CN111433262A - Polyester resin composition and biaxially stretched polyester film comprising same - Google Patents
Polyester resin composition and biaxially stretched polyester film comprising same Download PDFInfo
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- CN111433262A CN111433262A CN201880073906.2A CN201880073906A CN111433262A CN 111433262 A CN111433262 A CN 111433262A CN 201880073906 A CN201880073906 A CN 201880073906A CN 111433262 A CN111433262 A CN 111433262A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/42—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/42—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
- H01B3/421—Polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
- B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
- B29C55/143—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively firstly parallel to the direction of feed and then transversely thereto
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polyesters Or Polycarbonates (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
The present invention provides a polyester resin composition comprising a polyester resin comprising a polycondensate of a dicarboxylic acid component comprising terephthalic acid and isophthalic acid and a diol component comprising cyclohexanedimethanol, and a biaxially stretched polyester film comprising the polyester resin composition.
Description
Background
(A) Field of the invention
Cross Reference to Related Applications
This application claims the benefit of korean patent application No. 10-2017-0156747, filed on 22.11.2017 with the korean intellectual property office, the disclosure of which is incorporated herein by reference in its entirety.
The present invention relates to a polyester resin composition and a biaxially stretched polyester film comprising the same.
(b) Description of the related Art
Recently, in order to reduce the weight of automobiles, metal materials have been replaced with plastic materials, but plastic materials used for such automobile parts are required to have high heat resistance, and to be made thin in order to reduce the volume. Among the electric device parts of these automobile parts, an FFC (flexible flat cable) is a connection cable for connection between PCBs (printed circuit boards) or PBAs (printed board assemblies), and has a relatively smaller and thinner feature than a general connector. Further, since the FFC is flexible and thus foldable, it is often used as a connection connector inside an electronic device such as a mobile phone.
Conventionally, a PET (polyethylene terephthalate) stretched film is used for producing the FFC, but the PET stretched film has a heat resistance of about 130 ℃, and therefore, the FFC using the PET stretched film cannot be applied to main parts such as an automobile power train and an engine control part which require high heat resistance. Therefore, an attempt to improve heat resistance by a technique of coating/laminating a PET stretched film has been made, but it is difficult to make the PET stretched film have high heat resistance to withstand high temperatures of 150 ℃ or more.
On the other hand, a polyimide film having high heat resistance is also applied to FFC applications, but the polyimide film is a thermosetting resin and thus has a disadvantage of being difficult to reuse in the future.
Summary of The Invention
An object of the present invention is to provide a polyester resin composition excellent in high heat resistance and high moisture resistance and a biaxially stretched polyester film comprising the polyester resin composition.
According to an embodiment of the present invention, there may be provided a polyester resin composition comprising a polyester resin comprising a polycondensate of a dicarboxylic acid component comprising terephthalic acid and isophthalic acid and a diol component comprising cyclohexanedimethanol, wherein the polyester resin has a melting temperature of 250 ℃ or more, the polyester resin has a difference (Tm-Tmc) between a melting temperature (Tm) and a melt crystallization temperature (Tmc) of 45 ℃ or more, and the polyester resin has a difference (Tcc-Tg) between a cold crystallization temperature (Tcc) and a glass transition temperature (Tg) of 40 ℃ or more.
According to another embodiment of the present invention, a biaxially stretched polyester film formed using the polyester resin composition may be provided.
Hereinafter, a polyester resin composition according to a specific embodiment of the present invention and a biaxially stretched polyester film for a flexible flat cable comprising the same will be described in more detail.
The present inventors have found through experiments that a polyester resin comprising a polycondensate of a dicarboxylic acid component comprising terephthalic acid and isophthalic acid and a diol component comprising cyclohexanedimethanol, having a melting temperature of 250 ℃ or more, a difference (Tm-Tmc) between the melting temperature (Tm) and the melt crystallization temperature (Tmc) of 45 ℃ or more, and a difference (Tcc-Tg) between the cold crystallization temperature (Tcc) and the glass transition temperature (Tg) of 40 ℃ or more, can produce an unstretched sheet having a thickness of 1.0mm or more, which can be used to increase the stretching ratio in producing a stretched film and improve heat resistance and hygroscopicity, thereby completing the present invention.
