WO2023101191A1 - Film à base de polyester et procédé de production s'y rapportant - Google Patents

Film à base de polyester et procédé de production s'y rapportant Download PDF

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Publication number
WO2023101191A1
WO2023101191A1 PCT/KR2022/015165 KR2022015165W WO2023101191A1 WO 2023101191 A1 WO2023101191 A1 WO 2023101191A1 KR 2022015165 W KR2022015165 W KR 2022015165W WO 2023101191 A1 WO2023101191 A1 WO 2023101191A1
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WIPO (PCT)
Prior art keywords
polyester
based film
less
film
filler
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PCT/KR2022/015165
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English (en)
Korean (ko)
Inventor
임병재
허영민
연제원
Original Assignee
에스케이마이크로웍스 주식회사
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Priority claimed from KR1020210171765A external-priority patent/KR102680741B1/ko
Application filed by 에스케이마이크로웍스 주식회사 filed Critical 에스케이마이크로웍스 주식회사
Publication of WO2023101191A1 publication Critical patent/WO2023101191A1/fr

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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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • 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
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general

Definitions

  • Embodiments relate to a polyester-based film and a method for producing the same.
  • Electronic boards such as circuit boards, which are essential components in electronic devices, have conductive patterns formed on insulating base films, and in particular, flexible printed circuit boards (FPCB) mounted on smart devices such as mobile phones and tablet PCs are representative.
  • FPCB flexible printed circuit boards
  • FCCL Flexible Copper Clad Laminate
  • Flexible copper clad laminates are generally manufactured by laminating copper foil on one side or both sides of a base film. was used as a base film.
  • liquid crystal crystalline polymers or polyimide-based resins have problems in that they have high unit price and high permittivity and low moisture resistance.
  • polyester-based resins are excellent in mechanical properties such as durability, chemical resistance, heat resistance, and optical properties such as transparency, they are widely used as various industrial materials such as display devices as well as materials such as fibers, films, and molded products.
  • polyester-based films manufactured using such polyester-based resins have excellent heat resistance and hydrolysis resistance, but have difficulties in processes such as winding due to soft and high surface friction coefficients, and poor driving performance. .
  • Korean Patent Publication No. 2006-0060082 discloses a flexible copper-clad laminate film in which the surface of a polyimide film is modified and applied to copper foil, but such a polyimide film has a high unit price and high permittivity and low moisture resistance. There is a limit to performance improvement, and since the film is immersed in a solution in the reforming step, moisture resistance may be further deteriorated.
  • Patent Document 1 Korean Patent Publication No. 2006-0060082
  • embodiments are intended to provide a polyester-based film and a method for manufacturing the same, which are excellent in processability such as winding and running performance, as well as mechanical properties and optical properties.
  • a polyester-based film includes a co-polyester-based resin in which a diol and two or more dicarboxylic acids are copolymerized; and a filler, and R d according to Equation 1 below is 2.5 or less.
  • R max is the maximum height roughness ( ⁇ m) of the polyester film
  • R a is the center line average roughness ( ⁇ m) of the polyester-based film.
  • a method for manufacturing a polyester-based film includes preparing a resin composition by mixing a co-polyester-based resin in which diols and dicarboxylic acids are copolymerized with a filler; Melting and extruding the resin composition to prepare an unstretched sheet; preparing a stretched sheet by first stretching the unstretched sheet in a first direction and secondarily stretching the unstretched sheet in a second direction perpendicular to the first direction; and preparing a polyester-based film by heat-setting the stretched sheet at 200° C. to 260° C., wherein the polyester-based film has an R d of 2.5 or less according to Formula 1.
  • the polyester-based film according to the embodiment has excellent processability such as winding and running performance of the film by controlling the surface roughness, as well as excellent mechanical properties and optical properties.
