Polyester resin mixture and method for preparing same

Abstract

The present invention relates to a polyester resin mixture, a method for preparing same, and an article produced therefrom. The polyester resin mixture comprises: a crystalline polyester resin; and an amorphous polyester resin. An article prepared from the polyester resin mixture may exhibit excellent physical properties, such as transparency, heat resistance, and mechanical strength.

Description

Polyester resin mixture and method for manufacturing the same

[0001] The present invention relates to a polyester resin mixture having excellent transparency, moldability, productivity, etc., and a method for manufacturing said polyester resin mixture.

[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 eco-friendly, it is widely used in the manufacture of products such as films, partitions, panels, packaging materials, and containers.

[0003] The manufacture of the above-mentioned article can be achieved by drying a polyester resin obtained through a polymerization reaction to remove moisture, and then introducing the moisture-removed polyester resin into a molding process. However, since the surface of the polyester resin is mainly amorphous, there is a problem in that the drying efficiency and productivity of the polyester resin decrease because the polyester resin fuses together or sticks to the inner wall of the dryer during the process of introducing it into a dryer to dry.

[0004] To solve the above problem, a technique has been proposed to prevent fusion from occurring during the drying process by crystallizing the polyester resin. However, currently, there are limitations in optimizing the degree of crystallization of the polyester resin.

[0005] Meanwhile, attempts are being made to manufacture articles using a resin mixture in which one or more types of polyester resins are mixed to produce articles that have excellent physical properties such as heat resistance and mechanical strength while possessing transparency. However, as there are limitations in optimizing the degree of crystallization of the polyester resin included in the resin mixture, it is difficult to obtain articles with high transparency.

[0006] In order to solve the aforementioned conventional problems, the inventors conducted various studies, and as a result, it was confirmed that by blending a crystalline polyester resin with controlled melting heat (△H) at the melting temperature, the degree of crystallization of the polyester resin mixture is optimized, and a polyester resin mixture with excellent transparency, moldability, and productivity is obtained.

[0007] Accordingly, the objective of the present invention is to provide a polyester resin mixture with controlled degree of crystallinity and a method for manufacturing the same.

[0008] In addition, another objective of the present invention is to provide an article manufactured using the polyester resin mixture.

[0009] To solve the above problem, the present invention comprises: 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; and an amorphous polyester resin, wherein the amorphous polyester resin comprises one or more of polyethylene terephthalate glycol (PETG) resin and polycyclohexylenedimethylene terephthalate glycol (PCTG) resin, and when the crystalline polyester resin is heated to 280 ℃ at a scan rate of 10 ℃ / min and analyzed by differential scanning calorimetry (DSC), two or more melting temperatures (T m ) represents and provides a polyester resin mixture satisfying Formula 1 below:

[0010] [Equation 1] 4 < X / Y < 70

[0011] In the above Equation 1,

[0012] X is the sum of the heat of fusion (△H) of the melting temperature at 200°C or higher when the crystalline polyester resin is analyzed by DSC, and Y is the sum of the heat of fusion (△H) of the melting temperature at less than 200°C when the crystalline polyester resin is analyzed by DSC.

[0013] In addition, the present invention comprises: (1) a step of preparing a polyester resin by polymerizing a diol component and a dicarboxylic acid component; (2) a step of preparing a crystalline polyester resin by crystallizing the polyester resin one or more times; and (3) a step of mixing the crystalline polyester resin and an amorphous polyester resin, wherein the amorphous polyester resin comprises one or more of polyethylene terephthalate glycol resin and polycyclohexylenedimethylene terephthalate glycol resin, and when the crystalline polyester resin is heated to 280 ℃ at a scan rate of 10 ℃ / min and analyzed by differential scanning calorimetry (DSC), two or more melting temperatures (T m A method for manufacturing a polyester resin mixture satisfying Formula 1 above is provided, which represents )

[0014] The present invention also provides an article manufactured from the polyester resin mixture.

[0015] Since the polyester resin mixture according to the present invention comprises a crystalline polyester resin manufactured through a specific crystallization process and having a controlled heat of fusion (△H) at the melting temperature, when an article (e.g., an injection-molded article) is manufactured using this, it is possible to provide an article with excellent productivity, moldability, etc., and high transparency.

[0016] FIG. 1 is a flowchart showing the process of manufacturing a polyester resin mixture according to one embodiment of the present invention.

[0017] The present invention will be described in detail below. Hereinafter, the present invention is not limited to the contents described below, but may be modified in various forms as long as the essence of the invention is not altered.

[0018] 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.

[0019] 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.

[0020] 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.

[0021]

[0022] Polyester resin mixture

[0023] The polyester resin mixture according to the present invention comprises a crystalline polyester resin and an amorphous polyester resin, wherein the degree of crystallization is optimized due to the crystalline polyester resin, thereby minimizing the occurrence of fusion during the manufacturing process or molding process of the polyester resin mixture and ensuring the transparency of the article obtained through the molding process.

[0024] The polyester resin mixture according to the present invention is described in detail as follows.

[0025]

[0026] Crystalline polyester resin

[0027] The crystalline polyester resin included in the polyester resin mixture according to the present invention has a melting temperature and heat of melting controlled, so the degree of crystallization of the polyester resin mixture can be optimized.

[0028] Specifically, general polyester resins have a surface that is mostly amorphous, which causes a problem of fusion occurring during the production process or the molding process using them. Accordingly, attempts have been made to solve the above problem by crystallizing the polyester resin, but there are limitations in optimizing the degree of crystallization of the polyester resin.

[0029] In particular, if the crystallization of the polyester resin is insufficient, or conversely, if over-crystallization occurs, the problem of fusion is not resolved. For example, if over-crystallization—that is, if the crystallization temperature increases—melting of the polyester resin occurs between the exothermic and endothermic temperatures, and the fusion rate of the polyester resin increases. Furthermore, the molding temperature (processing temperature) of a crystalline polyester resin requires energy equivalent to the melting temperature and the area of ​​the heat of fusion; however, since the over-crystallized polyester resin has a significantly high heat of fusion, a large amount of energy is consumed in molding it, resulting in reduced moldability (processability).

