Polyesteramide resin, method for producing the same, and biaxially oriented film containing the same

Abstract

The present invention relates to a polyesteramide resin, a method for producing the same, and a biaxially stretched film containing the same. Specifically, the present invention provides a polyesteramide resin having a diamine residue introduced therein together with a diacid residue and a diol residue, a method for producing the same, and a biaxially stretched film containing the same.

Description

[Technical Field]

[0001] Cross-reference with related applications This application claims priority under Korean Patent Application No. 10-2021-0059158 dated May 7, 2021, and all content disclosed in the said Korean Patent Application is incorporated herein by reference.

[0002] This invention relates to a polyesteramide resin, a method for producing the same, and a biaxially oriented film containing the same. [Background technology]

[0003] Polyester resin is a material with excellent mechanical strength, heat resistance, transparency, and gas barrier properties.

[0004] A typical example of such polyester resins is polyethylene terephthalate (PET), which is a copolymer of terephthalic acid (TPA) and ethylene glycol (EG). Biaxially oriented PET films are used for packaging, displays, insulating materials, and in a variety of industrial fields.

[0005] However, PET has a low melting point (Tm) of 260°C, which limits its applicability to the surface mount technology commonly used in this industry these days.

[0006] To overcome the limitations of PET as described above, polycyclohexanedimethylene terephthalate (PCT), which has a higher Tm, has been proposed.

[0007] However, homo-PCT crystallizes quickly and is difficult to process into biaxially oriented films, so it is common to adjust the crystallization rate by introducing heterologous monomers such as isophthalic acid (IPA) and ethylene glycol.

[0008] However, PCT with introduced heterogeneous monomers exhibits reduced thermal properties such as glass transition temperature (Tg) and Tm compared to homo-PCT, and has the problem of low stretch ratio and difficulty in increasing tensile strength when processed into biaxially oriented films. [Overview of the project] [Problems that the invention aims to solve]

[0009] The present invention provides a polyesteramide resin with improved heat resistance (particularly thermal properties such as Tg) and film properties (particularly physical properties such as tensile strength and storage modulus) compared to generally known polyester resins, a method for producing the same, and a biaxially oriented film containing the same. [Means for solving the problem]

[0010] Specifically, embodiments of the present invention provide a polyesteramide resin in which a diacid component, a diol component, and a diamine component are copolymerized together, a method for producing the same, and a biaxially oriented film containing the same.

[0011] In particular, the diacid component and the diol component are blended in a specific molar ratio.

[0012] (Definition of terms) In this specification, "moiety" means a certain portion or unit derived from a particular compound when that particular compound participates in a chemical reaction and is included in the product of that chemical reaction.

[0013] Specifically, in the polyesteramide resin, the "residues" of the diacid component, the "residues" of the diol component, and the "residues" of the diamine component refer to the portion derived from the diacid component, the portion derived from the diol component, and the portion derived from the diamine component, respectively.

[0014] Polyesteramide resin One embodiment of the present invention provides a polyesteramide resin comprising: a diacid residue, which is a residue of a diacid component containing terephthalic acid; a diol residue, which is a residue of a diol component containing cyclohexanedimethanol; and a diamine residue, which is a residue of a diamine component containing bis(aminomethyl)cyclohexane; wherein the molar ratio of the diacid residue and the diol residue satisfies a specific range.

[0015] The polyesteramide resin ensures mechanical strength, heat resistance, and chemical resistance due to the diacid residue, and transparency and impact strength due to the diol residue, while also improving heat resistance (especially thermal properties such as Tg) and film properties (especially physical properties such as tensile strength and storage modulus) due to the diamine residue.

[0016] In particular, when the diol residue satisfies 70 to 99 mol% with respect to 100 mol% of the diacid residue, the effects of the diacid residue and the diol residue can be achieved in a balanced manner, while simultaneously realizing the effects of the diamine copolymerization, thereby improving the heat resistance of the polyesteramide resin and the physical properties of the film in a balanced manner.

[0017] The polyesteramide resin will be described in detail below.

[0018] Diacid residues As explained earlier, in the polyesteramide resin, the "residue" of the diacid component refers to the portion derived from the diacid component.

[0019] The diacid component corresponds to the main monomer that forms a polyesteramide resin through esterification and amidation reactions with the diol component and the diamine component, and a polycondensation reaction.

[0020] Specifically, the diacid component includes terephthalic acid, and the polyesteramide resin can have improved physical properties such as mechanical strength, heat resistance and chemical resistance owing to the terephthalic acid.

[0021] In addition to terephthalic acid, the diacid component may further include an aromatic dicarboxylic acid component, an aliphatic dicarboxylic acid component, or a mixture thereof. In this case, the diacid components other than terephthalic acid are contained in an amount of 1 to 20 mol% based on 100 mol% in total of the residues of all the diacid components.

[0022] The aromatic dicarboxylic acid component may be an aromatic dicarboxylic acid having 8 to 20 carbon atoms, specifically 8 to 14 carbon atoms, or a mixture thereof. Examples of the aromatic dicarboxylic acid include isophthalic acid, naphthalenedicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, 4,4'-stilbenedicarboxylic acid, 2,5-furandicarboxylic acid, and 2,5-thiophenedicarboxylic acid, but specific examples of the aromatic dicarboxylic acid are not limited thereto.

[0023] The aliphatic dicarboxylic acid component may be an aliphatic dicarboxylic acid component having 4 to 20 carbon atoms, preferably 4 to 12 carbon atoms, or a mixture thereof. Examples of the aliphatic dicarboxylic acid include cyclohexanedicarboxylic acid such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and linear, branched or cyclic aliphatic dicarboxylic acid components such as phthalic acid, sebacic acid, succinic acid, isodecyl succinic acid, maleic acid, fumaric acid, adipic acid, glutaric acid and azelaic acid, but specific examples of the aliphatic dicarboxylic acid are not limited thereto.

[0024] Diol component As explained earlier, in the polyesteramide resin, the "residue" of the diol component refers to the portion derived from the diol component.

[0025] The aforementioned diol component corresponds to the main monomer that forms the polyesteramide resin through esterification and polycondensation reactions with the aforementioned diacid component.