  • the polyester-based film has excellent dispersibility while satisfying 10-point average roughness (R z ), center line average roughness (R a ), and maximum height roughness (R max ) within preferred ranges, thereby providing mechanical properties and optical properties. It is possible to improve the surface properties at the same time without degrading.
  • Example 1 shows a scanning electron microscope (SEM) image of the polyester film of Example 1.
  • Figure 2 shows a scanning electron microscope (SEM) image of the polyester film of Example 2.
  • Figure 3 shows a scanning electron microscope (SEM) image of the polyester-based film of Example 3.
  • Figure 4 shows a scanning electron microscope (SEM) image of the polyester-based film of Comparative Example 1.
  • Embodiments are not limited to the contents disclosed below, and may be modified in various forms unless the gist of the invention is changed.
  • a polyester-based film includes a co-polyester-based resin in which a diol and two or more dicarboxylic acids are copolymerized; and a filler, and R d according to Equation 1 below is 2.5 or less.
  • R max is the maximum height roughness ( ⁇ m) of the polyester film
  • R a is the center line average roughness ( ⁇ m) of the polyester-based film.
  • a polyester film is generally manufactured using a roll, it is important to improve fairness such as winding property and driving performance in order to improve the quality of the polyester film produced.
  • organic and inorganic additives have been used to improve fairness such as film winding and running performance, but when these additives are used, there is a problem in that mechanical properties such as tensile strength and modulus, in particular, transparency are greatly deteriorated.
  • mechanical properties such as tensile strength and modulus, in particular, transparency are greatly deteriorated.
  • processability may be improved, but mechanical properties such as tensile strength and modulus of the prepared polyester film are lowered, and in particular, haze is reduced. increased, resulting in very low transparency.
  • the polyester-based film according to the embodiment includes a co-polyester-based resin in which a diol and two or more kinds of dicarboxylic acids are copolymerized and a filler, thereby effectively controlling the surface roughness of the film to improve fairness such as winding and driving performance of the film.
  • the polyester film has excellent dispersibility while satisfying 10-point average roughness (R z ), center line average roughness (R a ) and maximum height roughness (R max ) within preferred ranges, thereby improving mechanical properties and optical properties. Surface properties can also be improved at the same time without deterioration.
  • the polyester-based film has an R d of 2.5 or less according to Formula 1 below.
  • R max is the maximum height roughness ( ⁇ m) of the polyester-based film
  • R a is the center line average roughness ( ⁇ m) of the polyester-based film.
  • the R d represents the ratio between the surface roughness characteristics of the polyester film, and the R d may be 2.3 or less, 2.0 or less, 1.8 or less, or 1.6 or less, 0.3 to 2.5, 0.5 to 2.3, 0.5 to 2.1 , 0.6 to 1.8, 0.8 to 1.6 or 0.9 to 1.6.
  • the R d value satisfies the above range, it is possible to simultaneously improve mechanical properties and optical properties while controlling the surface roughness to a more preferable range to improve fairness such as winding and running performance of the film, and in particular, transparency by reducing haze. can maximize
  • the 10-point average roughness (R z ) of the polyester film is 0.8 ⁇ m or less.
  • the 10-point average roughness (R z ) of the polyester film may be 0.7 ⁇ m or less, 0.6 ⁇ m or less, 0.5 ⁇ m or less, or 0.3 ⁇ m or less, 0.01 ⁇ m to 0.8 ⁇ m, 0.05 ⁇ m to 0.6 ⁇ m, or 0.1 ⁇ m. ⁇ m to 0.5 ⁇ m or 0.15 ⁇ m to 0.3 ⁇ m.
  • the center line average roughness (R a ) of the polyester-based film is 0.05 ⁇ m or less.
  • the center line average roughness (R a ) of the polyester film may be 0.04 ⁇ m or less, 0.03 ⁇ m or less, or 0.02 ⁇ m or less, 0.001 ⁇ m to 0.05 ⁇ m, 0.005 ⁇ m to 0.04 ⁇ m, 0.01 ⁇ m to 0.03 ⁇ m, or It may be 0.01 ⁇ m to 0.03 ⁇ m.
