Resin composition, preparation method for same, polyester chips, and polyester film

Abstract

Provided are a resin composition, a preparation method for same, polyester chips, and polyester film, the resin composition having 2-methyl-1,3-dioxolane impurity content of 10 ppm or less by weight, and comprising a polyester resin containing residues derived from a furandicarboxylic acid-based compound and an alkylene glycol-based compound.

Description

Resin composition and method for producing the same, polyester chips, and polyester films

[0001] It relates to a resin composition and a method for producing the same, polyester chips, and polyester films.

[0002] Polyester resin refers to a polymer resin with an ester functional group in the main chain, and is used for various purposes in various industrial fields, such as packaging, displays, and insulating materials.

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

[0004] However, since the main raw material for terephthalic acid is paraxylene, which is manufactured by refining crude oil, 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, which can contribute to environmental pollution and climate change, including global warming.

[0005] Accordingly, efforts are being made to replace terephthalic acid with 2,5-furan dicarboxylic acid (FDCA) in the production of polyester resins. 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] One embodiment aims to improve the optical properties and color expression properties of polyester chips and polyester films by providing a resin composition that can be manufactured in an environmentally friendly manner and can suppress the generation of impurities, which are volatile substances.

[0007] In one embodiment, a polyester resin comprising a furan dicarboxylic acid-based compound-derived residue and an alkylene glycol-based compound-derived residue is included.

[0008] A resin composition is provided in which the content of 2-methyl-1,3-dioxolane, which is an impurity, is 10 ppm or less on a weight basis.

[0009] In another embodiment, a method for producing a resin composition is provided, comprising preparing a composition comprising a polyester resin including a residue derived from a furan dicarboxylic acid compound and a residue derived from an alkylene glycol compound, and controlling the content of 2-methyl-1,3-dioxolane, which is an impurity generated by light or heat, in the polyester resin to 10 ppm or less by weight.

[0010] In another embodiment, a polyester chip comprising the resin composition described above is provided.

[0011] In another embodiment, a polyester film comprising the above-described resin composition is provided.

[0012] One embodiment provides a resin composition that can be manufactured in an environmentally friendly manner and suppresses the generation of impurities, which are volatile substances, thereby improving the optical properties and color implementation properties of polyester chips and polyester films.

[0013] Below, specific implementation examples are described in detail so that those skilled in the art can easily implement the present invention. However, the present invention can be implemented in various different forms and is not limited to the implementation examples described herein.

[0014] The terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise.

[0015] When a part is said to "include" a component, this does not mean that it excludes other components, but rather that it may include other components, unless otherwise stated.

[0016] The term “moiety” as used herein refers to a certain portion 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. More specifically, the “moiety” derived from a furan dicarboxylic acid compound and the “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.

[0017] The term "alkyl" as used herein, unless otherwise stated, refers to saturated aliphatic hydrocarbons, including straight and branched chains, having a specific number of carbon atoms (i.e., carbon number). For example, the alkyl can typically be a C1 to C10 (i.e., having 1 to 10 carbon atoms) alkyl, for example, a C1 to C8 alkyl, a C1 to C5 alkyl, or a C1 to C3 alkyl. Examples of such alkyl 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.

[0018] The description of the "alkyl" mentioned above can be equally applied to the monovalent aliphatic hydrocarbon "alkyl group" and the divalent "alkylene". Meanwhile, the "alkyl group" including the "alkyl group" or "alkylene" mentioned above can be unsubstituted or substituted with an additional substituent, and the description of "substitution" can be applied to the following. For example, the alkyl group can be substituted with one or more halogen atoms, up to the total number of hydrogen atoms present on the alkyl moiety. For example, the C1 to C4 alkyl can be an alkyl substituted or unsubstituted with a halogen atom, and for example, it can be a C1 to C4 alkyl group substituted or unsubstituted with fluorine (F), and representative examples thereof can include trifluoromethyl (-CF3) or difluoroethyl (-CH2CHF2).

[0019] An alkyl 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 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.

[0020] "Substitution" means that at least one hydrogen atom is replaced by a halogen atom (F, Cl, Br, I), a hydroxy group or a salt thereof, a C1 to C20 alkoxy group, a nitro group, a cyano group, an amine group, an imino group, an azido group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a carbamyl group, a thiol group or a salt thereof, a thioether group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1 to C10 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C20 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 It may mean that it is substituted with a substituent of a heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, a C3 to C20 heteroaryl group, or a combination thereof. Or, for example, the "substitution" may mean that at least one hydrogen atom is substituted with a substituent of a halogen atom, a C1 to C10 alkyl group, a C6 to C20 aryl group, a C3 to C20 heteroaryl group, or a combination thereof.

[0021] 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.

[0022] 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.

[0023] resin composition

[0024] One embodiment provides a resin composition comprising a polyester resin including a furan dicarboxylic acid-based compound-derived residue and an alkylene glycol-based compound-derived residue, and having a content of 2-methyl-1,3-dioxolane, an impurity, of 10 ppm or less on a weight basis.

[0025] In response to the growing demand for environmentally friendly polyester resins, a manufacturing technology is being developed for polyester resins produced by reacting biomass-derived furan dicarboxylic acid compounds with alkylene glycol compounds. These polyester resins utilize biomass-derived furan dicarboxylic acid compounds instead of crude oil-derived terephthalic acid compounds, thereby preventing the depletion of crude oil resources. Furthermore, the resulting polyester resins exhibit biodegradability, making them environmentally friendly.