[0030] Polyester resin mixtures containing polyester resins that are insufficiently crystallized or over-crystallized may have an unstable degree of crystallization, and thus problems such as the occurrence of fusion and reduced moldability may still occur.

[0031] Therefore, in order to solve the problems such as the occurrence of fusion and the reduction of moldability mentioned above, it is necessary to control the degree of crystallization of the polyester resin mixture, and to this end, it is very important to control the melting temperature and heat of fusion of the crystalline polyester resin included in the polyester resin mixture.

[0032] Based on these points, the crystalline polyester resin according to the present invention satisfies a specific correlation derived from the melting temperature and heat of fusion, and as a result, the degree of crystallization of the polyester resin mixture can be optimized, thereby preventing fusion of the polyester resin mixture and improving moldability while also securing high transparency.

[0033] Specifically, 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 when analyzed by differential scanning calorimetry (DSC) after heating to 280 ℃ at a scan rate of 10 ℃ / min, two or more melting temperatures (T m It represents ) and satisfies the following Equation 1.

[0034] [Equation 1] 4 < X / Y < 70

[0035] In the above Equation 1,

[0036] X is the sum of the heat of fusion (△H) at melting temperatures of 200 ℃ or higher when the crystalline polyester resin is analyzed by DSC, and

[0037] Y is the sum of the heat of fusion (△H) of the melting temperature that appeared at less than 200 ℃ when the above crystalline polyester resin was analyzed by DSC.

[0038] According to the present invention, the crystalline polyester resin has two or more (specifically, two or more, three or more, four or more, or two to three) melting temperatures (T) when analyzed by DSC. mIt can be represented as ) and, based on a specific temperature (melting temperature) of 200 ℃, the degree of crystallization is optimized by satisfying Equation 1 above, thereby increasing the moldability and transparency of the polyester resin mixture containing it. The above 200 ℃ may represent the intermediate value between the crystallization temperature (Tc) and the melting temperature (Tm) of the crystalline polyester resin, and by applying this intermediate temperature, the amount of heat (melting temperature) required during the crystallization and molding process can be optimally controlled.

[0039] Specifically, the ratio of X / Y in Formula 1 above may be 4.1 to 69.9, 4.5 to 69.8, 5 to 69.7, 5.1 to 69.6, 5.3 to 69.5, 5.5 to 69, 5.8 to 68, 6 to 67, 6.3 to 66, 6.5 to 65, 6.8 to 60, 7 to 55, 7.5 to 50, 8 to 45, 8.5 to 40, 9 to 38, or 10 to 35. As the ratio of X / Y is controlled within the above range, a crystalline polyester resin having a desired degree of crystallization while minimizing fusion can be provided.

[0040] According to the present invention, the crystalline polyester resin has two or more melting temperatures (T) when analyzed by DSC. m The temperature range representing ) may be 140 to 250 ℃. More specifically, the two or more melting temperatures (T m) may be 140 to 245 ℃, 140 to 243 ℃, 140 to 242 ℃, 140 to 240 ℃, 140.1 to 239.5 ℃, 140.1 to 239 ℃, 140.2 to 238.7 ℃, 140.2 to 238.5 ℃, 141 to 238.3 ℃, 142 to 238 ℃, 145 to 237.5 ℃, 148 to 237 ℃, 150 to 236.8 ℃, 151 to 236.5 ℃, 153 to 236.3 ℃, 155 to 236 ℃, or 158 to 236 ℃. The above two or more melting temperatures (T m As ) appears within the above temperature range, a crystalline polyester resin having a desired degree of crystallinity can be provided.

[0041] The crystalline polyester resin may exhibit one or more, two or more, or three or more melting temperatures at a temperature below 200°C during DSC analysis, and may exhibit one or more, or two or more, melting temperatures at a temperature above 200°C.

[0042] Specifically, the crystalline polyester resin has a first melting temperature (T) below 200 ℃ during the DSC analysis. m1 It represents ), and the second melting temperature (T) at 200 ℃ or higher. m2 ) can be represented. For example, the crystalline polyester resin has a first-1 melting temperature (T) at less than 200 ℃ during the DSC analysis. m1-1 ) and the 1st-2nd melting temperature (T m1-2 It represents ), and the second melting temperature (T) at 200 ℃ or higher. m2 ) can be represented. The above 1-1 melting temperature (T m1-1 Specifically, ) may be 140 to 198 ℃, 141 to 195 ℃, 145 to 193 ℃, or 150 to 190 ℃. The above 1-2 melting temperature (T m1-2Specifically, ) may be greater than 185 to 210 ℃, 187 to 205 ℃, 188 to 200 ℃, or 189 to 195 ℃. The second melting temperature (T m2 Specifically, ) may be greater than 210 to 245 ℃, 215 to 243 ℃, 218 to 242 ℃, or 220 to 240 ℃.

[0043] According to the present invention, the first melting temperature (T m1 ) and the second melting temperature (T m2 The difference of ) (|T m1 - T m2 |) may be 40 to 105 ℃. Specifically, the above tea (|T m1 - T m2 |) may be 43 to 105 ℃, 45 to 103 ℃, 48 to 103 ℃, 50 to 101 ℃, 52 to 99 ℃, 54 to 98.8 ℃, 54.5 to 98.5 ℃, 55 to 95 ℃, 56 to 93 ℃, 57 to 90 ℃, 57.5 to 85 ℃, 58 to 80 ℃, 59 to 75 ℃, or 60 to 70 ℃. The first melting temperature (T m1 If there are two or more ), the lowest melting temperature among the two or more melting temperatures is the second melting temperature (T m2 If there are two or more ), the highest temperature among the two or more melting temperatures is each the first melting temperature (T m1 ) and the second melting temperature (T m2 Applying as ) the above difference (|T m1 - T m2 |) can be calculated.

[0044] According to the present invention, in Equation 1 above, when X is analyzed by DSC by heating to 280 ℃ at a scan rate of 10 ℃ / min, if one or more melting temperatures appear at 200 ℃ or higher, the sum of the heat of fusion (△H) at each melting temperature (△H sum1It 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 ) may be. Here, 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. This X value (the sum of the heat of fusion (△H) of the melting temperature at 200°C or higher) is not particularly limited, but may be 20 J / g or higher, and specifically, 20.2 J / g or higher, 23 J / g or higher, 24 J / g or higher, 25 J / g or higher, 27 J / g or higher, 29 J / g or higher, 30 J / g or higher, 31 J / g or higher, 33 J / g or higher, 35 J / g or higher, 37 J / g or higher, or 40 J / g or higher (e.g., 20 to 39 J / g, 22 to 38 J / g, 24 to 37 J / g, or 25 to 35 J / g). A crystalline polyester resin having a desired degree of crystallinity can be provided as the X value is within the above range.