  • the maximum height roughness (R max ) of the polyester-based film is 1.5 ⁇ m or less.
  • the maximum height roughness (R max ) of the polyester film may be 1.4 ⁇ m or less, 1.3 ⁇ m or less, 1.1 ⁇ m or less, or 1.0 ⁇ m or less, 0.1 ⁇ m to 1.5 ⁇ m, 0.2 ⁇ m to 1.4 ⁇ m, or 0.5 ⁇ m. to 1.3 ⁇ m, 0.6 ⁇ m to 1.1 ⁇ m, or 0.7 ⁇ m to 1.0 ⁇ m.
  • the surface roughness is controlled to a desirable range to wind and run the film.
  • Processability such as performance, can be improved, and surface properties can be improved at the same time without deteriorating mechanical properties and optical properties.
  • Surface roughness such as the 10-point average roughness (R z ), center line average roughness (R a ), and maximum height roughness (R max ) may be measured using a two-dimensional contact surface roughness meter (SE3300 manufactured by Kosaka).
  • the 10-point average roughness (R z ) is surface roughness according to KS B 0161.
  • R z the 10-point average roughness
  • the center line average roughness (R a ) is a surface roughness according to KS B 0161, and a straight line generated when a mountain is cut from a roughness curve to fill a valley is called a center line, and a measured length is taken in the direction of the center line, and from the center line It can be calculated by dividing the area of the upper part obtained by folding the lower part upwards by the measured length.
  • the maximum height roughness (R max ) is a surface roughness according to KS B 0161, a reference length is taken from a cross-sectional curve, and it is parallel to the center line of the cross-sectional curve and the highest peak and the deepest valley. Can be calculated as the distance between two parallel lines. there is.
  • the polyester-based film may have an RF of 0.8 or less according to Equation 2.
  • R max is the maximum height roughness ( ⁇ m) of the polyester-based film
  • F d is the kinetic friction coefficient of the polyester-based film.
  • the RF represents the ratio between the surface properties of the polyester-based film
  • the RF may be 0.75 or less, 0.7 or less, 0.65 or less, 0.6 or less, or 0.55 or less, 0.05 to 0.8, 0.05 to 0.8, 0.08 to 0.7 , 0.1 to 0.65, 0.15 to 0.6, 0.2 to 0.6 or 0.3 to 0.55.
  • the RF value satisfies the above range, surface roughness can be controlled to a more preferable range to simultaneously improve mechanical properties and optical properties, and in particular, transparency can be maximized by reducing haze.
  • the polyester-based film may have a dynamic coefficient of friction (F d ) of 0.6 or less, and a static coefficient of friction (F s ) of 0.75 or less.
  • the surface dynamic friction coefficient (F d ) of the film may be 0.5 or less or 0.55 or less
  • the surface static friction coefficient (F s ) of the film may be 0.74 or less, 0.73 or less, 0.7 or less, or 0.68 or less.
  • both mechanical properties and optical properties can be improved.
  • the surface roughness and the surface friction coefficient are not exactly proportional, and when the surface roughness and the surface friction coefficient satisfy the above ranges, respectively, haze can be reduced without deterioration of mechanical properties, thereby maximizing transparency.
  • Haze of the polyester film may be 8% or less.
  • the haze of the polyester film may be 8% or less, 6% or less, 5% or less, or 4.5% or less.
  • the polyester-based film according to the embodiment has excellent transparency while having excellent mechanical properties by having a haze that satisfies the above range while including a filler.
  • the transmittance of the polyester-based film may be 88% or more at a wavelength of 400 nm to 700 nm.
  • the transmittance of the polyester film at a wavelength of 400 nm to 700 nm may be 88.5% or more, 89% or more, or 89.5% or more.
