Polyester resin and article manufactured therefrom

Abstract

The present invention relates to a polyester resin and an article manufactured from the polyester resin, the polyester resin comprising: a diol repeating unit derived from a diol component; and a dicarboxylic acid repeating unit derived from a dicarboxylic acid component, wherein the polyester resin has the properties that, when the tanδ value is measured through dynamic mechanical analysis (DMA), the temperature at the tanδ peak is 100℃ or higher, and the content and composition of 1,4-cyclohexanedimethanol included in the diol component are controlled.

Description

Polyester resin and articles manufactured therefrom

[0001] The present invention relates to a polyester resin having excellent resilience to deformation occurring at high temperatures and exhibiting high heat resistance and mechanical strength, and to an article manufactured using the polyester resin.

[0002] Among polymer types, polyester resins are widely used as materials for beverage or food containers; various packaging films or sheets; and various interior and exterior materials such as panels, shelves, and partitions.

[0003] In particular, polyester resins used in the manufacture of articles such as the aforementioned food containers or packaging films are required to possess high heat resistance and mechanical strength. Specifically, articles manufactured from the aforementioned polyester resins must possess heat resistance sufficient to enable use in high-temperature microwave ovens, dishwashers, and the like, and impact strength sufficient to prevent breakage even under external impact.

[0004] To enhance the heat resistance and mechanical strength of polyester resins, techniques have been proposed that involve blending polyester resins with other resins or adding specific additives. However, these techniques have limited ability to simultaneously improve the heat resistance and mechanical strength of polyester resins, leading to problems such as increased manufacturing costs, decreased process efficiency, and decreased color characteristics (e.g., transparency).

[0005] Therefore, there is a need to develop a technology that can efficiently increase the heat resistance and mechanical strength of polyester resin.

[0006] Meanwhile, plastic products manufactured using materials like polyester resin generate greenhouse gases throughout the raw material extraction, manufacturing, distribution, use, and disposal stages. These greenhouse gases are a major contributor to global warming, and eco-friendly plastic technologies are needed to reduce their emissions.

[0007] Unlike conventional techniques that blend different resins or use specific additives, the present inventors have confirmed that a polyester resin with high heat resistance and mechanical strength can be obtained simply by controlling the polymerization raw materials of the polyester resin. Specifically, by applying a specific diol composition during the production of the polyester resin, it was confirmed that when the polyester resin is subjected to deformation under high-temperature conditions, the deformation recovery occurs quickly. This rapid recovery significantly enhances the heat resistance and mechanical strength of the polyester resin. Furthermore, it was confirmed that by applying a specific diol composition, a polyester resin with minimized greenhouse gas emissions can be obtained.

[0008] Accordingly, the object of the present invention is to provide a polyester resin having excellent resilience to deformation occurring at high temperatures, exhibiting high heat resistance and mechanical strength, and being environmentally friendly, and an article manufactured using the polyester resin.

[0009] In order to solve the above problem, the present invention provides a polyester resin comprising a diol repeating unit derived from a diol component and a dicarboxylic acid repeating unit derived from a dicarboxylic acid component, wherein when the tanδ value is measured through dynamic mechanical analysis (DMA), the temperature at the tanδ peak is 100°C or higher, and satisfies the following equation 1:

[0010] [Formula 1] 30 ≤ X × Y ≤ 60

[0011] In the above equation 1,

[0012] X is the mol% of 1,4-cyclohexanedimethanol (CHDM) with respect to 100 mol% of the above diol component,

[0013] Y is the molar ratio of trans-1,4-cyclohexanedimethanol (trans-CHDM) to the above 1,4-cyclohexanedimethanol (CHDM).

[0014] In addition, the present invention provides an article manufactured from the polyester resin.

[0015] The polyester resin according to the present invention is obtained by using a diol component containing 1,4-cyclohexanedimethaol having a specific composition as a polymerization raw material, thereby controlling physical properties (i.e., X × Y, tanδ peak temperature, deformation recovery (SR), T) within a specific range. m , impact strength, etc.), and thus has excellent resilience to deformation occurring at high temperatures, and thus has high heat resistance and mechanical strength, and excellent formability. In addition, the polyester resin according to the present invention is obtained by using a diol component including isosorbide as a polymerization raw material, and thus can minimize the generation of greenhouse gases such as carbon dioxide (CO2) during the process of manufacturing a product using the polyester resin and using and disposing of the manufactured product.

[0016] Therefore, when manufacturing a product using the polyester resin according to the present invention, a product having excellent heat resistance and mechanical strength and being environmentally friendly can be manufactured with high efficiency.

[0017] Hereinafter, the present invention will be described in detail. Herein, the present invention is not limited to the contents described below, and may be modified in various forms as long as the gist of the invention is not changed.

[0018] The word "comprising" or "including" in this specification is intended to specify particular features, regions, steps, processes, elements and / or components, and does not exclude the presence or addition of other features, regions, steps, processes, elements and / or components, unless specifically stated to the contrary.

[0019] In this specification, terms such as first, second, etc. are used to describe various components, and the components are not limited to these terms. These terms are used to distinguish one component from another.

[0020] All numbers and expressions indicating the amounts of components, reaction conditions, etc. described in this specification can be understood to be modified by the term “about” in all cases unless otherwise specified.

[0021] In this specification, singular expressions include plural expressions unless the context clearly indicates otherwise.

[0022]

[0023] 폴리에스테르 수지

[0024] A polyester resin according to the present invention comprises a diol repeating unit derived from a diol component; and a dicarboxylic acid repeating unit derived from a dicarboxylic acid component, and when the tanδ value is measured through dynamic mechanical analysis (DMA), the temperature at the tanδ peak is 100°C or higher, and satisfies the following equation 1.

[0025] [Equation 1] 30 ≤ X × Y ≤ 60

[0026] 상기 식 1에서,

[0027] X is the mol% of 1,4-cyclohexanedimethanol (CHDM) with respect to 100 mol% of the above diol component,

[0028] Y is the molar ratio of trans-1,4-cyclohexanedimethanol (trans-CHDM) to the above 1,4-cyclohexanedimethanol (CHDM).