[0026] However, when polyester resins manufactured using furan dicarboxylic acid compounds as raw materials are manufactured into chips and stored, byproducts such as 2-methyl-1,3-dioxolane are easily generated within the chips when exposed to sunlight or high temperatures. These byproducts are volatile substances that can be inhaled by the human body, and there is concern that they may adversely affect the optical properties of films manufactured through post-processing steps performed at high temperatures. In addition, furan dicarboxylic acid compounds used as raw materials for manufacturing polyester resins have low thermal stability, so polyester resins manufactured using them turn yellow or brown and exhibit low brightness, which is detrimental to the color implementation of products using them.

[0027] In one embodiment, the invention aims to improve the properties of a resin composition and a polyester film by suppressing the generation of impurities such as 2-methyl-1,3-dioxolane generated when a polyester resin containing a furan dicarboxylic acid-based compound-derived residue and an alkylene glycol-based compound-derived residue is exposed to sunlight or high temperatures and controlling the content below a certain level.

[0028] A resin composition according to one embodiment comprises a polyester resin comprising a residue derived from a furan dicarboxylic acid compound and a residue derived from an alkylene glycol compound. In this case, the polyester resin comprises a terminal group of the main chain. (Here, * indicates a bonding position) has a glycol chain terminal group, and when exposed to sunlight or high temperature, a decomposition reaction occurs, which decomposes into a carboxyl chain terminal group and acetaldehyde. Acetaldehyde reacts with alkylene glycol, which is a raw material for polyester resin, to easily generate impurities such as 2-methyl-1,3-dioxolane. However, these impurities may be inhaled into the human body, and may adversely affect the optical properties of the polyester resin, or may adversely affect the optical properties or color implementation of polyester films obtained through a post-processing process.

[0029] Accordingly, a resin composition according to one embodiment is characterized in that the content of 2-methyl-1,3-dioxolane, which is an impurity, is controlled to be low, on a weight basis (i.e., based on the total weight of the resin composition), to 10 ppm or less (including 0 ppm). By satisfying this, the amount of volatile substances that may be harmful to the human body can be reduced, and the deterioration of the physical properties of the resin composition and the polyester film caused by the substances can be prevented. Through this, not only can the purity of the polyester resin of the resin composition itself be increased to improve the optical properties, but also the optical properties and color implementation of the polyester film manufactured using the same can be contributed.

[0030] In the above resin composition, 2-methyl-1,3-dioxolane exists as an impurity, and since the less impurity it contains, the better, the lower limit of its content is not particularly limited. In particular, since it is preferable that the resin composition does not contain impurities, the case where the content of 2-methyl-1,3-dioxolane is 0 ppm by weight is also included.

[0031] For example, the resin composition may have a content of 2-methyl-1,3-dioxolane of 5 ppm or less by weight, for example, 4.1 ppm or less, 2.5 ppm or less, 2 ppm or less, or 1.4 ppm or less, and an example of a lower limit of the content of 2-methyl-1,3-dioxolane may be 0.1 ppm. Within this range, the inherent physical properties of the resin composition can be further improved, and the optical properties and color implementation effects of the polyester film can be maximized.

[0032] According to one embodiment, the resin composition may further include a hydrazine-based additive. In this case, the hydrazine-based additive may preferentially react with acetaldehyde, which is generated when the polyester resin decomposes upon exposure to sunlight or high temperatures. The hydrazine-based additive's participation in the reaction with acetaldehyde may contribute to suppressing the generation of the impurity 2-methyl-1,3-dioxolane.

[0033] For example, the resin composition may further include the above-described hydrazine-based additive, an additive represented by the following chemical formula 1A, an additive represented by the following chemical formula 1B, or a combination thereof. When such a hydrazine-based additive is used, acetaldehyde generated during the decomposition process of the polyester resin can effectively react with the hydrazine-based additive, and the content of 2-methyl-1,3-dioxolane, which is an impurity, can be minimized. Accordingly, when the hydrazine-based additive is used, thermal degradation of yellowing or browning of the polyester resin can be effectively suppressed, thereby further improving the optical properties and color implementation effect of the polyester film.

[0034] [Chemical Formula 1A]

[0035]

[0036] [Chemical Formula 1B]

[0037]

[0038] In the above chemical formula 1A, R1 to R4 are each independently hydrogen, or a substituted or unsubstituted C1 to C5 alkyl group, X is carbonic acid, hydrochloric acid, sulfuric acid, nitric acid, or a combination thereof,

[0039] In the above chemical formula 1B, X1 to X4 are each independently S, O, NR5, R5 is hydrogen, or a substituted or unsubstituted C1 to C5 alkyl group, and Y1 - and Y2 - are each independently -SO3 - , -Cl - , or a combination thereof, and Z + is NH4 + am.

[0040] For example, the resin composition may further include, as the above-described hydrazine-based additive, an additive represented by the following chemical formula 2A, an additive represented by the following chemical formula 2B, or a combination thereof.

[0041] [Chemical Formula 2A]

[0042]

[0043] [Chemical Formula 2B]

[0044]

[0045] In the above chemical formula 2A, R1 to R4 are each independently hydrogen, or a substituted or unsubstituted C1 to C5 alkyl group, X is carbonic acid, hydrochloric acid, sulfuric acid, nitric acid, or a combination thereof,

[0046] In the above chemical formula 2B, R5 and R6 are each independently hydrogen, or a substituted or unsubstituted C1 to C5 alkyl group, and Z + is NH4 + am.

[0047] For example, the resin composition may further include the hydrazine-based additive described above, an additive represented by the following chemical formula 3A, an additive represented by the following chemical formula 3B, or a combination thereof.