  • Tensile strength of the polyester film may be 19 kgf/mm 2 or less.
  • the tensile strength of the in-plane first direction of the polyester film may be 19 kgf/mm 2 or less, 18 kgf/mm 2 or less, 16 kgf/mm 2 or less, or 15 kgf/mm 2 or less, and 10 kgf/mm 2 or less.
  • mm 2 to 19 kgf/mm 2 10 kgf/mm 2 to 16 kgf/mm 2 or 10 kgf/mm 2 to 15 kgf/mm 2 .
  • the tensile strength in the second direction perpendicular to the first direction in the plane of the polyester film may be 19 kgf/mm 2 or less or 18.5 kgf/mm 2 or less, 10 kgf/mm 2 to 19 kgf/mm 2 , 12 kgf/mm 2 to 19 kgf/mm 2 , 13 kgf/mm 2 to 18.5 kgf/mm 2 or 14.5 kgf/mm 2 to 18.5 kgf/mm 2 .
  • the polyester-based film When the tensile strength of the polyester-based film satisfies the above range, it can be used in a variety of ways, such as for metal replacement, electronic boards or display devices, and can be more advantageous in implementing weight reduction due to excellent mechanical properties.
  • the first direction may be a width direction (TD) or a length direction (MD).
  • the first direction may be a length direction (MD)
  • the second direction perpendicular to the first direction may be a width direction (TD).
  • the elongation at break of the polyester-based film may be 30% or more.
  • the elongation at break in the first in-plane direction of the polyester-based film may be 30% or more, 35% or more, 40% or more, or 42% or more, and the second in-plane direction perpendicular to the first direction of the polyester-based film
  • the elongation at break in the direction may be 30% or more, 32% or more, or 34% or more.
  • the polyester film When the elongation at break of the polyester film satisfies the above range, it can be used in a variety of ways for metal replacement, electronic boards or display devices due to its excellent mechanical properties, and can be more advantageous in implementing weight reduction.
  • Modulus of the polyester-based film may be 320 kgf/mm 2 or less. Specifically, the modulus of the polyester-based film in the first direction in the plane is 320 kgf/mm 2 or less, 310 kgf/mm 2 or less, 300 kgf/mm 2 or less, 290 kgf/mm 2 or less, or 288 kgf/mm 2 or less.
  • the modulus of the polyester film in the second direction perpendicular to the first in-plane direction is 320 kgf/mm 2 or less, 310 kgf/mm 2 or less, 305 kgf/mm 2 or less, 300 kgf/mm 2 or less, or 299 kgf/mm 2 or less, 230 kgf/mm 2 to 320 kgf/mm 2 , 260 kgf/mm 2 to 310 kgf/mm 2 , 275 kgf/mm 2 to 320 kgf/mm 2 , 275 kgf/mm 2 to 300 kgf/mm 2 or 280 kgf/mm 2 to 299 kgf/mm 2 .
  • the tensile strength, elongation at break and modulus may be measured at room temperature according to ASTM D 882 by using a universal testing machine (4206-001, manufactured by INSTRON).
  • the polyester-based film may have a thickness of 1 ⁇ m to 500 ⁇ m, 5 to 250 ⁇ m, 10 to 150 ⁇ m, 10 ⁇ m to 100 ⁇ m, 10 ⁇ m to 80 ⁇ m, or 30 ⁇ m to 60 ⁇ m.
  • the polyester-based film includes a co-polyester-based resin in which a diol and two or more kinds of dicarboxylic acids are copolymerized.
  • the diol includes cyclohexanedimethanol or a derivative thereof.
  • the diol may include 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol or 1,4-cyclohexanedimethanol, preferably 1,4-cyclohexanedimethanol can include More specifically, the diol may include 1,4-cyclohexanedimethanol or a derivative thereof.
  • the diol may include 70 mol% or more of cyclohexanedimethanol or a derivative thereof.