[0029] The above equation 1 shows the relationship between the mol% of 1,4-cyclohexanedimethanol in the total diol component and the molar ratio of trans-1,4-cyclohexanedimethanol (trans-CHDM) in the 1,4-cyclohexanedimethanol, and the polyester resin according to the present invention satisfies a range of 30 to 60 in which the value (X × Y) obtained by multiplying the mol% and each numerical value (unit-excluding numerical value) of the mol% and the molar ratio is 30 to 60. Specifically, X is the mol% of 1,4-cyclohexanedimethanol included in the diol component based on 100 mol% of the diol component, and Y may mean the ratio of the amount of trans-1,4-cyclohexanedimethanol included in the total amount of 1,4-cyclohexanedimethanol.

[0030] In the above equation 1, when the X × Y value is less than 30 or more than 60, the glass transition temperature (T) which is highly related to the heat resistance of the polyester resin g ) and melting point (T m ) does not exhibit the desired level, so it is impossible to obtain a polyester resin having high heat resistance and excellent formability, and this does not achieve improvements in mechanical strength and processability of the polyester resin. However, since the polyester resin according to the present invention satisfies the above formula 1, it can have high heat resistance and mechanical strength and excellent formability.

[0031] According to the present invention, in the above formula 1, the X × Y value can be specifically 31 or more, 32 or more, 33 or more, 35 or more, 38 or more, 40 or more, 43 or more, 45 or more, 48 or more, 50 or more, or 52 or more, and 59 or less, 57 or less, 55 or less, 52 or less, 50 or less, 48 ​​or less, 45 or less, 43 or less, 40 or less, or 35 or less (e.g., 31 to 59, 32 to 59, 33 to 58, 33 to 57, 34 to 55, 35 to 54, 36 to 52, 38 to 50, or 40 to 47).

[0032] According to the present invention, when the tanδ value of the polyester resin is measured through the dynamic mechanical analysis (DMA), the temperature at the tanδ peak may be specifically 103°C or higher, 105°C or higher, 108°C or higher, 110°C or higher, or 113°C or higher, and 120°C or lower, 118°C or lower, 116°C or lower, or 115°C or lower (e.g., 100 to 120°C, 101 to 119°C, 102 to 119°C, 104 to 118°C, 107 to 117°C, 108 to 116°C, or 110 to 115°C). A polyester resin having high heat resistance can be provided as the temperature at the above tanδ peak is within the above range.

[0033] According to the present invention, the polyester resin has a melting point (T) when analyzed by differential scanning calorimetry (DSC). m ) may not appear (be measured). In addition, the polyester resin may have a melting point (T ) during the DSC analysis. m ) can appear below 250 ℃. Specifically, the melting point (T of the polyester resin m) may be 248 ℃ or less, 246 ℃ or less, 244 ℃ or less, 242 ℃ or less, 240 ℃ or less, 238 ℃ or less, or 235 ℃ or less (e.g., 225 to 250 ℃, 230 to 250 ℃, 231 to 249 ℃, 233 to 248 ℃, 234 to 247 ℃, or 235 to 245 ℃). The melting point (T of the polyester resin m ) does not appear or is below 250 ℃, so that the formability can be secured together with the heat resistance of the polyester resin. In particular, the melting point (T of the polyester resin m ) exceeds 250 ℃, the crystallinity of the polyester resin may increase excessively, which may significantly reduce the formability, so the melting point (T) of the polyester resin m ) is preferably below 250 ℃.

[0034] Here, in the DSC analysis, the melting point (T) of the polyester resin m ) appears, the melting point (T m ) may be specifically 30 J / g or less, 25 J / g or less, 23 J / g or less, 20 J / g or less, 18 J / g or less, 15 J / g or less, 13 J / g or less, 10 J / g or less, or 5 J / g or less (e.g., more than 0 to 30 J / g, 1 to 25 J / g, 2 to 20 J / g, 3 to 15 J / g, or 5 to 13 J / g).

[0035] In addition, the polyester resin has a glass transition temperature (T) when analyzed by differential scanning calorimetry (DSC). g ) may exceed 100 ℃. Specifically, the glass transition temperature (T g) may be 101 ℃ or more, 102 ℃ or more, 103 ℃ or more, 104 ℃ or more, or 105 ℃ or more, and 125 ℃ or less, 123 ℃ or less, 120 ℃ or less, 118 ℃ or less, 115 ℃ or less, 112 ℃ or less, or 110 ℃ or less (e.g., more than 100 to 125 ℃, 101 to 123 ℃, 102 to 120 ℃, 103 to 118 ℃, 105 to 115 ℃, or 107 to 113 ℃). The glass transition temperature (T of the polyester resin g ) is within the above range, when deformation of the polyester resin occurs at a high temperature, the deformation recovery ability of the polyester resin over time may be fast, and as a result, the polyester resin may have high heat resistance and mechanical strength.

[0036] According to the present invention, the polyester resin can exhibit a strain recovery (SR) controlled within a specific range. Specifically, when a 1 mm thick specimen manufactured from the polyester resin is subjected to dynamic mechanical analysis (DMA), the strain recovery (SR) according to Equation 2 below can exceed 45%.

[0037] [Formula 2] SR (%) = {1 - (S2- S0 / S1- S0)} × 100

[0038] In the above equation 2,

[0039] S0 is the initial length of a 1 mm thick specimen manufactured from the above polyester resin,

[0040] S1 is the glass transition temperature (T) of the polyester resin g ) - Temperature of 30 ℃ (T g - The length of the specimen measured after maintaining it for 3 minutes with a force applied so that the length of the specimen is 3% elongated at 30 ℃.

[0041] S2 is the length of the specimen measured after the force applied to the specimen was removed and it was left for 5 minutes.

[0042] Specifically, the polyester resin may have a strain recovery rate (SR) according to the above formula 2 of 46% or more, 48% or more, 50% or more, 51% or more, 53% or more, 55% or more, 58% or more, 60% or more, 61% or more, 63% or more, 65% or more, 68% or more, or 70% or more (e.g., more than 45 to 70%, 46 to 69%, 47 to 68%, 49 to 66%, 50 to 65%, or 52 to 63%). As the strain recovery rate (SR) is within the above range, the polyester resin has excellent resilience to deformation occurring at high temperatures, thereby providing a polyester resin with high mechanical strength.