[0048] [Chemical Formula 3A]

[0049]

[0050] [Chemical Formula 3B]

[0051]

[0052] In the above chemical formula 3A, R1 to R4 are each independently hydrogen, or a substituted or unsubstituted C1 to C5 alkyl group,

[0053] In the above chemical formula 3B, R5 and R6 are each independently hydrogen or a substituted or unsubstituted C1 to C5 alkyl group.

[0054] For example, the resin composition may further include the hydrazine-based additive described above, an additive represented by the following chemical formula 4A, an additive represented by the following chemical formula 4B, or a combination thereof.

[0055] [Chemical Formula 4A]

[0056]

[0057] [Chemical Formula 4B]

[0058]

[0059] According to one embodiment, the above-described hydrazine-based additive may be included in an amount of 0.001 wt% to 0.01 wt% based on 100 wt% of the resin composition. Within this range, the use of the hydrazine-based additive may not cause changes in the physical properties of the polyester resin, while improving the optical properties and viscosity properties of the resin composition and securing the optical properties and color-implementing effect of the polyester film may be more advantageous.

[0060] In one embodiment, each of R1 to R4 may independently be hydrogen, or a substituted or unsubstituted C1 to C3 alkyl group. Alternatively, each of R1 to R4 may independently be hydrogen, or a substituted or unsubstituted C1 or C2 alkyl group. Alternatively, each of R1 to R4 may independently be hydrogen, or an unsubstituted C1 or C2 alkyl group.

[0061] For example, R5 and R6 can each independently be hydrogen, or a substituted or unsubstituted C1 to C3 alkyl group. Alternatively, R5 and R6 can each independently be hydrogen, or a substituted or unsubstituted C1 or C2 alkyl group. Alternatively, R5 and R6 can each independently be hydrogen, or an unsubstituted C1 or C2 alkyl group.

[0062] The above polyester resin can be manufactured through a series of processes including an esterification reaction, a preliminary polymerization reaction, and a polycondensation reaction of a furan dicarboxylic acid compound and an alkylene glycol compound, and any conventional method can be applied to the specific method of manufacturing the polyester resin. Hereinafter, the residue derived from the furan dicarboxylic acid compound and the residue derived from the alkylene glycol compound will be described in detail.

[0063] Residue derived from furan dicarboxylic acid compounds

[0064] The above polyester resin contains a residue derived from a furan dicarboxylic acid compound (hereinafter referred to as “furan dicarboxylic acid compound-derived residue”) and exhibits excellent biodegradability due to the furan dicarboxylic acid compound.

[0065] The above furan dicarboxylic acid compound can be represented by the following chemical formula 11A:

[0066] [Chemical Formula 11A]

[0067]

[0068] In the above chemical formula 11A, L1 and L2 are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene.

[0069] For example, in the above chemical formula 11A, L1 and L2 can each independently be a single bond, or a substituted or unsubstituted C1 to C8 alkylene. Alternatively, in the above chemical formula 11A, L1 and L2 can each independently be a single bond, or a substituted or unsubstituted C1 to C5 alkylene. Alternatively, in the above chemical formula 11A, L1 and L2 can each independently be a single bond, or a substituted or unsubstituted C1 to C3 alkylene.

[0070] As a representative example, the furan dicarboxylic acid compound may be 2,5-furandicarboxylic acid, in which case both L1 and L2 of the chemical formula 11A may be single bonds.

[0071] The above furan dicarboxylic acid compound-derived residue can be represented by the following chemical formula 11B:

[0072] [Chemical Formula 11B]

[0073]

[0074] In the above chemical formula 11B, L1 and L2 are each independently a single bond, or a substituted or unsubstituted C1 to C10 alkylene, and * indicates a bonding position.

[0075] For example, in the above chemical formula 11B, L1 and L2 can each independently be a single bond, or a substituted or unsubstituted C1 to C8 alkylene. Alternatively, in the above chemical formula 11B, L1 and L2 can each independently be a single bond, or a substituted or unsubstituted C1 to C5 alkylene. Alternatively, in the above chemical formula 11B, L1 and L2 can each independently be a single bond, or a substituted or unsubstituted C1 to C3 alkylene.

[0076] As a representative example, the furan dicarboxylic acid compound may be 2,5-furandicarboxylic acid, in which case both L1 and L2 of the chemical formula 11B may be single bonds.

[0077] Residues derived from alkylene glycol compounds

[0078] The above polyester resin contains 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 21A.

[0080] [Chemical Formula 21A]

[0081]

[0082] In the above chemical formula 21A, L3 and L4 are each independently a substituted or unsubstituted C1 to C10 alkylene.

[0083] For example, in the above chemical formula 21A, L3 and L4 can each independently be a single bond, or a substituted or unsubstituted C1 to C8 alkylene. Alternatively, in the above chemical formula 21A, L3 and L4 can each independently be a single bond, or a substituted or unsubstituted C1 to C5 alkylene. Alternatively, in the above chemical formula 21A, L3 and L4 can each independently be a single bond, or a substituted or unsubstituted C1 to C3 alkylene.

[0084] As a representative example, the alkylene glycol compound may be ethylene glycol, and in this case, in the chemical formula 21A, L3 may be a C1 alkylene (i.e., methylene), and L4 may be a C1 alkylene (i.e., methylene).

[0085] The residue derived from the above alkylene glycol compound can be represented by the following chemical formula 21B.

[0086] [Chemical Formula 21B]

[0087]

[0088] In the above chemical formula 21B, L3 and L4 are each independently a substituted or unsubstituted C1 to C10 alkylene, and * indicates a bonding position.

