Crystalline polyester resin and article comprising same

Abstract

The present invention relates to a crystalline polyester resin and a preparation method for same. The crystalline polyester resin has the degree of crystallization required for a molding process and / or a recycling process whilst experiencing minimal fusion during the preparation process, and thus can exhibit excellent productivity, moldability, and recyclability.

Description

Crystalline polyester resin and articles containing the same

[0001] The present invention relates to a crystalline polyester resin having a controlled degree of crystallization that is suitable for use in molding (processing) applications and has excellent recyclability, and an article comprising said crystalline polyester resin.

[0002] Polyester resin is manufactured by polymerizing dicarboxylic acid and diol components; because it does not contain substances harmful to the human body and is environmentally friendly, it is widely used in the manufacture of products such as films, partitions, panels, packaging materials, and containers.

[0003] In manufacturing the above-mentioned article, the polyester resin must possess good moldability (processability) to ensure the quality of the article. However, since polyester resins generally produced through pelletizing processes such as extrusion and underwater cutting contain moisture, there was a problem in that the quality of the article obtained through molding deteriorated because the degree of polymerization decreased due to hydrolysis reactions caused by the moisture when using such resins for the molding process.

[0004] Conventionally, before feeding the polyester resin into the molding process, a process was performed to dry the polyester resin to remove moisture contained in the polyester resin. However, since the surface of the polyester resin is mostly amorphous, another problem arises where the drying efficiency and productivity of the polyester resin are reduced as the resin fuses together or sticks to the inner wall of the dryer during the drying process.

[0005] Meanwhile, while the use of plastic containers makes daily life convenient, indiscriminate disposal and excessive use are causing serious environmental problems. Accordingly, various measures are being devised for the recycling of used plastic containers.

[0006] The recycling process for the aforementioned waste plastic containers can be divided into a physical recycling process involving washing and crushing, and a chemical recycling process involving depolymerization. However, the efficiency of the recycling process is reduced because a pretreatment step of separating waste plastics by type is required to carry out the above recycling process.

[0007] Specifically, a representative example of a waste plastic container is a PET bottle manufactured using polyethylene terephthalate resin, which is one of the polyester resins. In order to recycle the PET bottle after use, the plastic components constituting the waste PET bottle must be separated by type. This is because if the waste PET bottle is fed into the recycling process without separation due to differences in crystallinity among the plastic components constituting the waste PET bottle, fusion occurs between the plastic components, making the recycling process impossible.

[0008] Attempts are being made to solve the problem of fusion occurring during the drying process or the recycling process by controlling the crystallinity of the polyester resin. However, currently, there are limitations in optimizing the degree of crystallinity of the polyester resin.

[0009] In order to solve the aforementioned conventional problems, the inventors conducted various studies and confirmed that by controlling the heat of fusion (△H) at the crystallization temperature and melting temperature of the polyester resin, the degree of crystallization (crystallization) of the polyester resin is optimized, thereby obtaining a crystalline polyester resin that is recyclable and can be utilized for molding (processing) purposes.

[0010] Accordingly, the objective of the present invention is to provide a crystalline polyester resin having an optimized degree of crystallinity and an article comprising the same.

[0011] To solve the above problem, the present invention provides a crystalline polyester resin comprising a diol repeating unit derived from a diol component; and a dicarboxylic acid repeating unit derived from a dicarboxylic acid component, which satisfies the following Equation 1 when analyzed by differential scanning calorimetry (DSC) after heating to 280 ℃ at a scan rate of 10 ℃ / min:

[0012] [Equation 1] 1 < (Y×Z) / X < 30

[0013] In the above Equation 1,

[0014] X is the sum of the heat of fusion (△H) of the melting temperature of the crystalline polyester resin that appeared at 200 ℃ or higher during the DSC analysis, Y is the sum of the heat of fusion (△H) of the melting temperature of the crystalline polyester resin that appeared at less than 200 ℃ during the DSC analysis, and Z is the crystallization temperature of the crystalline polyester resin.

[0015] In addition, the present invention provides a method for producing a crystalline polyester resin that satisfies Equation 1 when analyzed by differential scanning calorimetry (DSC) after heating to 280°C at a scan rate of 10°C / min, comprising: (1) a step of producing a polyester resin by polymerizing a diol component and a dicarboxylic acid component; and (2) a step of crystallizing the polyester resin.

[0016] The present invention also provides an article manufactured from the crystalline polyester resin.

[0017] The present invention can provide a crystalline polyester resin with an optimally controlled degree of crystallization to the level required in molding (processing) and recycling processes. Accordingly, the crystalline polyester resin is suitable for use in extrusion molding or injection molding, and can contribute to providing high-quality articles (e.g., injection-molded articles or extrusion-molded articles). Furthermore, when articles are manufactured using the crystalline polyester resin, the manufactured articles have excellent recyclability, allowing the recycling process to be carried out efficiently without separate separation work, even if they contain other plastic components (e.g., PET).

[0018] The present invention will be described in detail below. Hereinafter, the present invention is not limited to the contents described below, but can be modified in various forms as long as the essence of the invention is not altered.

[0019] In this specification, the use of the word “comprising” is intended to specify certain characteristics, regions, steps, processes, elements, and / or components, and unless specifically stated otherwise, it does not exclude the presence or addition of other characteristics, regions, steps, processes, elements, and / or components.

[0020] In this specification, terms such as "first," "second," etc. are used to describe various components, and said components are not limited to said terms. These terms are used for the purpose of distinguishing one component from another.

[0021] All numbers and expressions indicating the amounts of components, reaction conditions, etc. described in this specification may be understood to be modified by the term "about" in all cases unless otherwise specified.

[0022]

[0023] If the polyester resin is not sufficiently crystallized, or conversely, if over-crystallization occurs, a problem of fusion occurs during the drying process of the polyester resin (e.g., polyester resin pellets) or during the recycling process of articles made from the polyester resin. For example, if the crystallization temperature rises due to over-crystallization, melting of the polyester resin (e.g., polyester resin pellets) occurs between the exothermic and endothermic temperatures, and the fusion rate of the polyester resin increases (sticking together between polyester resin pellets). In addition, to mold (process) a crystalline polyester resin, energy equivalent to the area of ​​the heat of fusion at the melting temperature is required; however, since the over-crystallized polyester resin has a significantly high heat of fusion, a large amount of energy is consumed in molding it, which reduces moldability (processability). Therefore, in order to improve the moldability of the crystalline polyester resin obtained through the crystallization process, it is very important to control the heat of fusion at the melting temperature along with the crystallization temperature of the crystalline polyester resin. In addition, to increase the recyclability of the polyester resin, it is required to optimize the crystallinity (degree of crystallization) of the polyester resin, and this can also be achieved by controlling the heat of fusion at the melting temperature of the polyester resin.

[0024] Based on these points, the present invention ensures the productivity, moldability (processability), and recyclability of the crystalline polyester resin by optimizing the degree of crystallization (crystallization) of the crystalline polyester resin obtained after crystallization, while preventing fusion between polyester resins during the crystallization process. To this end, the manufacturing (crystallization) process of the crystalline polyester resin is controlled by specifying the correlation between the crystallization temperature and the heat of fusion at the melting temperature of the crystalline polyester resin. The present invention is described in detail as follows.

