Solid-state polymerized polyester resin and preparation method therefor

Abstract

The present invention relates to a solid-state polymerized polyester resin, a preparation method therefor, and an article manufactured therefrom. The solid-state polymerized polyester resin has a degree of crystallinity required in a molding process and / or a recycling process while minimizing fusion in a preparation process, and thus can exhibit excellent productivity, moldability, recyclability, and the like.

Description

Solid-state polymerized polyester resin and method for producing the same

[0001] The present invention relates to a solid-state polymerized polyester resin having excellent productivity and a required level of intrinsic viscosity, and a method for producing the solid-state polymerized polyester resin.

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

[0003] The above product can be manufactured by drying a polyester resin obtained through a polymerization reaction to remove moisture, and then introducing the dehydrated polyester resin into a molding process. However, the polyester resin exhibits a primarily amorphous surface, and thus, during the drying process in a dryer, the polyester resins may fuse with each other or adhere to the inner walls of the dryer, thereby reducing the drying efficiency and productivity of the polyester resin.

[0004] To address the above issues, a technique has been proposed to crystallize polyester resin, preventing fusion during the drying process. However, currently, there are limitations in optimizing the crystallinity of polyester resin.

[0005] Meanwhile, to enhance the heat resistance, mechanical strength, etc. of polyester resins, a solid-state polymerization process is performed on the polyester resin obtained through crystallization to manufacture polyester resins with controlled intrinsic viscosity and molecular weight. However, due to limitations in controlling the crystallinity of polyester resins, the aforementioned fusion problem still appears in the solid-state polymerization process, lowering the productivity of polyester resins manufactured through solid-state polymerization and making it difficult to obtain polyester resins with the required level of intrinsic viscosity.

[0006] In order to solve the above-mentioned conventional problems, the inventors of the present invention have conducted various studies, and as a result, it has been confirmed that a solid-state polymerized polyester resin having a controlled heat of fusion (△H) at the melting temperature can be obtained by solid-state polymerizing a crystalline polyester resin, thereby obtaining a solid-state polymerized polyester resin having a required level of intrinsic viscosity, excellent heat resistance, mechanical strength, etc., and exhibiting improved productivity.

[0007] Accordingly, the object of the present invention is to provide a solid-state polymerized polyester resin having excellent overall physical properties and productivity and a method for producing the same.

[0008] In addition, another object of the present invention is to provide an article manufactured using the above-described solid-phase polymerized polyester resin.

[0009] In order to solve the above problem, the present invention provides a solid-state polymerized polyester resin prepared by solid-state polymerizing a crystalline polyester resin including a diol repeating unit derived from a diol component and a dicarboxylic acid repeating unit derived from a dicarboxylic acid component, and when the crystalline polyester resin is heated to 280°C at a scan rate of 10°C / min and analyzed by differential scanning calorimetry (DSC), the solid-state polymerized polyester resin satisfies the following equation 1:

[0010] [Formula 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 that appeared at 200°C or higher during the DSC analysis of the crystalline polyester resin, and Y is the sum of the heat of fusion (△H) of the melting temperature that appeared at less than 200°C during the DSC analysis of the crystalline polyester resin.

[0013] In addition, the present invention provides a method for producing a solid-state polymerized polyester resin, comprising: (1) a step of polymerizing a diol component and a dicarboxylic acid component to produce a polyester resin; (2) a step of crystallizing the polyester resin at least once to produce a crystalline polyester resin; and (3) a step of solid-state polymerizing the crystalline polyester resin, wherein the crystalline polyester resin satisfies Equation 1 when analyzed by differential scanning calorimetry (DSC) at a scan rate of 10°C / min while heating to 280°C.

[0014] In addition, the present invention provides an article manufactured from the above-described solid-phase polymerized polyester resin.

[0015] The solid-state polymerized polyester resin according to the present invention can exhibit excellent productivity while having a required level of intrinsic viscosity because it is manufactured using a crystalline polyester resin whose heat of fusion (△H) at the melting temperature is controlled by manufacturing it through a specific crystallization process. In addition, the solid-state polymerized polyester resin has a crystallinity required in the recycling process, so that the recycling process can proceed in a state of being combined with a used waste product (for example, there is no need to separately perform a process of separating an article manufactured from the solid-state polymerized polyester resin from the waste product), and thus, recyclability can also be excellent.

[0016] Furthermore, when a product (e.g., an injection molded product) is manufactured using the solid-state polymerized polyester resin according to the present invention, productivity, moldability, etc. are improved, and an product having excellent overall physical properties such as heat resistance and mechanical strength can be provided.

[0017] Figure 1 is a flow chart showing a process for manufacturing a solid-state polymerized polyester resin according to the present invention.

[0018] Hereinafter, the present invention will be described in detail. Herein, the present invention is not limited to the contents described below, and may be modified in various forms as long as the gist of the invention is not changed.

[0019] The word "comprising" or "including" in this specification is intended to specify particular features, regions, steps, processes, elements and / or components, and does not exclude the presence or addition of other features, regions, steps, processes, elements and / or components, unless specifically stated to the contrary.

[0020] In this specification, terms such as first, second, etc. are used to describe various components, and the components are not limited to these terms. These terms are used to distinguish one component from another.

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

[0022]

[0023] Polyester resins manufactured through pelletizing processes such as extrusion and underwater cutting can be further subjected to a solid-state polymerization process to control their molecular weight and intrinsic viscosity in order to enhance heat resistance, mechanical strength, and other properties. To increase the productivity of the polyester resin, it is necessary to control the degree of crystallinity of the polyester resin fed into the solid-state polymerization process. If a polyester resin that is not sufficiently crystallized or an over-crystallized polyester resin is fed into the solid-state polymerization process, fusion between the polyester resins will occur, reducing the productivity of the polyester resin manufactured through the solid-state polymerization process. Furthermore, this can lead to problems such as the inability to increase the intrinsic viscosity of the polyester resin to the required level.

[0024] Accordingly, in order to optimize the degree of crystallinity of the polyester resin introduced into the solid-state polymerization process, the inventors of the present invention have conducted various studies, and as a result, they have confirmed that it is very important to control the melting temperature and heat of fusion of the crystalline polyester resin obtained through the crystallization process. This is because the degree of crystallization can be predicted based on the melting temperature and heat of fusion of the crystalline polyester resin. For example, a significantly low heat of fusion may mean that the polyester resin is not sufficiently crystallized, and a significantly high heat of fusion may mean that the polyester resin is over-crystallized.

[0025] When a solid-state polymerization process is performed on a polyester resin that is not sufficiently crystallized, the problem of fusion occurs because the crystallinity is not secured to the extent that solid-state polymerization can occur. Conversely, when a solid-state polymerization process is performed on a polyester resin that is over-crystallized, a lot of energy is consumed in the solid-state polymerization, which causes a decrease in the mobility of the polymer chain, making it difficult to obtain a polyester resin having a required level of intrinsic viscosity.

[0026] Based on these points, the present invention aims to manufacture a solid-state polymerized polyester resin using a crystalline polyester resin that satisfies a specific correlation derived from a melting temperature and a heat of fusion, thereby preventing the occurrence of fusion between polyester resins in a crystallization process and a solid-state polymerization process, while increasing the productivity of the solid-state polymerized polyester resin, and further providing a product of superior quality.

[0027]

[0028] Solid-state polymerized polyester resin

[0029] The solid-state polymerized polyester resin according to the present invention is produced by solid-state polymerizing 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. The crystalline polyester resin can have a degree of crystallinity that can minimize the occurrence of fusion during the crystallization process and the solid-state polymerization process by controlling the melting temperature and heat of fusion.

[0030] Specifically, the above crystalline polyester resin satisfies the following equation 1 when analyzed by differential scanning calorimetry (DSC) at a temperature of up to 280°C at a scan rate of 10°C / min.