[0089] For example, in the above chemical formula 21B, L3 and L4 can each independently be a substituted or unsubstituted C1 to C8 alkylene. Alternatively, in the above chemical formula 21B, L3 and L4 can each independently be a substituted or unsubstituted C1 to C5 alkylene. Alternatively, in the above chemical formula 21B, L3 and L4 can each independently be a substituted or unsubstituted C1 to C3 alkylene.

[0090] As a representative example, the alkylene glycol compound may be ethylene glycol, and in this case, in the chemical formula 21B, L3 may be a C1 alkylene (i.e., methylene), and L4 may be a C1 alkylene (i.e., methylene).

[0091] In the polyester resin, the molar ratio of the residue derived from the furan dicarboxylic acid compound and the residue derived from the alkylene glycol compound may be 9:1 to 1:9, 8:2 to 2:8, or 1:1 to 1:2. In this range, the effects of the residue derived from the furan dicarboxylic acid compound and the residue derived from the alkylene glycol compound can be harmoniously secured.

[0092] The above polyester resin may be an alternating copolymer, a random copolymer or a block copolymer.

[0093] In one embodiment, the polyester resin may be represented by the following chemical formula 31A.

[0094] [Chemical Formula 31A]

[0095]

[0096] In the above chemical formula 31A, the definition of each substituent is as described above.

[0097] For example, the polyester resin may be represented by the following chemical formula 31B:

[0098] [Chemical Formula 31B]

[0099]

[0100] As a representative example, the polyester resin represented by the above chemical formula 31A corresponds to a case where the furan dicarboxylic acid-based compound-derived residue is a furan dicarboxylic acid-derived residue, the ethylene glycol-based compound-derived residue is an ethylene glycol-derived residue, and the molar ratio of the ethylene glycol-derived residue and the ethylene glycol-derived residue is 1:1. For example, the polyester resin may be poly(ethylene furandicarboxylate) (PEF).

[0101] The polyester resin may have a number average molecular weight (Mn) of 20,000 g / mol or more, 21,000 g / mol or more, 22,000 g / mol or more, 23,000 g / mol or more, or 24,000 g / mol or more. In addition, the polyester resin may have a number average molecular weight (Mn) of 40,000 g / mol or less, 35,000 g / mol or less, or 32,000 g / mol or less. When the number average molecular weight of the polyester resin composition satisfies the above range, an appropriate viscosity can be secured, and film processing can be easily performed.

[0102] The polyester resin may have a ratio of weight average molecular weight (Mw) / number average molecular weight (Mn), i.e., a molecular weight distribution (MWD) of 1 or more, 1.2 or more, 1.4 or more, or 1.5 or more. In addition, the polyester resin may have a ratio of weight average molecular weight (Mw) / number average molecular weight (Mn), i.e., a molecular weight distribution (MWD) of 2.5 or less, 2 or less, 1.95 or less, or 1.92 or less. When this is satisfied, not only does process control become easier, but there is also an advantage of being able to reduce the defect rate of the product due to the uniform molecular weight distribution.

[0103] For example, the L* value according to the CIE1976 L*a*b* colorimetric system of the resin composition may be 58.0 to 75.5, for example, 58.99 to 75.5, 60.0 to 75.5, or 60.12 to 75.12. The higher the L* value, the closer the color is to white. Therefore, when the L* value is satisfied, polyester chips, polyester films, and processed products having excellent transmittance can be obtained.

[0104] In one embodiment, the b* value of the resin composition according to the CIE1976 L*a*b* colorimetric system may be 7.0 to 15.0, for example, 7.14 to 14.34, or 13.0 to 14.12. The lower the b* value, the lighter the yellow and the darker the blue. Therefore, when the b* value is satisfied, a polyester chip or polyester film exhibiting a light yellow color with reduced heat discoloration can be obtained.

[0105] In one embodiment, the intrinsic viscosity (Ⅳ) of the resin composition may be 0.6 dl / g to 0.8 dl / g, for example, 0.64 dl / g to 0.8 dl / g, or 0.64 dl / g to 0.66 dl / g. When this is satisfied, polyester chips with excellent processability can be obtained. Specifically, when the intrinsic viscosity (Ⅳ) is less than 0.6 dl / g, a lot of time is required for additional solid-state polymerization to reach an intrinsic viscosity of 0.8 dl / g or more required for bottle manufacturing, which may adversely affect productivity. In addition, when the intrinsic viscosity (Ⅳ) exceeds 0.8 dl / g, a large amount may not be discharged to the inner wall of the reactor, which may adversely affect production yield. Therefore, precise control of the intrinsic viscosity (Ⅳ) is necessary.

[0106] At this time, the intrinsic viscosity (Ⅳ) of the resin composition can be measured at 25°C using an Ostwald viscometer, and 10 ml of a solution in which 0.5 g of the resin composition and phenol and tetrachloroethane are mixed in a volume ratio of 1:1 in a 20 ml vial is placed in a 100°C oil bath to completely dissolve, and then the intrinsic viscosity (IV) can be measured at a temperature of 25°C using an Ostwald viscometer.

[0107] In the above resin composition, other than impurities including 2-methyl-1,3-dioxolane, etc., the remainder may be a polyester resin.

[0108] Method for producing a resin composition

[0109] One embodiment provides a method for producing a resin composition, comprising preparing a composition comprising a polyester resin including a residue derived from a furan dicarboxylic acid compound and a residue derived from an alkylene glycol compound, and controlling the content of 2-methyl-1,3-dioxolane, an impurity generated by light or heat, in the polyester resin to 10 ppm or less by weight.