[0026] Specifically, the diol component includes cyclohexanedimethanol (CHDM), which is a component that contributes to improving the transparency and impact strength of the polyesteramide.

[0027] The cyclohexanedimethanol may include one or more selected from the group consisting of 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol (1,4-CHDM). For example, 1,4-cyclohexanedimethanol can be used as the cyclohexanedimethanol, as shown in the examples described later.

[0028] The residues derived from the diol component in the polyesteramide resin are present in an amount of 70 to 99 mol%, based on 100 mol% of the diacid residues.

[0029] In contrast, if the content of the diol residue falls outside the range, the effect of the heat resistance of the polyesteramide resin and the physical properties of the film may be minimal.

[0030] In contrast, when the content of the diol residue satisfies the aforementioned range, the transparency and impact strength of the polyesteramide resin can be improved. Furthermore, within the aforementioned range, it is also possible to appropriately adjust the content of the diol residue, taking into consideration the physical properties of the desired polyesteramide resin.

[0031] For example, the diol residues in the polyesteramide resin are present in amounts of 70 mol% or more, 72 mol% or more, 74 mol% or more, 76 mol% or more, 78 mol% or more, or 80 mol% or more and 99 mol% or less, 98.5 mol% or less, 98 mol% or less, 98.5 mol% or less, or 97 mol% or less, based on 100 mol% of the diacid residues.

[0032] The aforementioned diol components include, in addition to cyclohexanedimethanol, ethylene glycol, isosorbide, 1,3-cyclobutanediol, 2,4-dimethylcyclobutane-1,3-diol, 2,4-diethylcyclobutane-1,3-diol, 2,2-dimethylcyclobutane-1,3-diol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, tricyclodecanedimethanol, pentacyclopentadecanedimethanol, decalindimethanol, tricyclotetradecanedimethanol, norbornanedimethanol, adamantanedimethanol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, bicyclo[2.2.2]octane-2,3-dimethanol, 1 The following may be additionally included: 3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1,4-cyclohexanediol, tricyclodecanediol, pentacyclopentadecanediol, decalindiol, tricyclotetradecanediol, norbornanediol, adamantanediol, 2,2-bis(4-hydroxycyclohexyl)propane, 3,3'-spiro-bis(1,1-dimethyl-2,3-dihydro-1H-inden-5-ol), dispiro[5.1.5.1]tetradecane-7,14-diol, 5,5'-(1-methylethylidene)bis(2-furanmethanol), 2,4:3,5-di-orthomethylene-D-mannitol, tetrahydrofuran-2,5-dimethanol, or mixtures thereof. In this case, diol components other than cyclohexanedimethanol are present in amounts of 1 to 20 mol% of the total 70 to 99 mol% of the total diol component residues.

[0033] The aforementioned ethylene glycol is a component that contributes to improving the transparency and impact strength of polyester copolymers produced together with cyclohexanedimethanol.

[0034] The isosorbide is used to improve the processability of the polyester copolymer produced. While the diol components of cyclohexanedimethanol and ethylene glycol improve the transparency and impact strength of the polyester copolymer, the shear fluidization properties must be improved and the crystallization rate must be delayed for processability to be achieved. However, it is difficult to achieve these effects with cyclohexanedimethanol and ethylene glycol alone. Therefore, when isosorbide is included as the diol component, the shear fluidization properties are improved and the crystallization rate is delayed while maintaining transparency and impact strength, thereby improving the processability of the polyester copolymer produced.

[0035] Diamine components In the polyesteramide resin, the diamine component is added together with the diacid component and the diol component, and is the main monomer that undergoes an amidation reaction and polycondensation reaction with the diacid component to form the polyesteramide resin.

[0036] Specifically, the diamine component includes bis(aminomethyl)cyclohexane (BAC), which is a compound with a molecular weight of 140-150 g / mol and a boiling point of 235-250°C, and is a component that contributes to improving the heat resistance of the polyesteramide resin (especially thermal properties such as Tg) and the physical properties of the film (especially physical properties such as tensile strength and storage modulus).

[0037] The bis(aminomethyl)cyclohexane may include 1,3-bis(aminomethyl)cyclohexane (1,3-BAC), 1,4-bis(aminomethyl)cyclohexane (1,4-BAC), or a mixture thereof. For example, as the bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane represented by the following chemical formula 1, or 1,4-bis(aminomethyl)cyclohexane represented by the following chemical formula 2, can be used, as shown in the examples described later.

[0038] [ka]

[0039] [ka]

[0040] More specifically, the residues derived from the diamine component in the polyesteramide resin are present in an amount of 1 to 30 mol% based on 100 mol% of the diacid residues.

[0041] If the content of the diamine residue exceeds the range, the content of the diol residue decreases relatively, which may result in a significant deterioration in the transparency and impact strength of the polyesteramide resin.

[0042] In contrast, if the content of the diamine residue does not reach the range, the effect of the polyesteramide resin may be minimal.

[0043] In contrast, when the content of the diamine residue satisfies the aforementioned range, the heat resistance of the polyesteramide resin and the physical properties of the film can be improved. Furthermore, within the aforementioned range, it is also possible to appropriately adjust the content of the diamine residue, taking into consideration the desired physical properties of the polyesteramide resin.

[0044] For example, the diamine residues in the polyesteramide resin are present in amounts of 1 mol% or more, 1.5 mol% or more, 2 mol% or more, 2.5 mol% or more, or 3 mol% or more and 30 mol% or less, 28 mol% or less, 26 mol% or less, 24 mol% or less, 22 mol% or less, or 20 mol% or less, based on 100 mol% of the diacid residues.

[0045] In addition to bis(aminomethyl)cyclohexane, the diamine component may further include 4,4'-methylenebis(2-methylcyclohexylamine), 4,4'-methylenebis(cyclohexylamine), 1,4-tetramethylenediamine, 1,6-hexamethylenediamine, 2,4,5-trimethyl-1,6-hexamethylenediamine, 5-amino-1,3,3-trimethylcyclohexanemethylamine, 1,4-bis(aminomethyl)cyclohexane, 2,2,4,4-tetramethyl-1,3-cyclobutanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, bi(cyclohexyl)-4,4'-diamine, 1,2-dicyclohexyl-1,2-ethanediamine, 1,3-xylylenediamine, 1,4-xylylenediamine, or mixtures thereof. In this case, diamine components other than bis(aminomethyl)cyclohexane are present in amounts of 1 to 10 mol% of the total 1 to 30 mol% of the total diamine component residues.