Specifically, the biaxially stretched polyester film of an embodiment comprises a polyester resin comprising a polycondensate of a dicarboxylic acid component comprising terephthalic acid and isophthalic acid and a diol component comprising cyclohexanedimethanol. Further, the melting temperature of the polyester resin may be 250 ℃ or more, 250 ℃ to 350 ℃, or 253 ℃ to 340 ℃. When the melting temperature of the polyester resin is lower than 250 ℃, there is a problem that the polyester resin has low heat resistance and thus cannot be applied to parts requiring high heat resistance.
The polyester resin may have a difference (Tm-Tmc) between a melting temperature (Tm) and a melt crystallization temperature (Tmc) of 45 ℃ or more, 45 ℃ to 120 ℃, or 50 ℃ to 115 ℃. When the difference between the melting temperature and the melt crystallization temperature of the polyester resin is less than 45 ℃, the polyester resin is rapidly crystallized while being cooled to a melt crystallization state (around Tmc) in a molten state (around Tm) after T-die to have a thickness of 1.0mm or more, and at the same time, there is a problem that it is difficult to form an unstretched sheet in a stretchable transparent state.
Further, the polyester resin may have a difference (Tcc-Tg) between a cold crystallization temperature (Tcc) and a glass transition temperature (Tg) of 40 ℃ or more, 40 ℃ to 100 ℃, or 43 ℃ to 90 ℃. When the difference between the cold crystallization temperature and the glass transition temperature of the polyester resin is less than 40 ℃, when the temperature is raised (heated) to perform the step of stretching the unstretched sheet, the section (section) reaching the cold crystallization state (Tcc) through the glass transition state (Tg) becomes short and thus rapidly crystallized, which results in difficulty in setting the stretching processing conditions, and thus stretching may become difficult.
That is, since the melting temperature of the polyester resin is 250 ℃ or more, it can exhibit high heat resistance. Further, since the difference between the melting temperature and the melt crystallization temperature is 45 ℃ or more, and the difference between the cold crystallization temperature and the glass transition temperature is 40 ℃ or more, moldability and tensile properties may be excellent.
The content of isophthalic acid contained in the polyester resin may be 3 to 20 mol%, 5 to 20 mol%, 6 to 18 mol%, 8 to 16 mol%, and 10 to 14 mol% based on the total dicarboxylic acid component. When the content of isophthalic acid exceeds 20 mol%, the high-temperature heat shrinkage rate at 150 ℃ or more is high, and thus, heat resistance may be deteriorated. When the content of isophthalic acid is less than 3 mol%, the thickness of the transparent unstretched sheet is considerably limited to about 0.1mm, and the stretching ratio is also limited. Therefore, when a stretched film is produced, the stretching ratio is reduced, and thus desired mechanical properties and heat resistance cannot be obtained.
The dicarboxylic acid component and the diol component contained in the polyester resin may have a molar ratio of 1:1 to 2, or 1:1.2 to 1.8. When the molar ratio of the dicarboxylic acid component and the diol component is less than 1:1, the melting temperature may decrease and the heat resistance may deteriorate. When the molar ratio exceeds 1:2, there is a problem that moldability is greatly deteriorated and thus desired mechanical properties cannot be obtained.
In addition to terephthalic acid and isophthalic acid, the dicarboxylic acid component may also include at least one other dicarboxylic acid component selected from the group consisting of: 2, 6-naphthalenedicarboxylic acid, dimethylisophthalic acid and dimethyl 2, 6-naphthalenedicarboxylic acid, but are not limited thereto. The content of the other dicarboxylic acid component may be 20 mol% or less, 0.1 mol% to 20 mol%, and 5 mol% to 15 mol% based on the total dicarboxylic acid component.