[0045] According to the present invention, in Equation 1 above, when Y is analyzed by DSC by heating to 280 ℃ at a scan rate of 10 ℃ / min, if one or more melting temperatures appear at less than 200 ℃, the sum of the heat of fusion (△H) at each melting temperature (△H sum2 It may mean ). For example, during the above DSC analysis, melting temperature c (T), which is one of two melting temperatures below 200 ℃. mc ) and melting temperature d(Tmd 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. This Y value (the sum of the heat of fusion (△H) of the melting temperature appearing at less than 200 ℃) is not particularly limited, but may be 0.1 to 10 J / g, and specifically, 0.2 to 9.5 J / g, 0.3 to 9.3 J / g, 0.5 to 9 J / g, 1 to 8.5 J / g, 2.5 to 8 J / g, 3 to 7.8 J / g, 3.3 to 7.5 J / g, 3.5 to 7 J / g, 3.8 to 6.5 J / g, 4 to 6 J / g, 4.2 to 5.8 J / g, or 4.4 to 5.5 J / g. A crystalline polyester resin having a desired degree of crystallinity can be provided as the Y value is within the above range.

[0046] Meanwhile, the crystalline polyester resin 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).

[0047] Here, 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 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.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] The above-mentioned crystalline polyester resin comprises dicarboxylic acid repeating units 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, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, phthalic acid, 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 dimethyl terephthalate, regenerated isophthalic acid, and It may include one or more selected from the group consisting of regenerated phthalic acid.

[0054] Here, the recycled terephthalic acid, recycled dimethyl terephthalate, recycled isophthalic acid, and recycled phthalic acid used as the dicarboxylic acid component 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.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] The crystalline polyester resin may further include repeating units (A) derived from a branching agent having three or more functional groups. Due to the branching agent, the crystalline polyester resin may have the repeating units (A) introduced into the side chains of the main chain or have a graft polymerization structure formed by the repeating units (A), thereby having high molecular weight and high crystallinity.

[0059] The content of the repeating unit (A) included in the crystalline polyester resin is not particularly limited, but may be 0.001 to 15 weight%, 0.005 to 13 weight%, 0.01 to 12 weight%, 0.02 to 10 weight%, or 0.03 to 5 weight% based on the total weight% of the diol repeating unit.

[0060] The above branching agent is not particularly limited, but specifically may be trimellitic acid, trimellitic anhydride, trimethylol propane, or a combination thereof.

[0061] The crystalline polyester resin may have an intrinsic viscosity (IV) (@35 ℃) of 0.5 to 1.3 dl / g. Specifically, the crystalline polyester resin may have an intrinsic viscosity (IV) of 0.51 to 1.3 dl / g, 0.53 to 1.29 dl / g, 0.56 to 1.28 dl / g, 0.56 to 1.27 dl / g, 0.59 to 1.25 dl / g, or 0.6 to 1.25 dl / g at 35 ℃.

[0062] The above crystalline polyester resin may have a fusion ratio of 5% or less according to Formula 2 below. Specifically, the crystalline polyester resin may have a fusion ratio of 4.8% or less, 4.6% or less, 4.5% or less, 4.3% or less, 4% or less, 3.8% or less, 3.5% or less, 3.3% or less, 3% or less, 2.5% or less, 2.3% or less, 2% or less, 1.8% or less, 1.5% or less, 1% or less, 0.8% or less, 0.5% or less, 0.3% or less, or 0.1% or less (e.g., 0.001 to 5%, 0.005 to 4%, 0.01 to 3%, or 0.1 to 2%), and as a result, the productivity of the crystalline polyester resin is very excellent, and moldability (processability) can be secured during the molding process.

[0063] [Equation 2] Fusion ratio (%) = (W F / W T )×100

[0064] In the above Equation 2,

[0065] W T is the total weight of crystalline polyester resin produced per unit time (1 hr), and

[0066] W F is the weight of the fusion material generated per ton of the above-mentioned produced crystalline polyester resin, and

[0067] The above-mentioned fused material is a material that cannot pass through a vibrator having a 12.5 mm mesh.

[0068] The above crystalline polyester resin may have a state (form) such as chips, pellets, or powder.

[0069] In addition, the crystalline polyester resin may be a homopolymer or a copolymer.

[0070] According to the present invention, the content of the crystalline polyester resin may be 1 to 90 weight% based on the total weight of the polyester resin mixture. Specifically, the content of the crystalline polyester resin included in the polyester resin mixture may be 5 to 85 weight%, 10 to 80 weight%, 15 to 75 weight%, 20 to 70 weight%, 25 to 65 weight%, or 30 to 60 weight% based on the total weight of the polyester resin mixture. As the content of the crystalline polyester resin is within the above range, the moldability and transparency of the polyester resin mixture may be superior.

[0071]

[0072] amorphous polyester resin

[0073] The amorphous polyester resin included in the polyester resin mixture according to the present invention can improve the moldability, transparency, chemical resistance, impact resistance, etc. of the polyester resin mixture. Specifically, the amorphous polyester resin includes one or more of polyethylene terephthalate glycol (PETG) resin and polycyclohexylenedimethylene terephthalate glycol (PCTG) resin.

[0074] The above polyethylene terephthalate glycol resin may be obtained through an esterification reaction and / or polycondensation reaction of a commonly known diol component (e.g., ethylene glycol, cyclohexanedimethanol) and a dicarboxylic acid component (e.g., terephthalic acid). Specifically, the above polyethylene terephthalate glycol resin is an amorphous resin obtained by polymerizing raw materials comprising ethylene glycol, cyclohexanedimethanol, and terephthalic acid, wherein the input content of cyclohexanedimethanol may be 10 to 35 weight% (e.g., 10 to 30 weight%, 10 to 25 weight%, or 12 to 25 weight%) based on the total weight of the raw materials. Such polyethylene terephthalate glycol resin has the advantage of being able to increase the transparency of the polyester resin mixture by having almost no whitening phenomenon, and can also improve impact resistance, chemical resistance, and moldability.