[0031] [Formula 1] 4 < X / Y < 70

[0032] In the above equation 1,

[0033] X is the sum of the heat of fusion (△H) of the melting temperature that appeared at 200 ℃ or higher during the DSC analysis of the above crystalline polyester resin,

[0034] Y is the sum of the heat of fusion (△H) of the melting temperature that appeared below 200 ℃ during the DSC analysis of the above crystalline polyester resin.

[0035] The above crystalline polyester resin satisfies the above formula 1 based on a specific temperature (melting temperature) of 200°C, thereby optimizing the crystallinity, thereby increasing the productivity of the solid-state polymerized polyester resin and enabling the control of the intrinsic viscosity to a required level. The above 200°C may mean a midpoint between the crystallization temperature (Tc) and the melting temperature (Tm) of the crystalline polyester resin, and by applying a temperature of this midpoint, the amount of heat (melting temperature) required in the crystallization process can be optimally controlled.

[0036] Specifically, the ratio of X / Y in the above formula 1 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, 10 to 35, 8 to 15, or 9 to 13. As the ratio of X / Y is controlled within the above range, a polyester resin having a required level of intrinsic viscosity can be provided while minimizing the occurrence of fusion in a solid-state polymerization process. For example, when the ratio of X / Y is 4 or less, it means that the crystallization of the crystalline polyester resin has not occurred sufficiently, resulting in a significant amount of fusion occurring in the solid-state polymerization process. In addition, when the ratio of X / Y is 70 or more, it means that the crystalline polyester resin has been over-crystallized, resulting in a large amount of energy being consumed in the solid-state polymerization process and making it difficult to increase the intrinsic viscosity to the required level.

[0037] 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) during the DSC analysis. m ) can be expressed.

[0038] Specifically, the crystalline polyester resin has two or more melting temperatures (T) during the DSC analysis. m ) may be in the temperature range of 140 to 250°C. More specifically, the two or more melting temperatures (T m) may be 140 to 245°C, 140 to 243°C, 140 to 242°C, 140 to 240°C, 140.1 to 239.5°C, 140.1 to 239°C, 140.2 to 238.7°C, 140.2 to 238.5°C, 141 to 238.3°C, 142 to 238°C, 145 to 237.5°C, 148 to 237°C, 150 to 236.8°C, 151 to 236.5°C, 153 to 236.3°C, 155 to 236°C, or 158 to 236°C. The above two or more melting temperatures (T m ) can provide a crystalline polyester resin having a desired degree of crystallinity as it appears within the above temperature range.

[0039] The above crystalline polyester resin may exhibit one or more, two or more, or three or more melting temperatures at a temperature below 200°C during the DSC analysis, and may exhibit one or more, or two or more melting temperatures at a temperature above 200°C.

[0040] Specifically, the crystalline polyester resin has a first melting temperature (T) below 200° C. during the DSC analysis. m1 ) and the second melting temperature (T ) is above 200 ℃. m2 ) can be expressed. For example, the crystalline polyester resin has a first-first melting temperature (T ) of less than 200 ℃ during the DSC analysis. m1-1 ) and the first-second melting temperature (T m1-2 ) and the second melting temperature (T ) is above 200 ℃. m2 ) can be expressed. The above 1-1 melting temperature (T m1-1 ) can be specifically 140 to 198 ℃, 141 to 195 ℃, 145 to 193 ℃, or 150 to 190 ℃. The first-second melting temperature (T m1-2) can be specifically 185 to 210 ℃, 187 to 205 ℃, 188 to 200 ℃, or 189 to 195 ℃. The second melting temperature (T m2 ) can be specifically 210 to 245°C, 215 to 243°C, 218 to 242°C, or 220 to 240°C.

[0041] Meanwhile, the first melting temperature (T m1 ) and the second melting temperature (T m2 )'s car (|T m1 - T m2 |) can be 40 to 105 ℃. Specifically, the above difference (|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 ) are two or more, the lowest melting temperature among the two or more melting temperatures is the second melting temperature (T m2 ) are two or more, the highest temperature among the two or more melting temperatures is referred to as the first melting temperature (T m1 ) and the second melting temperature (T m2 ) is applied to the above difference (|T m1 - T m2 |) can be produced.

[0042] According to the present invention, in the above formula 1, when X is heated to 280 ℃ at a scan rate of 10 ℃ / min and analyzed by DSC, if one or more melting temperatures appear above 200 ℃, the sum of the heat of fusion (△H) at each melting temperature (△H sum1) can mean. For example, in the DSC analysis, two melting temperatures, melting temperature a(T ) above 200 ℃ ma ) and melting temperature b(T mb ) appears, the above X is the melting temperature a(T ma ) heat of fusion (△H a ) and the melting temperature b(T mb ) heat of fusion (△H b ) is the sum of (△H a + △H b ) may be. Here, in the DSC analysis, one melting temperature a(T) is above 200 ℃. ma ) only appears, the above X is the melting temperature a(T ma ) heat of fusion (△H a ) may be a value of itself. This X value (the sum of the heat of fusion (△H) of the melting temperature shown at 200 ℃ or higher) is not particularly limited, but may be 20 J / g or more, and specifically, may be 20.2 J / g or more, 23 J / g or more, 24 J / g or more, 25 J / g or more, 27 J / g or more, 29 J / g or more, 30 J / g or more, 31 J / g or more, 33 J / g or more, 35 J / g or more, 37 J / g or more, or 40 J / g or more (e.g., 20 to 39 J / g, 22 to 38 J / g, 24 to 37 J / g, or 25 to 35 J / g). When the X value is within the above range, a crystalline polyester resin having a desired degree of crystallinity can be provided.

[0043] In addition, in the above formula 1, when Y is heated to 280 ℃ at a scan rate of 10 ℃ / min and analyzed by DSC, if one or more melting temperatures are found below 200 ℃, the sum of the heat of fusion (△H) at each melting temperature (△H sum2 ) can mean. For example, in the DSC analysis, the melting temperature c(T) is two melting temperatures below 200 ℃. mc ) and melting temperature d(T md) appears, the above Y is the melting temperature c(T mc ) heat of fusion (△H c ) and the melting temperature d(T md ) heat of fusion (△H d ) is the sum of (△H c + △H d ) may be. Here, in the DSC analysis, the melting temperature c(T) is one melting temperature below 200 ℃. mc ) only appears, the above Y is the melting temperature c(T mc ) heat of fusion (△H c ) may be its own value. This Y value (the sum of the heats of fusion (△H) of the melting temperature appearing below 200 ℃) is not particularly limited, but may be 0.1 to 10 J / g, and specifically, may be 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. When the Y value is within the above range, a crystalline polyester resin having a desired degree of crystallinity can be provided.

[0044] According to the present invention, the crystalline polyester resin comprises a diol repeating unit derived from a diol component. The above diol component is not particularly limited as long as it is a commonly known diol component, but specifically, bis-2-hydroxyethyl terephthalate, isosorbide, neopentyl glycol, ethylene glycol, diethylene glycol, cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD), 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, It may include at least one (e.g., at least two, at least three, at least four, or at least five) selected from the group consisting of 1,4-cyclohexanediol, 4-(hydroxymethyl)cyclohexylmethyl-4-(hydroxymethyl)cyclohexanecarboxylate, 4-(4-(hydroxymethyl)cyclohexylmethoxymethyl)cyclohexylmethanol, recycled bis-2-hydroxyethyl terephthalate, recycled isosorbide, recycled neopentylglycol, recycled ethylene glycol, recycled diethylene glycol, recycled cyclohexanedimethanol, and recycled 2,2,4,4-tetramethyl-1,3-cyclobutanediol (r-TMCD).

[0045] 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 above diol 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.

[0046] More specifically, the diol component may include at least one selected from the group consisting of a first diol component comprising ethylene glycol (EG), recycled ethylene glycol (r-EG), or a combination thereof; a second diol component comprising bis-2-hydroxyethyl terephthalate (BHET), recycled 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), recycled isosorbide (r-ISB), recycled neopentyl glycol (r-NPG), recycled diethylene glycol (r-DEG), recycled cyclohexanedimethanol (r-CHDM), or a combination thereof.