[0025]

[0026] Crystalline polyester resin

[0027] The crystalline 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 satisfies the following Equation 1 when analyzed by differential scanning calorimetry (DSC) after heating to 280 ℃ at a scan rate of 10 ℃ / min.

[0028] [Equation 1] 1 < (Y×Z) / X < 30

[0029] In the above Equation 1,

[0030] X is the sum of the heat of fusion (△H) of the melting temperature of the crystalline polyester resin at 200 ℃ or higher during the above DSC analysis, and

[0031] Y is the sum of the heat of fusion (△H) of the melting temperature of the crystalline polyester resin found at less than 200 ℃ during the above DSC analysis, and

[0032] Z is the crystallization temperature of the crystalline polyester resin.

[0033] When calculating the ratio (Y×Z) / X in Equation 1 above, only the numerical values ​​excluding the units of X, Y, and Z are applied.

[0034] The above crystalline polyester resin can have excellent moldability and recyclability as its degree of crystallization is optimized by satisfying Equation 1 based on a specific temperature of 200°C. The above 200°C may represent an approximate intermediate value between the crystallization temperature (Tc) and the melting temperature (Tm) of the crystalline polyester resin, and by applying this intermediate temperature, the degree of crystallization and the energy required during the molding process can be controlled to the required level.

[0035] Specifically, in the above Equation 1, the "(Y×Z) / X" value may be 1.5 to 29.5, 1.8 to 29, 2 to 28.5, 2.3 to 28, 2.5 to 27.5, 2.7 to 27, 3 to 26.5, 3.3 to 26, 3.5 to 25.5, 3.8 to 25, 4 to 24.5, 4.3 to 24, 4.5 to 23.5, 5 to 23, 6 to 22.5, 7 to 22, 9 to 21, 10 to 20, 12 to 19, or 14 to 18. As the "(Y×Z) / X" value is controlled within the above range, the degree of crystallization is optimized, thereby providing a crystalline polyester resin with excellent moldability and recyclability.

[0036] According to the present invention, the crystalline polyester resin can satisfy the following Equation 2 when analyzed by differential scanning calorimetry (DSC) after being heated to 280°C at a scan rate of 10°C / min.

[0037] [Equation 2] 4 < X / Y < 70

[0038] In the above Equation 2,

[0039] X is the sum of the heat of fusion (△H) of the melting temperature of the crystalline polyester resin at 200 ℃ or higher during the above DSC analysis, and

[0040] Y is the sum of the heat of fusion (△H) of the melting temperature of the crystalline polyester resin that appeared at less than 200 ℃ during the above DSC analysis.

[0041] Specifically, in the above Equation 2, the "X / Y" value may be 4.3 to 65, 4.5 to 63, 4.8 to 60, 5 to 55, 5.3 to 53, 5.5 to 50, 5.8 to 48, 6 to 45, 6.2 to 43, 6.4 to 41, 6.5 to 35, 6.8 to 30, 6.9 to 25, 7 to 23, 7.5 to 20, 8 to 18, 8.5 to 17.5, 8.8 to 17, 9 to 16.5, 9.2 to 15, or 9.5 to 13.5. As the "X / Y" value is controlled within the above range, the degree of crystallization is optimized, thereby providing a crystalline polyester resin with excellent moldability and recyclability.

[0042] In each of the above Equations 1 and 2, X is the sum of the heat of fusion (△H) at each melting temperature (△H) when the crystalline polyester resin is heated to 280 ℃ at a scan rate of 10 ℃ / min and analyzed by DSC, if one or more melting temperatures appear at 200 ℃ or higher. sum1 It may mean ). For example, during the above DSC analysis, melting temperature a(T), which is one of two melting temperatures at 200 ℃ or higher. ma ) and melting temperature b(T mb If ) appears, the above X is the melting temperature a(T ma Heat of fusion (△H) at ) a ) and the melting temperature b(T mb Heat of fusion (△H) at ) b The sum of ) (△H a + △H b ) It may be. In addition, during the above DSC analysis, melting temperature a(T), which is one melting temperature at 200 ℃ or higher. ma If only ) appears, the above X is the melting temperature a(T ma Heat of fusion (△H) at ) a) It may be the value itself. Such X value is not particularly limited, but may be 5 J / g or more, 7 J / g or more, 8 J / g or more, 10 J / g or more, 13 J / g or more, 15 J / g or more, 18 J / g or more, 20 J / g or more, 22 J / g or more, 25 J / g or more, 28 J / g or more, 30 J / g or more, or 32 J / g or more (e.g., 5 to 40 J / g, 8 to 38 J / g, 11 to 35 J / g, or 15 to 34 J / g).

[0043] In addition, in each of the above Equations 1 and 2, Y is the sum of the heat of fusion (△H) at each melting temperature (△H) when the crystalline polyester resin is heated to 280 ℃ at a scan rate of 10 ℃ / min and analyzed by DSC, if one or more melting temperatures appear below 200 ℃. sum2 It may mean ). For example, during the above DSC analysis, melting temperature c (T), which is two melting temperatures below 200 ℃. mc ) and melting temperature d(T md If ) appears, the above Y is the melting temperature c(T mc Heat of fusion (△H) at ) c ) and the melting temperature d(T md Heat of fusion (△H) at ) d The sum of ) (△H c + △H d ) may be. Here, during the above DSC analysis, melting temperature c (T), which is one melting temperature below 200 ℃. mc If only ) appears, the above Y is the melting temperature c(T mc Heat of fusion (△H) at ) c) It may be the value itself. Such Y value is not particularly limited, but may be 0.5 J / g or more, 1 J / g or more, 1.5 J / g or more, 1.8 J / g or more, 2 J / g or more, 2.3 J / g or more, 2.5 J / g or more, 2.8 J / g or more, 3 J / g or more, 3.3 J / g or more, 3.5 J / g or more, 4 J / g or more, or 4.5 J / g or more (e.g., 0.5 to 5 J / g, 1 to 4 J / g, 2 to 3.6 J / g, or 2.4 to 3.4 J / g).

[0044] A crystalline polyester resin having a desired degree of crystallization can be provided as the above X value and the above Y value are each within the above range.

[0045] The above crystalline polyester resin has one or more, two or more, three or more, or four or more melting temperatures (T) during the DSC analysis. m ) can be represented. Specifically, according to the present invention, the melting temperature (T) of the crystalline polyester resin m ) may be 140 to 250 ℃, and one or more melting temperatures (e.g., T) within the above temperature range ma , T mb , T mc , T md (etc.) may appear. More specifically, the melting temperature (T) of the crystalline polyester resin. m ) may be 145 to 249 ℃, 150 to 248 ℃, 155 to 247 ℃, 160 to 246 ℃, 165 to 245 ℃, 168 to 243 ℃, 170 to 240 ℃, 175 to 235 ℃, or 180 to 230 ℃. One or more of the above melting temperatures (T m As ) appears within the above temperature range, a crystalline polyester resin having a desired degree of crystallinity can be provided.

[0046] Specifically, the crystalline polyester resin has one melting temperature (e.g., a second melting temperature c (T)) at less than 140 to 200 ℃, 150 to 195 ℃, 160 to 190 ℃, or 170 to 185 ℃. mc )) may appear, and one melting temperature (e.g., melting temperature a(T) which is the first melting temperature) at 200 to 250 ℃, 205 to 245 ℃, 210 to 240 ℃, or 215 to 235 ℃. ma )) may appear.