[0075] According to the present invention, the content of the polyethylene terephthalate glycol resin may be greater than 0 and up to 80 weight% based on the total weight of the polyester resin mixture. Specifically, the content of the polyethylene terephthalate glycol resin included in the polyester resin mixture may be 3 to 75 weight%, 5 to 70 weight%, 10 to 65 weight%, 15 to 60 weight%, 20 to 55 weight%, or 25 to 50 weight% based on the total weight of the polyester resin mixture. As the content of the polyethylene terephthalate glycol resin is within the above range, the transparency and moldability of the polyester resin mixture may be superior.

[0076] The above polycyclohexylenedimethylene terephthalate glycol resin may be obtained through an esterification reaction and / or polycondensation reaction of a commonly known diol component (e.g., ethylene glycol, cyclohexanedimethanol) and a dicarboxylic acid component (e.g., terephthalic acid). Specifically, the above polycyclohexylenedimethylene terephthalate glycol resin is an amorphous resin obtained by polymerizing raw materials comprising ethylene glycol, cyclohexanedimethanol, and terephthalic acid, wherein the input content of the cyclohexanedimethanol may be 25 to 60 weight% (e.g., 25 to 55 weight%, 25 to 50 weight%, or 25 to 45 weight%) based on the total weight of the raw materials. These polycyclohexylene dimethylene terephthalate glycol resins have properties similar to the polyethylene terephthalate glycol resins mentioned above, and have the advantage of improving impact resistance, chemical resistance, and moldability along with the transparency of the polyester resin mixture.

[0077] According to the present invention, the content of the polycyclohexylenedimethylene terephthalate glycol resin may be greater than 0 and up to 80 weight% based on the total weight of the polyester resin mixture. Specifically, the content of the polycyclohexylenedimethylene terephthalate glycol resin included in the polyester resin mixture may be 3 to 75 weight%, 5 to 70 weight%, 10 to 65 weight%, 15 to 60 weight%, 20 to 55 weight%, or 25 to 50 weight% based on the total weight of the polyester resin mixture. As the content of the polycyclohexylenedimethylene terephthalate glycol resin is within the above range, the transparency and moldability of the polyester resin mixture may be superior.

[0078]

[0079] Polyethylene terephthalate resin

[0080] The polyester resin mixture according to the present invention may further include polyethylene terephthalate (PET) resin to improve moldability, heat resistance, mechanical strength, etc.

[0081] The above polyethylene terephthalate resin may be obtained through an esterification reaction and / or polycondensation reaction of a commonly known diol component (e.g., ethylene glycol) and a dicarboxylic acid component (e.g., terephthalic acid, isophthalic acid). The diol component and the dicarboxylic acid component may each be a virgin raw material (monomer) or a recycled raw material (monomer). For example, the above polyethylene terephthalate resin may be obtained by crushing and melting waste polyethylene terephthalate resin collected after use, or waste articles containing it.

[0082] Specifically, the polyethylene terephthalate resin may be recycled polyethylene terephthalate (recycled-PET) resin (e.g., mechanical recycled-PET, MR-PET) resin, chemical recycled-PET (CR-PET) resin), virgin polyethylene terephthalate (virgin-PET) resin, or a combination thereof.

[0083] Such polyethylene terephthalate resin may be a crystalline polyethylene terephthalate resin. Specifically, the polyethylene terephthalate resin may have a crystallization temperature (Tc) of 190°C or lower, 180°C or lower, or 170°C or lower (e.g., 130 to 170°C).

[0084] According to the present invention, the content of the polyethylene terephthalate resin may be greater than 0 and up to 50 weight% based on the total weight of the polyester resin mixture. Specifically, the content of the polyethylene terephthalate resin included in the polyester resin mixture may be 1 to 45 weight%, 5 to 40 weight%, 10 to 35 weight%, 15 to 30 weight%, 20 to 30 weight%, or 20 to 25 weight% based on the total weight of the polyester resin mixture. As the content of the polyethylene terephthalate resin is within the above range, the transparency of the polyester resin mixture may be superior.

[0085]

[0086] As such, the polyester resin mixture according to the present invention includes a crystalline polyester resin and an amorphous polyester resin in which the heat of fusion (△H) at the melting temperature is controlled, thereby minimizing the occurrence of fusion during the manufacturing process or molding process, and thus enabling the manufacture of articles with excellent moldability, productivity, and high transparency.

[0087] Specifically, the polyester resin mixture according to the present invention may be a mixture comprising the crystalline polyester resin and the polyethylene terephthalate glycol (PETG) resin; a mixture comprising the crystalline polyester resin, the polyethylene terephthalate glycol (PETG) resin, and the polycyclohexylenedimethylene terephthalate glycol (PCTG) resin; a mixture comprising the crystalline polyester resin, the polyethylene terephthalate glycol (PETG) resin, and the polyethylene terephthalate (PET) resin; a mixture comprising the crystalline polyester resin, the polycyclohexylenedimethylene terephthalate glycol (PCTG) resin, and the polyethylene terephthalate (PET) resin; or a mixture comprising the crystalline polyester resin, the polyethylene terephthalate glycol (PETG) resin, the polycyclohexylenedimethylene terephthalate glycol (PCTG) resin, and the polyethylene terephthalate (PET) resin.

[0088]

[0089] Method for manufacturing a polyester resin mixture

[0090] A method for preparing a polyester resin mixture according to the present invention comprises: (1) a step of preparing a polyester resin by polymerizing a diol component and a dicarboxylic acid component; (2) a step of preparing a crystalline polyester resin by crystallizing the polyester resin one or more times; and (3) a step of mixing the crystalline polyester resin and an amorphous polyester resin, wherein the amorphous polyester resin comprises one or more of polyethylene terephthalate glycol resin and polycyclohexylenedimethylene terephthalate glycol resin, and when the crystalline polyester resin prepared through steps (1) and (2) is heated to 280 ℃ at a scan rate of 10 ℃ / min and analyzed by differential scanning calorimetry (DSC), the crystalline polyester resin has two or more melting temperatures (Tm It represents ) and satisfies the following Equation 1.