[0110] Since the above-described manufacturing method is a method for manufacturing a resin composition according to one embodiment, the following will omit any description overlapping with that described above regarding the resin composition, and will describe in detail the processes for manufacturing the resin composition according to one embodiment.

[0111] First, a composition comprising a polyester resin containing a residue derived from a furan dicarboxylic acid compound and a residue derived from an alkylene glycol compound is prepared. The polyester resin containing a residue derived from a furan dicarboxylic acid compound and a residue derived from an alkylene glycol compound may be obtained and used as a commercially available polyester resin, or may be manufactured using a method commonly known in the art.

[0112] In one embodiment, the production of the polyester resin may include esterifying a monomer mixture comprising a furan dicarboxylic acid-based compound and an alkylene glycol-based compound, prepolymerizing the product of the esterification reaction, and polycondensing the product of the prepolymerization. The description of the furan dicarboxylic acid-based compound and the alkylene glycol-based compound is the same as described above, and hereinafter, each step of the esterification reaction, prepolymerization reaction, and polycondensation reaction will be described in detail.

[0113] In a method for manufacturing a resin composition according to one embodiment, a monomer mixture including a furan dicarboxylic acid-based compound and an alkylene glycol-based compound may be subjected to an esterification reaction. In this step, an oligomer having a low degree of polymerization may be formed.

[0114] The monomer mixture in the esterification reaction step may contain 100 to 200 moles of the alkylene glycol compound based on 100 moles of the furan dicarboxylic acid compound. When the contents of the furan dicarboxylic acid compound and the alkylene glycol compound are within the above range, the viscosity increase rate in the condensation reaction can be increased, and the color of the polymer can be improved.

[0115] Meanwhile, considering the amount of material that is lost or unreacted during the esterification reaction, the alkylene glycol compound may be used in an excess of about 120% based on the furan dicarboxylic acid compound. Accordingly, by adjusting the molar ratio of the reactants within the above range, a copolymer in which the content of each residue is controlled within the above range may be formed. More specifically, based on 100 mol of the furan dicarboxylic acid compound, the alkylene glycol compound may be included in an amount of 100 mol or more, 110 mol or more, 115 mol or more, or 120 mol or more, and 200 mol or less, 190 mol or less, 180 mol or less, or 150 mol or less.

[0116] The esterification reaction may be performed under a nitrogen (N2) atmosphere, a temperature range of 180 to 220°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.

[0117] The above esterification 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.

[0118] The above esterification reaction may be carried out in the presence of an esterification reaction catalyst including a titanium (Ti)-based compound, a tin (Sn)-based compound, an antimony (Sb)-based compound, or the like. In particular, the esterification reaction catalyst can improve the reaction rate from the beginning of the reaction and shorten the time that the polyester resin composition is exposed to heat. 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 the efficiency of the esterification reaction can be greatly improved.

[0119] Next, the esterification reaction product can be pre-polymerized to produce an oligomer having a higher degree of polymerization than the esterification reaction product. More specifically, water is generated during the reaction between the furan dicarboxylic acid compound and the alkylene glycol compound, and the esterification reaction is completed when the furan dicarboxylic acid compound completely dissolves and reaches the Clear point.

[0120] The above pre-polymerization can be performed under temperature-controlled conditions (thermal pre-condensation). More specifically, the pre-polymerization can be performed including the steps of: raising the temperature until it reaches a temperature range of 220 to 280°C or 220 to 260°C; and maintaining the temperature while pre-polymerizing the esterification reaction product. In addition, during the temperature increase, the pressure can be reduced until it reaches 0 to 1 atm or 0 to 0.5 atm, and then the reached pressure can also be maintained while maintaining the reached temperature. When the reached temperature, reached pressure, reaction time, etc. during the pre-polymerization are within the above-described ranges, sufficient reaction occurs, thereby improving the properties of the final polyester and reducing the possibility of yellowing.

[0121] After the above-mentioned pre-polymerization, the above-mentioned pre-polymerized polymer can be subjected to a polycondensation reaction. The polycondensation reaction can be performed at a temperature of 220 to 280°C or 220 to 260°C and a pressure of 1 torr or less or 0.4 torr to 0.8 torr for 2 to 6 hours. When the temperature, pressure, reaction time, etc. during the polycondensation are within the above-mentioned ranges, glycol, which is a by-product of the polycondensation reaction, can be effectively removed, so that the final reaction product exhibits an appropriate intrinsic viscosity, and the possibility of the appearance of the manufactured polyester turning yellow can be reduced.

[0122] 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.

[0123] In the above composition, the content of 2-methyl-1,3-dioxolane, an impurity generated by light or heat, is controlled to 10 ppm or less by weight in the polyester resin.

[0124] In one embodiment, adjusting the content of the 2-methyl-1,3-dioxolane to 10 ppm or less by weight may be accomplished by performing the four-step heat treatment described below during the manufacturing process of the polyester resin, or by adding a hydrazine-based additive.

[0125] In one embodiment, when manufacturing the polyester resin, the method may include performing the esterification reaction, pre-polymerization, and polycondensation reactions described above in the same manner, and then additionally performing the four-step heat treatment described below on the resultant product of the polycondensation reaction.

[0126] For example, the four heat treatments may include a first heat treatment, a second heat treatment, a third heat treatment, and a fourth heat treatment performed at different temperatures. For example, the second heat treatment may be performed at a temperature higher than the temperature of the first heat treatment, the third heat treatment may be performed at a temperature higher than the temperature of the second heat treatment, and the fourth heat treatment may be performed at a temperature higher than the temperature of the third heat treatment. When these conditions are met, the viscosity of the resin composition can be increased, and the content of 2-methyl-1,3-dioxolane, which is an impurity generated by light or heat in the polyester resin, can be effectively reduced.