[0047] According to the present invention, the crystalline polyester resin may have a crystallization temperature (Z) of 140 to 200 ℃ (specifically, 145 to 195 ℃, 150 to 190 ℃, 155 to 185 ℃, or 160 to 180 ℃). The crystallization temperature (Z) may refer to the temperature at which irregular molecular chains present in the polyester resin are arranged in a certain direction to form a regularity and undergo crystallization. Specifically, the crystallization temperature (Z) may refer to the temperature at which the polyester resin is crystallized (heat treated) to ensure that the polyester resin obtained by esterification reaction (or ester exchange reaction) and condensation polypolymerization reaction of the polymerization raw materials has a desired degree of crystallization. As the crystallization temperature (Z) is within the above range, a crystalline polyester resin having a desired degree of crystallization can be obtained, thereby improving the moldability and recyclability of the crystalline polyester resin.

[0048] Meanwhile, the crystalline polyester resin according to the present invention comprises a diol repeating unit derived from a diol component. The above diol components are not particularly limited as long as they are commonly known diol components, but specifically include bis-2-hydroxyethyl terephthalate, isosorbide, neopentyl glycol, ethylene glycol, diethylene glycol, cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-methylene-1,3-propanediol, 2-ethyl-1,3-propanediol, 2-isopropyl-1,3-propanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, 3-methyl-2,4-pentanediol, 1,6-hexanediol, and 1,2-cyclohexanediol. It may include one or more selected from the group consisting of 1,4-cyclohexanediol, 4-(hydroxymethyl)cyclohexylmethyl-4-(hydroxymethyl)cyclohexanecarboxylate (CHDM derivative), 4-(4-(hydroxymethyl)cyclohexylmethoxymethyl)cyclohexylmethanol (CHDM derivative), regenerated bis-2-hydroxyethyl terephthalate, regenerated isosorbide, regenerated neopentyl glycol, regenerated ethylene glycol, regenerated diethylene glycol, regenerated cyclohexanedimethanol, and regenerated 2,2,4,4-tetramethyl-1,3-cyclobutanediol (e.g., two or more, three or more, four or more, or five or more).

[0049] The recycled bis-2-hydroxyethyl terephthalate, recycled isosorbide, recycled neopentyl glycol, recycled ethylene glycol, recycled diethylene glycol, recycled cyclohexanedimethanol, and recycled 2,2,4,4-tetramethyl-1,3-cyclobutanediol used as the above diol components may refer to recycled raw materials (monomers) obtained by undergoing a commonly known depolymerization process of used waste polyester resin or waste polyester articles, but are not limited thereto.

[0050] More specifically, the diol component may comprise one or more selected from the group consisting of: a first diol component comprising ethylene glycol (EG), regenerated ethylene glycol (r-EG), or a combination thereof; a second diol component comprising bis-2-hydroxyethyl terephthalate (BHET), regenerated bis-2-hydroxyethyl terephthalate (r-BHET), or a combination thereof; and a third diol component comprising isosorbide (ISB), neopentyl glycol (NPG), diethylene glycol (DEG), cyclohexanedimethanol (CHDM), regenerated isosorbide (r-ISB), regenerated neopentyl glycol (r-NPG), regenerated diethylene glycol (r-DEG), regenerated cyclohexanedimethanol (r-CHDM), or a combination thereof.

[0051] The amount of the first diol component used (amount added during reaction) is not particularly limited, but based on the total mole% of the diol component, it may be 50 to 99 mole%, 60 to 99 mole%, 70 to 99 mole%, 70 to 98 mole%, 75 to 98 mole%, 75 to 97 mole%, or 80 to 90 mole%. Accordingly, the crystalline polyester resin may include repeating units (a) derived from the first diol component. Since the amount of the first diol component used is within the above range, a crystalline polyester resin with excellent basic physical properties can be manufactured economically.

[0052] The amount of the second diol component used (amount added during reaction) is not particularly limited, but based on the total mole% of the diol component, it may be 5 to 99 mole%, 5.5 to 95 mole%, 10 to 90 mole%, 15 to 80 mole%, 20 to 80 mole%, 25 to 75 mole%, or 30 to 70 mole%. Accordingly, the crystalline polyester resin may include repeating units (b) derived from the second diol component. Since the amount of the second diol component used is within the above range, a crystalline polyester resin having a viscosity level required in the molding process can be manufactured, thereby providing an article (molded article) of excellent quality.

[0053] The amount of the third diol component used (amount added during reaction) is not particularly limited, but may be 20 mol% or less based on the total mol% of the diol component. Specifically, the amount of the third diol component used may be 1 to 20 mol%, 2 to 20 mol%, 2.5 to 19 mol%, 3 to 18 mol%, 3 to 17.5 mol%, 4 to 17 mol%, 4 to 16 mol%, or 4.5 to 15 mol% based on the total mol% of the diol component. Accordingly, the crystalline polyester resin may include repeating units (c) derived from the third diol component. Since the amount of the third diol component used is within the above range, a crystalline polyester resin with excellent moldability (processability) in addition to basic physical properties can be manufactured.

[0054] For example, considering the basic physical properties and moldability (processability) of the crystalline polyester resin, the amount of isosorbide or recycled isosorbide among the third diol components may be 0 to 8 mol%, 0.1 to 6 mol%, 0.3 to 4 mol%, or 0.4 to 3.5 mol% based on the total mol% of the diol components. In addition, the amount of diethylene glycol or recycled diethylene glycol among the third diol components may be 0.5 to 10 mol%, 1 to 7 mol%, 1.5 to 5 mol%, or 2 to 4 mol% based on the total mol% of the diol components. In addition, the amount of cyclohexanedimethanol or regenerated cyclohexanedimethanol among the third diol components may be 0 to 14 mole%, 1 to 12 mole%, 2 to 10 mole%, or 3 to 9 mole% based on the total mole% of the diol components.

[0055] The crystalline polyester resin according to the present invention comprises a dicarboxylic acid repeating unit derived from a dicarboxylic acid component. The above dicarboxylic acid component is not particularly limited as long as it is a commonly known dicarboxylic acid component, but specifically includes terephthalic acid, isophthalic acid, phthalic acid, dimethyl isophthalate, dimethyl phthalate, dimethyl terephthalate, phthalic anhydride, 2,6-naphthalene dicarboxylic acid, dimethyl 2,6-naphthalene dicarboxylate, diphenyl dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, dimethyl 1,4-cyclohexane dicarboxylate, dimethyl 1,3-cyclohexane dicarboxylate, sebacic acid, succinic acid, isodecylic succinic acid, maleic acid, maleic anhydride, fumaric acid, adipic acid, glutaric acid, azelaic acid, regenerated terephthalic acid, regenerated isophthalic acid, regenerated phthalic acid, and regenerated dimethyl It may include one or more selected from the group consisting of terephthalates.

[0056] The recycled terephthalic acid, recycled isophthalic acid, recycled phthalic acid, and recycled dimethyl terephthalate used as the above-mentioned dicarboxylic acid components may refer to recycled raw materials (monomers) obtained by subjecting used waste polyester resin or waste polyester articles to a commonly known depolymerization process, but are not limited thereto.