[0043] This strain recovery rate (SR) tends to increase proportionally when the content of 1,4-cyclohexanedimethanol included in the diol component increases or the ratio of trans-1,4-cyclohexanedimethanol (trans-CHDM) in the 1,4-cyclohexanedimethanol increases. Considering this, the present invention has the characteristic of controlling the content of 1,4-cyclohexanedimethanol and the ratio of trans-1,4-cyclohexanedimethanol (trans-CHDM) in 1,4-cyclohexanedimethanol in order to obtain a polyester resin having excellent heat resistance and mechanical strength by increasing the strain recovery rate (SR), which will be described later. At this time, the 1,4-cyclohexanedimethanol may mean virgin 1,4-cyclohexanedimethanol (virgin CHDM), recycled 1,4-cyclohexanedimethanol (recycled CHDM), or a combination thereof.

[0044] According to the present invention, the polyester resin comprises a dicarboxylic acid repeating unit derived from a dicarboxylic acid component. The dicarboxylic acid component is not particularly limited as long as it is a commonly known dicarboxylic acid component, but specifically may include at least one selected from the group consisting of terephthalic acid, recycled terephthalic acid, dimethyl terephthalic acid, isophthalic acid, dimethyl terephthalate, 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, dimethyl 1,4-cyclohexane dicarboxylate, dimethyl 1,3-cyclohexane dicarboxylate, 2,6-naphthalenedicarboxylic acid, diphenyl dicarboxylic acid, 4,4'-stilbene dicarboxylic acid, 2,5-furandicarboxylic acid, and 2,5-thiophenedicarboxylic acid. For example, the dicarboxylic acid component may include terephthalic acid, isophthalic acid, dimethyl terephthalate, or a combination thereof.

[0045] According to the present invention, the polyester resin comprises a diol repeating unit derived from a diol component. The above diol component is not particularly limited as long as it is a commonly known diol component, but specifically, it is at least one selected from the group consisting of ethylene glycol, recycled ethylene glycol, diethylene glycol, recycled diethylene glycol, 1,4-cyclohexanedimethanol, recycled 1,4-cyclohexanedimethanol, isosorbide, recycled isosorbide, bis-2-hydroxyethyl terephthalate, recycled bis-2-hydroxyethyl terephthalate, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-propanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol and derivatives thereof (for example, 2 or more, 3 or more, or 4 or more) may be included.

[0046] For example, the diol component may essentially include 1,4-cyclohexanedimethanol or recycled 1,4-cyclohexanedimethanol. The content of the 1,4-cyclohexanedimethanol or recycled 1,4-cyclohexanedimethanol contained in the diol component is not particularly limited, but may be 10 to 90 mol% based on 100 mol% of the diol component, and specifically, may be 15 to 85 mol%, 20 to 80 mol%, 25 to 78 mol%, 30 to 75 mol%, 35 to 74 mol%, 40 to 73 mol%, 45 to 72 mol%, or 50 to 70 mol%. As the content of the above 1,4-cyclohexanedimethanol or the above recycled 1,4-cyclohexanedimethanol is within the above range, a polyester resin having a strain recovery rate (SR) controlled within the desired range according to the above formula 2 can be obtained, thereby providing a polyester resin having excellent heat resistance and mechanical strength.

[0047] According to the present invention, the 1,4-cyclohexanedimethanol includes trans-1,4-cyclohexanedimethanol (trans-CHDM), which is a trans-structure isomer, and cis-1,4-cyclohexanedimethanol (cis-CHDM), which is a cis-structure isomer. The present invention can provide a polyester resin having significantly improved heat resistance and mechanical strength by controlling the ratio of trans-CHDM among them to be high. Specifically, the 1,4-cyclohexanedimethanol can include the trans-CHDM and the cis-CHDM in a content ratio (molar ratio) of 60:40 to 85:15. For example, the content ratio of the trans-CHDM: cis-CHDM may be 62:38 to 83:17, 64:36 to 81:19, 65:35 to 80:20, 66:34 to 79:21, or 67:33 to 78:22. For example, the content of the trans-CHDM contained in the 1,4-cyclohexanedimethanol may be 60 to 85 mol%, 62 to 83 mol%, 64 to 81 mol%, 65 to 80 mol%, 66 to 79 mol%, or 67 to 78 mol% based on 100 mol% of 1,4-cyclohexanedimethanol. In addition, the content of the cis-CHDM contained in the 1,4-cyclohexanedimethanol may be 15 to 40 mol%, 17 to 38 mol%, 19 to 36 mol%, 20 to 35 mol%, 21 to 34 mol%, or 22 to 33 mol% based on 100 mol% of 1,4-cyclohexanedimethanol. When the content ratio (molar ratio) is within the above range, a polyester resin having excellent heat resistance, mechanical strength, and high-temperature deformation recovery can be provided.

[0048] This 1,4-cyclohexanedimethanol may be obtained by isomerizing 1,4-cyclohexanedimethanol having a low cis-CHDM content to increase the trans-CHDM content using a conventional method. In addition, the 1,4-cyclohexanedimethanol may be obtained by artificially increasing the trans-CHDM content by separating the cis-CHDM component using a conventional method. For example, the 1,4-cyclohexanedimethanol may be obtained by a method of increasing the trans-CHDM content by adding an alkali catalyst to 1,4-cyclohexanedimethanol and applying heat, a separation method utilizing the boiling point difference of 1,4-cyclohexanedimethanol containing trans-CHDM / cis-CHDM, or a method of increasing the trans-CHDM content through a hydrogenation reaction of 1,4-cyclohexanedicarboxylic acid dialkyl ester.

[0049] Meanwhile, the diol component may include, together with the 1,4-cyclohexanedimethanol, at least one (two or more, or three or more) selected from the group consisting of ethylene glycol, recycled ethylene glycol, isosorbide, recycled isosorbide, bis-2-hydroxyethyl terephthalate, recycled bis-2-hydroxyethyl terephthalate, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol as a comonomer. By including the comonomer in the diol component, a polyester resin having excellent heat resistance, mechanical strength, and environmental friendliness can be provided. In particular, the above isosorbide is a biomaterial produced through a chemical process based on components derived from plant resources such as corn, and has a lower sensitivity to global warming potential (GWP) than other dicarboxylic acid components (e.g., terephthalic acid) or other diol components, so a polyester resin manufactured using the isosorbide can have significantly lower greenhouse gas emissions.