[0046] As shown in the examples described later, it has been confirmed that the glass transition temperature (Tg) and zero shear viscosity (ZSV) of the polyesteramide resin produced by additionally including the diamine component are significantly higher than those of the polyester resin produced using the diacid component and the diol component.

[0047] This shows that, compared to polyester resins consisting of diacid residues and diol residues, the addition of diamine residues to the main chain increases the glass transition temperature, melt viscosity, and zero shear viscosity of polyesteramide resins.

[0048] Furthermore, as shown in the test examples described later, it has been confirmed that the biaxially oriented film produced using the polyesteramide resin has significantly higher glass transition temperature, tensile strength in each direction, elongation, and modulus compared to the biaxially oriented film produced using the polyester resin.

[0049] This shows that, compared to polyester resins consisting of diacid residues and diol residues, the additional introduction of diamine residues into the main chain increases melt viscosity and process stability during the extrusion process for biaxially oriented film production, resulting in a more uniform thickness of the final biaxially oriented polyesteramide film and improved various physical properties.

[0050] On the other hand, according to the test examples described later, it has been confirmed that as the molar percentage of diamine residues in the polyesteramide resin increases, the glass transition temperature and the heating crystallization temperature (Tcc) generally increase, while the melting point (Tm), cooling crystallization temperature (Tmc), intrinsic viscosity (IV), and zero shear viscosity generally tend to decrease.

[0051] Furthermore, as shown in the test examples described later, it was confirmed that as the molar percentage of diamine residues in the polyesteramide resin increases, the intrinsic viscosity and elongation of the biaxially oriented film decrease, but the glass transition temperature, tensile strength in each direction, and modulus increase, and the film thickness tends to increase.

[0052] In connection with this, the residue composition in the polyesteramide resin can be adjusted within the range described above, taking into consideration the physical properties of the target resin and film. Furthermore, as explained earlier, the residue composition in the polyesteramide resin can be controlled by appropriately adjusting the monomer composition.

[0053] Molar content of residue components As explained earlier, based on 100 mol% of the diacid residues in the polyesteramide resin, the diol residues are present in an amount of 70-99 mol%, and the diamine residues are present in an amount of 1-30 mol%, and the content of each residue can be appropriately adjusted within this range.

[0054] However, when adjusting the content of each of the aforementioned residues, the molar ratio of the diacid residue and the diol residue must satisfy a specific range.

[0055] Based on 100 mol% of the aforementioned diacid residue, the diol residue must satisfy a value of 70 to 99 mol%.

[0056] If the diol residue is present in excess beyond the aforementioned range, the content of the diamine residue will relatively decrease, which may significantly impair the heat resistance of the polyesteramide resin and the physical properties of the film.

[0057] In contrast, if the diol residue does not reach the aforementioned range, the effect of the diol residue may be minimal.

[0058] In contrast, when the molar content of the diacid residue and the diol residue satisfies the aforementioned range, the diacid residue, the diol residue, and the diamine residue are blended in such a balanced manner that the heat resistance of the polyesteramide resin and the physical properties of the film can be improved. Furthermore, within the aforementioned range, it is also possible to appropriately adjust the molar content of the diacid residue and the diol residue, taking into consideration the physical properties of the desired polyesteramide resin.

[0059] For example, based on 100 mol% of the diacid residue, the diol residue can be adjusted to 70-99 mol%, 75-98 mol%, or 80-97 mol%.

[0060] On the other hand, with respect to 100 mol% of the diacid residue, the diamine residue may be 1 to 30 mol%.

[0061] Furthermore, based on 100 mol% of the diacid residue, the total of the diol residue and the diamine residue may be 100 mol%. Here, this includes 70-99 mol% of the diol residue and 1-30 mol% of the diamine residue.

[0062] Within this range, as the mol% of the diamine residue increases, the mol% of the diol residue decreases, the glass transition temperature and the heating crystallization temperature generally increase, and the melting point, cooling crystallization temperature, intrinsic viscosity, and zero shear viscosity generally tend to decrease.

[0063] Taking these trends into consideration, the molar percentages of the diol residue and the diamine residue can be adjusted.

[0064] For example, the molar percentage of the diamine residue relative to 100 mol% of the diacid residue can be adjusted to 1-30 mol%, 2-25 mol%, or 3-20 mol%. Also, the molar percentage of the diol residue relative to 100 mol% of the diacid residue can be adjusted to 70-99 mol%, 75-98 mol%, or 80-97 mol%.

[0065] Physical properties of polyesteramide resin As previously mentioned, the polyesteramide resin ensures mechanical strength, heat resistance, and chemical resistance due to the diacid residue, and transparency and impact strength due to the diol residue, while also improving heat resistance (especially thermal properties such as Tg) and film properties (especially physical properties such as tensile strength and storage modulus) due to the diamine residue.

[0066] Specifically, the polyesteramide resin may have a glass transition temperature (Tg) of 80 to 150°C, specifically 90 to 140°C; a heating crystallization temperature (Tcc) of 120 to 200°C, specifically 130 to 190°C; a melting point (Tm) of 240 to 300°C, specifically 250 to 290°C; and a cooling crystallization temperature (Tmc) of 180 to 250°C, specifically 190 to 240°C.

[0067] Furthermore, the polyesteramide resin may have an intrinsic viscosity (IV) of 0.40 to 1.20 dl / g, specifically 0.50 to 1.00 dl / g.

[0068] Furthermore, the polyesteramide resin may have a zero shear viscosity at 290°C of 300 to 600 Pa·s, specifically 350 to 550 Pa·s.

[0069] The methods for measuring each of the aforementioned physical properties will be demonstrated in the experimental examples described later.

[0070] Method for producing polyesteramide resin Another embodiment of the present invention provides a method for producing a polyesteramide resin by supplying a diacid component and a diol component in specific proportions together with a diamine component and water to a reactor and copolymerizing them.