[0047] The amount of the first diol component used (amount added during reaction) is not particularly limited, but may be 50 to 99 mol%, 60 to 99 mol%, 70 to 99 mol%, 70 to 98 mol%, 75 to 98 mol%, 75 to 97 mol%, or 80 to 90 mol%, based on the total mol% of the diol component. Accordingly, the crystalline polyester resin may include a repeating unit (a) derived from the first diol component. When the amount of the first diol component used is within the above range, a crystalline polyester resin having excellent basic physical properties can be economically manufactured.

[0048] The amount of the second diol component used (amount added during reaction) is not particularly limited, but may be 5 to 99 mol%, 5.5 to 95 mol%, 10 to 90 mol%, 15 to 80 mol%, 20 to 80 mol%, 25 to 75 mol%, or 30 to 70 mol% based on the total mol% of the diol component. Accordingly, the crystalline polyester resin may include a repeating unit (b) derived from the second diol component. When the amount of the second diol component used is within the above range, a crystalline polyester resin having a required level of viscosity can be produced.

[0049] 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 a repeating unit (c) derived from the third diol component. When the amount of the third diol component used is within the above range, a crystalline polyester resin having excellent processability in addition to basic physical properties can be manufactured.

[0050] For example, considering the basic physical properties and processability of the crystalline polyester resin, the amount of isosorbide or regenerated 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 regenerated 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 recycled cyclohexanedimethanol among the third diol components may be 0 to 14 mol%, 1 to 12 mol%, 2 to 10 mol%, or 3 to 9 mol% based on the total mol% of the diol components.

[0051] The above crystalline polyester resin contains 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, terephthalic acid, isophthalic acid, dimethyl isophthalate, phthalic acid, 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, isodecylsuccinic acid, maleic acid, maleic anhydride, fumaric acid, adipic acid, glutaric acid, azelaic acid, regenerated terephthalic acid, regenerated dimethyl terephthalate, regenerated It may include at least one selected from the group consisting of isophthalic acid and recycled phthalic acid.

[0052] 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 products to a commonly known depolymerization process, but are not limited thereto.

[0053] More specifically, the dicarboxylic acid component may include at least one selected from the group consisting of a first dicarboxylic acid component including terephthalic acid (TPA), dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate (DMT), recycled terephthalic acid (r-TPA), recycled dimethyl terephthalate (r-DMT), or a combination thereof; and a second dicarboxylic acid component including 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, recycled isophthalic acid, recycled phthalic acid, or a combination thereof.

[0054] The amount of the first dicarboxylic acid component used (the amount added during the reaction) is not particularly limited, but may be 95 mol% or more, 96 mol% or more, 97 mol% or more, 98 mol% or more, or 99 mol% or more (e.g., 95 to 100 mol%, more than 95 to 100 mol%, 96 to 99.5 mol%, 97 to 99 mol%, or 98 to 98.5 mol%) based on the total mol% of the dicarboxylic acid component. Accordingly, the crystalline polyester resin may include a repeating unit (z) derived from the first dicarboxylic acid component.

[0055] The amount of the second dicarboxylic acid component used (amount added during reaction) is not particularly limited, but may be 5 mol% or less, 4 mol% or less, 3 mol% or less, 2 mol% or less, or 1 mol% or less (e.g., 0 to 5 mol%, more than 0 to 4.5 mol%, 0.5 to 4 mol%, 1 to 3 mol%, or 1.5 to 2 mol%) based on the total mol% of the dicarboxylic acid component. Accordingly, the crystalline polyester resin may include a repeating unit (w) derived from the second dicarboxylic acid component.

[0056] According to the present invention, the crystalline polyester resin may further include a repeating unit (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 unit (A) introduced into a side chain of the main chain or may have a graft polymerization structure by the repeating unit (A), thereby having a high molecular weight and high crystallinity.

[0057] The content of the repeating unit (A) included in the crystalline polyester resin is not particularly limited, but may be 0.001 to 15 wt%, 0.005 to 13 wt%, 0.01 to 12 wt%, 0.02 to 10 wt%, or 0.03 to 5 wt% based on the total weight% of the diol repeating unit.

[0058] The branching agent is not particularly limited, but may be specifically trimellitic acid, trimellitic anhydride, trimellitic anhydride, trimethylol propane, or a combination thereof.

[0059] The crystalline polyester resin may have an intrinsic viscosity (IV) (@35°C) of 0.5 to 1.3 dl / g. Specifically, the intrinsic viscosity (IV) of the crystalline polyester resin may be 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, 0.6 to 1.25 dl / g, or 0.5 to 0.86 dl / g at 35°C.

[0060] The crystalline polyester resin may have a fusion ratio of 5% or less according to the following formula 4. 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%), thereby greatly increasing the productivity of the solid-state polymerized polyester resin.

[0061] [Formula 4] C f = (C1 / C T ) × 100

[0062] In the above equation 4,

[0063] C T is the total weight of the above crystalline polyester resin produced per unit time (1 hr),

[0064] C1 is the weight of the fused material generated per ton of the above-mentioned crystalline polyester resin produced,

[0065] The above-mentioned fusion material is a material that cannot pass through a vibrator having a 12.5 mm mesh.

[0066] Meanwhile, the crystalline polyester resin may have a state (form) such as chips, pellets, or powder.

[0067] Additionally, the crystalline polyester resin may be a homopolymer or a copolymer.

[0068] According to the present invention, the polyester resin (solid-state polymerized polyester resin) manufactured by solid-state polymerizing the crystalline polyester resin may have an intrinsic viscosity (IV) (@35°C) of 0.5 to 1.5 dl / g. Specifically, the intrinsic viscosity (IV) of the solid-state polymerized polyester resin may be 0.6 to 1.48 dl / g, 0.65 to 1.46 dl / g, 0.68 to 1.43 dl / g, 0.7 to 1.4 dl / g, 0.74 to 1.35 dl / g, 0.78 to 1.3 dl / g, or 0.8 to 1.25 dl / g at 35°C.

[0069] In addition, the solid-state polymerized polyester resin may have an intrinsic viscosity increase rate of 1 to 6% according to the following formula 2. Specifically, the intrinsic viscosity increase rate may be 1.1 to 5.8%, 1.2 to 5.5%, 1.5 to 5.3%, 1.8 to 5%, 2 to 4.8%, 2.4 to 4.5%, 2.8 to 4.3%, 3 to 4.2%, or 3.4 to 4.1%.

[0070] [Formula 2] Intrinsic viscosity increase rate = {(IV s - IV c ) / H s} × 100

[0071] In the above equation 2,

[0072] IV s is the intrinsic viscosity of the above solid-phase polymerized polyester resin,

[0073] IV c is the intrinsic viscosity of the above crystalline polyester resin,

[0074] H sis the solid-state polymerization reaction time of the above-mentioned crystalline polyester resin.

[0075] According to the present invention, since the solid-state polymerized polyester resin is manufactured by solid-state polymerizing the crystalline polyester resin and has an optimized crystallinity, the occurrence of fusion during the manufacturing process can be minimized, thereby exhibiting excellent productivity. For example, the solid-state polymerized polyester resin may have a total fusion ratio of less than 10% according to the following formula 3. Specifically, the total fusion ratio may be 0 to 9.5%, greater than 0 to 9%, greater than 0 to 8.5%, 0.01 to 8%, 0.01 to 7.5%, 0.05 to 7%, 0.1 to 6.5%, 0.5 to 6%, 1 to 5.5%, 1.5 to 5%, or 2 to 4.5%. The above total fusion ratio can be calculated by continuously conducting a manufacturing process of the above crystalline polyester resin and the above solid-state polymerized polyester resin.