In addition, the diol component may also include aliphatic diols having 2 to 20 carbon atoms. For example, the diol component may also include at least one other diol component selected from the group consisting of: ethylene glycol, diethylene glycol, 1, 4-butanediol, 1, 3-propanediol, and neopentyl glycol, but is not limited thereto. The content of the other diol component may be 20 mol% or less, 0.1 mol% to 20 mol%, and 5 mol% to 15 mol% based on the total diol component.
The polyester resin may have an Intrinsic Viscosity (IV) of 0.4dl/g to 1.2dl/g, 0.5dl/g to 1.0dl/g, or 0.7dl/g to 0.9 dl/g. When the intrinsic viscosity is less than 0.4dl/g, the melting temperature may decrease, and thus the heat resistance may decrease. When the intrinsic viscosity is more than 1.2dl/g, moldability is greatly deteriorated, and thus desired mechanical properties cannot be obtained.
The polyester resin can have a number average molecular weight of 15,000 to 50,000g/mol, 20,000 to 45,000g/mol, or 25,000 to 40,000 g/mol. When the number average molecular weight is less than 15,000g/mol, the melting temperature may decrease, and thus the heat resistance may decrease. When the number average molecular weight is more than 50,000g/mol, moldability is greatly deteriorated, and thus desired mechanical properties cannot be obtained.
Further, the polyester resin may have a weight average molecular weight of 50,000 to 150,000g/mol, 60,000 to 140,000g/mol, or 70,000 to 130,000 g/mol. When the weight average molecular weight is less than 50,000g/mol, the melting temperature may decrease, and thus the heat resistance may decrease. When the weight average molecular weight is more than 150,000g/mol, moldability is greatly deteriorated, and thus desired mechanical properties cannot be obtained.
The polyester resin preferably has a melt crystallization temperature of 150 ℃ to 230 ℃. When the melt crystallization temperature of the polyester resin is lower than 150 ℃, the heat-setting effect is reduced during a post-processing process or during the use of an actually stretched film, and thus it may be difficult to impart dimensional stability to the final stretched film. In particular, high shrinkage may occur. When the melt crystallization temperature is higher than 230 ℃, it may be difficult to produce a transparent unstretched sheet during film extrusion.
According to another embodiment of the present invention, a biaxially stretched polyester film formed using the polyester resin composition may be provided. The biaxially stretched polyester film exhibits heat resistance at high temperatures of 150 ℃ to 200 ℃, and thus can be applied to integrated safety parts (over safety parts), such as automobile power trains, engine controls, and steering devices. In particular, the biaxially stretched polyester film may be used as a material for a Flexible Flat Cable (FFC) requiring excellent heat resistance, moisture resistance, and electrical insulation properties.
Typically, as a material for the flexible flat cable, a PET film capable of controlling the thickness of the film up to 1.2mm when unstretched is used, but the PET film has heat resistance of about 130 ℃, and thus has a problem of being easily heated. Therefore, an attempt has been made to apply to parts requiring heat resistance by using a polycyclohexanedimethylene terephthalate (PCT) film, but the conventional PCT film has a high glass transition temperature (Tg) and melting temperature (Tm).
However, the conventional PCT film also has a high melt crystallization temperature (Tmc), and therefore, immediately after extrusion using a T-die, crystallization proceeds rapidly, and the thickness of a transparent unstretched sheet is considerably limited to about 0.1mm, which is problematic. When the thickness of the transparent unstretched sheet is as thin as about 0.1mm, the stretching ratio may be reduced during the stretching process. Meanwhile, since the conventional PCT film has a low cold crystallization temperature (Tcc), when a temperature is raised (heated) to perform a process of stretching the unstretched sheet, a section reaching the cold crystallization state (Tcc) through a glass transition state (Tg) becomes short and rapidly crystallizes, which results in difficulty in setting stretching processing conditions, and thus stretching may become difficult.