[0071] Specifically, the present invention provides a method for producing a polyesteramide resin comprising the steps of: esterifying and amidating a monomer mixture containing a diacid component including terephthalic acid, a diol component including cyclohexanedimethanol, and a diamine component including bis(aminomethyl)cyclohexane (Step 1); and polycondensing the esterification and amidation reaction products (Step 2).

[0072] However, the molar ratio of the diol component to the diacid component in the monomer mixture satisfies 0.7 to 1.3.

[0073] This makes it possible to manufacture the polyesteramide resin of the aforementioned embodiment.

[0074] The above-mentioned manufacturing method is carried out in a batch, semi-continuous, or continuous manner, and the esterification and amidation reactions (step 1) and the polycondensation reaction (step 2) are carried out under an inert gas atmosphere.

[0075] If necessary, the solid-phase polymerization reaction can be carried out further. Specifically, after the polycondensation reaction (step 2), the process may additionally include a step of crystallizing the produced polyesteramide resin (step 3) and a step of solid-phase polymerization of the crystallized polyesteramide resin (step 4).

[0076] The following explanation will omit any repetition of the information previously mentioned and will describe in detail, step by step, the method for producing the polyesteramide resin.

[0077] Production of monomer mixtures The molar ratio of the diol component to the diacid component in the monomer mixture must be between 0.7 and 1.3.

[0078] This is for producing a polyesteramide resin in which the diol residue is contained in an amount of 70 to 99 mol%, based on 100 mol% of the diacid residue.

[0079] However, the above range can be appropriately adjusted considering the composition of the target polyesteramide resin. For example, the molar ratio of the diol component to the diacid component can be adjusted to 0.7-1.3, 0.8-1.3, 0.9-1.3, or 1.0-1.3.

[0080] The monomer mixture may contain 1 to 30 moles of the diamine component based on 100 moles of the diacid component.

[0081] Specifically, the molar ratio of the diamine component to the diacid component may be 0.01 to 0.30.

[0082] However, the above range can be appropriately adjusted considering the composition of the target polyesteramide resin. For example, the molar ratio of the diamine component to the diacid component can be adjusted to 0.01-0.30, 0.02-0.25, or 0.03-0.20.

[0083] Alternatively, a slurry can be produced by adding water to a monomer mixture containing the diacid component, the diol component, and the diamine component. In this case, the esterification and amidation reactions are carried out in the slurry.

[0084] By adding water to the monomer mixture to produce a slurry, the fluidity and reactivity during esterification and amidation reactions can be improved compared to when water is not added.

[0085] In particular, the imidation reaction involves a series of steps in which the diacid component and the diamine component undergo an acid-base reaction during the heating process to form a salt, and thereafter, once the reaction temperature is reached, the salt undergoes an amidation reaction to produce water as a byproduct.

[0086] The diacid component and the diamine component can more easily undergo an acid-base reaction in a highly fluid slurry with added water to form a salt, compared to when water is not added.

[0087] As a result, the Tg and IV of the polyesteramide resin copolymerized in the slurry with added water are all higher compared to when no water is added.

[0088] Based on a total slurry of 100% by weight, the monomer mixture of the diacid component, the diol component, and the diamine component is present in an amount of 60-97% by weight, and water is present in an amount of 3-40% by weight.

[0089] Esterification and amidation reactions The esterification and amidation reactions can be carried out in the presence of a catalyst, and a variety of metal and organic compound reaction catalysts can be used.

[0090] The esterification and amidation reactions are carried out at a rate of 0-10.0 kgf / cm². 2 This can be done at a pressure and temperature of 150-300°C.

[0091] The esterification and amidation reaction conditions can be appropriately adjusted according to the specific properties of the polyesteramide resin to be produced, the ratio of each component, or the process conditions. For example, the esterification and amidation reaction conditions can be set to 0-5.0 kgf / cm². 2 More specifically, 0.1-3.0 kgf / cm² 2 Pressure; temperature of 200-290°C, more specifically 220-280°C.

[0092] Polycondensation reaction The polycondensation reaction can be carried out by reacting the esterification and amidation reaction products at a temperature of 150 to 320°C and under reduced pressure of 600 to 0.01 Torr for 1 to 24 hours.

[0093] Such polycondensation reactions are carried out at reaction temperatures of 150–320°C, specifically 200–300°C, more specifically 250–290°C; and under reduced pressure conditions of 600–0.01 Torr, specifically 200–0.05 Torr, more specifically 100–0.1 Torr.

[0094] By applying reduced pressure conditions to the polycondensation reaction, cyclohexanedimethanol, the main byproduct of the polycondensation reaction, can be removed from the system. However, if the polycondensation reaction is performed outside the reduced pressure range of 400 to 0.01 Torr, the removal of byproducts may be insufficient.

[0095] Furthermore, if the polycondensation reaction occurs outside the temperature range of 150-320°C, if the reaction proceeds below 150°C, cyclohexanedimethanol, the main by-product of the polycondensation reaction, cannot be effectively removed from the system, resulting in a low intrinsic viscosity of the final reaction product and potentially degrading the physical properties of the resulting polyesteramide resin. If the reaction proceeds above 320°C, there is a higher possibility that the resulting polyesteramide resin will yellow in appearance.

[0096] The polycondensation reaction is carried out for an average reaction time of 1 to 24 hours until the intrinsic viscosity of the final reaction product reaches the target level.

[0097] additives Before initiating the esterification and amidation reactions, polycondensation catalysts, stabilizers, colorants, crystallizers, antioxidants, branching agents, etc., can be added to the slurry or to the reaction intermediate products.

[0098] However, the timing of adding the additive is not limited to this, and it may be added at any point during the manufacturing process of the polyesteramide resin.

[0099] As the polycondensation catalyst, one or more commonly used materials such as titanium, germanium, antimony, aluminum, and tin compounds can be appropriately selected and used.

[0100] Examples of the aforementioned titanium-based catalysts include tetraethyl titanate, acetyl tripropyl titanate, tetrapropyl titanate, tetrabutyl titanate, polybutyl titanate, 2-ethylhexyl titanate, octylene glycol titanate, lactate titanate, triethanolamine titanate, acetyl acetonate titanate, ethyl acetoacetate ester titanate, isostearyl titanate, titanium dioxide, titanium dioxide / silicon dioxide complex, and titanium dioxide / zirconium dioxide complex.