[0091] The manufacturing method according to the present invention can produce a polyester resin mixture with excellent transparency, moldability, and productivity by controlling the crystallization temperature of the polyester resin stepwise in step (2) to obtain a crystalline polyester resin satisfying the following formula 1, and mixing it with an amorphous polyester resin. This is explained in detail with reference to FIG. 1 as follows. Here, the detailed explanation of the following formula 1 is omitted as it is the same as described above.

[0092] [Equation 1] 4 < X / Y < 70

[0093] In the above Equation 1,

[0094] X is the sum of the heat of fusion (△H) at melting temperatures of 200 ℃ or higher when the crystalline polyester resin is analyzed by DSC, and

[0095] Y is the sum of the heat of fusion (△H) of the melting temperature that appeared at less than 200 ℃ when the above crystalline polyester resin was analyzed by DSC.

[0096]

[0097] Step (1): Preparation of polyester resin

[0098] 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.

[0099] 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.

[0100] 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.

[0101] The catalyst may be a methylate of sodium or magnesium; a nitrate, 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, ethyl acetoacetic ester titanate, isostearyl titanate, titanium dioxide, germanium dioxide, germanium tetrachloride, germanium ethylene glycoside, germanium acetate, or a combination thereof.

[0102] 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).

[0103] The above crystallizing agent may include a crystallization nucleating agent, a UV absorber, a polyolefin resin, a polyamide resin, etc.

[0104] The above antioxidants may include hindered phenolic compounds, phosphite compounds, thioether compounds, etc.

[0105] The above branching agent may be trimellitic acid, trimellitic anhydride, trimethylol propane, or a combination thereof.

[0106] 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.

[0107] 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.

[0108]

[0109] 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 polyester resin mixture 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.

[0110] 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, or 5 to 11 hours).

[0111]

[0112] Step (2): Preparation of crystalline polyester resin through crystallization

[0113] The above step (2) is a step of crystallizing the polyester resin obtained through the above step (1) one or more times. Specifically, the crystallization of the polyester resin may be performed two or more times, three or more times, or four or more times.

[0114] According to the present invention, the temperature at which the crystallization of the polyester resin is performed is not particularly limited, but may be 105 to 185 ℃ (specifically 106 to 184 ℃, 107 to 183 ℃, 108 to 182 ℃, 109 to 181 ℃, or 110 to 180 ℃). As the crystallization is performed within the above range, a crystalline polyester resin with an optimized degree of crystallization can be produced while minimizing fusion between polyester resins during the crystallization process.

[0115] According to the present invention, the crystallization of the polyester resin can be performed under temperature conditions that increase in stages. Specifically, when the crystallization of the polyester resin 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 폴리에스테르 수지의 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 상승되는 온도 조건으로 수행됨에 따라 결정화 과정에서 폴리에스테르 수지 간에 융착이 최소화되면서 결정화도가 최적화된 결정성 폴리에스테르 수지를 제조할 수 있다.

[0116] According to the present invention, the step (2) specifically comprises: (2-1) a step of first crystallizing the polyester resin of the step (1) at 105 to 135 ℃ (specifically 108 to 133 ℃, or 110 to 130 ℃); (2-2) a step of secondarily crystallizing the polyester resin crystallized in the step (2-1) at 120 to 175 ℃ (specifically 120 to 170 ℃, or 125 to 155 ℃); and (2-3) a step of thirdly crystallizing the polyester resin crystallized in the step (2-2) at 140 to 180 ℃ (specifically 145 to 180 ℃, or 150 to 180 ℃). In this way, as the crystallization is carried out in three stages and the temperature of each crystallization is controlled within the specific range, crystals are uniformly formed on the inside and outside of the polyester resin, and the fusion between polyester resins caused by surface melting during the crystallization process can be minimized. Accordingly, a crystalline polyester resin with an optimized degree of crystallization can be manufactured efficiently (improving productivity).

[0117] Meanwhile, the first crystallization temperature, the second crystallization temperature, and the third crystallization temperature may be different from each other.

[0118] In addition, the 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).

[0119] 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 needed to control viscosity and molecular weight.

[0120]

[0121] Step (3): Mixing the resins

[0122] Step (3) above is a step of preparing a resin mixture by mixing the crystalline polyester resin and the amorphous polyester resin obtained through Step (1) and Step (2). The description of the amorphous polyester resin is omitted as it is the same as described above.

[0123] According to the present invention, polyethylene terephthalate resin may be further added to the mixture of step (3). Specifically, through step (3), a resin mixture comprising the crystalline polyester resin, the amorphous polyester resin, and the polyethylene terephthalate resin may be prepared. The description of the polyethylene terephthalate resin is omitted as it is the same as described above.

[0124] The above mixing can be carried out through commonly known methods. Specifically, the above mixing can be performed by stirring at room temperature or at a temperature above the melting temperature of each resin (e.g., room temperature mixing or melt kneading).

[0125]

[0126] article

[0127] The article according to the present invention is manufactured from the polyester resin mixture described above. Specifically, the article according to the present invention may be manufactured by introducing the polyester resin mixture 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 product manufactured through injection molding.

[0128] Since the above-described article is manufactured using the polyester resin mixture described above, it may have excellent quality (e.g., transparency, heat resistance, mechanical strength, appearance, etc.). Such an article is not particularly limited but may be a film; a sheet; or small and large containers (e.g., containers for cosmetics or food, etc.).

[0129] The present invention will be explained in more detail below through examples. However, the following examples are merely illustrative of the present invention and do not limit the scope of the present invention.

[0130]

[0131] [Example 1]

[0132] Step (1): Preparation of polyester resin

[0133] 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 10 L 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.

[0134] 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.

[0135] Afterwards, the obtained polyester resin pellets were dried at 50°C for 10 hours before crystallization.

[0136] Step (2): Preparation of crystalline polyester resin

[0137] The above-described 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 in three stages while gradually increasing the temperature according to the movement position of the polyester resin pellets to obtain a crystalline polyester resin. At this time, the first crystallization of the polyester resin pellets was carried out at 110 ℃, the second crystallization of the first-crystallised polyester resin pellets was carried out at 130 ℃, and the third crystallization of the second-crystallised polyester resin pellets was carried out at 165 ℃.

