 g to 2050 g and 1 mol of glycerin (90.093 g) was added instead of 1 mol of 2,5-furandicarboxylic acid (156.09 g).

[0214] 100.9 g of monosodium glycerin was obtained as the manufactured crystallizer (C), and the yield was approximately 90%.

[0215]

[0216] [Preparation of polyester resin composition]

[0217] Examples 1-1 to 3-3, and Comparative Examples 1 to 5.

[0218] In a reaction vessel, 2,5-furandicarboxylic acid (FDCA), ethylene glycol (EG), tetrabutyl titanate (TBT) and a crystallizer as described in Table 1 below are added, and then the temperature is raised to 210°C for 1 hour while stirring at 120 rpm under a nitrogen pressure of 2.0 to 2.5 bar, and the temperature is maintained thereafter, and the esterification reaction is performed for 3.5 hours. When the effluent produced as a by-product becomes 90% or more of the theoretical effluent, the esterification reaction is terminated after switching to normal pressure.

[0219] The pressure was gradually reduced to a vacuum of less than 1 torr over 1 hour and the temperature was raised to 260°C.

[0220] A polycondensation reaction was performed for 5 hours at a final temperature of 260°C and a pressure of 0.5 torr, and when the motor load reached a polymerization termination torque of 40 rpm and 120 Torque, the reaction was stopped, pressurized, and discharged into cold water to obtain a pelletized polyester resin composition.

[0221] Classification Composition Process Temperature FDCAEGTBT Crystallizer ESPC Example 1-11 eq 1.2 eq 10 ppm Crystallizer (A) 50 ppm 210°C 260°C Example 1-21 eq 1.2 eq 10 ppm Crystallizer (A) 200 ppm 210°C 260°C Example 1-31 eq 1.2 eq 10 ppm Crystallizer (A) 1000 ppm 210°C 260°C Example 2-11 eq 1.2 eq 10 ppm Crystallizer (B) 50 ppm 210°C 260°C Example 2-21 eq 1.2 eq 10 ppm Crystallizer (B) 200 ppm 210°C 260°C Example 2-31 eq 1.2 eq 10 ppm Crystallizer (B) 1000ppm210℃260℃Example 3-11eq1.2eq10ppmCrystallizing agent (C) 50ppm210℃260℃Example 3-21eq1.2eq10ppmCrystallizing agent (C) 200ppm210℃260℃Example 3-31eq1.2eq10ppmCrystallizing agent (C) 1000ppm210℃260℃Comparative example 11eq1.2eq10ppmX210℃260℃Comparative example 21eq1.2eq10ppmSodium saccharin 200ppm210℃260℃Comparative example 31eq1.2eq10ppmSodium carbonate 200ppm210℃260℃Comparative example 41eq1.2eq10ppm Sodium benzoate 200ppm210℃260℃ Comparative example 51eq1.2eq10ppm Sodium stearate 200ppm210℃260℃

[0222] -FDCA: 2,5-furandicarboxylic acid

[0223] -EG: Ethylene glycol

[0224] -TBT: tetrabutyl titanate

[0225] -eq: equivalent

[0226] -ES: Esterification reaction

[0227] -PC: polycondensation reaction

[0228]

[0229] Test example: Physical property evaluation

[0230] (1) Gel chromatography (GPC)

[0231] Polyester resin compositions manufactured according to Examples 1-1 to 3-3 and Comparative Examples 1 to 5 are subjected to gel chromatography under the following conditions.