[0057] More specifically, the dicarboxylic acid component may comprise one or more selected from the group consisting of: a first dicarboxylic acid component comprising terephthalic acid (TPA), dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate (DMT), regenerated terephthalic acid (r-TPA), regenerated dimethyl terephthalate (r-DMT), or a combination thereof; and a second dicarboxylic acid component comprising isophthalic acid, phthalic acid, phthalic anhydride, 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, dimethyl 1,4-cyclohexane dicarboxylate, dimethyl 1,3-cyclohexane dicarboxylate, regenerated isophthalic acid, regenerated phthalic acid, or a combination thereof.

[0058] The amount of the first dicarboxylic acid component used (amount added during reaction) is not particularly limited, but based on the total mole% of the dicarboxylic acid component, it may be 95 mole% or more, 96 mole% or more, 97 mole% or more, 98 mole% or more, or 99 mole% or more (e.g., 95 to 100 mole%, more than 95 to 100 mole%, 96 to 99.5 mole%, 97 to 99 mole%, or 98 to 98.5 mole%). Accordingly, the crystalline polyester resin may include repeating units (z) derived from the first dicarboxylic acid component.

[0059] The amount of the second dicarboxylic acid component used (amount added during reaction) is not particularly limited, but based on the total mole% of the dicarboxylic acid component, it may be 5 mole% or less, 4 mole% or less, 3 mole% or less, 2 mole% or less, or 1 mole% or less (e.g., 0 to 5 mole%, greater than 0 to 4.5 mole%, 0.5 to 4 mole%, 1 to 3 mole%, or 1.5 to 2 mole%). Accordingly, the crystalline polyester resin may include repeating units (w) derived from the second dicarboxylic acid component.

[0060] According to the present invention, the crystalline polyester resin may further comprise a repeating unit (A) (or a structure derived from the branching agent) derived from a branching agent having three or more functional groups. Due to the branching agent, the crystalline polyester resin may have the repeating unit (A) introduced into the side chain of the main chain or have a graft polymerization structure formed by the repeating unit (A), thereby having a high molecular weight and crystallinity.

[0061] According to the present invention, the content of the repeating unit (A) included in the crystalline polyester resin is not particularly limited, but may be 0.01 to 15 parts by weight per 100 parts by weight of the diol repeating unit, and specifically may be 0.05 to 13 parts by weight, 0.1 to 12 parts by weight, 0.5 to 10 parts by weight, or 1 to 5 parts by weight.

[0062] The above branching agent is not particularly limited, but specifically may be trimellitic acid, trimellitic anhydride, trimethylol propane, or a combination thereof.

[0063] According to the present invention, the crystalline polyester resin may have an intrinsic viscosity (IV) (@35 ℃) of 0.5 to 1.5 dl / g. Specifically, the crystalline polyester resin may have an intrinsic viscosity (IV) of 0.5 to 1.3 dl / g, 0.5 to 1.2 dl / g, 0.5 to 1.1 dl / g, 0.5 to 1 dl / g, 0.5 to 0.95 dl / g, or 0.5 to 0.9 dl / g at 35 ℃.

[0064] The crystalline polyester resin according to the present invention may have a state (form) such as chips, pellets, or powder.

[0065] In addition, the crystalline polyester resin according to the present invention may be a homopolymer or a copolymer. Specifically, the crystalline 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).

[0066] According to the present invention, the crystalline polyester resin can be suitably applied for extrusion molding or injection molding as it has an optimized degree of crystallization. Specifically, the crystalline polyester resin may be an extrusion molding polyester resin or an injection molding polyester resin.

[0067]

[0068] Method for manufacturing crystalline polyester resin

[0069] A method for manufacturing a crystalline polyester resin according to the present invention comprises: (1) a step of manufacturing a polyester resin by polymerizing a diol component and a dicarboxylic acid component; and (2) a step of crystallizing the polyester resin. When the crystalline polyester resin obtained through steps (1) and (2) is heated to 280°C at a scan rate of 10°C / min and analyzed by differential scanning calorimetry (DSC), it satisfies the following Equation 1. This method for manufacturing a crystalline polyester resin according to the present invention can obtain a crystalline polyester resin satisfying the following Equation 1 by controlling the crystallization temperature in step (2), thereby providing a crystalline polyester resin with excellent moldability and recyclability. The details thereof are described as follows. Here, a detailed explanation of the following Equation 1 is omitted as it is identical to what has been described above.

[0070] [Equation 1] 1 < (Y×Z) / X < 30

[0071] In the above Equation 1,

[0072] X is the sum of the heat of fusion (△H) of the melting temperature of the crystalline polyester resin at 200 ℃ or higher during the above DSC analysis, and

[0073] Y is the sum of the heat of fusion (△H) of the melting temperature of the crystalline polyester resin found at less than 200 ℃ during the above DSC analysis, and

[0074] Z is the crystallization temperature of the crystalline polyester resin.

[0075]

[0076] Step (1): Preparation of polyester resin

[0077] Step (1) above is a step of manufacturing a polyester resin (e.g., a polyester resin with an amorphous surface) by esterifying (or ester exchange) the diol component and the dicarboxylic acid component to obtain a reaction product (e.g., an oligomer), and then subjecting it to a condensation polymerization reaction. A detailed description of the diol component and the dicarboxylic acid component is omitted as it is the same as described above.

[0078] The conditions under which the above esterification reaction (or ester exchange reaction) is performed may not be particularly limited. Specifically, the temperature at which the above esterification reaction is performed may be 220 to 300 ℃, 225 to 290 ℃, 230 to 280 ℃, 235 to 275 ℃, 240 to 270 ℃, or 245 to 265 ℃. In addition, the pressure at which the above esterification reaction is performed may be 0.05 to 5 kgf / ㎠, 0.1 to 4 kgf / ㎠, 0.1 to 3 kgf / ㎠, 0.5 to 2.5 kgf / ㎠, or 1 to 2 kgf / ㎠. As the above esterification reaction is performed under the above conditions, a reaction product (oligomer) having a desired molecular weight can be obtained in high yield while minimizing the generation of by-products.

[0079] In the reactor where the above esterification reaction (or ester exchange reaction) takes place, one or more additives selected from the group consisting of catalysts, colorants, crystallizing agents, antioxidants, and branching agents may be further introduced along with the above diol component and the above dicarboxylic acid component.

[0080] The catalyst may be a methylate of sodium, magnesium, etc.; an acetate, borate, fatty acid salt, or carbonate of Ge, Zn, Cd, Mn, Co, Ca, Ba, etc.; or an oxide or hydrate of Ge, Mg, Pb, Mn, Ti, Sb, Sn, Al, etc. For example, the catalyst may be 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.

[0081] The above-mentioned colorants may include organic compounds such as cobalt-based compounds, anthraquinone-based compounds, perinone-based compounds, azo-based compounds, and methine-based compounds (e.g., cobalt acetate, cobalt propionate, Clariant’s Polysynthren Blue RLS toner, Clariant’s Solvaperm Red BB toner).

[0082] The above crystallizing agent may include a crystallization nucleating agent, a UV absorber, a polyolefin resin, a polyamide resin, etc.

[0083] The above antioxidants may include hindered phenolic compounds, phosphite compounds, thioether compounds, etc.

[0084] The above branching agent may be trimellitic acid, trimellitic anhydride, trimethylol propane, or a combination thereof.