[0076] [Formula 3] Total fusion ratio (%) = C f + S f

[0077] In the above equation 3,

[0078] C f is the fusion ratio of the crystalline polyester resin according to the following formula 4,

[0079] S f is the fusion ratio of the above solid-state polymerized polyester resin according to the following formula 5,

[0080] [Formula 4] C f = (C1 / C T ) × 100

[0081] [Formula 5] S f = (S1 / S T ) × 100

[0082] In the above equations 4 and 5,

[0083] C Tis the total weight of the above crystalline polyester resin produced per unit time (1 hr),

[0084] C1 is the weight of the fused material generated per ton of the above-mentioned crystalline polyester resin produced,

[0085] S T is the total weight of the above solid polymerized polyester resin produced per unit time (1 hr),

[0086] S1 is the weight of the fused material generated per ton of the above-mentioned solid polymerized polyester resin produced,

[0087] The above-mentioned fusion product (fusion product of crystalline polyester resin and / or fusion product of solid-state polymerized polyester resin) is a material that cannot pass through a vibrator having a 12.5 mm mesh.

[0088] In addition, since the above-mentioned solid-state polymerized polyester resin can be manufactured from the above-mentioned crystalline polyester resin and have a crystallinity level equivalent to that of products such as PET bottles, even if an article manufactured using the above-mentioned solid-state polymerized polyester resin (e.g., a film label) is put into a recycling process in a state combined with a used waste product, the recycling process can be carried out efficiently.

[0089] The solid-state polymerized polyester resin may be a homopolymer or a copolymer. Specifically, the solid-state polymerized 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).

[0090]

[0091] Method for producing a solid-phase polymerized polyester resin

[0092] The method for producing a solid-state polymerized polyester resin according to the present invention comprises: (1) a step of polymerizing a diol component and a dicarboxylic acid component to produce a polyester resin; (2) a step of crystallizing the polyester resin at least once to produce a crystalline polyester resin; and (3) a step of solid-state polymerizing the crystalline polyester resin. When the crystalline polyester resin produced through the steps (1) and (2) is heated to 280°C at a scan rate of 10°C / min and analyzed by differential scanning calorimetry (DSC), the following equation 1 is satisfied.

[0093] The manufacturing method according to the present invention obtains a crystalline polyester resin satisfying the following formula 1 by controlling the crystallization temperature of the polyester resin stepwise in the step (2) above, and manufactures a polyester resin by solid-state polymerization of the obtained crystalline polyester resin, thereby obtaining a polyester resin (solid-state polymerized polyester resin) having excellent overall physical properties and productivity, which will be described in detail with reference to Fig. 1 as follows. Here, a detailed description of the following formula 1 is omitted because it is the same as described above.

[0094] [Formula 1] 4 < X / Y < 70

[0095] In the above equation 1,

[0096] X is the sum of the heat of fusion (△H) of the melting temperature that appeared at 200 ℃ or higher during the DSC analysis of the above crystalline polyester resin,

[0097] Y is the sum of the heat of fusion (△H) of the melting temperature that appeared below 200 ℃ during the DSC analysis of the above crystalline polyester resin.

[0098]

[0099] Step (1): Preparation of polyester resin

[0100] The above step (1) is a step of manufacturing a polyester resin (e.g., a polyester resin having an amorphous surface) by subjecting a diol component and a dicarboxylic acid component to an esterification reaction (or esterification exchange reaction) to obtain a reactant (e.g., an oligomer), and then subjecting the reactant to a condensation polymerization reaction. A detailed description of the diol component and the dicarboxylic acid component is the same as described above, and thus is omitted.

[0101] The conditions under which the esterification reaction (or esterification transesterification reaction) is performed may not be particularly limited. Specifically, the temperature at which the esterification reaction is performed may be 220 to 300°C, 225 to 290°C, 230 to 280°C, 235 to 275°C, 240 to 270°C, or 245 to 265°C. In addition, the pressure at which the esterification reaction is performed may be 0.05 to 5 kgf / cm2, 0.1 to 4 kgf / cm2, 0.1 to 3 kgf / cm2, 0.5 to 2.5 kgf / cm2, or 1 to 2 kgf / cm2. As the esterification reaction is performed under the above conditions, a reactant (oligomer) having a desired molecular weight can be obtained in high yield while minimizing the production of side products.

[0102] In the reactor where the above esterification reaction (or esterification exchange reaction) takes place, one or more additives selected from the group consisting of a catalyst, a coloring agent, a crystallizer, an antioxidant, and a branching agent may be added together with the above diol component and the above dicarboxylic acid component.

[0103] As the catalyst, sodium or magnesium methylate; acetate, borate, fatty acid salt, or carbonate of Ge, Zn, Cd, Mn, Co, Ca, Ba, etc.; or oxides or hydrates of Ge, Mg, Pb, Mn, Ti, Sb, Sn, Al, etc. can be used. For example, as the catalyst, 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 can be used.

[0104] As the above coloring agent, organic compounds such as cobalt compounds, anthraquionone compounds, perinone compounds, azo compounds, and methine compounds (e.g., cobalt acetate, cobalt propionate, Clariant's Polysynthren Blue RLS toner, Clariant's Solvaperm Red BB toner) can be used.

[0105] As the above crystallizing agent, a crystal nucleating agent, an ultraviolet absorber, a polyolefin resin, a polyamide resin, etc. can be used.

[0106] As the above antioxidant, hindered phenol compounds, phosphite compounds, thioether compounds, etc. can be used.

[0107] As the branching agent, trimellitic acid, trimellitic anhydride, trimethylol propane, or a combination thereof may be used.

[0108] The reactants obtained through the above esterification reaction (or esterification transesterification reaction) may then be introduced into a polycondensation reactor to perform 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°C, 245 to 310°C, 250 to 300°C, 255 to 295°C, or 265 to 290°C. In addition, the pressure at which the polycondensation reaction is performed may be a pressure (reduced pressure) lower than atmospheric pressure (e.g., 1 atm). As the polycondensation reaction is performed under the above conditions, a polyester resin (polymer) with excellent processability can be efficiently produced.

[0109] Thereafter, the polyester resin obtained through the above-described condensation polymerization reaction can be pelletized through processes such as extrusion and underwater cutting. That is, the polyester resin can be a polyester resin pellet.

[0110]

[0111] The polyester resin (e.g., polyester resin pellets) obtained through step (1) as described above may be subjected to step (2) described below to obtain the desired degree of crystallinity. Here, the polyester resin may be subjected to a drying process before step (2) described below. That is, the method for producing a solid-state polymerized polyester resin according to the present invention may further include a step of drying the polyester resin obtained in step (1) between steps (1) and (2) in order to further optimize the degree of crystallinity of the crystalline polyester resin.

[0112] The drying of the polyester resin can be carried out in a commonly 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°C (specifically, 40 to 85°C, 45 to 85°C, 50 to 80°C, or 50 to 70°C) for 3 to 12 hours (specifically, 4 to 12 hours, or 5 to 11 hours).

[0113]

[0114] Step (2): Preparation of crystalline polyester resin through crystallization

[0115] The above step (2) is a step of crystallizing the polyester resin obtained through the above step (1) at least once. Specifically, the crystallization of the polyester resin may be performed at least twice, at least three times, or at least four times.

[0116] According to the present invention, the temperature at which crystallization of the polyester resin is performed is not particularly limited, but may be 105 to 185°C (specifically, 106 to 184°C, 107 to 183°C, 108 to 182°C, 109 to 181°C, or 110 to 180°C). As the crystallization is performed within the above range, a crystalline polyester resin with an optimized degree of crystallinity can be manufactured while minimizing fusion between polyester resins during the crystallization process.

[0117] According to the present invention, the crystallization of the polyester resin can be performed under temperature conditions that increase step by step. Specifically, when the crystallization of the polyester resin is performed in the first and second stages, the second crystallization temperature (T2) can 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.