[0232] - Instrument: EcoSEC HLC-8320 GPC

[0233] - Column (maker, model no.): TSKgel guardcolumn SuperAW-H + 2 x TSKgel SuperAWM-H

[0234] - Eluent: HFIP + 0.01 N NaTFA

[0235] - Temperature: 40℃

[0236] - Flow rate: 0.3 mL / min

[0237] - Injection volume, sample concentration: 15 ㎕, 3 mg / mL

[0238] - Standard: PMMA

[0239] - Detector: RI

[0240]

[0241] (2) Crystallinity

[0242] The polyester resin compositions manufactured according to Examples 1-1 to 3-3 and Comparative Examples 1 to 5 were heated from room temperature (25°C) to 300°C at a heating rate of 20°C / min under nitrogen at a pressure of 20 psi using a DSC Q20 measuring device from TA instrument, and then cooled from 300°C to room temperature (25°C) at a cooling rate of 20°C / min to perform the first rum. Thereafter, the temperature was increased from room temperature (25°C) to 250°C at a heating rate of 5°C / min to measure the crystallinity (T0) of the polyester resin composition in which only the polycondensation reaction was completed.

[0243] In addition, the polyester resin composition was heated to 130°C using a vacuum oven and maintained at 130°C for 2 hours. At this time, the problem of the resins being fused together occurred, so the fused resins were dropped 2-3 times using a rubber hammer. After that, the temperature was raised to 160°C for 1 hour and a vacuum state was maintained for 48 hours to obtain a 100% crystallized polyester resin composition. The crystallinity (T) of the 100% crystallized polyester resin composition 100 ) was measured.

[0244] At this time, the degree of crystallinity was calculated according to Equation 1 below.

[0245] [Formula 1]

[0246] Crystallinity = T0 / T 100 100

[0247] In Equation 1, T0 is the crystallinity of the polyester resin composition in which only the polycondensation reaction is completed, and T 100 is the crystallinity of a 100% crystallized polyester resin composition.

[0248]

[0249] (3) Colorimeter

[0250] The polyester resin compositions manufactured according to Examples 1-1 to 3-3 and Comparative Examples 1 to 5 were filled to more than half of the capacity of a colorimeter measuring container (80 g), and the L*, a*, and b* values ​​were measured using a Chip colorimeter, SA-4000, manufactured by Nippon Denshoku.

[0251]

[0252] (4) Intrinsic viscosity (IV)

[0253] 0.5 g of the polyester resin compositions manufactured according to Examples 1-1 to 3-3 and Comparative Examples 1 to 5 were placed in a 20 ml vial and placed in a 100° C. oil bath containing 10 ml of a mixed solvent (phenol / tetrachloroethane = molar ratio of 1:1) to completely dissolve the composition. Then, the intrinsic viscosity was measured using an Ostwald viscometer at 25° C.

[0254]

[0255] (5) Glass transition temperature (Tg)

[0256] The glass transition temperature of the polyester resin compositions manufactured according to Examples 1-1 to 3-3 and Comparative Examples 1 to 5 was measured using a DSC Q20 measuring device from TA instrument.

[0257] Specifically, the glass transition temperature of the polyester resin composition was measured while heating the temperature from room temperature (25°C) to 300°C at a heating rate of 20°C / min under a pressure of 20 psi under nitrogen.

[0258]

[0259] (6) Transmittance and yellowness

[0260] The polyester resin compositions prepared in Examples 1-1 to 3-3 and Comparative Examples 1 to 5 were melted in an extruder at a temperature of 180°C to 260°C. The melt was compressed through an extrusion die, formed into a sheet, and rapidly cooled. The sheet thus obtained was stretched 3.3 times in the machine direction (MD) and then 3.3 times in the transverse direction (TD).

[0261] In order to provide dimensional stability to the above-mentioned stretched film, a biaxially stretched film was obtained by heat-setting at 120°C to 160°C under tension, and the biaxially stretched film was cut into a size of 10 cm in width and 10 cm in length to prepare a specimen.

[0262]

[0263] 1) Transmittance

[0264] For the above specimen, the parallel transmittance and diffuse transmittance of the specimen were measured according to the ASTM D1003-97 method using a CM-3600A measuring instrument from Minolta.

[0265] The transmittance (Y(D65)) was obtained by adding the parallel transmittance and the diffuse transmittance.

[0266]

[0267] 2) Yellow Index

[0268] The yellow index of the above specimen was measured according to the ASTM E313 method using a CM-3600A measuring instrument from Minolta.