[0085] The reactant obtained through the above esterification reaction (or ester exchange reaction) may subsequently be introduced into a polycondensation reactor to carry out a polycondensation reaction. The conditions under which the polycondensation reaction is performed may not be particularly limited. Specifically, the temperature at which the polycondensation reaction is performed may be 240 to 320 ℃, 245 to 310 ℃, 250 to 300 ℃, 255 to 295 ℃, or 265 to 290 ℃. In addition, the pressure at which the polycondensation reaction is performed may be a pressure lower than atmospheric pressure (e.g., 1 atmosphere) (reduced pressure). As the polycondensation reaction is performed under the above conditions, a polyester resin (polymer) with excellent moldability (processability) can be efficiently produced.

[0086] Subsequently, the polyester resin obtained through the above condensation reaction can be pelletized through processes such as extrusion and underwater cutting. That is, the polyester resin may be polyester resin pellets.

[0087]

[0088] The polyester resin (e.g., polyester resin pellets) obtained through such step (1) may undergo step (2) described later to obtain a desired degree of crystallization. Here, the polyester resin may undergo a drying process before undergoing step (2) described later. That is, the method for manufacturing a crystalline polyester resin according to the present invention may further include a step of drying the polyester resin obtained in step (1) between step (1) and step (2) in order to further optimize the degree of crystallization of the crystalline polyester resin while preventing fusion between the polyester resins.

[0089] The drying of the polyester resin can be carried out in a conventionally known dryer (e.g., a fluidized bed type dryer). The conditions under which the drying is performed are not particularly limited, but considering the drying efficiency and productivity of the polyester resin, the drying can be carried out at 40 to 90 ℃ (specifically, 40 to 85 ℃, 45 to 85 ℃, 50 to 80 ℃, or 50 to 70 ℃) for 3 to 12 hours (specifically, 4 to 12 hours, 6 to 11 hours, or 8 to 10 hours).

[0090]

[0091] Step (2): Preparation of crystalline polyester resin through crystallization

[0092] The above step (2) is a step of crystallizing the polyester resin obtained through the above step (1). Specifically, the crystallization of the polyester resin may be performed one or more times, two or more times, three or more times, or four or more times.

[0093] According to the present invention, the temperature at which the crystallization is performed is not particularly limited, but may be 140 to 200 ℃ (specifically, 145 to 195 ℃, 150 to 190 ℃, 155 to 185 ℃, or 160 to 180 ℃). As the crystallization is performed within the above temperature range, a crystalline polyester resin with an optimized degree of crystallization can be produced while minimizing fusion between polyester resins during the crystallization process.

[0094] The above crystallization can be performed under temperature conditions that increase in stages. Specifically, if the crystallization is carried out in a first and second stage, the second crystallization temperature (T2) may be higher than the first crystallization temperature (T1) (T1 <T2). 또한 상기 결정화가 1차 내지 3차에 걸쳐 이루어질 경우, 3차 결정화 온도(T3)는 2차 결정화 온도(T2)보다 높고, 2차 결정화 온도(T2)는 1차 결정화 온도(T1)보다 높을 수 있다(T1<T2<T3). 상기 결정화가 단계별로 상승하는 온도 조건으로 수행됨에 따라 결정화 과정에서 폴리에스테르 수지 간에 융착이 최소화되면서 결정화도가 최적화된 결정성 폴리에스테르 수지를 제조할 수 있다.

[0095] The above crystallization may be performed under atmospheric pressure or reduced pressure conditions, and a commonly known fluidizing agent may be added to the crystallization process to increase the fluidity of the polyester resin (polyester resin pellets).

[0096] The crystalline polyester resin produced through the crystallization of step (2) as described above may further undergo a commonly known solid-state polymerization process as necessary to control viscosity and molecular weight. Specifically, the method for producing a crystalline polyester resin according to the present invention may further include a step of solid-state polymerizing the polyester resin crystallized through step (2).

[0097] The conditions under which the solid-state polymerization is performed may not be particularly limited. Specifically, the temperature at which the solid-state polymerization is performed may be 170 to 260 ℃, 180 to 250 ℃, 185 to 245 ℃, 190 to 240 ℃, or 195 to 240 ℃. In addition, the pressure at which the solid-state polymerization is performed may be a pressure lower than atmospheric pressure (e.g., 1 atmosphere) (reduced pressure). As the solid-state polymerization is performed under the above conditions, a solid-state polymerized crystalline polyester resin having a required level of intrinsic viscosity can be efficiently produced.

[0098]

[0099] article

[0100] The article according to the present invention is manufactured from the crystalline polyester resin described above. Specifically, the article according to the present invention may be manufactured by introducing the crystalline polyester resin described above into a molding process such as injection molding, extrusion molding, extrusion blow molding, injection blow molding, press molding, or vacuum molding. For example, the article may be an injection-molded article manufactured through injection molding or an extrusion-molded article manufactured through extrusion molding.

[0101] Since the article according to the present invention is manufactured using the aforementioned crystalline polyester resin, it may have excellent quality (e.g., heat resistance, mechanical strength, appearance, etc.). In addition, since the article is manufactured using the aforementioned crystalline polyester resin, it may also have excellent recycling process efficiency when a recycling process is carried out after use.

[0102] These articles are not particularly limited but may be films; sheets; small and large containers (e.g., containers for cosmetics or food); or lids (caps), etc.

[0103] The present invention will be explained in more detail through the following examples. However, the following examples are merely illustrative of the present invention and do not limit the scope of the present invention.

[0104]

[0105] [Example 1]

[0106] Step (1): Preparation of polyester resin

[0107] Regenerated bis-2-hydroxyethyl terephthalate (r-BHET, 2515.3 kg), terephthalic acid (TPA, 6575.6 kg), isosorbide (ISB, 309.8 kg), ethylene glycol (EG, 2624.5 kg), 1,4-cyclohexanedimethanol (CHDM, 633.8 kg), diethylene glycol (DEG, 70.0 kg), Ge catalyst (1.0 kg), Ti catalyst (1.0 kg), phosphoric acid (1.5 kg), blue toner (0.01 kg), and red toner (0.005 kg) were introduced into a reactor connected to a column and a condenser capable of cooling by water. Next, the temperature of the reactor was raised to 265 ℃, and an esterification reaction (ES) was carried out at a temperature of 265 ℃ under a pressure of 2 kgf / ㎠ to obtain a transparent reaction product.

[0108] Next, the above reactant was transferred to a polycondensation reactor, and a polycondensation reaction (PA) was carried out at 270 °C while maintaining the pressure of the polycondensation reactor at a level lower than atmospheric pressure. When the intrinsic viscosity (melt intrinsic viscosity) (IV) of the reactant inside the polycondensation reactor reached 0.60 dl / g, the reactant was discharged to the outside of the polycondensation reactor and formed into strands. Subsequently, polyester resin pellets were obtained by solidifying with a cooling liquid and then pelletizing the 100 cut pellets so that the average weight of each pellet was approximately 1.0 to 2.5 g.

[0109] Afterwards, the obtained polyester resin pellets were dried at 50°C for 10 hours before crystallization.

[0110] Step (2): Crystallization of polyester resin

[0111] The above-mentioned dried polyester resin pellets were fed into a crystallization reactor at a rate of 1 ton per hour (feed rate: 1 ton / hr), and a crystallization process was performed at a temperature of 160 to 180 ℃ to obtain a crystalline polyester resin.