[0101] Furthermore, the germanium-based catalysts include germanium dioxide and composites using it.

[0102] Generally, phosphorus-based compounds such as phosphoric acid, trimethyl phosphate, and triethyl phosphate can be used as the stabilizer, and the amount added may be 10 to 500 ppm relative to the weight of the final polyesteramide resin, based on the amount of phosphorus element.

[0103] If the amount of stabilizer added is less than 10 ppm, the stabilizing effect will be insufficient, and the polymer may turn yellow. If it exceeds 500 ppm, the desired high degree of polymerization polyesteramide resin may not be obtained.

[0104] Furthermore, examples of colorants added to improve the color of the polyesteramide resin include conventional colorants such as cobalt acetate and cobalt propionate, and the amount added may be 10 to 200 ppm relative to the weight of the final polyesteramide resin, based on the amount of cobalt element.

[0105] If necessary, anthraquionone-based compounds, perinone-based compounds, azo-based compounds, methine-based compounds, etc., can be used as organic compound colorants. Commercially available products include toners such as Clarient's Polysynthren Blue RLS or Clarient's Solvaperm Red BB. The amount of the organic compound colorant added can be adjusted to 0-50 ppm relative to the weight of the final polymer. If the colorant is used in a content outside this range, yellowing of the polyesteramide resin may not be sufficiently prevented, or its physical properties may be reduced.

[0106] Examples of the crystallizing agent include nucleating agents, ultraviolet absorbers, polyolefin resins, and polyamide resins.

[0107] Examples of the aforementioned antioxidants include hindered phenol antioxidants, phosphite antioxidants, thioether antioxidants, or mixtures thereof.

[0108] Examples of the branching agent include conventional branching agents having three or more functional groups, such as trimellitic anhydride, trimethylol propane, trimellitic acid, or mixtures thereof.

[0109] Furthermore, the polycondensation reaction can use a polycondensation catalyst containing a titanium-based compound, a germanium-based compound, an antimony-based compound, an aluminum-based compound, a tin-based compound, or a mixture thereof.

[0110] Examples of the aforementioned titanium compounds include tetraethyl titanate, acetyl tripropyl titanate, tetrapropyl titanate, tetrabutyl titanate, 2-ethylhexyl titanate, octylene glycol titanate, lactate titanate, triethanolamine titanate, acetyl acetonate titanate, ethyl acetoacetate ester titanate, isostearyl titanate, and titanium dioxide. Examples of the aforementioned germanium compounds include germanium dioxide, germanium tetrachloride, germanium ethylene glycoside, germanium acetate, complexes using these, or mixtures thereof. Preferably, germanium dioxide can be used, and such germanium dioxide can be crystalline or amorphous, and glycol-soluble varieties can also be used.

[0111] Biaxially oriented film In yet another embodiment of the present invention, a biaxially oriented film is provided, comprising the polyesteramide resin of the above-described embodiment.

[0112] The biaxially oriented film has excellent heat resistance (especially thermal properties such as Tg) and film properties (especially physical properties such as tensile strength and storage modulus), particularly due to the diamine residues in the polyesteramide resin.

[0113] Manufacturing method for biaxially oriented film The biaxially oriented film can be manufactured by biaxially stretching the polyesteramide resin.

[0114] Specifically, the biaxially oriented film can be produced by the steps of: melt-extruding the polyesteramide resin to produce an unstretched polyesteramide film containing a resin layer formed from the polyesteramide resin; and biaxially stretching the unstretched polyesteramide film at a temperature above the glass transition temperature of the polyesteramide resin.

[0115] In the manufacturing stage of the unstretched polyesteramide film, the polyesteramide resin can be melt-extruded at a temperature of Tm ± 30°C to minimize thermal decomposition of the polymer.

[0116] Specifically, the manufacturing step of the unstretched polyesteramide film is carried out at a temperature of 240-310°C or 250-300°C.

[0117] If the melt extrusion temperature is below 240°C, the polymer may not melt, and if it exceeds 310°C, the thermal decomposition of the polymer increases, which can damage or break the film during stretch molding, making it difficult to achieve the desired physical properties.

[0118] The unstretched polyesteramide film can be cooled to an appropriate temperature. Thereafter, the unstretched polyesteramide film can be stretched at a temperature above the glass transition temperature of the polyesteramide resin.

[0119] The stretching step of the unstretched polyesteramide film is carried out at a temperature of 80 to 200°C, specifically 90 to 190°C, and more specifically 100 to 180°C, allowing the unstretched polyesteramide film to be stretched at a high magnification.

[0120] Specifically, for biaxial stretching, the unstretched polyamide film can be stretched 2 to 6 times, specifically 2 to 5 times, in the machine direction (MD), and 2 to 6 times, specifically 2 to 5 times, in the transverse direction (TD).

[0121] More specifically, when stretching the unstretched polyester film, the product of the machine direction stretching ratio and the transverse direction stretching ratio can be adjusted to 12 to 30.

[0122] After biaxial stretching of the unstretched polyester amide film, a heat setting step may be additionally included to impart dimensional stability to the obtained biaxially stretched polyester amide film.

[0123] The heat setting step is performed at a temperature of 80 to 250°C.

[0124] The thickness of the unstretched polyester amide film is 200 to 1000 µm, and the thickness of the biaxially stretched polyester amide film may be 5 to 500 µm.

[0125] The biaxially stretched film has a glass transition temperature (Tg, measured by DMA) of 100 to 250°C, specifically 100 to 200°C; a machine direction (MD) tensile strength of 5 to 25 kgf / mm 2 , specifically 5 to 20 kgf / mm 2 ; a transverse direction (TD) tensile strength of 5 to 35 kgf / mm 2 , specifically 5 to 30 kgf / mm 2 ; a machine direction (MD) modulus of 100 to 400 kgf / mm 2 , specifically 100 to 350 kgf / mm 2 ; and a transverse direction (TD) modulus of 100 to 500 kgf / mm 2 , specifically 100 to 450 kgf / mm 2 . Effects of the Invention

[0126] The polyesteramide resin of the above embodiment achieves a good balance of the effects of the diacid residue and the diol residue, while also achieving the effect of the diamine, thereby exhibiting superior heat resistance (especially thermal properties such as Tg) compared to generally known polyester resins.