However, the polyester resin according to an embodiment has a difference (Tm-Tmc) between a melting temperature (Tm) and a melting crystallization temperature (Tmc) of 45 ℃ or more, and the polyester resin has a difference (Tcc-Tg) between a cold crystallization temperature (Tcc) and a glass transition temperature (Tg) of 40 ℃ or more, and thus, a crystallization rate may be slowed down shortly after extrusion, so that the maximum thickness of a transparent unstretched sheet may be controlled to about 1.2mm, which is a level similar to the thickness of a transparent unstretched sheet of a PET film. In addition, since the crystallization rate may be slowed down in the stretching step, the stretching of the unstretched sheet may be facilitated, and the heat resistance of the polyester film may be improved.
The biaxially stretched polyester film according to other embodiments may be a multilayer film or a laminated (heat-bonded) film having two or more layers, in which the above polyester resin composition is coextruded.
Specifically, after two or more of the polyester resin compositions are melted in different extruders, the melted resins are sent into a mold to be laminated into two or more layers, and then, a non-stretched multilayer film (or laminated film) may be provided by a method such as blowing or casting. The respective layers included in the unstretched multilayer film are transparent and may have a thickness of about 1.2mm or more. At this time, the two or more polyester resin compositions may be the same composition, or different compositions having different components or contents. Meanwhile, the unstretched multilayer film is biaxially stretched in the machine direction and the transverse direction to obtain a biaxially stretched polyester film excellent in heat resistance and the like.
The biaxially stretched polyester film may have a heat shrinkage rate of less than 0.5%, 0.01% to 0.4%, or 0.01% to 0.3% at 150 ℃ for 30 minutes, and a heat shrinkage rate of less than 1.0%, 0.01% to 0.9%, or 0.01% to 0.8% at 200 ℃ for 30 minutes. Since the biaxially stretched polyester film has a very low thermal shrinkage at a temperature of 150 ℃ to 200 ℃, it can be confirmed that it is excellent in heat resistance.
In addition, the biaxially stretched polyester film has excellent moisture resistance, and specifically, when the temperature is 85 ℃ and the relative humidity is 85%, the moisture absorption rate may be 1% or less, 0.01% to 0.9%, or 0.01% to 0.8%.
Meanwhile, the method for producing the biaxially stretched polyester film is not limited thereto, but for example, the polyester resin composition may be vacuum-dried to sufficiently remove moisture, then supplied to an extruder, melt-extruded at a temperature of 200 ℃ to 300 ℃, and molded into a sheet shape from a T-shaped spinneret. The sheet-like product thus obtained may be cooled and fixed on a mirror-like cooling drum (mirror-like cooling drum) to obtain an unstretched sheet. At this time, in order to improve adhesion to the casting drum (cast drum), it is preferable to use an electrostatic application method. Thereafter, the obtained unstretched sheet is stretched in the longitudinal direction (machine direction, MD). Preferably, the longitudinal direction stretching reduces the crystal orientation and promotes thermal crystallization. After stretching in the longitudinal direction, stretching is performed in the transverse direction (width direction, TD; trans-machine direction) and subjected to heat treatment, thereby obtaining a biaxially stretched film.
At this time, the stretching ratio may be 2 times to 5 times, preferably 2.5 times to 5 times, more preferably 2.5 times to 4.0 times in the longitudinal direction, and may be 2.5 times to 5 times, preferably 3 times to 4.5 times, more preferably 3.2 times to 4.2 times in the transverse direction.
The stretching temperature may be in the range of glass transition temperature (Tg) +5 ℃ to Tg +50 ℃ of the polyester resin, or in the range of Tg +10 ℃ to Tg +40 ℃. At this time, as Tg is lowered, tensile properties are improved, but cracks may occur. In particular, when the stretching temperature is in the range of Tg +10 ℃ to Tg +40 ℃, the brittleness of the resulting film can be improved.