[0127] In one embodiment, all of the four heat treatments may be performed at a temperature range of 50°C to 300°C. For example, the first heat treatment may be performed at 40°C to 90°C, the second heat treatment may be performed at 100°C to 150°C, the third heat treatment may be performed at 160°C to 200°C, and the fourth heat treatment may be performed at 201°C to 250°C. In this range, the generation of the impurity 2-methyl-1,3-dioxolane may be effectively suppressed, thereby obtaining a polyester film having excellent optical properties and color expression.

[0128] For example, the first heat treatment may include heating to 40° C. to 90° C. for 30 minutes to 1 hour and then maintaining for 30 minutes to 1 hour, the second heat treatment may include heating to 100° C. to 150° C. for 30 minutes to 1 hour and then maintaining for 30 minutes to 1 hour, the third heat treatment may include heating to 160° C. to 200° C. for 30 minutes to 2 hours and then maintaining for 30 minutes to 1 hour, and the fourth heat treatment may include heating to 201° C. to 250° C. for 30 minutes to 2 hours and then maintaining for 1 hour to 10 hours. In this range, the generation of the impurity 2-methyl-1,3-dioxolane can be effectively suppressed, thereby obtaining a polyester film with excellent optical properties and color realization.

[0129] Meanwhile, another embodiment provides a polyester chip comprising the aforementioned resin composition. In addition, another embodiment provides a polyester film comprising the aforementioned resin composition.

[0130] 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.

[0131] Example 1

[0132] In a hopper of a first autoclave reactor with a capacity of 10 L, 2,5-furan dicarboxylic acid (FDCA, 5.48 mol, 856.9 g) as a furan dicarboxylic acid compound and ethylene glycol (EG, 6.58 mol, 408.9 g) as an alkylene glycol compound were charged at an equivalent ratio of 1:1.2.

[0133] Next, 10 ppm of a Ti-based chelate catalyst (AC436) as an esterification reaction (ES) catalyst based on metal, and 10 ppm based on 1 kg of an aminoguanidine bicarbonate complex as an additive represented by the following chemical formula 5A were added, stirred at 120 rpm, and the reaction was carried out for 3.5 hours under a pressure of 2.5 bar (approximately 2.467 atm), a temperature of 210°C, and a nitrogen atmosphere. After 3.5 hours of reaction, the esterification reaction was terminated when the effluent generated as a byproduct after switching to normal pressure was 90% or more compared to the theoretical effluent.

[0134] [Chemical Formula 5A]

[0135]

[0136] Next, the temperature inside the reactor was increased for 1 hour to reach a temperature range of 260°C, and then the pressure was gradually reduced using a vacuum pump for 1 hour to reach a vacuum state of 0.8 torr or less, while conducting preliminary polymerization.

[0137] Next, a polycondensation reaction was performed for 2 to 6 hours under a vacuum condition of 0.5 torr or less at 260°C, and the resultant polycondensation reaction was dried when the load transmitted to the torque meter of the autoclave reached the desired load, thereby manufacturing a polyester resin having a number-average molecular weight (Mn) of 24,840 g / mol and an MWD of 1.89.

[0138] Example 2

[0139] A polyester resin having a number average molecular weight (Mn) of 24,440 g / mol and an MWD of 1.92 was manufactured in substantially the same manner as in Example 1, except that 100 ppm of the additive represented by the above chemical formula 5A was added.

[0140] Example 3

[0141] A polyester resin having a number average molecular weight (Mn) of 24,750 g / mol and an MWD of 1.82 was manufactured in substantially the same manner as Example 1, except that an additive represented by the following chemical formula 5B was added instead of the additive represented by the chemical formula 5A.

[0142] [Chemical Formula 5B]

[0143]

[0144] Example 4

[0145] A polyester resin having a number average molecular weight (Mn) of 24,850 g / mol and an MWD of 1.8 was manufactured in substantially the same manner as in Example 1, except that 100 ppm of the additive represented by the chemical formula 5B was added instead of the additive represented by the chemical formula 5A.

[0146] Example 5

[0147] A polyester resin was manufactured in substantially the same manner as in Comparative Example 1 below, except that the resultant of the above polycondensation reaction was placed in a vacuum oven, and the vacuum inside the oven was maintained at 0.5 Torr using a vacuum pump, and the first heat treatment (heating to 60°C for 30 minutes and then maintaining for 1 hour) was performed, followed by the second heat treatment (heating the resultant to 140°C for 1 hour and then maintaining for 1 hour), followed by the third heat treatment (heating the resultant to 200°C for 1 hour and then maintaining for 1 hour), and followed by the fourth heat treatment (heating the resultant to 210°C for 1 hour and then maintaining for 6 hours) to obtain a polyester resin having a number average molecular weight (Mn) of 32,000 g / mol and an MWD of 1.85 at room temperature and pressure.

[0148] Comparative Example 1

[0149] A polyester resin having a number average molecular weight (Mn) of 24,800 g / mol and an MWD of 1.91 was manufactured in substantially the same manner as in Example 1, except that aminoguanidine bicarbonate, represented by the above chemical formula 5A, was not used.