[0127] Furthermore, the biaxially oriented film containing the polyesteramide resin of the above embodiment can exhibit superior physical properties (especially physical properties such as tensile strength and storage modulus) compared to generally known polyester resins.

[0128] In addition, the polyesteramide resin of the above embodiment can be produced by copolymerizing the diamine component together with the diacid component and the diol component, which are blended in a specific molar ratio. [Modes for carrying out the invention]

[0129] The following are preferred embodiments for understanding the present invention. However, these embodiments are provided only to facilitate understanding the present invention and do not limit its scope.

[0130] Example 1 In a 5 kg batch reactor, 1,514 g of terephthalic acid (TPA), 1,855 g of 1,4-cyclohexanedimethanol (1,4-CHDM), 38.9 g of 1,3-bis(aminomethyl)cyclohexane (1,3-BAC), 186 g of water, 0.15 g of titanium oxide catalyst (Sachtleben), and 0.36 g of triethyl phosphate were added. At this time, the molar ratio of CHDM to TPA was 1.27, and water accounted for 5.2% by weight of 100% by weight of the entire slurry containing the monomer mixture and water.

[0131] After adding the aforementioned raw materials, 1.0 kgf / cm² 2The mixture was pressurized and heated to 280°C for 3 hours while carrying out the esterification and amidation reactions (stage 1). Subsequently, the temperature was raised to 290°C, and the polycondensation reaction (stage 2) was carried out for 150 minutes under a vacuum of 0.5 to 1.0 Torr. The final reactant was then discharged as a strand from the reactor and pelletized after passing through a cooling tank to produce polyesteramide resin.

[0132] Example 2 In a 5 kg batch reactor, 1,514 g of TPA, 1,643 g of 1,4-CHDM, 64.8 g of 1,3-BAC, 164 g of water, 0.15 g of titanium oxide catalyst (Sachtleben), and 0.36 g of triethyl phosphate were added. At this time, the molar ratio of CHDM to TPA was 1.25, and the slurry containing the monomer mixture and water contained 5.1 wt% water. Polyesteramide resin was then produced in the same manner as in Example 1.

[0133] Example 3 In a 5 kg batch reactor, 1,515 g of TPA, 1,578 g of 1,4-CHDM, 130 g of 1,3-BAC, 158 g of water, 0.15 g of titanium oxide catalyst (Sachtleben), and 0.36 g of triethyl phosphate were added. At this time, the molar ratio of CHDM to TPA was 1.20, and the slurry containing the monomer mixture and water contained 4.9 wt% water. Polyesteramide resin was then produced in the same manner as in Example 1.

[0134] Example 4 In a 5 kg batch reactor, 1,516 g of TPA, 1,448 g of 1,4-CHDM, 260 g of 1,3-BAC, 145 g of water, 0.15 g of titanium oxide catalyst (Sachtleben), and 0.36 g of triethyl phosphate were added. At this time, the molar ratio of CHDM to TPA was 1.10, and the slurry containing the monomer mixture and water contained 4.5 wt% water. Polyesteramide resin was then produced in the same manner as in Example 1.

[0135] Example 5 In a 5 kg batch reactor, 1,517 g of TPA, 1,463 g of 1,4-CHDM, 390 g of 1,4-bis(aminomethyl)cyclohexane (1,4-BAC), 146 g of water, 0.15 g of titanium oxide catalyst (Sachtleben), and 0.36 g of triethyl phosphate were added. At this time, the molar ratio of CHDM to TPA was 1.10, and the slurry containing the monomer mixture and water contained 4.3 wt% water. Polyesteramide resin was then produced in the same manner as in Example 1.

[0136] Comparative Example 1 In a 5 kg batch reactor, 1,514 g of TPA, 1,708 g of 1,4-CHDM, 0.15 g of titanium oxide catalyst (Sachtleben), and 0.36 g of triethyl phosphate were added. At this time, the molar ratio of CHDM to TPA was 1.30, and the polyesteramide resin was produced in the same manner as in Example 1.

[0137] Comparative Examples 2-4 Polyester resins for Comparative Examples 2-4 were produced in the same manner as for Comparative Example 1, using the compositional ratios of TPA, IPA, 1,4-CHDM, and EG as shown in Table 2 below.

[0138] Comparative Example 5 In a 5 kg batch reactor, 1,517 g of TPA, 1,976 g of 1,4-CHDM, 390 g of 1,4-BAC, 0.15 g of titanium oxide catalyst (Sachtleben), and 0.36 g of triethyl phosphate were added. At this time, the molar ratio of CHDM to TPA was 1.50, and no water was added to the monomer mixture slurry. Polyesteramide resin was then produced in the same manner as in Example 1.

[0139] Test Example 1: Physical Properties of Resins The physical properties of each resin sample in Examples 1-5 and Comparative Examples 1-5 were evaluated using the following method, and the evaluation results are shown in Tables 1-3 below.

[0140] 1) Residual composition of the final product The residue composition (mol%) of each resin sample in Examples 1-4 and Comparative Examples 1-4 was determined by dissolving the sample in CDCl3 solvent at a concentration of 3 mg / mL and then observing the 1H-NMR spectrum obtained at 25°C using a nuclear magnetic resonance spectrometer (JEOL, 600 MHz FT-NMR).

[0141] 2) Thermal properties: glass transition temperature (Tg), heating crystallization temperature (Tcc), melting point (Tm), and cooling crystallization temperature (Tmc) The thermal properties of each compound in Examples 1-5 and Comparative Examples 1-5 were evaluated using a differential scanning calorimeter (DSC).

[0142] Specifically, a resin sample was filled into an aluminum fan, heated from 30°C to 320°C at a rate of 10°C / min, maintained at 320°C for 2 minutes, then cooled down to 30°C at a rate of -150°C / min, and then heated again to 320°C at a rate of 10°C / min to obtain an endothermic curve.