  • the copolyester-based resin contains cyclohexanedimethanol or a derivative thereof in an amount of 72 mol% or more, 75 mol% or more, 85 mol% or more, 88 mol% or more, or 90 mol% based on the total number of moles of the diol. or more, 93 mol% or more, 95 mol% or more, 97 mol% or more, 99 mol% or more, or 100 mol%.
  • Flexibility, durability, and hydrolysis resistance can be improved by including cyclohexanedimethanol or a derivative thereof in the diol, and durability, heat resistance, and hydrolysis resistance can be maximized when the diol is composed of only cyclohexanedimethanol. .
  • the diol may include at least one selected from the group consisting of ethylene glycol, neopentyl glycol, and diethylene glycol, if necessary.
  • the copolymerized polyester-based resin contains 1 mol% to 30 mol%, 1 mol% to 1 mol% of at least one selected from the group consisting of ethylene glycol, neopentyl glycol and diethylene glycol based on the total number of moles of the diol. 20 mol%, 1 mol% to 15 mol%, 1 mol% to 10 mol%, or 1 mol% to 5 mol%.
  • the dicarboxylic acid may include two or more dicarboxylic acids.
  • the dicarboxylic acid may include a first dicarboxylic acid and a second dicarboxylic acid, the first dicarboxylic acid may be terephthalic acid, and the second dicarboxylic acid may be isophthalic acid. there is.
  • the dicarboxylic acid may include 70 mol% to 99 mol% of terephthalic acid and 1 mol% to 30 mol% of isophthalic acid.
  • the copolyester-based resin contains 73 mol% to 99 mol%, 75 mol% to 99 mol%, 80 mol% to 98 mol%, 83 mol% of terephthalic acid based on the total number of moles of the dicarboxylic acid.
  • % to 98 mol% or 85 mol% to 98 mol% or 1 mol% to 28 mol%, 1 mol% to 25 mol%, 1 mol% to 20 mol%, 2 mol% to 2 mol% isophthalic acid 15 mol%, 3 mol% to 13 mol%, 3 mol% to 10 mol%, or 3 mol% to 8 mol%.
  • contents of terephthalic acid and isophthalic acid satisfy the above ranges, flexibility, durability, heat resistance and hydrolysis resistance may be improved.
  • the co-polyester-based resin may include an additional dicarboxylic acid other than the first and second dicarboxylic acids.
  • the additional dicarboxylic acid may include dimethyl terephthalic acid, and for example, the co-polyester-based resin is present in an amount of 1 mol% to 15 mol%, 1 mol% to 10 mol% based on the total number of moles of the dicarboxylic acid. Or 3 mol% to 7 mol% of dimethyl terephthalic acid may be further included.
  • the co-polyester-based resin according to the embodiment may include a polycyclohexylenedimethylene terephthalate (PCT) resin.
  • PCT polycyclohexylenedimethylene terephthalate
  • the copolymerized polyester-based resin includes polycyclohexylenedimethylene terephthalate (PCT) resin, it has excellent heat resistance and chemical resistance compared to polyethylene terephthalate (PET) resin and polybutylene terephthalate (PBT) resin. and hygroscopicity. Therefore, mechanical properties such as tensile strength and modulus may be improved while crystallinity increases due to excellent crystallization characteristics during the manufacturing process through melt extrusion, stretching, etc. at a high temperature.
  • PCT polycyclohexylenedimethylene terephthalate
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • the copolyester-based resin contains 1 mol% to 30 mol% of isophthalic acid as dicarboxylic acid, it may be excessively high as cyclohexylenedimethylene is included. It is more advantageous to increase the handleability of the polymer by lowering the melting point (Tm) while lowering the possible crystallization rate.
  • the polyester-based film may include 85% by weight or more of the co-polyester-based resin.