[0269]

[0270] (2) Elastic modulus, tensile strength and elongation

[0271] ASTM D638-V Type specimens were produced using polyester resin compositions manufactured according to Examples 1-1 to 3-3 and Comparative Examples 1 to 5 using a microcompounder extrusion machine at an extrusion temperature of 220°C to 260°C and a screw speed of 100 rpm to 120 rpm.

[0272] The manufactured specimens were mounted using the vice grips of the UTM 5566A universal testing machine from Instron.

[0273] The strength at the point of fracture of the specimen when it was stretched at a rate of 5 mm / min at room temperature (25℃) was defined as the tensile strength, the increased length was defined as the elongation, and the slope of the load with respect to the initial deformation was defined as the tensile modulus.

[0274]

[0275] The physical property results according to the above test examples are shown in Tables 2 and 3 below.

[0276] Classification Polyester resin composition GPC results Mw (g / mol) Mn (g / mol) PDI Example 1-152,290 24,900 2.1 Example 1-249,600 24,800 2 Example 1-349,302 24,900 1.98 Example 2-147,980 24,990 1.92 Example 2-252,275 25,500 2.05 Example 2-353,212 24,750 2.15 Example 3-150,388 24,700 2.04 Example 3-249,650 24,950 1.99 Example 3-350,050 24,900 2.01 Comparative example Comparative Example 167,230,24,900,2.7 Comparative Example 262,37,324,850,2.51 Comparative Example 361,75,224,800,2.49 Comparative Example 459,77,424,700,2.42 Comparative Example 561,87,124,650,2.51

[0277] Crystallinity (%)L*b*Tg(℃)IVY(D65)(%)YIModulus(GPa)Strength(MPa)Elongation(%)Example 1-14061.113.8880.65189.90.752.410425Example 1-25062.112.188.30.6590.50.562.811250Example 1-35562.81288.50.65290.60.552.911550Example 2-13559.11488.20.65489.90.772.410730Example 2-24060.2413.988.40.6689.90.762.611045 Example 2-34560.3413.588.90.64990.00.722.711230 Example 3-13058.8913.888.10.64889.90.752.310230 Example 3-23759.1213.89880.65389.90.762.510550 Example 3-34260.113.188.50.65290.20.672.711050Comparative Example 12558.1214.188.10.65289.80.782.110220Comparative Example 24556.116.188.20.65189.11.012.410630Comparative Example 34257.115.988.40.6589.20.982.510725Comparative Example 44056.915.288.10.64889.40.912.410530Comparative Example 53555.117.188.30.64788.71.12.310435

[0278]

[0279] result

[0280] It can be confirmed that the crystallinity of Examples 1-1 to 3-3 including the crystallizer manufactured according to Manufacturing Examples 1 to 3 is higher than that of Comparative Example 1 not including the crystallizer. That is, it can be confirmed that the crystallization rate is accelerated.

[0281] However, it can be confirmed that the crystallinity of Examples 1-1 to 3-3 is similar to or better than that of Comparative Examples 2 to 4, which include a crystallizer including a known sodium salt rather than a crystallizer according to the present disclosure, and that no discoloration due to heat occurs.

[0282] This is thought to be because, in the case of the crystallizer containing the sodium salt used in Comparisons 2 to 4, thermal discoloration occurs throughout the polyester resin composition due to thermal decomposition in the polyester reaction that occurs at high temperatures, unlike the crystallizer according to Manufacturing Examples 1 to 3, which is included in the polyester repeating unit formed through esterification bonds.

[0283]

[0284] Although the preferred embodiments have been described in detail above, the scope of the rights 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 rights.

Claims

1. A polymer comprising a repeating unit represented by the following chemical formula 1, and A crystallizer comprising a sodium salt of a polycarboxylic acid or a sodium salt of a polyhydric alcohol, The yellow index is 0.9 or less as measured according to the ASTM E313 method using a Minolta CM-3600A measuring instrument. Polyester resin composition: [Chemical Formula 1] In the above chemical formula 1, A above 11 is a divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms, which is straight or branched chain, above n 11 is the number of repeating units, an integer in the range of 100 to 200.