[0118] According to the present invention, the step (2) may specifically include: (2-1) a step of first crystallizing the polyester resin of the step (1) at 105 to 135°C (specifically, 108 to 133°C, or 110 to 130°C); (2-2) a step of second crystallizing the polyester resin crystallized in the step (2-1) at 120 to 175°C (specifically, 120 to 170°C, or 125 to 155°C); and (2-3) a step of third crystallizing the polyester resin crystallized in the step (2-2) at 140 to 180°C (specifically, 145 to 180°C, or 150 to 180°C). As the crystallization is carried out in three stages and each crystallization temperature is controlled within the specific range, crystals are uniformly formed on the inside and outside of the polyester resin, while adhesion between polyester resins due to surface melting during the crystallization process can be minimized. Accordingly, a crystalline polyester resin with an optimized crystallinity can be efficiently (with improved productivity) manufactured.

[0119] Meanwhile, the first crystallization temperature, the second crystallization temperature, and the third crystallization temperature may be different from each other.

[0120] Additionally, the crystallization can be performed under conditions of normal pressure or reduced pressure, and a commonly known fluidizing agent can be added to the crystallization process to increase the fluidity of the polyester resin (polyester resin pellets).

[0121]

[0122] Step (3): Solid-state polymerization

[0123] The above step (3) is a step of manufacturing a polyester resin (solid-state polymerized polyester resin) by solid-state polymerizing the crystalline polyester resin obtained through the above steps (1) and (2). Through the above solid-state polymerization, a solid-state polymerized polyester resin having a required level of intrinsic viscosity and molecular weight can be provided.

[0124] The conditions under which the above solid-state polymerization is performed may not be particularly limited. Specifically, the temperature at which the above solid-state polymerization is performed may be 170 to 260°C, 180 to 250°C, 185 to 245°C, 190 to 240°C, or 195 to 240°C. In addition, the pressure under which the above solid-state polymerization is performed may be a pressure (reduced pressure) lower than atmospheric pressure (e.g., 1 atm). When the above solid-state polymerization is performed under the above conditions, a solid-state polymerized polyester resin having a required level of intrinsic viscosity can be efficiently produced.

[0125]

[0126] article

[0127] The article according to the present invention is manufactured from the above-described solid-state polymerized polyester resin. Specifically, the article according to the present invention may be manufactured by introducing the above-described solid-state polymerized polyester resin into a molding process such as injection molding, extrusion molding, extrusion blow molding, injection blow molding, pressure molding, or vacuum molding. For example, the article may be an injection-molded product manufactured through injection molding.

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

[0129] Hereinafter, the present invention will be described in more detail through examples. However, the following examples are intended only to illustrate the present invention and are not intended to limit the scope of the present invention.

[0130]

[0131] [Example 1]

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

[0133] Into a 10 ㎥ reactor connected to a column and a water-cooled condenser, 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 charged. Next, after raising the temperature of the reactor to 265 ℃, an esterification reaction (ES) was performed at 265 ℃ under a pressure of 2 kgf / ㎠ to obtain a transparent reactant.

[0134] Next, the reactants were transferred to a polycondensation reactor, and a polycondensation reaction (PA) was performed at 270°C while maintaining the pressure of the polycondensation reactor lower than atmospheric pressure. When the intrinsic viscosity (melt intrinsic viscosity) (IV) of the reactants inside the polycondensation reactor reached 0.60 dl / g, the reactants were discharged outside the polycondensation reactor and stranded. Subsequently, after solidifying with a cooling liquid, a pelletizing process was performed so that the average weight of 100 cut pellets was approximately 1.0 to 2.5 g, thereby obtaining polyester resin pellets.

[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 polyester resin pellets, which were dried as described above, were fed into a crystallization reactor at a rate of 1 ton per hour (feeding rate: 1 ton / hr), and a crystallization process was performed three times while gradually increasing the temperature according to the moving position of the polyester resin pellets, thereby obtaining a crystalline polyester resin. At this time, the first crystallization of the polyester resin pellets was performed at 110°C, the second crystallization of the first-crystallized polyester resin pellets was performed at 130°C, and the third crystallization of the second-crystallized polyester resin pellets was performed at 165°C.

[0138] Step (3): Preparation of solid-phase polymerized polyester resin

[0139] The polyester resin pellets obtained through the above-mentioned third crystallization were introduced into a solid-state polymerization reactor, and the temperature of the solid-state polymerization reactor was gradually increased to 205°C under a nitrogen atmosphere, and then the solid-state polymerization reaction was performed at 205°C. The solid-state polymerization reaction was performed for 12 hours, and the obtained product was discharged from the solid-state polymerization reactor, thereby producing a solid-state polymerized polyester resin (copolymer).

[0140]

[0141] [Example 2]

[0142] Step (1): Preparation of polyester resin

[0143] 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), a Ti catalyst (1.0 kg), phosphoric acid (1.5 kg), blue toner (0.01 kg), and red toner (0.01 kg) were charged into a 10 ㎥ reactor connected to a column and a water-cooled condenser. Next, the temperature of the reactor was raised to 255 ℃, and an esterification reaction (ES) was performed at 255 ℃ under a pressure of 1 kgf / ㎠ to obtain a transparent reactant.

[0144] Next, the reactants were transferred to a polycondensation reactor, and a polycondensation reaction (PA) was performed at 285°C while maintaining the pressure of the polycondensation reactor lower than atmospheric pressure. When the intrinsic viscosity (melt intrinsic viscosity) (IV) of the reactants inside the polycondensation reactor reached 0.50 dl / g, the reactants were discharged outside the polycondensation reactor and stranded. Subsequently, after solidifying with a cooling liquid, a pelletizing process was performed so that the average weight of 100 cut pellets was approximately 1.0 to 2.5 g, thereby obtaining polyester resin pellets.

[0145] Step (2): Preparation of crystalline polyester resin

[0146] The polyester resin pellets obtained above (not dried) were fed into a crystallization reactor at a rate of 1 ton per hour (feeding rate: 1 ton / hr), and a crystallization process was performed three times while gradually increasing the temperature according to the moving position of the polyester resin pellets, thereby obtaining a crystalline polyester resin. At this time, the first crystallization of the polyester resin pellets was performed at 115°C, the second crystallization of the first-crystallized polyester resin pellets was performed at 120°C, and the third crystallization of the second-crystallized polyester resin pellets was performed at 160°C.

[0147] Step (3): Preparation of solid-phase polymerized polyester resin

[0148] The polyester resin pellets obtained through the above-mentioned third crystallization were introduced into a solid-state polymerization reactor, and the temperature of the solid-state polymerization reactor was gradually increased to 210°C under a nitrogen atmosphere, and then the solid-state polymerization reaction was performed at 210°C. The solid-state polymerization reaction was performed for 12 hours, and the obtained product was discharged from the solid-state polymerization reactor, thereby producing a solid-state polymerized polyester resin (copolymer).

[0149]

[0150] [Example 3]

[0151] Step (1): Preparation of polyester resin

[0152] 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 charged into a 10 ㎥ reactor connected to a column and a water-cooled condenser. Next, the temperature of the reactor was raised to 260 ℃, and an esterification reaction (ES) was performed at 260 ℃ under a pressure of 1 kgf / ㎠ to obtain a transparent reactant.

[0153] Next, the reactants were transferred to a polycondensation reactor, and a polycondensation reaction (PA) was performed at 275°C while maintaining the pressure of the polycondensation reactor lower than atmospheric pressure. When the intrinsic viscosity (melt intrinsic viscosity) (IV) of the reactants inside the polycondensation reactor reached 0.78 dl / g, the reactants were discharged outside the polycondensation reactor and stranded. Subsequently, after solidifying with a cooling liquid, a pelletizing process was performed so that the average weight of 100 cut pellets was approximately 1.0 to 2.5 g, thereby obtaining polyester resin pellets.

[0154] Afterwards, the obtained polyester resin pellets were dried at 40°C for 9 hours before crystallization.