  • the content of the co-polyester-based resin is 88% by weight or more, 90% by weight or more, 93% by weight or more, 95% by weight or more, 98% by weight or more, 99% by weight or more based on the total weight of the polyester-based film. % or more than 100%, 85% to 100%, 90% to 100%, 95% to 100% or 98% to 100%.
  • the co-polyester-based resin may further include at least one additive selected from the group consisting of an ultraviolet stabilizer, a heat stabilizer, an antioxidant, and an inert particle.
  • the UV stabilizer may be at least one selected from the group consisting of benzophenone-based, benzotriazole-based, cyanoacrylate-based, and salicylic acid ester-based compounds
  • the heat stabilizer may be an iodine-based compound
  • the antioxidant may be a phosphorus-based antioxidant, a phenol-based antioxidant, or a sulfur-based antioxidant
  • the inert particle may be silica or potassium carbonate, but is not limited thereto.
  • the content of the additive is 0.5% to 15% by weight, 1% to 13% by weight, 1.2% to 12% by weight, 1.5% to 10% by weight, 1.7% by weight based on the total weight of the co-polyester-based resin. % to 8% or 1.8% to 7.5%.
  • the polyester-based film may include a filler.
  • the polyester film according to the embodiment has a 10-point average roughness (R z ), center line average roughness (R a ) and maximum height roughness (R max ) of the polyester film according to the type, physical properties and content of the filler. ), as well as mechanical properties such as friction coefficient, tensile strength, elongation at break and modulus, and optical properties such as haze and light transmittance may vary.
  • the polyester-based film by including the filler, controls the surface roughness to a desirable range and has excellent optical properties, particularly low haze, and excellent transparency without deteriorating mechanical properties.
  • the surface roughness characteristics and optical characteristics of the film may be significantly different depending on the particle size, shape, and physical properties of the filler.
  • the filler may include at least one selected from the group consisting of titanium dioxide, barium sulfate, calcium carbonate, magnesium carbonate, zinc carbonate, zinc oxide, magnesium oxide, alumina, and silica. Specifically, when the filler includes silica, it may be preferable in terms of optical properties, but is not limited thereto.
  • the filler may be spherical having a spherical shape.
  • the polyester film can further improve dispersibility and control the surface roughness more effectively, as compared to the case of including a bulky filler in the form of a lump. may have characteristics.
  • the filler may include spherical silica beads, and when the filler includes spherical silica beads, surface roughness can be more effectively controlled and haze can be reduced to maximize transparency.
  • the average particle diameter (D sem ) of the filler may be 0.01 ⁇ m to 2.0 ⁇ m.
  • the average particle diameter (D sem ) of the filler is 0.01 ⁇ m to 1.9 ⁇ m, 0.01 ⁇ m to 1.8 ⁇ m, 0.02 ⁇ m to 1.3 ⁇ m, 0.03 ⁇ m to 1.0 ⁇ m, 0.05 ⁇ m to 0.8 ⁇ m, 0.1 ⁇ m to 0.5 ⁇ m, or It may be 0.15 ⁇ m to 0.4 ⁇ m.
  • polyester-based films have limitations in mechanical properties such as tensile strength, elongation at break, and modulus that can be improved by adjusting process conditions such as stretching temperature, elongation rate, and heat setting temperature.
  • the polyester-based film according to the embodiment may further improve mechanical properties such as tensile strength, elongation at break and modulus without additional process cost by maintaining existing process conditions by including a filler having an average particle diameter satisfying the above range. there is.
  • the D 10 of the filler may be 0.05 ⁇ m to 0.5 ⁇ m.
  • the D 10 of the filler may be 0.05 ⁇ m to 0.45 ⁇ m, 0.1 ⁇ m to 0.4 ⁇ m, 0.13 ⁇ m to 0.36 ⁇ m, 0.18 ⁇ m to 0.33 ⁇ m, 0.2 ⁇ m to 0.31 ⁇ m, or 0.21 ⁇ m to 0.28 ⁇ m.