[0138]

[0139] [Example 2]

[0140] Step (1): Preparation of polyester resin

[0141] 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 10 L 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 255 ℃ under a pressure of 1 kgf / ㎠ to obtain a transparent reaction product.

[0142] 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.

[0143] Step (2): Preparation of crystalline polyester resin

[0144] 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 in three stages while gradually increasing the temperature according to the movement position of the polyester resin pellets to obtain a crystalline polyester resin. At this time, the first crystallization of the polyester resin pellets was carried out at 115 ℃, the second crystallization of the first-crystallised polyester resin pellets was carried out at 120 ℃, and the third crystallization of the second-crystallised polyester resin pellets was carried out at 160 ℃.

[0145]

[0146] [Example 3]

[0147] Step (1): Preparation of polyester resin

[0148] Regenerated bis-2-hydroxyethyl terephthalate (r-BHET, 6569.4 kg), terephthalic acid (TPA, 8157.5 kg), isophthalic acid (IPA, 429.3 kg), ethylene glycol (EG, 2180.8 kg), diethylene glycol (DEG, 109.7 kg), Ge catalyst (1.0 kg), and phosphoric acid (1.5 kg) were introduced into a 10 L reactor connected to a column and a condenser capable of cooling by water. Next, the temperature of the reactor was raised to 260 ℃, and an esterification reaction (ES) was carried out at 260 ℃ under a pressure of 1 kgf / ㎠ to obtain a transparent reaction product.

[0149] Next, the above reactant was transferred to a polycondensation reactor, and a polycondensation reaction (PA) was carried out at 275 °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 0.78 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.

[0150] Afterwards, the obtained polyester resin pellets were dried at 40°C for 9 hours before crystallization.

[0151] Step (2): Preparation of crystalline polyester resin

[0152] The above-described 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 in three stages while gradually increasing the temperature according to the movement position of the polyester resin pellets to obtain a crystalline polyester resin. At this time, the first crystallization of the polyester resin pellets was carried out at 120 ℃, the second crystallization of the first-crystallised polyester resin pellets was carried out at 135 ℃, and the third crystallization of the second-crystallised polyester resin pellets was carried out at 150 ℃.

[0153]

[0154] [Example 4]

[0155] Step (1): Preparation of polyester resin

[0156] 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 10 L 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.

[0157] 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.

[0158] Step (2): Preparation of crystalline polyester resin

[0159] 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 in three stages while gradually increasing the temperature according to the movement position of the polyester resin pellets to obtain a crystalline polyester resin. At this time, the first crystallization of the polyester resin pellets was carried out at 110 ℃, the second crystallization of the first-crystallised polyester resin pellets was carried out at 170 ℃, and the third crystallization of the second-crystallised polyester resin pellets was carried out at 180 ℃.

[0160]

[0161] [Example 5]

[0162] Step (1): Preparation of polyester resin

[0163] Polyester resin pellets were obtained through the same process as in Example 1.

[0164] Afterwards, the obtained polyester resin pellets were dried at 55°C for 4 hours before crystallization.

[0165] Step (2): Preparation of crystalline polyester resin

[0166] The above-described 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 in three stages while gradually increasing the temperature according to the movement position of the polyester resin pellets to obtain a crystalline polyester resin. At this time, the first crystallization of the polyester resin pellets was carried out at 125 ℃, the second crystallization of the first-crystallised polyester resin pellets was carried out at 130 ℃, and the third crystallization of the second-crystallised polyester resin pellets was carried out at 140 ℃.

[0167]

[0168] [Example 6]

[0169] Step (1): Preparation of polyester resin

[0170] Polyester resin pellets were obtained through the same process as in Example 3.

[0171] Step (2): Preparation of crystalline polyester resin

[0172] 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 in three stages while gradually increasing the temperature according to the movement position of the polyester resin pellets to obtain a crystalline polyester resin. At this time, the first crystallization of the polyester resin pellets was carried out at 130 ℃, the second crystallization of the first-crystallised polyester resin pellets was carried out at 150 ℃, and the third crystallization of the second-crystallised polyester resin pellets was carried out at 180 ℃.

[0173]

[0174] [Comparative Example 1]

[0175] Step (1): Preparation of polyester resin

[0176] Polyester resin pellets were obtained through the same process as in Example 3.

[0177] Step (2): Preparation of crystalline polyester resin

[0178] 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 in three stages while gradually lowering the temperature according to the movement position of the polyester resin pellets to obtain a crystalline polyester resin. At this time, the first crystallization of the polyester resin pellets was carried out at 160 ℃, the second crystallization of the first-crystallised polyester resin pellets was carried out at 140 ℃, and the third crystallization of the second-crystallised polyester resin pellets was carried out at 120 ℃.

[0179]

[0180] [Comparative Example 2]

[0181] Step (1): Preparation of polyester resin

[0182] Polyester resin pellets were obtained through the same process as in Example 3.

[0183] Afterwards, the obtained polyester resin pellets were dried at 55°C for 3 hours before crystallization.

[0184] Step (2): Preparation of crystalline polyester resin

[0185] The above-described 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 in three stages while gradually increasing the temperature according to the movement position of the polyester resin pellets to obtain a crystalline polyester resin. At this time, the first crystallization of the polyester resin pellets was carried out at 140 ℃, the second crystallization of the first-crystallised polyester resin pellets was carried out at 160 ℃, and the third crystallization of the second-crystallised polyester resin pellets was carried out at 200 ℃.

[0186]

[0187] [Comparative Example 3]

[0188] Step (1): Preparation of polyester resin

[0189] Polyester resin pellets were obtained through the same process as in Example 4.

[0190] Step (2): Preparation of crystalline polyester resin

[0191] 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 by gradually increasing the temperature according to the movement position of the polyester resin pellets to obtain a crystalline polyester resin. At this time, the first crystallization of the polyester resin pellets was carried out at 100 ℃, the second crystallization of the first-crystallised polyester resin pellets was carried out at 160 ℃, and the third crystallization of the second-crystallised polyester resin pellets was carried out at 190 ℃.