[0050] The content of the ethylene glycol or the recycled ethylene glycol included in the diol component is not particularly limited, but may be 1 to 70 mol% based on 100 mol% of the diol component, and specifically, may be 5 to 65 mol%, 7 to 60 mol%, 9 to 55 mol%, 11 to 50 mol%, or 13 to 45 mol%.

[0051] The content of the isosorbide or the regenerated isosorbide included in the diol component is not particularly limited, but may be 1 to 50 mol% based on 100 mol% of the diol component, and specifically, may be 4 to 45 mol%, 7 to 40 mol%, 10 to 35 mol%, 13 to 30 mol%, or 16 to 25 mol%.

[0052] Meanwhile, the recycled monomers (i.e., recycled terephthalic acid, recycled ethylene glycol, recycled diethylene glycol, recycled 1,4-cyclohexanedimethanol, recycled isosorbide, and recycled bis-2-hydroxyethyl terephthalate) included in the dicarboxylic acid component and the diol component may refer to recycled monomers obtained by subjecting a used waste polyester resin or a waste polyester article to a commonly known depolymerization process. Even when such recycled monomers are used, the present invention can provide a polyester resin having excellent heat resistance and mechanical strength by optimizing the composition of the diol component.

[0053] According to the present invention, the high mechanical strength of the polyester resin can be confirmed through impact strength. For example, when measuring the impact strength of a 3.2 mm thick specimen manufactured from the polyester resin, the impact strength may be 800 J / m or more. Specifically, the impact strength may be 810 J / m or more, 820 J / m or more, 830 J / m or more, 840 J / m or more, or 850 J / m or more (e.g., 800 to 860 J / m, 820 to 855 J / m, or 840 to 853 J / m).

[0054] According to the present invention, the polyester resin may have an intrinsic viscosity (melt intrinsic viscosity) (IV) of 0.64 to 0.78 dl / g. Specifically, the intrinsic viscosity may be 0.64 to 0.77 dl / g, 0.65 to 0.77 dl / g, 0.65 to 0.76 dl / g, 0.66 to 0.75 dl / g, or 0.68 to 0.74 dl / g. When the intrinsic viscosity of the polyester resin is within the above range, it is possible to manufacture an article having desired physical properties while ensuring the formability of the polyester resin.

[0055] According to the present invention, the polyester resin can be evaluated as having environmental friendliness when evaluating the degree of environmental impact (e.g., Global Warming Potential, GWP) through a life cycle assessment (LCA). Specifically, the polyester resin may have a greenhouse gas (GHG) emission measured according to the ISO 14040 standard of 1.5 kgCO2 / kg or less, 1.3 kgCO2 / kg or less, 1.2 kgCO2 / kg or less, 1.1 kgCO2 / kg or less, 1.07 kgCO2 / kg or less, 1.05 kgCO2 / kg or less, 1.03 kgCO2 / kg or less, or 1.02 kgCO2 / kg or less.

[0056] Meanwhile, according to the present invention, the polyester resin may further include a component derived from at least one additive selected from the group consisting of an oxidation stabilizer, a branching agent, a coloring agent, a crystallizer, a catalyst, a stabilizer, and an ultraviolet absorber.

[0057] The above-mentioned oxidation stabilizer is not particularly limited, but may include at least one selected from the group consisting of hindered phenol compounds, phosphite compounds, and thioether compounds.

[0058] The branching agent may be a compound having three or more functional groups, and specifically may include at least one selected from the group consisting of trimellitic anhydride, trimellitic acid, pyromelletic dianhydride, glycerol, trimethylol propane, pentaerythritol, citric acid, tartaric acid, and 3-hydroxyglutaric acid.

[0059] The coloring agent is not particularly limited, but may include at least one selected from the group consisting of cobalt compounds, anthraquionone compounds, perinone compounds, azo compounds, and methine compounds. Specifically, cobalt acetate, cobalt propionate, Clarient's Polysynthren Blue RLS toner, Clarient's Solvaperm Red BB toner, etc. may be used as the coloring agent.

[0060] The catalyst is not particularly limited, but may include methylates of sodium and magnesium; acetates, borates, fatty acid salts, or carbonates of Zn, Cd, Mn, Co, Ca, Ba, etc.; or oxides or hydrates of Mg, Pb, Mn, Ti, Sb, Sn, Al, Ge, etc. Specifically, the catalyst may include tetraethyl titanate, acetyltripropyl titanate, tetrapropyl titanate, tetrabutyl titanate, 2-ethylhexyl titanate, octylene glycol titanate, triethanolamine titanate, acetylacetonate titanate, ethylacetoacetic ester titanate, isostearyl titanate, titanium dioxide, germanium dioxide, germanium tetrachloride, germanium ethylene glycoside, germanium acetate, or a combination thereof.

[0061] The above stabilizer is not particularly limited, but may include phosphorus compounds such as phosphoric acid, trimethyl phosphate, and triethyl phosphate.

[0062] According to the present invention, the polyester resin may have a form such as chips, pellets, or powder.

[0063] In addition, the polyester resin may be a homopolymer or a copolymer. Specifically, the polyester resin may be selected from the group consisting of polyethylene terephthalate (PET), polyethylene terephthalate glycol (PETG), polyester sulfone (PES), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polybutylene adipate-co-terephthalate (PBAT), polypropylene adipate-co-terephthalate (PPAT), polycyclohexanedimethyl terephthalate (PCT), and thermoplastic polyester elastomer (TPEE).

[0064]

[0065] Method for manufacturing polyester resin

[0066] The polyester resin according to the present invention can be manufactured through a process of polycondensation reaction followed by a conventionally known esterification reaction or esterification exchange reaction. Specifically, the method for manufacturing the polyester resin according to the present invention may include a step (S-1) of introducing a diol component and a dicarboxylic acid component into a reactor; a step (S-2) of manufacturing an oligomer by esterification reaction of the diol component and the dicarboxylic acid component; and a step (S-3) of manufacturing the oligomer by polycondensation reaction.