Further, the stretching speed in the longitudinal direction may be 22 to 500m/min, 25 to 400m/min, or 25 to 200 m/min. In this case, when the machine direction stretching speed is 22m/min or more, it is advantageous to maintain the orientation property expected in the present invention, and crystallinity is imparted according to the machine direction stretching speed, and thus the stretching ratio, the transverse direction stretching speed, may be varied according to the machine direction stretching condition.
According to the present invention, a polyester resin composition excellent in high heat resistance and high moisture resistance and a polyester film comprising the polyester resin composition can be provided.
Brief Description of Drawings
Fig. 1 is a graph showing the measurement results of the moisture absorption rate of the films of example 1(PCT) and comparative example 1 (PET).
Fig. 2 is a graph showing the measurement results of the hydrolysis resistance rate (high viscosity retention rate) of the films of example 1(PCT) and comparative example 1 (PET).
Fig. 3 is a photograph of the film surface taken when evaluating the hydrolysis resistance rate (high viscosity retention rate) of the films of example 1(PCT) and comparative example 1 (PET).
Fig. 4 is photographs of the film surface taken before and after oligomer evaluation of example 1(PCT) and comparative example 1 (PET).
Detailed description of the embodiments
The present invention is described in more detail in the following examples. However, these examples are for illustrative purposes only, and the contents of the present invention are not limited thereto.
Example 1
1) Preparation of polyester resin composition
2.0kg of 1, 4-cyclohexanedimethanol, 1.8kg of a dicarboxylic acid containing terephthalic acid and isophthalic acid in a molar ratio of 95 mol%: 5 mol%, 0.4g of triethyl phosphate, 0.2g of a titanium oxide based catalyst (Hombicast PC from Sachtleben, content of 15% by weight of Ti atoms in the catalyst) and 0.2g of antimony trioxide (content of 83.5% by weight of antimony atoms in the catalyst) were charged into a reactor. Then, the temperature was increased to 280 ℃ for 3 hours under normal pressure to perform the esterification reaction. Then, the esterification reaction product is heated to a temperature of 295 ℃ for 150 minutes under a pressure of 0.5 torr to 1 torr and undergoes polycondensation to produce a polyester resin, and then the polyester resin is processed into chips.
2) Production of biaxially stretched polyester film
The polyester resin chips were melt-extruded in an extruder, molded into a sheet, and cooled. The obtained sheet was stretched 3.6 times in the Machine Direction (MD) and then 3.8 times in the Transverse Direction (TD). The stretched film was heat-set at 238 ℃ to obtain a biaxially stretched polyester film.
Example 2 and example 3
A biaxially stretched polyester film was obtained in the same manner as the preparation method of example 1, except that the content of isophthalic acid was used in the molar ratio shown in table 1 below.
Comparative example 1
1.2kg of terephthalic acid and 1.2kg of ethylene glycol were charged into a reaction tank and subjected to normal polymerization at 258 ℃ to produce a polyethylene terephthalate (PET) polymer, and then the polyethylene terephthalate polymer was processed into chips. It was melt-extruded in an extruder, molded into a sheet, cooled, stretched 3.7 times in the Machine Direction (MD) and then 4.0 times in the Transverse Direction (TD) to produce a polyethylene terephthalate film.