[0155] Step (2): Preparation of crystalline polyester resin

[0156] The polyester resin pellets, which were dried as described above, were fed into a crystallization reactor at a rate of 1 ton per hour (feeding rate: 1 ton / hr), and a crystallization process was performed three times while gradually increasing the temperature according to the moving position of the polyester resin pellets, thereby obtaining a crystalline polyester resin. At this time, the first crystallization of the polyester resin pellets was performed at 120°C, the second crystallization of the first-crystallized polyester resin pellets was performed at 135°C, and the third crystallization of the second-crystallized polyester resin pellets was performed at 150°C.

[0157] Step (3): Preparation of solid-phase polymerized polyester resin

[0158] The polyester resin pellets obtained through the above-mentioned third crystallization were introduced into a solid-state polymerization reactor, and the temperature of the solid-state polymerization reactor was gradually increased to 215°C under a nitrogen atmosphere, and then the solid-state polymerization reaction was performed at 215°C. The solid-state polymerization reaction was performed for 12 hours, and the obtained product was discharged from the solid-state polymerization reactor, thereby producing a solid-state polymerized polyester resin (copolymer).

[0159]

[0160] [Example 4]

[0161] Step (1): Preparation of polyester resin

[0162] Into a 10 ㎥ reactor connected to a column and a water-cooled condenser, 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 charged. Next, after raising the temperature of the reactor to 250 ℃, an esterification reaction (ES) was performed at 250 ℃ under a pressure of 1 kgf / ㎠ to obtain a transparent reactant.

[0163] Next, the reactants were transferred to a polycondensation reactor, and a polycondensation reaction (PA) was performed at 285°C while maintaining the pressure of the polycondensation reactor lower than atmospheric pressure. When the intrinsic viscosity (melt intrinsic viscosity) (IV) of the reactants inside the polycondensation reactor reached 0.85 dl / g, the reactants were discharged outside the polycondensation reactor and stranded. Subsequently, after solidifying with a cooling liquid, a pelletizing process was performed so that the average weight of 100 cut pellets was approximately 1.0 to 2.5 g, thereby obtaining polyester resin pellets.

[0164] Step (2): Preparation of crystalline polyester resin

[0165] The polyester resin pellets obtained above (not dried) were fed into a crystallization reactor at a rate of 1 ton per hour (feeding rate: 1 ton / hr), and a crystallization process was performed three times while gradually increasing the temperature according to the moving position of the polyester resin pellets, thereby obtaining a crystalline polyester resin. At this time, the first crystallization of the polyester resin pellets was performed at 110°C, the second crystallization of the first-crystallized polyester resin pellets was performed at 170°C, and the third crystallization of the second-crystallized polyester resin pellets was performed at 180°C.

[0166] Step (3): Preparation of solid-phase polymerized polyester resin

[0167] The polyester resin pellets obtained through the above-mentioned third crystallization were introduced into a solid-state polymerization reactor, and the temperature of the solid-state polymerization reactor was gradually increased to 210°C under a nitrogen atmosphere, and then the solid-state polymerization reaction was performed at 210°C. The solid-state polymerization reaction was performed for 12 hours, and the obtained product was discharged from the solid-state polymerization reactor, thereby producing a solid-state polymerized polyester resin (copolymer).

[0168]

[0169] [Example 5]

[0170] Step (1): Preparation of polyester resin

[0171] Polyester resin pellets were obtained through the same process as in Example 1.

[0172] Afterwards, the obtained polyester resin pellets were dried at 55°C for 4 hours before crystallization.

[0173] Step (2): Preparation of crystalline polyester resin

[0174] The polyester resin pellets, which were dried as described above, were fed into a crystallization reactor at a rate of 1 ton per hour (feeding rate: 1 ton / hr), and a crystallization process was performed three times while gradually increasing the temperature according to the moving position of the polyester resin pellets, thereby obtaining a crystalline polyester resin. At this time, the first crystallization of the polyester resin pellets was performed at 125°C, the second crystallization of the first-crystallized polyester resin pellets was performed at 130°C, and the third crystallization of the second-crystallized polyester resin pellets was performed at 140°C.

[0175] Step (3): Preparation of solid-phase polymerized polyester resin

[0176] The polyester resin pellets obtained through the above-mentioned third crystallization were introduced into a solid-state polymerization reactor, and the temperature of the solid-state polymerization reactor was gradually increased to 195°C under a nitrogen atmosphere, and then the solid-state polymerization reaction was performed at 195°C. The solid-state polymerization reaction was performed for 12 hours, and the obtained product was discharged from the solid-state polymerization reactor, thereby producing a solid-state polymerized polyester resin (copolymer).

[0177]

[0178] [Example 6]

[0179] Step (1): Preparation of polyester resin

[0180] Polyester resin pellets were obtained through the same process as in Example 3.

[0181] Step (2): Preparation of crystalline polyester resin

[0182] The polyester resin pellets obtained above (not dried) were fed into a crystallization reactor at a rate of 1 ton per hour (feeding rate: 1 ton / hr), and a crystallization process was performed three times while gradually increasing the temperature according to the moving position of the polyester resin pellets, thereby obtaining a crystalline polyester resin. At this time, the first crystallization of the polyester resin pellets was performed at 130°C, the second crystallization of the first-crystallized polyester resin pellets was performed at 150°C, and the third crystallization of the second-crystallized polyester resin pellets was performed at 180°C.

[0183] Step (3): Preparation of solid-phase polymerized polyester resin

[0184] The polyester resin pellets obtained through the above-mentioned third crystallization were introduced into a solid-state polymerization reactor, and the temperature of the solid-state polymerization reactor was gradually increased to 215°C under a nitrogen atmosphere, and then the solid-state polymerization reaction was performed at 215°C. The solid-state polymerization reaction was performed for 12 hours, and the obtained product was discharged from the solid-state polymerization reactor, thereby producing a solid-state polymerized polyester resin (copolymer).

[0185]

[0186] [Comparative Example 1]

[0187] Step (1): Preparation of polyester resin

[0188] Polyester resin pellets were obtained through the same process as in Example 3.

[0189] Step (2): Preparation of crystalline polyester resin

[0190] The polyester resin pellets obtained above (not dried) were fed into a crystallization reactor at a rate of 1 ton per hour (feeding rate: 1 ton / hr), and a crystallization process was performed three times while gradually increasing the temperature according to the moving position of the polyester resin pellets, thereby obtaining a crystalline polyester resin. At this time, the first crystallization of the polyester resin pellets was performed at 160°C, the second crystallization of the first-crystallized polyester resin pellets was performed at 140°C, and the third crystallization of the second-crystallized polyester resin pellets was performed at 120°C.

[0191] Step (3): Preparation of solid-phase polymerized polyester resin

[0192] The polyester resin pellets obtained through the above-mentioned third crystallization were introduced into a solid-state polymerization reactor, and the temperature of the solid-state polymerization reactor was gradually increased to 215°C under a nitrogen atmosphere, and then the solid-state polymerization reaction was performed at 215°C. The solid-state polymerization reaction was performed for 12 hours, and the obtained product was discharged from the solid-state polymerization reactor, thereby producing a solid-state polymerized polyester resin (copolymer).

[0193]

[0194] [Comparative Example 2]

[0195] Step (1): Preparation of polyester resin

[0196] Polyester resin pellets were obtained through the same process as in Example 3.

[0197] Afterwards, the obtained polyester resin pellets were dried at 55°C for 3 hours before crystallization.

[0198] Step (2): Preparation of crystalline polyester resin

[0199] The polyester resin pellets, which were dried as described above, were fed into a crystallization reactor at a rate of 1 ton per hour (feeding rate: 1 ton / hr), and a crystallization process was performed three times while gradually increasing the temperature according to the moving position of the polyester resin pellets, thereby obtaining a crystalline polyester resin. At this time, the first crystallization of the polyester resin pellets was performed at 140°C, the second crystallization of the first-crystallized polyester resin pellets was performed at 160°C, and the third crystallization of the second-crystallized polyester resin pellets was performed at 200°C.