[0143] From the aforementioned endothermic curve, Tg, Tcc, and Tm were determined. Next, an exothermic curve was obtained when the temperature was maintained at 320°C for 2 minutes and then cooled to 30°C at a rate of -10°C / min. From this exothermic curve, Tmc was determined.

[0144] 3) Intrinsic viscosity (IV) The resin sample was dissolved in orthochlorophenol (o-chlorophenol) at a concentration of 1.2 g / dl at 150°C, and then its intrinsic viscosity was measured using an Ubbelohde viscosity tube.

[0145] When the temperature of the viscosity tube is maintained at 35°C, and the time it takes for the solvent to pass through the internal section ab of the viscosity tube (efflux time) is denoted as t, and the time it takes for the solution to pass through is denoted as T0, the specific viscosity is defined as follows, and the intrinsic viscosity is determined using the following correction formula.

[0146]

number

[0147] In this case, A was set to 0.247 as the Huggins constant, and c was set to a concentration value of 1.2 g / dl.

[0148]

number

[0149] 4) Zero shear viscosity (ZSV) The zero shear viscosity for each resin in Examples 1-4 and Comparative Examples 1-4 was measured using a parallel plate rheometer.

[0150] Specifically, the zero shear viscosity value of the complex viscosity obtained by measuring the resin sample at 290°C within the range of angular frequency 0.1 to 500 rad / s was taken.

[0151] [Table 1]

[0152] [Table 2]

[0153] [Table 3]

[0154] According to Tables 1 and 2, the polyesteramide resins of Examples 1 to 4 are at roughly the same level as the polyester resins of Comparative Examples 1 to 4 in terms of melting point (Tm), heating crystallization temperature (Tcc), cooling crystallization temperature (Tmc), and intrinsic viscosity (IV). However, in terms of glass transition temperature (Tg) and zero shear viscosity (ZSV), the polyesteramide resins of Examples 1 to 4 are significantly higher than those of the polyester resins of Comparative Examples 1 to 4.

[0155] This shows that, compared to polyester resins consisting of diacid residues and diol residues, the addition of diamine residues to the main chain increases the glass transition temperature, melt viscosity, and zero shear viscosity of polyesteramide resins.

[0156] On the other hand, according to Table 1, as the content of diamine residues in the polyesteramide resins of Examples 1 to 4 increases, Tg and Tcc generally increase, while Tm, Tmc, IV, and ZSV generally tend to decrease.

[0157] In connection with this, the residue composition in the polyesteramide resin can be adjusted within the scope of the aforementioned embodiment, taking into consideration the physical properties of the target resin. Furthermore, as explained earlier, the residue composition in the polyesteramide resin can be controlled by appropriately adjusting the monomer composition.

[0158] Furthermore, according to Table 3, it can be confirmed that the polyesteramide resin of Example 5 has higher Tg and IV than the polyesteramide resin of Comparative Example 5.

[0159] Specifically, the diacid component and the diamine component can more easily undergo an acid-base reaction to form a salt in a highly fluid slurry with added water compared to when water is not added. This indicates that the amidation reaction proceeds more easily in a slurry with added water compared to when water is not added. As a result, a polyester amide resin with higher Tg and IV was produced in Example 5 compared to Comparative Example 5.

[0160] Test Example 2: Physical Properties of Biaxially Oriented Film (1) Manufacturing of biaxially oriented film Biaxially oriented films were manufactured using the polyesteramide resins of Examples 2 and 3 and the polyester resin of Comparative Example 2.

[0161] Specifically, the resin chips were melted in an extruder at a temperature of 280-290°C.

[0162] The molten material was extruded through a die to form a sheet and then rapidly cooled. The resulting sheet was stretched 3.0 times in the longitudinal direction (MD) and then 3.7 times in the transverse direction (TD). To impart dimensional stability to the stretched film, it was heat-set under tension at 220°C to obtain a biaxially oriented film.

[0163] (2) Evaluation of physical properties of biaxially oriented film The physical properties of the biaxially oriented films of Examples 2 and 3 and the biaxially oriented film of Comparative Example 2 were evaluated using the following method, and the evaluation results are shown in Table 4 below.

[0164] 1) Intrinsic viscosity (IV) The evaluation was performed using the same method as in Test Example 1.

[0165] 2) Glass transition temperature (Tg) The biaxially oriented films of Examples 2 and 3, and the biaxially oriented film of Comparative Example 2 were each cut to a width of 5.3 mm and a length of approximately 40 mm. Using a dynamic mechanical analysis (DMA), the temperature was raised from 30°C to 180°C at a frequency of 1 Hz and a heating rate of 3°C / min, and the highest point of the measured tanδ was calculated as the Tg of the film.

[0166] 3) Tensile strength, elongation, and storage modulus Using a universal testing machine UTM 5566A (Instron), samples with a length of 5 cm or more and a width of 1.5 cm were attached to clips spaced 5 cm apart in both the MD and TD directions. Stress-strain curves were then obtained at room temperature at a rate of 200 mm / min until fracture occurred while the samples were stretched.

[0167] The strength at the point where the sample fractured was defined as the tensile strength, the length of elongation as the elongation rate, and the slope of the load relative to the initial deformation as the storage modulus.

[0168] 4) Thickness Using a thickness tester (Labthink), we measured the thickness at 5 points in the width direction and took the average value.

[0169] [Table 4]

[0170] According to Table 4, the polyesteramide biaxially oriented film has a higher Tg, higher tensile strength, elongation, and modulus in each direction, and a more uniform thickness compared to the polyester biaxially oriented film. Specifically, from the perspective of IV, the polyesteramide biaxially oriented films of Examples 2 and 3 are at a similar level to the polyester film of Comparative Example 2.

[0171] However, in terms of Tg, as well as tensile strength in each direction, elongation, and modulus, the polyesteramide biaxially oriented films of Examples 2 and 3 are significantly higher than the polyester film of Comparative Example 2.

[0172] This shows that, compared to polyester resins consisting of diacid residues and diol residues, the additional introduction of diamine residues into the main chain increases the melt viscosity and process stability during the extrusion process for the production of biaxially oriented polyesteramide resin films, resulting in a more uniform thickness of the final biaxially oriented polyesteramide film and improved various physical properties.