Comparative example 2 to comparative example 4
A biaxially stretched polyester film was obtained in the same manner as the preparation method of example 1, except that the content of isophthalic acid was used in the molar ratio shown in table 1 below,
evaluation of
1. Measurement of glass transition temperature and the like by DSC analysis
The polyester resins of examples 1 to 3 and comparative examples 1 to 5 were analyzed by DSC (differential scanning calorimeter), and the glass transition temperature (Tg), the cold crystallization temperature (Tcc), the melting temperature (Tm), and the melt crystallization temperature (Tmc) were measured. Specifically, using DSC, the polyester resin was heated from 30 ℃ to 320 ℃ at a heating rate of 10 ℃/min, then held for 5 minutes, quenched to 30 ℃, and then held for 5 minutes. Subsequently, the glass transition temperature (Tg), the cold crystallization temperature (Tcc) and the melting temperature (Tm) were measured while increasing the temperature from 30 ℃ to 320 ℃ at a heating rate of 10 ℃/min. After holding at 320 ℃ for 5 minutes, the melt crystallization temperature (Tmc) was measured while cooling to 30 ℃ at a cooling rate of 10 ℃/min, and the results are shown in table 1 below.
2. Maximum thickness measurement of transparent unstretched sheet
The polyester resins of examples 1 to 3 and comparative examples 1 to 5 were melt-extruded in an extruder, and the maximum thickness of the unstretched sheet in a transparent state was measured before stretching in the Machine Direction (MD) and Transverse Direction (TD), and the results are shown in table 1 below.
3. Measurement of maximum draw ratio
The unstretched sheets of examples 1 to 3 and comparative examples 1 to 5 were biaxially stretched in both the machine direction and the transverse direction, the maximum stretching ratio was measured, and the results are shown in table 1 below.
4. Measurement of area Heat shrinkage
The films of examples 1 to 3 and comparative examples 1 to 5 were cut such that one edge was parallel to the machine direction (longitudinal direction) and the other edge was perpendicular to the machine direction (transverse direction), thereby preparing a square film sample of 10cm × 10cm square the film was held at 150 ℃ for 30 minutes in an oven in which air was circulated, and then the sample was taken out, and the length changes in the machine direction and the transverse direction were measured at room temperature.
[ equation 1]
Heat shrinkage (%) - (L)0-L)/L0]×100
In the equation L0Is the length before heat treatment and L is the length after heat treatment.
5. Evaluation of tensile elongation holding ratio
The films of example 1(PCT) and comparative example 1(PET) were maintained at a temperature of 121 ℃, a relative humidity of 100%, and an atmospheric Pressure of 2atm for 48 hours and 60 hours (Pressure Cooker Test), and then tensile elongation retention rates were measured, and the results are shown in table 1 below.
6. Evaluation of moisture absorption resistance
The films of example 1(PCT) and comparative example 1(PET) were held at a temperature of 85 ℃ and a relative humidity of 85% for 5000 hours, and then the weight gain was measured and plotted in fig. 1. Further, the moisture absorption rate after 5000 hours was calculated, and the results are shown in the following table 1.
7. Evaluation of hydrolysis resistance
(1) Measurement of intrinsic viscosity
After the films of example 1 and comparative example 1 were dissolved in o-chlorophenol at a concentration of 1.2g/dl, the intrinsic viscosity was measured at 35 ℃ using an Ubbelodhee viscosity tube.
(2) Measurement of hydrolysis resistance (unique viscosity retention)
The films of example 1 and comparative example 1 were maintained at a temperature of 85 ℃ and a relative humidity of 85% for 5000 hours, and then the degree of intrinsic viscosity maintenance was measured, and the results are shown in the graph of fig. 2. Further, the hydrolysis resistance rate (high viscosity retention rate) after 5000 hours is shown in the following table 1. In addition, the surfaces of example 1(PCT) and comparative example 1(PET) after 5000 hours were photographed and shown in fig. 3.
8. Oligomer evaluation
To investigate the elution of oligomers in the films of example 1 and comparative example 1, they were subjected to a heat treatment in an oven at 150 ℃ for about 60 minutes, and measured by observing the change using a haze meter. The results are shown in table 1 below.
A fog meter: NIPPON DENSHOKU NDH-7000 type
9. Evaluation of dielectric breakdown Voltage
The films of example 1 and comparative example 1 were used to produce a flexible flat cable, AC 1,000V was applied to adjacent conductors for 60 seconds to read the voltage when the films were broken and short-circuited, and the results are shown in table 1 below.