[0067] According to the present invention, the step (S-1) is a step of introducing a diol component and a dicarboxylic acid component into a reactor. Descriptions of each of the diol component and the dicarboxylic acid component are the same as those described above, and thus are omitted.

[0068] When the diol component and the dicarboxylic acid component are introduced into the reactor, the molar ratio between them (number of moles of the diol component / number of moles of the dicarboxylic acid component) is not particularly limited, but considering the efficiency of the esterification reaction and polycondensation reaction described below, it may be 1.05 to 1.30, 1.07 to 1.28, 1.09 to 1.26, 1.11 to 1.24, or 1.13 to 1.22.

[0069] The above reactor may be a batch reactor or a continuous reactor.

[0070] Additionally, one or more additives selected from the group consisting of an oxidation stabilizer, a branching agent, a coloring agent, a crystallizer, a catalyst, a stabilizer, and an ultraviolet absorber may be further added to the reactor.

[0071] According to the present invention, the step (S-2) is a step of producing an oligomer by esterifying the diol component and the dicarboxylic acid component. The conditions under which the esterification reaction is performed may not be particularly limited.

[0072] Specifically, the temperature at which the esterification reaction is performed may be 220 to 300°C, 225 to 290°C, 230 to 285°C, 235 to 280°C, 240 to 275°C, or 250 to 270°C. In addition, the pressure at which the esterification reaction is performed may be 0.1 to 5 kgf / cm2, 0.1 to 4 kgf / cm2, 0.3 to 3 kgf / cm2, 0.5 to 2 kgf / cm2, or 1 to 2 kgf / cm2. As the esterification reaction is performed under the above conditions, an oligomer having a desired molecular weight can be obtained in high yield while minimizing the production of side products.

[0073] According to the present invention, the step (S-3) is a step of subjecting the oligomer to a polycondensation reaction. The conditions under which the polycondensation reaction is performed may not be particularly limited.

[0074] Specifically, the temperature at which the polycondensation reaction is performed may be 250 to 320°C, 255 to 310°C, 260 to 300°C, 265 to 290°C, or 270 to 285°C. In addition, the pressure at which the polycondensation reaction is performed may be a pressure (reduced pressure) lower than atmospheric pressure (e.g., 1 atm). When the polycondensation reaction is performed under the above conditions, a polyester resin (polymer) having crystallinity and secured formability can be efficiently produced.

[0075] Meanwhile, the method for producing a polyester resin according to the present invention may further include a step of subjecting the reactant to a solid-state polymerization reaction in order to control the intrinsic viscosity (IV), molecular weight, etc. of the reactant obtained through the condensation polymerization reaction of step (S-3), if necessary. The solid-state polymerization reaction conditions are not particularly limited and may be appropriately set depending on the intrinsic viscosity, molecular weight, etc. of the desired polyester resin.

[0076]

[0077] article

[0078] Articles according to the present invention are manufactured from the polyester resin described above. Specifically, by applying the polyester resin to a molding process, articles having various shapes and uses can be manufactured. Because these articles are manufactured from the polyester resin described above, they can exhibit excellent heat resistance and mechanical strength.

[0079] The method for molding the polyester resin to manufacture the above product is not particularly limited as long as it is a commonly known method, and specific examples thereof include injection molding, extrusion molding, pressure molding, vacuum molding, and blow molding.

[0080] These items may be containers, films, sheets, or interior / exterior materials, and specifically, may be food containers or packaging films that require high heat resistance and mechanical strength.

[0081] The present invention is described in more detail through the following examples. However, the following examples are intended only to illustrate the present invention and are not intended to limit the scope of the present invention.

[0082]

[0083] [Example 1]

[0084] Terephthalic acid (TPA, 2494.4 g), ethylene glycol (EG, 149.1 g), 1,4-cyclohexanedimethanol (CHDM, 1514.7 g), isosorbide (ISB, 745.9 g), a Ge-based catalyst (16.9 g), and a stabilizer (8.7 g) were added to a 10 L reactor connected to a column and a water-cooled condenser. Next, the temperature of the reactor was raised to 270 °C, and an esterification reaction (ES) was performed at 270 °C under a pressure of 0.5 kgf / cm2 to obtain a transparent reactant.

[0085] Next, the reactants were transferred to a polycondensation reactor, and a polycondensation reaction (PA) was performed at 280°C while maintaining the pressure of the polycondensation reactor lower than atmospheric pressure. When the intrinsic viscosity (IV) of the reactants inside the polycondensation reactor reached 0.65 dl / g, the reactants were discharged outside the polycondensation reactor and formed into strands. Thereafter, the strands were solidified with a cooling liquid and then granulated to an average weight of about 12 to 14 mg, thereby producing a polyester resin.

[0086]

[0087] [Example 2]

[0088] Terephthalic acid (TPA, 2217.7 g), ethylene glycol (EG, 248.5 g), 1,4-cyclohexanedimethanol (CHDM, 1365.9 g), isosorbide (ISB, 546.1 g), a Ge-based catalyst (9.0 g), and a stabilizer (3.8 g) were added to a 10 L reactor connected to a column and a water-cooled condenser. Next, the temperature of the reactor was raised to 258°C, and an esterification reaction (ES) was performed at 258°C under a pressure of 2 kgf / cm2 to obtain a transparent reactant.

[0089] Next, the reactants were transferred to a polycondensation reactor, and a polycondensation reaction (PA) was performed at 270°C while maintaining the pressure of the polycondensation reactor lower than atmospheric pressure. When the intrinsic viscosity (IV) of the reactants inside the polycondensation reactor reached 0.75 dl / g, the reactants were discharged outside the polycondensation reactor and formed into strands. Thereafter, the strands were solidified with a cooling liquid and then granulated to an average weight of about 12 to 14 mg, thereby producing a polyester resin.

[0090]

[0091] [Example 3]

[0092] Terephthalic acid (TPA, 2565.8 g), ethylene glycol (EG, 287.5 g), 1,4-cyclohexanedimethanol (CHDM, 1224.2 g), isosorbide (ISB, 812.4 g), a Ge-based catalyst (12.5 g), and a stabilizer (2.8 g) were added to a 10 L reactor connected to a column and a water-cooled condenser. Next, the temperature of the reactor was raised to 265 ℃, and an esterification reaction (ES) was performed at 265 ℃ under a pressure of 1 kgf / ㎠ to obtain a transparent reactant.