[0112]

[0113] [Example 2]

[0114] Step (1): Preparation of polyester resin

[0115] Regenerated bis-2-hydroxyethyl terephthalate (r-BHET, 5125.6 kg), terephthalic acid (TPA, 5024.7 kg), isosorbide (ISB, 52.6 kg), ethylene glycol (EG, 2229.7 kg), 1,4-cyclohexanedimethanol (CHDM, 484.3 kg), diethylene glycol (DEG, 71.3 kg), Ge catalyst (1.0 kg), phosphoric acid (1.5 kg), cobalt acetate (0.4 kg), blue toner (0.03 kg), and red toner (0.01 kg) were introduced into a reactor connected to a column and a condenser capable of cooling by water. Next, the temperature of the reactor was raised to 250 ℃, and an esterification reaction (ES) was carried out at a temperature of 250 ℃ under a pressure of 1 kgf / ㎠ to obtain a transparent reaction product.

[0116] Next, the above reactant was transferred to a polycondensation reactor, and a polycondensation reaction (PA) was carried out at 285 °C while maintaining the pressure of the polycondensation reactor at a level lower than atmospheric pressure. When the intrinsic viscosity (melt intrinsic viscosity) (IV) of the reactant inside the polycondensation reactor reached 0.85 dl / g, the reactant was discharged to the outside of the polycondensation reactor and formed into strands. Subsequently, polyester resin pellets were obtained by solidifying with a cooling liquid and then pelletizing the 100 cut pellets so that the average weight of each pellet was approximately 1.0 to 2.5 g.

[0117] Step (2): Crystallization of polyester resin

[0118] The above-mentioned polyester resin pellets (without drying) were fed into a crystallization reactor at a rate of 1 ton per hour (feed rate: 1 ton / hr), and a crystallization process was performed at a temperature of 160 to 180 ℃ to obtain a crystalline polyester resin.

[0119]

[0120] [Example 3]

[0121] Step (1): Preparation of polyester resin

[0122] Terephthalic acid (TPA, 8462.5 kg), ethylene glycol (EG, 4874.5 kg), 1,4-cyclohexanedimethanol (CHDM, 326.3 kg), diethylene glycol (DEG, 72.1 kg), Ti catalyst (1.0 kg), phosphoric acid (1.5 kg), blue toner (0.01 kg), and red toner (0.01 kg) were introduced into a reactor connected to a column and a condenser capable of cooling by water. Next, the temperature of the reactor was raised to 255 ℃, and an esterification reaction (ES) was carried out at a temperature of 255 ℃ under a pressure of 1 kgf / ㎠ to obtain a transparent reaction product.

[0123] Next, the above reactant was transferred to a polycondensation reactor, and a polycondensation reaction (PA) was carried out at 285 °C while maintaining the pressure of the polycondensation reactor at a level lower than atmospheric pressure. When the intrinsic viscosity (melt intrinsic viscosity) (IV) of the reactant inside the polycondensation reactor reached 0.50 dl / g, the reactant was discharged to the outside of the polycondensation reactor and formed into strands. Subsequently, polyester resin pellets were obtained by solidifying with a cooling liquid and then pelletizing the 100 cut pellets so that the average weight of each pellet was approximately 1.0 to 2.5 g.

[0124] Step (2): Crystallization of polyester resin

[0125] The above-mentioned polyester resin pellets (without drying) were fed into a crystallization reactor at a rate of 1 ton per hour (feed rate: 1 ton / hr), and a crystallization process was performed at a temperature of 160 to 180 ℃ to obtain a crystalline polyester resin.

[0126]

[0127] [Example 4]

[0128] Step (1): Preparation of polyester resin

[0129] Polyester resin pellets were obtained by drying through the same process as in Example 1.

[0130] Step (2): Crystallization of polyester resin

[0131] A crystalline polyester resin was obtained through the same process as in Example 1.

[0132] Step (3): Preparation of solid-state polymerized crystalline polyester resin

[0133] The polyester resin pellets (crystalline polyester resin) obtained through the above crystallization were introduced into a solid-state polymerization reactor, and the temperature of the solid-state polymerization reactor was gradually raised to 200°C under a nitrogen atmosphere, after which the solid-state polymerization reaction was carried out at 200°C. A solid-state polymerized crystalline polyester resin was obtained by carrying out the solid-state polymerization reaction for 20 hours and then discharging the resulting product from the solid-state polymerization reactor.

[0134]

[0135] [Example 5]

[0136] Step (1): Preparation of polyester resin

[0137] Polyester resin pellets were obtained through the same process as in Example 3.

[0138] Step (2): Crystallization of polyester resin

[0139] A crystalline polyester resin (without drying) was obtained through the same process as in Example 3.

[0140] Step (3): Preparation of solid-state polymerized crystalline polyester resin

[0141] The polyester resin pellets (crystalline polyester resin) obtained through the above crystallization were introduced into a solid-state polymerization reactor, and the temperature of the solid-state polymerization reactor was gradually raised to 210 ℃ under a nitrogen atmosphere, after which the solid-state polymerization reaction was carried out at 210 ℃. A solid-state polymerized crystalline polyester resin was obtained by carrying out the solid-state polymerization reaction for 15 hours and then discharging the resulting product from the solid-state polymerization reactor.

[0142]

[0143] [Comparative Example 1]

[0144] Step (1): Preparation of polyester resin

[0145] Terephthalic acid (TPA, 6632.5 kg), ethylene glycol (EG, 2003.8 kg), 1,4-cyclohexanedimethanol (CHDM, 4475.5 kg), diethylene glycol (DEG, 56.5 kg), Ti catalyst (1.0 kg), phosphoric acid (1.5 kg), blue toner (0.01 kg), and red toner (0.01 kg) were introduced into a reactor connected to a column and a condenser capable of cooling by water. Next, the temperature of the reactor was raised to 275 ℃, and an esterification reaction (ES) was carried out at a temperature of 275 ℃ under a pressure of 1 kgf / ㎠ to obtain a transparent reaction product.

[0146] Next, the above reactant was transferred to a polycondensation reactor, and a polycondensation reaction (PA) was carried out at 285 °C while maintaining the pressure of the polycondensation reactor at a level lower than atmospheric pressure. When the intrinsic viscosity (melt intrinsic viscosity) (IV) of the reactant inside the polycondensation reactor reached 0.60 dl / g, the reactant was discharged to the outside of the polycondensation reactor and formed into strands. Subsequently, polyester resin pellets were obtained by solidifying with a cooling liquid and then pelletizing the 100 cut pellets so that the average weight of each pellet was approximately 1.0 to 2.5 g.

[0147] Step (2): Crystallization of polyester resin

[0148] The above-mentioned polyester resin pellets (without drying) were fed into a crystallization reactor at a rate of 1 ton per hour (feed rate: 1 ton / hr), and a crystallization process was performed at a temperature of 160 to 180 ℃ to obtain a crystalline polyester resin.