[0200] Step (3): Preparation of solid-phase polymerized polyester resin

[0201] The polyester resin pellets obtained through the above-mentioned third crystallization were introduced into a solid-state polymerization reactor, and the temperature of the solid-state polymerization reactor was gradually increased to 215°C under a nitrogen atmosphere, and then the solid-state polymerization reaction was performed at 215°C. The solid-state polymerization reaction was performed for 12 hours, and the obtained product was discharged from the solid-state polymerization reactor, thereby producing a solid-state polymerized polyester resin (copolymer).

[0202]

[0203] [Comparative Example 3]

[0204] Step (1): Preparation of polyester resin

[0205] Polyester resin pellets were obtained through the same process as in Example 4.

[0206] Step (2): Preparation of crystalline polyester resin

[0207] The polyester resin pellets obtained above (not dried) were fed into a crystallization reactor at a rate of 1 ton per hour (feeding rate: 1 ton / hr), and a crystallization process was performed while gradually increasing the temperature according to the moving position of the polyester resin pellets, thereby obtaining a crystalline polyester resin. At this time, the first crystallization of the polyester resin pellets was performed at 100°C, the second crystallization of the first-crystallized polyester resin pellets was performed at 160°C, and the third crystallization of the second-crystallized polyester resin pellets was performed at 190°C.

[0208] Step (3): Preparation of solid-phase polymerized polyester resin

[0209] The polyester resin pellets obtained through the above-mentioned third crystallization were introduced into a solid-state polymerization reactor, and the temperature of the solid-state polymerization reactor was gradually increased to 190°C under a nitrogen atmosphere, and then the solid-state polymerization reaction was performed at 190°C. The solid-state polymerization reaction was performed for 12 hours, and the obtained product was discharged from the solid-state polymerization reactor, thereby producing a solid-state polymerized polyester resin (copolymer).

[0210]

[0211] [Comparative Example 4]

[0212] Step (1): Preparation of polyester resin

[0213] Polyester resin pellets were obtained through the same process as in Example 1.

[0214] Step (2): Preparation of crystalline polyester resin

[0215] The polyester resin pellets obtained above (not dried) were fed into a crystallization reactor at a rate of 1 ton per hour (feeding rate: 1 ton / hr) and only primary crystallization was performed at 170°C to obtain a crystalline polyester resin.

[0216] As only the above primary crystallization was performed, severe fusion occurred between polyester resin pellets, and as crystallization was not sufficient, the subsequent solid-state polymerization reaction could not proceed.

[0217]

[0218] [Comparative Example 5]

[0219] Step (1): Preparation of polyester resin

[0220] Polyester resin pellets were obtained through the same process as in Example 3.

[0221] Afterwards, the obtained polyester resin pellets were dried at 40°C for 3 hours before crystallization.

[0222] Step (2): Preparation of crystalline polyester resin

[0223] The polyester resin pellets, which were dried as described above, were fed into a crystallization reactor at a rate of 1 ton per hour (feeding rate: 1 ton / hr), and a crystallization process was performed twice while gradually increasing the temperature according to the moving position of the polyester resin pellets, thereby obtaining a crystalline polyester resin. At this time, the first crystallization of the polyester resin pellets was performed at 70°C, and the second crystallization of the first-crystallized polyester resin pellets was performed at 160°C.

[0224] Step (3): Preparation of solid-phase polymerized polyester resin

[0225] The polyester resin pellets obtained through the above secondary crystallization were introduced into a solid-state polymerization reactor, and the temperature of the solid-state polymerization reactor was gradually increased to 210°C under a nitrogen atmosphere, after which the solid-state polymerization reaction was performed at 210°C. At this time, in the solid-state polymerization reaction, fusion occurred between most of the reactants, making it impossible to obtain a solid-state polymerized polyester resin for which the solid-state intrinsic viscosity (IV) could be measured.

[0226]

[0227] [Example 1]

[0228] The crystalline polyester resins manufactured in Examples 1 to 6 and Comparative Examples 1 to 5 were analyzed by differential scanning calorimetry (DSC) to determine the melting temperature (T m ) was confirmed to appear, and the results are shown in Tables 1 and 2 below. The DSC analysis was performed as follows.

[0229] DSC analysis device: Mettler Toledo's DSC 1 model was used.

[0230] Sample preparation: Approximately 6 to 10 mg of crystalline polyester resin was taken and filled into an aluminum pan.

[0231] Scan conditions: DSC curves were obtained by heating from room temperature to 280 ℃ at a rate of 10 ℃ / min and annealing at 280 ℃ for 3 minutes.

[0232] Melting temperature (T m ) Verification: The temperature showing an endothermic peak during the heating process in the obtained DSC curve was defined as the melting temperature.

[0233] Afterwards, the melting temperature (T m ) was used to calculate the heat of fusion (△H) and the X / Y ratio (rounded to the second decimal place).

[0234]

[0235] [Example 2]

[0236] For the crystalline polyester resins and solid-state polymerized polyester resins manufactured in Examples 1 to 6 and Comparative Examples 1 to 5, respectively, the weight (kg) of the fused material generated per ton for the total production volume (kg / hr) was measured, and the total fusion ratio was calculated according to Equation 3 below, and the results are shown in Tables 1 and 2 below.

[0237] [Formula 3] Total fusion ratio (%) = Cf + S f

[0238] In the above equation 3,

[0239] C f is the fusion ratio of the crystalline polyester resin according to the following formula 4,

[0240] S f is the fusion ratio of the above solid-state polymerized polyester resin according to the following formula 5,

[0241] [Formula 4] C f = (C1 / C T ) × 100

[0242] [Formula 5] S f = (S1 / S T ) × 100

[0243] In the above equations 4 and 5,

[0244] C T is the total weight of the above crystalline polyester resin produced per unit time (1 hr),

[0245] C1 is the weight of the fused material generated per ton of the above-mentioned crystalline polyester resin produced,

[0246] S T is the total weight of the above solid polymerized polyester resin produced per unit time (1 hr),

[0247] S1 is the weight of the fused material generated per ton of the above-mentioned solid polymerized polyester resin produced,

[0248] The above-mentioned fusion material is a material that cannot pass through a vibrator having a 12.5 mm mesh.

[0249]

[0250] [Example 3]

[0251] For the crystalline polyester resins and solid-state polymerized polyester resins manufactured in Examples 1 to 6 and Comparative Examples 1 to 5, respectively, the intrinsic viscosity increase rate was calculated according to Equation 2 below, and the results are shown in Tables 1 and 2 below. At this time, the intrinsic viscosity of each resin was measured at 35°C using a conventional method.

[0252] [Formula 2] Intrinsic viscosity increase rate = {(IV s - IV c ) / H s} × 100

[0253] In the above equation 2,

[0254] IV s is the intrinsic viscosity of the above solid-phase polymerized polyester resin,

[0255] IV c is the intrinsic viscosity of the above crystalline polyester resin,

[0256] H s is the solid-state polymerization reaction time of the above-mentioned crystalline polyester resin.