[0093] Next, the reactants were transferred to a polycondensation reactor, and a polycondensation reaction (PA) was performed at 270°C while maintaining the pressure of the polycondensation reactor lower than atmospheric pressure. When the intrinsic viscosity (IV) of the reactants inside the polycondensation reactor reached 0.65 dl / g, the reactants were discharged outside the polycondensation reactor and formed into strands. Thereafter, the strands were solidified with a cooling liquid and then granulated to an average weight of about 12 to 14 mg, thereby producing a polyester resin.

[0094]

[0095] [Example 4]

[0096] Terephthalic acid (TPA, 2968.6 g), 1,4-cyclohexanedimethanol (CHDM, 1982.9 g), 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCBD, 901.3 g), a Ge-based catalyst (15.7 g), and a stabilizer (1.8 g) were added to a 10 L reactor connected to a column and a water-cooled condenser. Next, the temperature of the reactor was raised to 265 ℃, and an esterification reaction (ES) was performed at 265 ℃ under a pressure of 1.5 kgf / ㎠ to obtain a transparent reactant.

[0097] Next, the reactants were transferred to a polycondensation reactor, and a polycondensation reaction (PA) was performed at 272°C while maintaining the pressure of the polycondensation reactor lower than atmospheric pressure. When the intrinsic viscosity (IV) of the reactants inside the polycondensation reactor reached 0.75 dl / g, the reactants were discharged outside the polycondensation reactor and formed into strands. Thereafter, the strands were solidified with a cooling liquid and then granulated to an average weight of about 12 to 14 mg, thereby producing a polyester resin.

[0098]

[0099] [Example 5]

[0100] Terephthalic acid (TPA, 2486.0 g), 1,4-cyclohexanedimethanol (CHDM, 1466.4 g), isosorbide (ISB, 699.7 g), regenerated bis-2-hydroxyethyl terephthalate (r-BHET, 380.4 g), a Ge-based catalyst (12.5 g), and a stabilizer (6.5 g) were added to a 10 L reactor connected to a column and a water-cooled condenser. Next, the temperature of the reactor was raised to 265 ℃, and an esterification reaction (ES) was performed at 265 ℃ under a pressure of 1 kgf / cm2 to obtain a transparent reactant.

[0101] Next, the reactants were transferred to a polycondensation reactor, and a polycondensation reaction (PA) was performed at 275°C while maintaining the pressure of the polycondensation reactor lower than atmospheric pressure. When the intrinsic viscosity (IV) of the reactants inside the polycondensation reactor reached 0.73 dl / g, the reactants were discharged outside the polycondensation reactor and formed into strands. Thereafter, the strands were solidified with a cooling liquid and then granulated to an average weight of about 12 to 14 mg, thereby producing a polyester resin.

[0102]

[0103] [Comparative Example 1]

[0104] Terephthalic acid (TPA, 3007.2 g), ethylene glycol (EG, 1010.9 g), 1,4-cyclohexanedimethanol (CHDM, 782.6 g), isosorbide (ISB, 238.0 g), a Ge-based catalyst (6.1 g), and a stabilizer (1.4 g) were added to a 10 L reactor connected to a column and a water-cooled condenser. Next, the temperature of the reactor was raised to 255 °C, and an esterification reaction (ES) was performed at 255 °C under a pressure of 2 kgf / cm2 to obtain a transparent reactant.

[0105] Next, the reactants were transferred to a polycondensation reactor, and a polycondensation reaction (PA) was performed at 265°C while maintaining the pressure of the polycondensation reactor lower than atmospheric pressure. When the intrinsic viscosity (IV) of the reactants inside the polycondensation reactor reached 0.75 dl / g, the reactants were discharged outside the polycondensation reactor and formed into strands. Thereafter, the strands were solidified with a cooling liquid and then granulated to an average weight of about 12 to 14 mg, thereby producing a polyester resin.

[0106]

[0107] [Comparative Example 2]

[0108] Terephthalic acid (TPA, 2674.9 g), ethylene glycol (EG, 539.5 g), 1,4-cyclohexanedimethanol (CHDM, 812.1 g), isosorbide (ISB, 847.0 g), a Ge-based catalyst (8.8 g), and a stabilizer (3.3 g) were added to a 10 L reactor connected to a column and a water-cooled condenser. Next, the temperature of the reactor was raised to 265 ℃, and an esterification reaction (ES) was performed at 265 ℃ under a pressure of 1 kgf / ㎠ to obtain a transparent reactant.

[0109] Next, the reactants were transferred to a polycondensation reactor, and a polycondensation reaction (PA) was performed at 275°C while maintaining the pressure of the polycondensation reactor lower than atmospheric pressure. When the intrinsic viscosity (IV) of the reactants inside the polycondensation reactor reached 0.64 dl / g, the reactants were discharged outside the polycondensation reactor and formed into strands. Thereafter, the strands were solidified with a cooling liquid and then granulated to an average weight of about 12 to 14 mg, thereby producing a polyester resin.

[0110]

[0111] [Comparative Example 3]

[0112] Terephthalic acid (TPA, 2341.2 g), ethylene glycol (EG, 288.6 g), 1,4-cyclohexanedimethanol (CHDM, 974.9 g), isosorbide (ISB, 864.8 g), a Ge-based catalyst (10.3 g), and a stabilizer (2.5 g) were added to a 10 L reactor connected to a column and a water-cooled condenser. Next, the temperature of the reactor was raised to 262 ℃, and an esterification reaction (ES) was performed at 262 ℃ under a pressure of 1 kgf / cm2 to obtain a transparent reactant.

[0113] Next, the reactants were transferred to a polycondensation reactor, and a polycondensation reaction (PA) was performed at 270°C while maintaining the pressure of the polycondensation reactor lower than atmospheric pressure. When the intrinsic viscosity (IV) of the reactants inside the polycondensation reactor reached 0.60 dl / g, the reactants were discharged outside the polycondensation reactor and formed into strands. Thereafter, the strands were solidified with a cooling liquid and then granulated to an average weight of about 12 to 14 mg, thereby producing a polyester resin.