[0150] Comparative Example 2

[0151] A polyester resin having a number average molecular weight (Mn) of 24,340 g / mol and an MWD of 1.71 was manufactured in substantially the same manner as in Comparative Example 1, except that 2,5-furandicarboxylic acid (FDCA) as a furan dicarboxylic acid compound and ethylene glycol (EG) as an alkylene glycol compound were charged in an equivalent ratio of 1:1.3 into a hopper of a first autoclave reactor having a capacity of 10 L.

[0152] Comparative Example 3

[0153] A polyester resin having a number average molecular weight (Mn) of 25,000 g / mol and an MWD of 1.82 was manufactured in substantially the same manner as in Comparative Example 1, except that 2,5-furandicarboxylic acid (FDCA) as a furan dicarboxylic acid compound and ethylene glycol (EG) as an alkylene glycol compound were charged in an equivalent ratio of 1:1.5 into a hopper of a first autoclave reactor having a capacity of 10 L.

[0154] Comparative Example 4

[0155] A polyester resin having a number average molecular weight (Mn) of 24,860 g / mol and an MWD of 1.97 was manufactured in substantially the same manner as in Comparative Example 1, except that the Ti-based chelate catalyst (AC436) was added at 50 ppm based on metal.

[0156] Comparative Example 5

[0157] A polyester resin having a number average molecular weight (Mn) of 24,760 g / mol and an MWD of 1.95 was manufactured in substantially the same manner as in Comparative Example 1, except that 5 ppm of phosphoric acid (PA) P was additionally added as a heat stabilizer during the esterification reaction (ES).

[0158] Evaluation Example 1: Evaluation of the physical properties of polyester chips

[0159] In Examples 1 to 5 and Comparative Examples 1 to 5, the valve at the bottom of the reactor for each polycondensation reaction was opened, and the resin composition containing the manufactured polyester resin was drawn out in the form of a thread, which was then cooled in a water bath. Then, the thread-shaped resin composition was placed between rollers using a pelletizer and operated, and cut with a cutter at the end to produce polyester chips having a constant width and thickness. The physical properties of each polyester chip thus manufactured were evaluated using the following method, and are shown in Table 1 below.

[0160] Evaluation of 2-methyl-1,3-dioxolane content

[0161] 2-Methyl-1,3-dioxolane (manufacturer: Sigma-Aldrich, product number: 292206) was prepared, and a calibration curve was drawn for each content using GC-MS at concentrations of 1 ppm, 10 ppm, 50 ppm, and 100 ppm of 2-methyl-1,3-dioxolane in chloroform, and the reliability was controlled to be 99.95% or higher.

[0162] 0.2 g of each polyester chip manufactured from Examples 1 to 5 and Comparative Examples 1 to 5 was measured using the ASTM F 2013 measurement method, and 2-methyl-1,3-dioxolane was measured at the same retention time as the calibration curve. The content of 2-methyl-1,3-dioxolane in the polyester chip was measured from the difference in area with the calibration curve by content, and is shown in Table 1.

[0163] Colorimetric evaluation

[0164] After filling more than half of the capacity of a container dedicated to chip measurement with polyester chips and maintaining the remainder with air, the L* and b* values ​​were measured using a Chip colorimeter from Nippon Denshoku (sa-4000), and the values ​​are shown in Table 1 below.

[0165] Intrinsic viscosity (Ⅳ) evaluation

[0166] After completely dissolving 0.5 g of polyester chips and 10 ml of a 1:1 (v:v) solution of phenol and tetrachloroethane in a 20 ml vial in an oil bath at 100 °C, the intrinsic viscosity (Ⅳ) was measured at 25 °C using an Ostwald viscometer, and the results are shown in Table 1 below.

[0167] Chip properties Content of 2-methyl-1,3-dioxolane (ppm) L*b* Intrinsic viscosity (Ⅳ) Example 11.461.0913.490.651 Example 2161.4513.120.642 Example 31.160.4914.090.649 Example 40.860.1214.120.651 Example 52.475.127.140.8 Comparative example 11259.1214.290.65 Comparative example 21358.1215.130.64 Comparative example 31458.0716.120.654 Comparative example 41558.1415.190.651 Comparative example 51258.4915.290.649

[0168] Referring to Table 1 above, in the case of Examples 1 to 5, the content of 2-methyl-1,3-dioxolane was 10 ppm or less, and through this, it can be confirmed that the transmittance is excellent as the L* value is high compared to Comparative Examples 1 to 5, and the thermal discoloration is low as the b* value is low, so that the polyester chip color is excellent.

[0169] Evaluation Example 2: Evaluation of physical properties of polyester film

[0170] In Evaluation Example 1, a polyester film was manufactured using each of the polyester chips manufactured from Examples 1 to 5 and Comparative Examples 1 to 5. Specifically, each polyester chip was melted in an extruder at 180°C to 260°C, and then the melt was extruded through a die to form a sheet and rapidly cooled. The obtained sheet was stretched 3.0 times in the machine direction (MD) and then 3.7 times in the transverse direction (TD), and the stretched film was heat-set at 120°C to 160°C under tension to provide dimensional stability, thereby manufacturing a biaxially oriented polyester film.

[0171] Y transmittance (D65) evaluation

[0172] For the polyester films manufactured from Examples 1 to 5 and Comparative Examples 1 to 5, specimens were prepared by cutting them into a size of 10 cm × 10 cm (longitudinal length × transverse length). The parallel transmittance and diffuse transmittance of the specimens were measured using a Minolta CM-3600A measuring device according to the ASTM D1003-97 measurement method. The transmittance is defined as the sum of the parallel transmittance and the diffuse transmittance, and the transmittance was obtained and shown in Table 2 below.