[0149] Step (3): Preparation of solid-state polymerized crystalline polyester resin

[0150] The polyester resin pellets (crystalline polyester resin) obtained through the above crystallization were introduced into a solid-state polymerization reactor, and the temperature of the solid-state polymerization reactor was gradually raised to 230 ℃ under a nitrogen atmosphere, after which the solid-state polymerization reaction was carried out at 230 ℃. A solid-state polymerized crystalline polyester resin was obtained by carrying out the solid-state polymerization reaction for 20 hours and then discharging the resulting product from the solid-state polymerization reactor.

[0151]

[0152] [Comparative Example 2]

[0153] Step (1): Preparation of polyester resin

[0154] Terephthalic acid (TPA, 8090.5 kg), ethylene glycol (EG, 4290 kg), 1,4-cyclohexanedimethanol (CHDM, 1169.7 kg), diethylene glycol (DEG, 68.9 kg), Ti catalyst (1.0 kg), phosphoric acid (1.5 kg), blue toner (0.01 kg), and red toner (0.01 kg) were introduced into a reactor connected to a column and a condenser capable of cooling by water. Next, the temperature of the reactor was raised to 255 ℃, and an esterification reaction (ES) was carried out at a temperature of 255 ℃ under a pressure of 1 kgf / ㎠ to obtain a transparent reaction product.

[0155] Next, the above reactant was transferred to a polycondensation reactor, and a polycondensation reaction (PA) was carried out at 265 °C while maintaining the pressure of the polycondensation reactor at a level lower than atmospheric pressure. When the intrinsic viscosity (melt intrinsic viscosity) (IV) of the reactant inside the polycondensation reactor reached 0.65 dl / g, the reactant was discharged to the outside of the polycondensation reactor and formed into strands. Subsequently, polyester resin pellets were obtained by solidifying with a cooling liquid and then pelletizing the 100 cut pellets so that the average weight of each pellet was approximately 1.0 to 2.5 g.

[0156] Step (2): Crystallization of polyester resin

[0157] The above-mentioned polyester resin pellets (without drying) were fed into a crystallization reactor at a rate of 1 ton per hour (feed rate: 1 ton / hr), and a crystallization process was performed at a temperature of 160 to 180 ℃ to obtain a crystalline polyester resin.

[0158]

[0159] [Test Example 1]

[0160] The crystalline polyester resins prepared in Examples 1 to 5 and Comparative Examples 1 to 2, respectively, were analyzed by Differential Scanning Calorimetry (DSC) to determine the melting temperature (T m We checked whether ) appeared, and the results are shown in Tables 1 and 2 below. The above DSC analysis was performed as follows.

[0161] DSC analyzer: Mettler Toledo's DSC 1 model was applied.

[0162] Sample preparation: About 6 to 10 mg of crystalline polyester resin was taken and filled into an aluminum pan.

[0163] Scan conditions: A DSC curve was obtained by heating from room temperature to 280 ℃ at a rate of 10 ℃ / min and annealing at 280 ℃ for 3 minutes.

[0164] Melting temperature (T m ) Verification: The temperature at which an endothermic peak appears during the heating process in the obtained DSC curve was defined as the melting temperature. Subsequently, the melting temperature (T m The heat of fusion (△H) and the values ​​of "(Y×Z) / X" and "X / Y" using it were calculated (rounded).

[0165]

[0166] [Test Example 2]

[0167] Crystalline polyester resins prepared in Examples 1 to 5 and Comparative Examples 1 to 2, respectively, were injection molded using an ENGEL 80 press machine at a melting temperature of 250 to 270 ℃ (mold temperature: 30 ℃, injection speed: 80 mm / s, holding pressure: 20 bar, cycle time: 40 s) to produce plate-type injection specimens with a thickness of 3 mm, and then the moldability was evaluated according to the following criteria, and the results are shown in Tables 1 and 2 below.

[0168] ◎: No fish-eyes or un-melt (unmelted resin pellets) in the injection molded specimens, and continuous injection molding is possible.

[0169] ○: No unmelt in the injection molded specimen, one or fewer fish-eyes occur, and a continuous injection process is possible.

[0170] △: Two or more un-melt and fish-eyes occur in the injection molded specimen, but the continuous injection process is possible.

[0171] ×: Continuous injection process impossible due to fusion between resin pellets

[0172]

[0173] [Test Example 3]

[0174] Crystalline polyester resins prepared in Examples 1 to 5 and Comparative Examples 1 to 2, respectively, were extruded using a Bakum extrusion machine at a melting temperature of 220 to 250 °C (extrusion speed: 20 rpm, holding pressure: 120 bar, die gap: 55 %, cycle time: 50 s) to produce plate-shaped extruded specimens with a thickness of 3 mm, and then the moldability was evaluated according to the following criteria, and the results are shown in Tables 1 and 2 below.

[0175] ◎: No fish-eyes or un-melt (unmelted resin pellets) in the extruded specimen, and continuous extrusion process is possible.

[0176] ○: No unmelt in the extruded specimen, one or fewer fish-eyes occur, and a continuous extrusion process is possible.

[0177] △: Two or more un-melt and fish-eyes occur in the extruded specimen, but the continuous extrusion process is possible.

[0178] ×: Continuous extrusion process is impossible due to fusion between resin pellets

[0179]

[0180] Classification Example 1 Example 2 Example 3 Example 4 Example 5 Resin pellets obtained by crystallization at 160 ℃ T at less than 200 ℃ m1 (T mc )173.52171.82173.75175.29174.22T m1 △H at 3.59 2.44 3.15 2.69 2.97 200 ℃ or higher T m2 (T ma )228.75227.7236.32226.87239.57T m2 At △H 27.49 27.31 32.79 22.14 32.95 200 ℃ less than T m Sum of △H (Y) at 3.59 2.44 3.15 2.69 2.97 200 ℃ or higher T mSum of △H at (X) 27.49 27.31 32.79 22.14 32.95 X / Y 7.66 11.19 10.4 18.23 11.09 (Y Х Z) / X 20.9 14.3 15.4 19.4 14.4 Z (Crystallization temperature, ℃) = 160 Resin pellets obtained by crystallization at 170 ℃ T below 200 ℃ m1 (T mc )183.32181.29182.9184.28184.34T m1 △H at 3.25 2.06 3.32 2.71 2.62 200 T at ℃ or higher m2 (T ma )219.79219.73236.03221.71240.39T m2 At △H 25.06 23.2 30.8 19.2 13 3.8 6 200 ℃ Less than T m Sum of △H (Y) at 3.25 2.06 3.32 2.71 2.62 200 ℃ or higher T m Sum of △H at (X) 25.06 23.2 30.8 19.2 133.86 X / Y 7.7 11 1.2 6 9.2 8 7.09 12.92 (Y Х Z) / X 22.0 15.1 18.3 24.0 13.2 Z (Crystallization temperature, ℃) = 170 Resin pellets obtained by crystallization at 180 ℃ T below 200 ℃ m1 (T mc )191.11189.32191.24191.83191.98T m1 △H at 2.4 30.2 23.1 11.2 81.9 4 200 ℃ or higher T m2 (T ma )222.68222.49235.8224.23231.41T m2 At △H2 3.45 8.9 227.15 16.79 33.88 200 ℃ Less than T m Sum of △H (Y) at 2.43 0.22 3.11 1.28 1.94200 ℃ or higher T m Sum of △H at (X) 23.45 8.9 227.15 16.79 33.88 X / Y 9.65 40.55 8.73 13.12 17.46 (Y Х Z) / X 18.74 420.61 3.71 0.3 Z (Crystallization Temperature, ℃) = 180 Injection Moldability ◎◎○○○ Extrusion Moldability ○○◎◎◎