[0114]

[0115] [Comparative Example 4]

[0116] Terephthalic acid (TPA, 2287.9 ​​g), ethylene glycol (EG, 153.8 g), 1,4-cyclohexanedimethanol (CHDM, 1647.3 g), isosorbide (ISB, 362.2 g), a Ge-based catalyst (9.5 g), and a stabilizer (4 g) were added to a 10 L reactor connected to a column and a water-cooled condenser. Next, the temperature of the reactor was raised to 267 ℃, and an esterification reaction (ES) was performed at 267 ℃ under a pressure of 1 kgf / ㎠ to obtain a transparent reactant.

[0117] Next, the reactants were transferred to a polycondensation reactor, and a polycondensation reaction (PA) was performed at 285°C while maintaining the pressure of the polycondensation reactor lower than atmospheric pressure. When the intrinsic viscosity (IV) of the reactants inside the polycondensation reactor reached 0.70 dl / g, the reactants were discharged outside the polycondensation reactor and formed into strands. Thereafter, the strands were solidified with a cooling liquid and then granulated to an average weight of about 12 to 14 mg, thereby producing a polyester resin.

[0118]

[0119] [Comparative Example 5]

[0120] Terephthalic acid (TPA, 2596.1 g), ethylene glycol (EG, 77.6 g), 1,4-cyclohexanedimethanol (CHDM, 1756.6 g), isosorbide (ISB, 570.8 g), a Ge-based catalyst (13.4 g), and a stabilizer (6.1 g) were added to a 10 L reactor connected to a column and a water-cooled condenser. Next, the temperature of the reactor was raised to 263 ℃, and an esterification reaction (ES) was performed at 263 ℃ under a pressure of 1 kgf / ㎠ to obtain a transparent reactant.

[0121] Next, the reactants were transferred to a polycondensation reactor, and a polycondensation reaction (PA) was performed at 282°C while maintaining the pressure of the polycondensation reactor lower than atmospheric pressure. When the intrinsic viscosity (IV) of the reactants inside the polycondensation reactor reached 0.68 dl / g, the reactants were discharged outside the polycondensation reactor and formed into strands. Thereafter, the strands were solidified with a cooling liquid and then granulated to an average weight of about 12 to 14 mg, thereby producing a polyester resin.

[0122]

[0123] [Example 1]

[0124] The polyester resins manufactured in each of the examples and comparative examples were analyzed by differential scanning calorimetry (DSC) to determine the melting point (T m ) was confirmed to appear. At this time, DSC analysis of the polyester resin was performed as follows.

[0125] DSC analysis device: Mettler Toledo's DSC 1 model was used.

[0126] Sample preparation: Take about 6 to 10 mg of polyester resin and fill an aluminum pan.

[0127] Scan conditions: DSC curves were obtained by heating from room temperature to 280 ℃ at a rate of 10 ℃ / min under a nitrogen atmosphere, then cooling to 30 ℃ at a rate of -300 ℃ / min, and then heating again to 280 ℃ at a rate of 2 ℃ / min. The temperature at which an endothermic peak appears during the heating process in the obtained DSC curve was designated as the melting point (T m ) was defined as follows. In addition, the melting point (T m ) was used to calculate the heat of fusion (△H).

[0128]

[0129] [Example 2]

[0130] The polyester resins manufactured in the Examples and Comparative Examples were injection-molded at a temperature of 250 to 300°C to manufacture specimens with a thickness of 3 mm (width 17.5 mm, length 12.5 mm), and the manufactured specimens were subjected to dynamic mechanical analysis (DMA) (TA Instrument Q800) in single cantilever mode at a temperature increase rate of 10°C / min from 30°C to 150°C to obtain tanδ curves. Thereafter, the temperature at the maximum value (tanδ peak) of the obtained tanδ curve was confirmed, and this was defined as the heat resistance of the polyester resin.

[0131]

[0132] [Example 3]

[0133] The polyester resins manufactured in the examples and comparative examples were each injected at a temperature of 250 to 300°C to manufacture specimens with a thickness of 1 mm (width 17.5 mm, length 12.5 mm), and dynamic mechanical analysis (DMA) (TA Instrument Q800) was performed on the manufactured specimens (stress relaxation mode measurement), and then the strain recovery rate (SR) was calculated according to Equation 2 below.

[0134] [Formula 2] SR (%) = {1 - (S2- S0 / S1- S0)} × 100

[0135] In the above equation 2,

[0136] S0 is the initial length of a 1 mm thick specimen manufactured from the above polyester resin,

[0137] S1 is the glass transition temperature (T) of the polyester resin g ) - The length of the specimen measured after maintaining it for 3 minutes with a force applied so that the length of the specimen is 3% elongated at a temperature of 30 ℃,

[0138] S2 is the length of the specimen measured after the force applied to the specimen was removed and it was left for 5 minutes.

[0139]

[0140] [Test Example 4]

[0141] The polyester resins manufactured in each of the Examples and Comparative Examples were injection-molded at 250 to 300°C to manufacture specimens (63.3 mm wide, 12.5 mm long) having a thickness of 3.2 mm, and the impact strength (J / m) was measured according to ASTM D256, and then evaluated according to the following criteria. For the impact strength measurement, NO. 258 PC-S IMPACT TESTER (product name) of YASUDA SEIKI SEISAKUSHO was used (hammer capacity: 2.75 J).

[0142] ○: Impact strength of 800 J / m or more

[0143] ×: Impact strength less than 800 J / m

[0144]

[0145] [Example 5]

[0146] The polyester resins manufactured in the examples and comparative examples were dissolved in orthochlorophenol (OCP) at 100°C at a concentration of 0.12%, and then the intrinsic viscosity (IV, dl / g) was measured using a Ubbelrod viscometer in a constant temperature bath at 35°C.

[0147]

[0148] [Example 6]

[0149] The polyester resins manufactured in each of the examples and comparative examples were injection-molded at 250 to 300°C to manufacture specimens with a thickness of 1 mm (width 17.5 mm, length 12.5 mm), and then the formability was evaluated according to the following criteria.