2. In paragraph 1, In the above chemical formula 1, A 11 containing a butylene group, a propylene group, an ethylene group, or a combination thereof; Polyester resin composition.

3. In paragraph 1, The above polymer further comprises a terminal group represented by the following chemical formula 2-1: Polyester resin composition: [Chemical Formula 2-1] In the above chemical formula 2-1, A above 21 is a divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms and is straight-chain or branched.

4. In paragraph 1, The polymer further comprises a repeating unit represented by the following chemical formula 2-2, a repeating unit represented by the following chemical formula 2-3, or a combination thereof. Polyester resin composition: [Chemical Formula 2-2] [Chemical Formula 2-3] In the above chemical formulas 2-2 and 2-3, A above 21 is a divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms, which is straight or branched chain, above n 21 is the number of repeating units, and n is the number of repeating units. 21 is an integer within the range of 100 to 200.

5. In paragraph 1, The crystallizing agent comprises sodium 2,5-furandicarboxylate, monosodium citrate, monosodium glycerin or a combination thereof. Polyester resin composition.

6. In paragraph 1, The above crystallizing agent is included in a range of 0.005 wt% to 0.1 wt% with respect to 100 wt% of the polyester resin composition. Polyester resin composition.

7. In paragraph 1, The above polyester resin composition further comprises a titanium-based catalyst. Polyester resin composition.

8. In paragraph 1, The above polyester resin composition has a crystallinity of 28% or more calculated according to the following formula 1. Polyester resin composition: [Formula 1] Crystallinity = T0 / T 100 100 In Equation 1, T0 is the crystallinity of the polyester resin composition in which only the polycondensation reaction is completed, and T 100 is the crystallinity of a polyester resin composition that is 100% crystallized.

9. In paragraph 1, The above polyester resin composition has an L* of 57.5 or more as measured using a SA-400 colorimeter. Polyester resin composition.

10. In paragraph 1, The above polyester resin composition has a b* of 15 or less as measured using a SA-400 colorimeter. Polyester resin composition.

11. A step of esterifying a dicarboxylic acid compound including a diol compound and a furan dicarboxylic acid compound in the presence of a crystallizer; A step of producing a polyester resin composition by subjecting the above esterification reaction product to a polycondensation reaction; The above crystallizing agent comprises a sodium salt of a polyhydric carboxylic acid or a sodium salt of a polyhydric alcohol, The above polyester resin composition has a yellowness index (YI) of 0.9 or less as measured using a CM-3600A spectrophotometer. A method for producing a polyester resin composition.

12. In paragraph 11, The above diol compound is a method for producing a polyester resin composition represented by the following chemical formula 3: [Chemical Formula 3] In the above chemical formula 3, A above 11 is a divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms and is straight-chain or branched.

13. In paragraph 11, The above furan dicarboxylic acid compound is a method for producing a polyester resin composition, which is a compound represented by the following chemical formula 4: [Chemical Formula 4] In the above chemical formula 4, Above R 32 and R 33 are each independently a hydroxy group or an alkoxy group.

14. In paragraph 11, The above dicarboxylic acid compound further includes an aromatic dicarboxylic acid compound, an aliphatic dicarboxylic acid compound, or a mixture thereof. The above aromatic dicarboxylic acid compound includes isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, diphenyl dicarboxylic acid, 4,4'-stilbenedicarboxylic acid, 2,5-thiophenedicarboxylic acid, or a mixture thereof. The above aliphatic dicarboxylic acid compound comprises malonic acid, succinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, fumaric acid, 2,2-dimethylglutaric acid, suberic acid, maleic acid, itaconic acid, maleic acid, or a mixture thereof. A method for producing a polyester resin composition.

15. In paragraph 11, The above esterification reaction step is performed at a temperature of 160° C. to 260° C. for 1 to 8 hours. The above polycondensation reaction is carried out at a temperature of 220°C to 300°C for 1 to 7 hours. A method for producing a polyester resin composition.

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