[0257]

[0258] Classification Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Crystallization temperature (℃) 1st crystallization 110 115 120 110 125 130 2nd crystallization 130 120 135 170 130 150 3rd crystallization 165 160 150 180 140 180 200 ℃ or less T m1-1 170.2165.9140.2155.2165.23180.2T m1-1 In △ H2.71.13.444.40.250.3T m1-2 -190.4--189.2-T m1-2 In △ H-6.5--0.5- △ Sum of H(Y)2.77.63.444.40.750.3200 ℃ or moreT m2 227.7230.62238.6230.1227.52235.1T m2 In △H25.3731.1337.5130.524.1320.3 △ Sum of H (X) 25.37 31.13 37.5 130.5 24.13 20.3 X / Y 9.4 4.11 0.9 6.9 32.26 7.7 Crystalline polyester resin fusion ratio (%) 10.5 0.5 342 Total fusion ratio (%) 2.9 3.9 2.7 4.4 8.5 6.0 Intrinsic viscosity increase rate (%) 3.2 2.5 3.5 5.0 1.3 4.0

[0259] Classification Comparison Example 1 Comparison Example 2 Comparison Example 3 Comparison Example 4 Comparison Example 5 Crystallization Temperature (℃) 1st crystallization 160 140 100 170 70 2nd crystallization 140 160 160-160 3rd crystallization 120 200 190--Less than 200 ℃ T m1-1 155.2--Fusion occurs between resin pellets (crystallization is impossible)-T m1-1 In △ H0.5T m1-2 -T m1-2 In △ H △ Sum of H (Y) 0.5200 ℃ or moreT m2-1 236.5-210.5234T m2-1 In △ H38.210.19.8T m2-2 -237.1237.1-T m2-2 In △ H35.525.5- △ H's sum (X) 38.2 35.5 35.6 9.8 X / Y 76.4 --- Crystalline polyester resin fusion ratio (%) 7 10 2 17 0 4 0 Total fusion ratio (%) 14.6 12.0 2 3.0 Not measurable Not measurable Intrinsic viscosity increase rate (%) 0.8 0.6 0.8 Not measurable Not measurable

[0260] Referring to Table 1 above, in Examples 1 to 6 according to the present invention, a solid-state polymerized polyester resin was manufactured using a crystalline polyester resin having a very low fusion ratio of 5% or less while the X / Y ratio was controlled within the range of the present invention, thereby showing a low total fusion ratio, and thus it can be confirmed that the productivity of the solid-state polymerized polyester resin is excellent. In addition, it can be confirmed that a solid-state polymerized polyester resin having the desired physical properties was obtained by showing a high intrinsic viscosity increase rate.

[0261] On the other hand, referring to Table 2 above, in Comparative Examples 1 to 5, it can be confirmed that the solid-state polymerized polyester resin was manufactured using a crystalline polyester resin that was not sufficiently crystallized or was over-crystallized, resulting in a high total fusion ratio, which significantly reduced the productivity of the solid-state polymerized polyester resin or made it impossible to manufacture the solid-state polymerized polyester resin.

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 is manufactured by solid-state polymerization, The above crystalline polyester resin is a solid-state polymerized polyester resin that satisfies the following equation 1 when analyzed by differential scanning calorimetry (DSC) at a scan rate of 10°C / min up to 280°C: [Formula 1] 4 < X / Y < 70 In the above equation 1, X is the sum of the heat of fusion (△H) of the melting temperature that appeared at 200 ℃ or higher during the DSC analysis of the above crystalline polyester resin, Y is the sum of the heat of fusion (△H) of the melting temperature that appeared below 200 ℃ during the DSC analysis of the above crystalline polyester resin.

2. In paragraph 1, The above crystalline polyester resin has two or more melting temperatures (T) during the DSC analysis. m ) is a solid-state polymerized polyester resin.

3. In paragraph 2, The melting temperature (T) of the above crystalline polyester resin m ) is a solid-state polymerized polyester resin having a temperature of 140 to 250°C.

4. In paragraph 1, A solid-state polymerized polyester resin having an intrinsic viscosity increase rate of 1 to 6% according to the following formula 2: [Formula 2] Intrinsic viscosity increase rate = {(IV s - IV c ) / H s } × 100 In the above equation 2, IV s is the intrinsic viscosity of the above solid-phase polymerized polyester resin, IV c is the intrinsic viscosity of the above crystalline polyester resin, H s is the solid-state polymerization reaction time of the above-mentioned crystalline polyester resin.

5. In paragraph 1, A solid-state polymerized polyester resin having a total fusion ratio of less than 10% according to the following formula 3: [Formula 3] Total fusion ratio (%) = C f + S f In the above equation 3, C f is the fusion ratio of the crystalline polyester resin according to the following formula 4, S f is the fusion ratio of the above solid-state polymerized polyester resin according to the following formula 5, [4] C f = (C1 / C T ) × 100 [Formula 5] S f = (S1 / S T ) × 100 In the above equations 4 and 5, C T is the total weight of the above crystalline polyester resin produced per unit time (1 hr), C1 is the weight of the fused material generated per ton of the above-mentioned crystalline polyester resin produced, S T is the total weight of the above solid polymerized polyester resin produced per unit time (1 hr), S1 is the weight of the fused material generated per ton of the above-mentioned solid polymerized polyester resin produced, The above-mentioned fusion material is a material that cannot pass through a vibrator having a 12.5 mm mesh.

6. In paragraph 1, The above dicarboxylic acid component comprises at least one selected from the group consisting of terephthalic acid, isophthalic acid, dimethyl isophthalate, phthalic acid, 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, isodecylsuccinic acid, maleic acid, maleic anhydride, fumaric acid, adipic acid, glutaric acid, azelaic acid, recycled terephthalic acid, recycled dimethyl terephthalate, recycled isophthalic acid, and recycled phthalic acid. High-performance polymerized polyester resin.

7. In paragraph 1, The above diol component is 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 solid-state polymerized polyester resin comprising at least one selected from the group consisting of 4-(hydroxymethyl)cyclohexylmethyl-4-(hydroxymethyl)cyclohexanecarboxylate, 4-(4-(hydroxymethyl)cyclohexylmethoxymethyl)cyclohexylmethanol, 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.

8. In paragraph 1, A solid-state polymerized polyester resin comprising at least one selected from the group consisting of a first diol component comprising ethylene glycol, recycled ethylene glycol, or a combination thereof; a second diol component comprising bis-2-hydroxyethyl terephthalate, recycled bis-2-hydroxyethyl terephthalate, or a combination thereof; and a third diol component comprising isosorbide, neopentyl glycol, diethylene glycol, cyclohexanedimethanol, recycled isosorbide, recycled neopentyl glycol, recycled diethylene glycol, recycled cyclohexanedimethanol, or a combination thereof.

9. In paragraph 8, A solid-state polymerized 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 component.

10. In paragraph 1, A solid-state polymerized polyester resin having an intrinsic viscosity (IV) of 0.5 to 1.5 dl / g.

11. In paragraph 1, A solid-state polymerized polyester resin, wherein the above-mentioned crystalline polyester resin further comprises a repeating unit derived from a branching agent having three or more functional groups.

12. In paragraph 11, A solid-state polymerized polyester resin, wherein the content of repeating units derived from the above branching agent is 0.001 to 15 wt% based on the total wt% of the diol repeating units. 13.(1) A step of manufacturing a polyester resin by polymerizing a diol component and a dicarboxylic acid component; (2) a step of crystallizing the polyester resin at least once to produce a crystalline polyester resin; and (3) comprising a step of solid-state polymerizing the above crystalline polyester resin, The above crystalline polyester resin is heated to 280°C at a scan rate of 10°C / min and analyzed by differential scanning calorimetry (DSC), and a method for producing a solid-state polymerized polyester resin satisfying the following equation 1: [Formula 1] 4 < X / Y < 70 In the above equation 1, X is the sum of the heat of fusion (△H) of the melting temperature that appeared at 200 ℃ or higher during the DSC analysis of the above crystalline polyester resin, Y is the sum of the heat of fusion (△H) of the melting temperature that appeared below 200 ℃ during the DSC analysis of the above crystalline polyester resin.

14. In paragraph 13, A method for producing a solid-state polymerized polyester resin, wherein crystallization of the polyester resin in the above step (2) is performed at a temperature range of 105 to 185°C.

15. In paragraph 13, A method for producing a solid-state polymerized polyester resin, wherein crystallization of the polyester resin in the above step (2) is performed under temperature conditions that increase step by step.

16. In paragraph 13, A method for producing a solid-state polymerized polyester resin, further comprising a step of drying the polyester resin obtained in step (1) before performing the above step (2).

17. An article manufactured from the solid-phase polymerized polyester resin of paragraph 1.

18. In paragraph 17, An article wherein the above article is an injection molded article.

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