[0150] ○: No screw fusion of resin during injection molding

[0151] ×: Screw fusion of resin occurs during injection molding

[0152]

[0153] The evaluation results for the above test examples are summarized in Tables 1 and 2 below.

[0154]

[0155] Classification Example 1 Example 2 Example 3 Example 4 Example 5 CHDM content (mol%) in X diol component 70 7 15 0 7 7 6 5 Y Trans-CHDM molar ratio in CHDM 0.77 0.69 0.67 0.71 0.73 Trans-CHDM ratio in CHDM (mol%) 7 7 6 9 6 7 7 3 X × Y 5 3.94 8.99 3 3.55 4.67 4 7.45 Intrinsic viscosity (dl / g) 0.65 0.75 0.65 0.75 0.73 Temperature at tanδ peak (℃) 1 18 10 9 1 1 5 1 1 7 1 1 4 T m (℃)246246Not displayed250244T m ΔH(J / g)1011-12SR(%)66.949.3464957.1Impact strength(J / m)○○○○○Formability○○○○○

[0156] Comparison Example 1 Comparison Example 2 Comparison Example 3 Comparison Example 4 Comparison Example 5 CHDM content (mol%) in X diol component 30 35 45 8 378 Trans-CHDM molar ratio in Y CHDM 0.75 0.67 0.60 0.75 0.85 Trans-CHDM ratio in CHDM (mol%) 75 6 76 0 75 8 5 X × Y 2 2.5 2 3.4 5 2 7.0 6 2.2 5 6 6.3 Intrinsic viscosity (dl / g) 0.75 0.64 0.60 0.70 0.68 Temperature at tanδ peak (℃) 90 10 9 11 0 10 5 11 7 T m (℃)Not displayedNot displayedNot displayed257259T m ΔH(J / g)---4036SR(%)1537405160Impact strength(J / m)×××○○Formability○○○××

[0157] Referring to Table 1 and Table 2 above, it can be confirmed that the polyester resins of Examples 1 to 5 according to the present invention have excellent heat resistance and mechanical strength, as the temperature at the tanδ peak is high while the X×Y value and SR are controlled within the ranges targeted by the present invention. In addition, T mIt can also be confirmed that the temperature is controlled to 250°C or lower, resulting in excellent formability. Therefore, it can be predicted that when manufacturing a product using the polyester resin according to the present invention, a product with excellent heat resistance and mechanical strength can be manufactured with high efficiency.

[0158] On the other hand, it can be confirmed that the polyester resins of Comparative Examples 1 to 5 have poor heat resistance, mechanical strength, or formability because the X×Y values ​​are not controlled within the range targeted by the present invention. Specifically, it can be seen that the polyester resins of Comparative Examples 1 to 3 have significantly poor mechanical strength as the SR deviates from the range targeted by the present invention. In addition, the polyester resins of Comparative Examples 4 and 5 have T m It can be seen that this excessively high value reduces formability.

Claims

1. A diol repeating unit derived from a diol component; and a dicarboxylic acid repeating unit derived from a dicarboxylic acid component, When the tanδ value is measured through dynamic mechanical analysis (DMA), the temperature at the tanδ peak is 100 ℃ or higher. A polyester resin satisfying the following equation 1: [Formula 1] 30 ≤ X × Y ≤ 60 In the above equation 1, X is the mole % of 1,4-cyclohexanedimethanol (CHDM) with respect to 100 mole % of the above diol component, Y is the molar ratio of trans-1,4-cyclohexanedimethanol (trans-CHDM) to the above 1,4-cyclohexanedimethanol (CHDM).

2. In paragraph 1, A polyester resin having a strain recovery rate (SR) exceeding 45% according to the following formula 2: [Formula 2] SR (%) = {1 - (S2- S0 / S1- S0)} × 100 In the above equation 2, S0 is the initial length of a 1 mm thick specimen manufactured from the polyester resin, S1 is the glass transition temperature (T) of the polyester resin. g ) - The length of the specimen measured after applying a force that elongates the length of the specimen by 3% at a temperature of 30 ℃ for 3 minutes, S2 is the length of the specimen measured after the force applied to the specimen was removed and it was left for 5 minutes.

3. In paragraph 1, When analyzed by differential scanning calorimetry (DSC), the melting point (T m ) does not appear, or the melting point (T) is below 250 ℃. m ) appears, polyester resin.

4. In paragraph 1, A polyester resin, wherein the 1,4-cyclohexanedimethanol (CHDM) contained in the above diol component contains trans-1,4-cyclohexanedimethanol (trans-CHDM) and cis-1,4-cyclohexanedimethanol (cis-CHDM) in a content ratio of 60:40 to 85:

15.

5. In paragraph 1, A polyester resin having an impact strength of 800 J / m or more of a 3.2 mm thick specimen manufactured from the polyester resin.

6. In paragraph 1, A polyester resin having an intrinsic viscosity (IV) of 0.64 to 0.78 dl / g.

7. In paragraph 1, A polyester resin, wherein the dicarboxylic acid component comprises at least one selected from the group consisting of terephthalic acid, regenerated terephthalic acid, dimethyl terephthalic acid, isophthalic acid, dimethyl terephthalate, 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, dimethyl 1,4-cyclohexane dicarboxylate, dimethyl 1,3-cyclohexane dicarboxylate, 2,6-naphthalenedicarboxylic acid, diphenyl dicarboxylic acid, 4,4'-stilbene dicarboxylic acid, 2,5-furandicarboxylic acid, and 2,5-thiophenedicarboxylic acid.

8. In paragraph 1, A polyester resin, wherein the diol component comprises at least one selected from the group consisting of ethylene glycol, recycled ethylene glycol, diethylene glycol, recycled diethylene glycol, 1,4-cyclohexanedimethanol, recycled 1,4-cyclohexanedimethanol, isosorbide, recycled isosorbide, bis-2-hydroxyethyl terephthalate, recycled bis-2-hydroxyethyl terephthalate, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-propanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and derivatives thereof.

9. In paragraph 1, A polyester resin, wherein the diol component comprises 45 to 85 mol% of 1,4-cyclohexanedimethanol based on 100 mol% of the diol component.

10. An article manufactured from a polyester resin according to any one of claims 1 to 9.