[0181] Classification Comparative Example 1 Comparative Example 2 Resin pellets obtained by crystallization at 160 ℃ T at less than 200 ℃ m1 172.5171.0T m1 △H at 0.25 12.5 200 ℃ or higher T m2 250.1210.4T m2 At △H4 3.50 200 ℃ less than T m Sum of △H (Y) at 0.25 12.5 200 ℃ or higher T m Sum of △H at (X) 43.50X / Y 174 - (Y Х Z) / X 0.9 - Z (crystallization temperature, °C) = 160 Resin pellets obtained by crystallization at 170 °C T at temperatures below 200 °C m1 181182.5T m1 △H at 0.23 11.32 200 ℃ or higher T m2 241.2201.4T m2 At △H39.20200 ℃ less than T m Sum of △H (Y) at 0.231 1.32200 ℃ or higher T m Sum of △H at (X) 39.20X / Y 170.43-(YХZ) / X1-Z(crystallization temperature, °C) = 170 Resin pellets obtained by crystallization at 180 °C T below 200 °C m1 190.5190.2T m1 △H at 0.17 8.46 200 ℃ or higher T m2 243.9204.1T m2 At △H3 6.680200 ℃ less than T m Sum of △H (Y) at 0.17 8.46 200 ℃ or higher T m Sum of △H at (X) 36.680 X / Y 215.76 - (Y / Z) / X 0.8 - Z (crystallization temperature, °C) = 180 Injection moldability △ × Extrusion moldability △ ×

[0182] Referring to Tables 1 and 2 above, it can be confirmed that the crystalline polyester resins of Examples 1 to 5 according to the present invention have excellent moldability as the degree of crystallinity is optimized, with the "(Y×Z) / X" and "X / Y" values ​​controlled within the range of the present invention.

Claims

It comprises a diol repeating unit derived from a diol component; and a dicarboxylic acid repeating unit derived from a dicarboxylic acid component, A crystalline polyester resin satisfying the following Equation 1 when analyzed by differential scanning calorimetry (DSC) after heating to 280 ℃ at a scan rate of 10 ℃ / min: [Equation 1] 1 < (Y×Z) / X < 30 In the above Equation 1, X is the sum of the heat of fusion (△H) of the melting temperature of the crystalline polyester resin at 200 ℃ or higher during the above DSC analysis, and Y is the sum of the heat of fusion (△H) of the melting temperature of the crystalline polyester resin found at less than 200 ℃ during the above DSC analysis, and Z is the crystallization temperature of the crystalline polyester resin. In Article 1, A crystalline polyester resin satisfying the following Equation 2 during the above DSC analysis: [Equation 2] 4 < X / Y < 70 In the above Equation 2, X and Y are as defined in Article 1. In Article 1, A crystalline polyester resin having a crystallization temperature (Z) of 140 to 200 ℃. In Article 1, The melting temperature (T) of the above crystalline polyester resin m A crystalline polyester resin having a temperature of 140 to 250°C. In Article 1, A crystalline dicarboxylic acid component comprising one or more selected from the group consisting of terephthalic acid, isophthalic acid, phthalic acid, dimethyl isophthalate, dimethyl phthalate, dimethyl terephthalate, phthalic anhydride, 2,6-naphthalene dicarboxylic acid, dimethyl 2,6-naphthalene dicarboxylate, diphenyl dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, dimethyl 1,4-cyclohexane dicarboxylate, dimethyl 1,3-cyclohexane dicarboxylate, sebacic acid, succinic acid, isodecyl succinic acid, maleic acid, maleic anhydride, fumaric acid, adipic acid, glutaric acid, azelaic acid, regenerated terephthalic acid, regenerated isophthalic acid, regenerated phthalic acid, and regenerated dimethyl terephthalate Polyester resin. In Article 1, The above diol components are bis-2-hydroxyethyl terephthalate, isosorbide, neopentyl glycol, ethylene glycol, diethylene glycol, cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-methylene-1,3-propanediol, 2-ethyl-1,3-propanediol, 2-isopropyl-1,3-propanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, 3-methyl-2,4-pentanediol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, A crystalline polyester resin comprising one or more selected from the group consisting of 4-(hydroxymethyl)cyclohexylmethyl-4-(hydroxymethyl)cyclohexanecarboxylate, 4-(4-(hydroxymethyl)cyclohexylmethoxymethyl)cyclohexylmethanol, regenerated bis-2-hydroxyethyl terephthalate, regenerated isosorbide, regenerated neopentyl glycol, regenerated ethylene glycol, regenerated diethylene glycol, regenerated cyclohexanedimethanol, and regenerated 2,2,4,4-tetramethyl-1,3-cyclobutanediol. In Article 1, A crystalline polyester resin comprising one or more selected from the group consisting of: a first diol component comprising ethylene glycol, regenerated ethylene glycol, or a combination thereof; a second diol component comprising bis-2-hydroxyethyl terephthalate, regenerated bis-2-hydroxyethyl terephthalate, or a combination thereof; and a third diol component comprising isosorbide, neopentyl glycol, diethylene glycol, cyclohexanedimethanol, regenerated isosorbide, regenerated neopentyl glycol, regenerated diethylene glycol, regenerated cyclohexanedimethanol, or a combination thereof. In Article 7, A crystalline polyester resin in which the amount of the third diol component used is 20 mol% or less based on the total mol% of the diol components. In Article 1, A crystalline polyester resin having an intrinsic viscosity (IV) of 0.5 to 1.5 dl / g. In Article 1, A crystalline polyester resin further comprising repeating units derived from a branching agent having three or more functional groups. In Article 10, A crystalline polyester resin having a content of repeating units derived from the above branching agent of 0.01 to 15 parts by weight per 100 parts by weight of the above diol repeating units. In Article 1, A crystalline polyester resin for extrusion molding or injection molding. (1) A step of manufacturing a polyester resin by polymerizing a diol component and a dicarboxylic acid component; and (2) A step of crystallizing the above polyester resin, and A method for manufacturing a crystalline polyester resin satisfying the following Equation 1 when analyzed by differential scanning calorimetry (DSC) after heating to 280 ℃ at a scan rate of 10 ℃ / min: [Equation 1] 1 < (Y×Z) / X < 30 In the above Equation 1, X is the sum of the heat of fusion (△H) of the melting temperature of the crystalline polyester resin at 200 ℃ or higher during the above DSC analysis, and Y is the sum of the heat of fusion (△H) of the melting temperature of the crystalline polyester resin found at less than 200 ℃ during the above DSC analysis, and Z is the crystallization temperature of the crystalline polyester resin. In Article 13, A method for manufacturing a crystalline polyester resin in which the crystallization in step (2) is performed at a temperature range of 140 to 200 ℃. In Article 13, A method for manufacturing a crystalline polyester resin, further comprising the step of drying the polyester resin obtained in step (1) before performing step (2). In Article 13, A method for manufacturing a crystalline polyester resin, further comprising the step of solid-state polymerizing the polyester resin crystallized through the above step (2). Article manufactured from the crystalline polyester resin of claim 1. In Article 17, An article in which the above article is an injection molded article or an extrusion molded article.