[0173] Yellow Index and b* value evaluation

[0174] For the polyester films manufactured from Examples 1 to 5 and Comparative Examples 1 to 5, specimens were prepared by cutting them into a size of 10 cm × 10 cm (longitudinal length × transverse length). The yellowness index and b* value of the specimens were measured according to the ASTM E313 method, and are shown in Table 2 below.

[0175] Haze Evaluation

[0176] For the polyester films manufactured from Examples 1 to 5 and Comparative Examples 1 to 5, the haze of the films was measured using a Haze meter, a Murakami Color Research Lab. (hm-150) facility, and the results are shown in Table 2 below.

[0177] After processing of polyester film, physical properties Y (D65) yellowness b* haze Example 192.5 10.5 10.6 10.4 Example 292.14 0.4 90.5 90.5 Example 392.4 90.46 0.58 0.4 Example 492.12 0.45 0.54 0.3 Example 590.5 50.6 10.7 10.5 Comparative Example 189.1 11.5 11.45 1.1 Comparative Example 289.0 11.5 91.5 11.0 Comparative Example 388.9 91.6 11.5 91.0 Comparative Example 488.7 91.7 11.68 1.1 Comparative Example 589.2 11.4 91.4 10.9

[0178] Referring to Table 2 above, it can be confirmed that in the case of Examples 1 to 5, compared to Comparative Examples 1 to 5, the transmittance (D65) is high, so that the transmittance is excellent, but the yellowness and b* value are low, so that there is little heat discoloration, and the haze is low, so that all have excellent optical properties.

[0179] 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 polyester resin comprising a residue derived from a furan dicarboxylic acid compound and a residue derived from an alkylene glycol compound, A resin composition having a content of 2-methyl-1,3-dioxolane, which is an impurity, of 10 ppm or less on a weight basis.

2. A resin composition having a b* value of 7.0 to 15.0 according to the CIE1976 L*a*b* colorimetric system.

3. In paragraph 1, A resin composition having an L* value of 58.0 to 75.5 according to the CIE1976 L*a*b* colorimetric system.

4. In paragraph 1, A resin composition further comprising a hydrazine-based additive.

5. In paragraph 1, A resin composition further comprising an additive represented by the following chemical formula 1A, an additive represented by the following chemical formula 1B, or a combination thereof: [Chemical Formula 1A] [Chemical Formula 1B] In the above chemical formula 1A, R1 to R4 are each independently hydrogen, or a substituted or unsubstituted C1 to C5 alkyl group, X is carbonic acid, hydrochloric acid, sulfuric acid, nitric acid, or a combination thereof, In the above chemical formula 1B, X1 to X4 are each independently S, O, NR5, R5 is hydrogen, or a substituted or unsubstituted C1 to C5 alkyl group, and Y1 - and Y2 - are each independently -SO3 - , -Cl - , or a combination of these, and Z + is NH4 + am.

6. In paragraph 1, A resin composition further comprising an additive represented by the following chemical formula 2A, an additive represented by the following chemical formula 2B, or a combination thereof: [Chemical Formula 2A] [Chemical Formula 2B] In the above chemical formula 2A, R1 to R4 are each independently hydrogen, or a substituted or unsubstituted C1 to C5 alkyl group, X is carbonic acid, hydrochloric acid, sulfuric acid, nitric acid, or a combination thereof, In the above chemical formula 2B, R5 and R6 are each independently hydrogen, or a substituted or unsubstituted C1 to C5 alkyl group, and Z + is NH4 + am.

7. In paragraph 1, A resin composition further comprising an additive represented by the following chemical formula 3A, an additive represented by the following chemical formula 3B, or a combination thereof: [Chemical Formula 3A] [Chemical Formula 3B] In the above chemical formula 3A, R1 to R4 are each independently hydrogen, or a substituted or unsubstituted C1 to C5 alkyl group, In the above chemical formula 3B, R5 and R6 are each independently hydrogen, or a substituted or unsubstituted C1 to C5 alkyl group.

8. In paragraph 1, A resin composition further comprising an additive represented by the following chemical formula 4A, an additive represented by the following chemical formula 4B, or a combination thereof: [Chemical Formula 4A] [Chemical Formula 4B] 9. In paragraph 1, A resin composition having a content of 2-methyl-1,3-dioxolane of 5 ppm or less on a weight basis.

10. In paragraph 1, A resin composition having a content of 2-methyl-1,3-dioxolane of 2 ppm or less on a weight basis.

11. Prepare a composition comprising a polyester resin containing a residue derived from a furan dicarboxylic acid compound and a residue derived from an alkylene glycol compound, A method for producing a resin composition, wherein the polyester resin comprises adjusting the content of 2-methyl-1,3-dioxolane, an impurity generated by light or heat, to 10 ppm or less by weight in the above composition:

12. In paragraph 11, A method for producing a resin composition, wherein the content of 2-methyl-1,3-dioxolane is adjusted to 10 ppm or less by weight, including four stages of heat treatment during the production process of the polyester resin, or adding a hydrazine-based additive.

13. In paragraph 12, The above four stages of heat treatment include first heat treatment, second heat treatment, third heat treatment, and fourth heat treatment performed at different temperatures, The above first heat treatment is performed at 40°C to 90°C, The above second heat treatment is performed at 100°C to 150°C, The above third heat treatment is performed at 160 ℃ to 200 ℃, A method for producing a resin composition, wherein the fourth heat treatment is performed at 201°C to 250°C.

14. A polyester chip comprising a resin composition according to paragraph 1.

15. A polyester film comprising a resin composition according to paragraph 1.

Images