[ TABLE 1]
-IPA: isophthalic acid (IPA) content relative to 100 mol% of dicarboxylic acid component contained in polyester resin
-p.c.t.: known as the pressure cooker test (p.c.t) or autoclave test, a test that assesses whether a product can withstand a high temperature/high humidity environment. The test was carried out at a temperature of 121 ℃, a relative humidity of 100% and an atmospheric pressure of 2 atm.
From table 1, it was confirmed that the PCT films of examples 1 to 3 had low heat shrinkage and thus excellent heat resistance, and were excellent in moisture absorption resistance, hydrolysis resistance, and electrical characteristics, compared to the PET film of comparative example 1.
Further, it was confirmed that the PCT films of example 1 to example 3 had higher maximum stretching ratios and lower heat shrinkage rates than those of the PCT films of comparative example 2 to comparative example 5. Further, it was confirmed that the PCT films of example 1 to example 3 can control the thickness of the unstretched sheet to be thicker than the PCT films of comparative example 2 and comparative example 3.
Claims (16)
1. A polyester resin composition comprising a polyester resin comprising a polycondensate of a dicarboxylic acid component comprising terephthalic acid and isophthalic acid and a diol component comprising cyclohexanedimethanol,
wherein the polyester resin has a melting temperature of 250 ℃ or more,
the polyester resin has a difference (Tm-Tmc) between a melting temperature (Tm) and a melt crystallization temperature (Tmc) of 45 ℃ or more, and
the polyester resin has a difference (Tcc-Tg) between a cold crystallization temperature (Tcc) and a glass transition temperature (Tg) of 40 ℃ or higher.
2. The polyester resin composition according to claim 1,
wherein the content of the isophthalic acid is 3 to 20 mol% based on the total dicarboxylic acid component.
3. The polyester resin composition according to claim 1,
wherein the dicarboxylic acid component further comprises at least one other dicarboxylic acid component selected from the group consisting of: 2, 6-naphthalenedicarboxylic acid, dimethylisophthalic acid and dimethyl 2, 6-naphthalenedicarboxylic acid, and
the content of the other dicarboxylic acid component is 20 mol% or less based on the total dicarboxylic acid component.
4. The polyester resin composition according to claim 1,
wherein the diol component further comprises at least one other diol component selected from the group consisting of: ethylene glycol, diethylene glycol, 1, 4-butanediol, 1, 3-propanediol and neopentyl glycol, and
the content of the other diol component is 20 mol% or less based on the total diol component.
5. The polyester resin composition according to claim 1,
wherein the dicarboxylic acid component and the diol component have a molar ratio of 1:1 to 2.
6. The polyester resin composition according to claim 1,
wherein the polyester resin has an Intrinsic Viscosity (IV) of 0.4dl/g to 1.2 dl/g.
7. The polyester resin composition according to claim 1,
wherein the polyester resin has a number average molecular weight of 15,000 to 50,000 g/mol.
8. The polyester resin composition according to claim 1,
wherein the polyester resin has a weight average molecular weight of 50,000g/mol to 150,000 g/mol.
9. The polyester resin composition according to claim 1,
wherein the polyester resin has a melt crystallization temperature of 150 ℃ to 230 ℃.
10. A biaxially stretched polyester film formed using the polyester resin composition according to any one of claims 1 to 9.
11. A biaxially stretched polyester film according to claim 10,
the polyester film is a multilayer film or a laminated film having two or more layers, in which the polyester resin composition is coextruded.
12. A biaxially stretched polyester film according to claim 10,
wherein the biaxially stretched polyester film is used for a flexible flat cable.
13. A biaxially stretched polyester film according to claim 10,
wherein the biaxially stretched polyester film has a thermal shrinkage at 150 ℃ for 30 minutes of less than 0.5%, and a thermal shrinkage at 200 ℃ for 30 minutes of less than 1.0%.