[0192]

[0193] [Comparative Example 4]

[0194] Step (1): Preparation of polyester resin

[0195] Polyester resin pellets were obtained through the same process as in Example 1.

[0196] Step (2): Crystallization of polyester resin

[0197] A crystalline polyester resin was obtained by feeding the above-mentioned polyester resin pellets (without drying) into a crystallization reactor at a rate of 1 ton per hour (feed rate: 1 ton / hr) and performing only primary crystallization at 170 ℃.

[0198]

[0199] [Test Example 1]

[0200] The crystalline polyester resins prepared in Examples 1 to 6 and Comparative Examples 1 to 4, 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.

[0201] DSC analyzer: Mettler Toledo's DSC 1 model was applied.

[0202] Sample preparation: About 6 to 10 mg of crystalline polyester resin was taken and filled into an aluminum pan.

[0203] 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.

[0204] Melting temperature (T m ) Verification: The temperature exhibiting the endothermic peak 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 X / Y ratio (rounded to the second decimal place) using this were calculated.

[0205]

[0206] [Test Example 2]

[0207] For the crystalline polyester resins prepared in Examples 1 to 6 and Comparative Examples 1 to 4, respectively, the weight (kg) of the fused material generated per ton of total production (kg / hr) was measured, and the fusion ratio according to Equation 2 below was calculated, and the results are shown in Tables 1 and 2 below.

[0208] [Equation 2] Fusion ratio (%) = (W F / W T )×100

[0209] In the above Equation 2,

[0210] W T is the total weight (total production volume) of crystalline polyester resin produced per unit time (1 hr), and

[0211] W F is the weight of the fusion generated per ton of the above-mentioned produced crystalline polyester resin (dividing the total production volume into 1-ton portions to classify it as crystalline polyester resin samples, and measuring the weight of the fusion contained in the samples),

[0212] The above fused material (polyester resin fused material) is a material that cannot pass through a vibrator having a 12.5 mm mesh.

[0213]

[0214] Classification Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Crystallization Temperature (°C) 1st Crystallization 1 10 1 15 1 20 1 10 1 25 1 30 2nd Crystallization 1 30 1 20 1 35 1 70 1 30 1 50 3rd Crystallization 1 65 1 60 1 50 1 80 1 40 1 80 Fusion Ratio (%) 1 0.5 0.5 3 4 2 200 °C Less than T m1-1 170.2165.9140.2155.2165.23180.2T m1-1 ΔH at 2.7 1.1 3.4 4 4.4 0.2 5 0.3T m1-2 -190.4--189.2-T m1-2 Sum of ΔH - 6.5 - 0.5 - ΔH (Y) at 2.7 7.6 3.4 4.4 0.7 5 0.3 200 ℃ or higher T m2 227.7230.62238.6230.1227.52235.1T m2 ΔH at 25.3731.1337.5130.524.1320.3 Sum of ΔH(X) 25.3731.1337.5130.524.1320.3X / Y 9.44.110.96.932.267.7

[0215] Classification Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Crystallization Temperature (°C) 1st Crystallization 160 140 100 170 2nd Crystallization 140 160 160 - 3rd Crystallization 120 200 190 - Fusion Ratio (%) 7 10 21 70 200 Less than °C T m1-1155.2--Fusion occurs between resin pellets (crystallization impossible)T m1-1 ΔH0.5T at m1-2 -T m1-2 Sum of ΔH(Y) at 0.5200 ℃ or higher T m2-1 236.5-210.5T m2-1 ΔH38.210.1T at m2-2 -237.1237.1T m2-2 Sum of ΔH at 35.5 25.5 ΔH(X) 38.2 35.5 35.6 X / Y 76.4--

[0216] Referring to Table 1 above, it can be seen that the crystalline polyester resins of Examples 1 to 6 according to the present invention have a very low fusion rate of 5% or less during the crystallization process, and have an optimized degree of crystallization with the X / Y ratio controlled within the range of the present invention.

[0217] On the other hand, referring to Table 2 above, it can be seen that the crystalline polyester resin of Comparative Example 1, which was crystallized under temperature conditions that gradually decreased, the crystalline polyester resins of Comparative Examples 2 and 3, in which the crystallization temperature was outside the range of the present invention, and the crystalline polyester resin of Comparative Example 4, in which only primary crystallization was performed at a low temperature, all have a high fusion ratio and did not undergo sufficient crystallization.

[0218]

[0219] [Preparation Example 1]

[0220] A polyester resin mixture was prepared by mixing 10 wt% of the crystalline polyester resin prepared in Example 1, 60 wt% of polyethylene terephthalate glycol (PETG) resin (SK Chemicals Co., Ltd., K2012), and 30 wt% of polycyclohexylene dimethylene terephthalate glycol (PCTG) resin (SK Chemicals Co., Ltd., J2003) at room temperature using a conventional method.

[0221]

[0222] [Preparation Examples 2 to 11]

[0223] A polyester resin mixture was prepared through the same process as in Preparation Example 1, except that the composition of Table 3 below was applied.

[0224]

[0225] [Comparative Manufacturing Examples 1 to 4]

[0226] A polyester resin mixture was prepared through the same process as in Preparation Example 1, except that the composition of Table 3 below was applied.

[0227]

[0228] [Test Example 3]

[0229] After producing injection specimens with a thickness of 3 mm by injection molding the polyester resin mixtures of Manufacturing Examples 1 to 11 and Comparative Manufacturing Examples 1 to 4 using a conventional method, the haze of the produced injection specimens was measured according to ASTM D1003, and the results are shown in Table 3 below.