[0173] On the other hand, as the molar content of diamine residues in the polyesteramide resin of Examples 2 and 3 increases, the IV and elongation of the biaxially oriented film decrease, but the Tg, tensile strength in each direction, and modulus increase, and the film thickness tends to increase.

[0174] In connection with this, the residue composition in the polyesteramide resin can be adjusted within the scope of the aforementioned embodiment, taking into consideration the physical properties of the target film. Furthermore, as explained earlier, the residue composition in the polyesteramide resin can be controlled by appropriately adjusting the monomer composition.

Claims

1. Diacid residues are residues of diacid components, including terephthalic acid; Diol residues, which are residues of the diol component containing 1,4-cyclohexanedimethanol; and A diamine residue, which is a residue of a diamine component containing bis(aminomethyl)cyclohexane; Based on 100 mol% of the aforementioned diacid residue, the above-mentioned diol residue is present in an amount of 70 to 99 mol%, Based on 100 mol% of the aforementioned diacid residue, the aforementioned diamine residue is contained in an amount of 1 to 20 mol%, Polyester amide resin.

2. The aforementioned diol component is Ethylene glycol, isosorbide, 1,3-cyclobutanediol, 2,4-dimethylcyclobutane-1,3-diol, 2,4-diethylcyclobutane-1,3-diol, 2,2-dimethylcyclobutane-1,3-diol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, tricyclodecanedimethanol, pentacyclopentadecanedimethanol, decalindimethanol, tricyclotetradecanedimethanol, norbornanedimethanol, adamantanedimethanol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, bicyclo[2.2.2]octane-2,3-dimethanol, 1,3-cyclohexanedi The following are further comprising ol, 1,4-cyclohexanediol, 2-methyl-1,4-cyclohexanediol, tricyclodecanediol, pentacyclopentadecanediol, decalindiol, tricyclotetradecanediol, norbornanediol, adamantanediol, 2,2-bis(4-hydroxycyclohexyl)propane, 3,3'-spiro-bis(1,1-dimethyl-2,3-dihydro-1H-inden-5-ol), dispiro[5.1.5.1]tetradecane-7,14-diol, 5,5'-(1-methylethylidene)bis(2-furanmethanol), 2,4:3,5-di-orthomethylene-D-mannitol, tetrahydrofuran-2,5-dimethanol, or mixtures thereof. The polyesteramide resin according to claim 1.

3. The bis(aminomethyl)cyclohexane is, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, or mixtures thereof The polyesteramide resin according to claim 1.

4. The aforementioned diamine component is 4,4'-methylenebis(2-methylcyclohexylamine), 4,4'-methylenebis(cyclohexylamine), 1,4-tetramethylenediamine, 1,6-hexamethylenediamine, 2,4,5-trimethyl-1,6-hexamethylenediamine, 5-amino-1,3,3-trimethylcyclohexanemethylamine, 1,4-bis(aminomethyl)cyclohexane, 2,2,4,4-tetramethyl-1,3-cyclobutanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, bi(cyclohexyl)-4,4'-diamine, 1,2-dicyclohexyl-1,2-ethanediamine, 1,3-xylylenediamine, 1,4-xylylenediamine, or further comprising mixtures thereof. The polyesteramide resin according to claim 1.

5. The aforementioned polyesteramide resin is The glass transition temperature (Tg) is 80 to 150°C. The polyesteramide resin according to claim 1.

6. The aforementioned polyesteramide resin is Using a differential scanning calorimeter (DSC), the temperature was increased from 30°C to 320°C at a rate of 10°C / min, maintained at 320°C for 2 minutes, then cooled to 30°C at a rate of -150°C / min, and then increased again to 320°C at a rate of 10°C / min. The measured temperature of crystallization (Tcc) was between 120 and 200°C. The polyesteramide resin according to claim 1.

7. The aforementioned polyesteramide resin is The melting point (Tm) is 240-300°C. The polyesteramide resin according to claim 1.

8. The aforementioned polyesteramide resin is Using a differential scanning calorimeter (DSC), the temperature was increased from 30°C to 320°C at a rate of 10°C / min, maintained at 320°C for 2 minutes, then cooled to 30°C at a rate of -150°C / min, then increased again to 320°C at a rate of 10°C / min, maintained at 320°C for 2 minutes, and then cooled to 30°C at a rate of -10°C / min. The measured cooling crystallization temperature (Tmc) was between 180 and 250°C. The polyesteramide resin according to claim 1.

9. The aforementioned polyesteramide resin is The intrinsic viscosity (IV) is 0.40 to 1.20 dl / g. The polyesteramide resin according to claim 1.

10. A step of esterifying and amidating a monomer mixture containing a diacid component including terephthalic acid, a diol component including 1,4-cyclohexanedimethanol, and a diamine component including bis(aminomethyl)cyclohexane; and The step of polycondensing the esterification and amidation reaction products; The molar ratio of the diol component to the diacid component in the monomer mixture is 0.7 to 1.

3. The monomer mixture contains 1 to 20 moles of the diamine component based on 100 moles of the diacid component. The step of preparing a slurry containing the monomer mixture and water before the esterification and amidation reactions; The esterification and amidation reactions are carried out in the slurry. A method for producing polyesteramide resin.

11. Of the total slurry amount of 100% by weight, the monomer mixture is present in an amount of 60 to 97% by weight, and water is present in an amount of 3 to 40% by weight. A method for producing a polyesteramide resin according to claim 10.

12. The esterification and amidation reactions described above are This is done in the presence of a phosphorus stabilizer. A method for producing a polyesteramide resin according to claim 10.

13. The polycondensation reaction described above is The polycondensation reaction is carried out in the presence of a catalyst for titanium compounds, germanium compounds, antimony compounds, aluminum compounds, tin compounds, or mixtures thereof. A method for producing a polyesteramide resin according to claim 10.

14. A biaxially oriented film comprising the polyesteramide resin according to any one of claims 1 to 9.

15. The biaxially oriented film is It is stretched 2 to 6 times in the longitudinal direction (MD) and 2 to 6 times in the transverse direction (TD). The biaxially oriented film according to claim 14.

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