14. A biaxially stretched polyester film according to claim 10,
wherein the biaxially stretched polyester film is stretched 2 to 5 times in a Machine Direction (MD) and 2 to 5 times in a Transverse Direction (TD).
15. A biaxially stretched polyester film according to claim 10,
wherein the biaxially stretched polyester film has a tensile elongation retention of 50% or more after the lapse of 48 hours and a tensile elongation retention of 30% or more after the lapse of 60 hours in a pressure cooker test at a temperature of 121 ℃, a relative humidity of 100% and an atmospheric pressure of 2 atm.
16. A biaxially stretched polyester film according to claim 10,
wherein the biaxially stretched polyester film has a moisture absorption resistance of 1% or less when the temperature is 85 ℃ and the relative humidity is 85%.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2017-0156747 | 2017-11-22 | ||
| KR20170156747 | 2017-11-22 | ||
| PCT/KR2018/013639 WO2019103370A1 (en) | 2017-11-22 | 2018-11-09 | Polyester resin composition and biaxially oriented polyester film comprising same |
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| Publication Number | Publication Date |
|---|---|
| CN111433262A true CN111433262A (en) | 2020-07-17 |
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| CN201880073906.2A Pending CN111433262A (en) | 2017-11-22 | 2018-11-09 | Polyester resin composition and biaxially stretched polyester film comprising same |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP2021504512A (en) |
| KR (1) | KR20190059216A (en) |
| CN (1) | CN111433262A (en) |
| DE (1) | DE112018005965T5 (en) |
| WO (1) | WO2019103370A1 (en) |
Cited By (3)
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| CN113248883A (en) * | 2021-06-04 | 2021-08-13 | 山东大学 | Medical flexible electromagnetic shielding film and preparation method and application thereof |
| CN115536992A (en) * | 2021-06-29 | 2022-12-30 | Skc株式会社 | Polyester resin composition, polyester film and flexible flat cable |
| TWI840726B (en) * | 2021-01-26 | 2024-05-01 | 南韓商愛思開邁克沃股份有限公司 | Polyester-based film, preperation method thereof, and membrane electrode assembly comprising same |
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| CN112789156A (en) | 2018-10-08 | 2021-05-11 | 伊士曼化工公司 | Crystallizable shrinkable films and thermoformable sheets made from resin blends |
| KR20210035932A (en) * | 2019-09-24 | 2021-04-02 | 진영글로벌 주식회사 | FFC with PCT film and Method for making the FFC |
| KR102369349B1 (en) * | 2019-10-02 | 2022-03-02 | 에스케이씨 주식회사 | Film and laminate for electronic board, and electronic board comprising same |
| WO2021086082A1 (en) * | 2019-10-31 | 2021-05-06 | 에스케이씨 주식회사 | Polyester film, method for manufacturing same, and method for recycling polyethylene terephthalate container using same |
| KR102258534B1 (en) | 2019-10-31 | 2021-05-31 | 에스케이씨 주식회사 | Polyester film and method for reproducing polyester container using same |
| KR102645450B1 (en) | 2021-12-20 | 2024-03-08 | 에스케이마이크로웍스 주식회사 | Polyester resin composition, polyester film, and flexible flat cable |
| KR20240003300A (en) | 2022-06-30 | 2024-01-08 | 에스케이마이크로웍스 주식회사 | Polyester film, and cable comprising the same |
| KR20240135440A (en) * | 2023-03-02 | 2024-09-11 | 에스케이마이크로웍스 주식회사 | Flexible laminate, polyester film, flexible flat cable, and flexible electronic board |
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Also Published As
| Publication number | Publication date |
|---|---|
| DE112018005965T5 (en) | 2020-07-30 |
| JP2021504512A (en) | 2021-02-15 |
| KR20190059216A (en) | 2019-05-30 |
| WO2019103370A1 (en) | 2019-05-31 |
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