[0230] ○: 3 or more

[0231] ×: Less than 3

[0232]

[0233] Crystalline Polyester Resin Per Capita Resin Content (Weight%) Haze Crystalline Polyester Resin PETG Resin PCTG Resin PET Resin Preparation Example 1 Example 1 1060300× Preparation Example 2 Example 2 119800× Preparation Example 3 Example 3 1040050× Preparation Example 4 Example 4 4030030× Preparation Example 5 Example 5 3050200× Preparation Example 6 Example 6 2070010× Preparation Example 7 Example 2 3035305× Preparation Example 8 Example 3901000× Preparation Example 9 Example 4 20401030× Preparation Example 10 Example 5 406000× Preparation Example 11 Example 6 605350× Comparative Preparation Example 1-0202060○Comparative Manufacturing Example 2-007030○Comparative Manufacturing Example 3 Comparative Example 395050○Comparative Manufacturing Example 4 Comparative Example 46002020○PETG Resin - SK Chemicals Co., Ltd., K2012PCTG Resin - SK Chemicals Co., Ltd., J2003PET Resin - TPA / IPA / EG / DEG, IV: 0.75 dl / g, Tc: 140 ℃, Tm: 250 ℃

[0234] Referring to Table 3 above, it can be seen that the polyester resin mixtures of Preparation Examples 1 to 11, in which the crystalline polyester resin according to the present invention is mixed with one or more of PETG resin, PCTG resin, and PET resin, have excellent transparency.

[0235] On the other hand, it can be seen that the polyester resin mixtures of Comparative Examples 1 to 4, which contain crystalline polyester resin that has not undergone sufficient crystallization, have reduced transparency.

Claims

1. 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; and It includes an amorphous polyester resin, The above amorphous polyester resin comprises one or more of polyethylene terephthalate glycol resin and polycyclohexylene dimethylene terephthalate glycol resin, and When the above crystalline polyester resin is heated to 280 ℃ at a scan rate of 10 ℃ / min and analyzed by differential scanning calorimetry (DSC), two or more melting temperatures (T m A polyester resin mixture representing ) and satisfying Formula 1 below: [Equation 1] 4 < X / Y < 70 In the above Equation 1, X is the sum of the heat of fusion (△H) at melting temperatures of 200 ℃ or higher when the crystalline polyester resin is analyzed by DSC, and Y is the sum of the heat of fusion (△H) of the melting temperature that appeared at less than 200 ℃ when the above crystalline polyester resin was analyzed by DSC.

2. In Paragraph 1, A polyester resin mixture in which the content of the crystalline polyester resin is 1 to 90 weight% based on the total weight of the polyester resin mixture.

3. In Paragraph 1, A polyester resin mixture in which the content of the polyethylene terephthalate glycol resin is greater than 0 and up to 80 weight% based on the total weight of the polyester resin mixture.

4. In Paragraph 1, A polyester resin mixture in which the content of the polycyclohexylene dimethylene terephthalate glycol resin is greater than 0 and up to 80 weight% based on the total weight of the polyester resin mixture.

5. In Paragraph 1, A polyester resin mixture further comprising polyethylene terephthalate resin.

6. In Paragraph 5, A polyester resin mixture in which the content of the polyethylene terephthalate resin is greater than 0 to 50 weight% based on the total weight of the polyester resin mixture.

7. In Paragraph 5, The above polyethylene terephthalate resin is a polyester resin mixture that is recycled polyethylene terephthalate (recycled-PET) resin, virgin polyethylene terephthalate (virgin-PET) resin, or a combination thereof.

8. In Paragraph 1, The melting temperature (T) of the above crystalline polyester resin m A polyester resin mixture having a temperature of 140 to 250°C.

9. In Paragraph 1, When the above crystalline polyester resin is analyzed by the above DSC, the first melting temperature (T) is less than 200 ℃. m1 It represents ), and the second melting temperature (T) at 200 ℃ or higher. m2 Representing ), The above first melting temperature (T m1 ) and the second melting temperature (T m2 The difference of ) (|T m1 - T m2 A polyester resin mixture in which |) is 40 to 105 ℃.

10. In Paragraph 1, A polyester resin mixture having a sum (X) of the heat of fusion (△H) at a melting temperature of 200 ℃ or higher, when the above crystalline polyester resin is analyzed by DSC, of ​​20 J / g or more.

11. In Paragraph 1, A polyester resin mixture having a sum (Y) of the heat of fusion (△H) at a melting temperature of less than 200 ℃ when the above crystalline polyester resin is analyzed via DSC, of ​​0.1 to 10 J / g.

12. In Paragraph 1, A polyester comprising one or more selected from the group consisting of the above dicarboxylic acid component terephthalic acid, isophthalic acid, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, phthalic acid, 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 dimethyl terephthalate, regenerated isophthalic acid, and regenerated phthalic acid. Resin mixture.

13. In Paragraph 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 polyester resin mixture 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. 14.(1) A step of manufacturing a polyester resin by polymerizing a diol component and a dicarboxylic acid component; (2) a step of producing a crystalline polyester resin by crystallizing the above polyester resin one or more times; and (3) A step of mixing the crystalline polyester resin and the amorphous polyester resin, and The above amorphous polyester resin comprises one or more of polyethylene terephthalate glycol resin and polycyclohexylene dimethylene terephthalate glycol resin, and When the above crystalline polyester resin is heated to 280 ℃ at a scan rate of 10 ℃ / min and analyzed by differential scanning calorimetry (DSC), two or more melting temperatures (T m A method for preparing a polyester resin mixture that represents ) and satisfies Formula 1 below: [Equation 1] 4 < X / Y < 70 In the above Equation 1, X is the sum of the heat of fusion (△H) at melting temperatures of 200 ℃ or higher when the crystalline polyester resin is analyzed by DSC, and Y is the sum of the heat of fusion (△H) of the melting temperature that appeared at less than 200 ℃ when the above crystalline polyester resin was analyzed by DSC.

15. In Paragraph 14, A method for preparing a polyester resin mixture, wherein in step (2) above, the crystallization of the polyester resin is performed in a temperature range of 105 to 185 ℃.

16. In Paragraph 14, A method for preparing a polyester resin mixture in which the crystallization of the polyester resin in step (2) is performed under a temperature condition in which the temperature increases stepwise.

17. In Paragraph 14, The above step (2) (2-1) A step of first crystallizing the polyester resin of step (1) at 105 to 135 ℃; (2-2) a step of secondary crystallizing the polyester resin crystallized in step (2-1) at 120 to 175 ℃; and (2-3) A method for preparing a polyester resin mixture comprising the step of tertiarily crystallizing the polyester resin crystallized in step (2-2) at 140 to 180 ℃.

18. In Paragraph 14, A method for manufacturing a polyester resin mixture in which polyethylene terephthalate resin is further mixed in step (3) above.

19. An article manufactured from the polyester resin mixture of claim 1.

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