  • D 50 of the filler may be 0.12 ⁇ m to 0.65 ⁇ m.
  • the D 50 of the filler may be 0.14 ⁇ m to 0.55 ⁇ m, 0.16 ⁇ m to 0.5 ⁇ m, 0.18 ⁇ m to 0.35 ⁇ m, 0.22 ⁇ m to 0.32 ⁇ m, or 0.25 ⁇ m to 0.3 ⁇ m.
  • D 90 of the filler may be 0.25 ⁇ m to 0.75 ⁇ m.
  • the D 90 of the filler may be 0.26 ⁇ m to 0.65 ⁇ m, 0.28 ⁇ m to 0.58 ⁇ m, 0.31 ⁇ m to 0.52 ⁇ m, 0.35 ⁇ m to 0.48 ⁇ m, or 0.36 ⁇ m to 0.46 ⁇ m.
  • the particle diameter of the filler may be measured by a laser diffraction particle size distribution measurement method, for example, a wet laser diffraction particle size distribution measurement method.
  • 0.3 g of the filler is mixed with 30 ml of isopropyl alcohol and ultrasonicated for 5 minutes at a power of 45 W to prepare a dispersion, and the particle size distribution of the filler in the dispersion may be measured with a particle size distribution analyzer.
  • the cumulative 50% particle size based on the volume was indicated as D 50 .
  • the polyester film may include the filler in an amount of 500 ppm to 2,000 ppm.
  • the content of the filler may be 550 ppm to 2,000 ppm, 600 ppm to 2,000 ppm, 700 ppm to 1,500 ppm, or 800 ppm to 1,300 ppm based on the total weight of the polyester film.
  • a method for manufacturing a polyester-based film includes preparing a resin composition by mixing a co-polyester-based resin in which diols and dicarboxylic acids are copolymerized with a filler; Melting and extruding the resin composition to prepare an unstretched sheet; preparing a stretched sheet by first stretching the unstretched sheet in a first direction and secondarily stretching the unstretched sheet in a second direction perpendicular to the first direction; and preparing a polyester-based film by heat-setting the stretched sheet at 200° C. to 260° C., wherein the polyester-based film has an R d of 2.5 or less according to Formula 1.
  • a resin composition is prepared by mixing a co-polyester-based resin in which diols and dicarboxylic acids are copolymerized with a filler .
  • the co-polyester-based resin may be formed by polymerization after a diol and a dicarboxylic acid undergo transesterification. Descriptions of the diol, dicarboxylic acid, and co-polyester-based resin are as described above.
  • a copolymerized polyester-based resin may be prepared by mixing a diol and a dicarboxylic acid, performing an ester exchange reaction by introducing a transesterification catalyst, and then proceeding with a polymerization reaction.
  • the catalyst for the transesterification reaction may be at least one selected from the group consisting of manganese acetate tetrahydrate, calcium acetate, and zinc acetate.
  • the amount of the transesterification catalyst may be 0.02 part by weight to 0.2 part by weight, 0.02 part by weight to 0.1 part by weight, or 0.05 part by weight to 0.1 part by weight based on the total weight of the dicarboxylic acid.
  • stabilizers such as trimethylphosphate
  • titanium such as titanium isopropoxide, tetrapropyl titanate, tetrabutyl titanate or tetraisopropyl titanate, germanium oxide, germanium methoxide, germanium ethoxide, tetramethyl germanium, te
  • the content of the polymerization catalyst may be 0.00001 wt % to 0.001 wt % or 0.00005 wt % to 0.0005 wt % based on the total weight of the co-polyester resin.
  • a resin composition may be prepared by adding and mixing a filler to the co-polyester-based resin prepared above. Description of the filler is as described above.
  • the step of preparing the resin composition may include the step of first mixing the co-polyester-based resin and the filler, and the step of secondarily mixing the first mixture with a base resin. .
  • the quality of the polyester film produced by first mixing the co-polyester-based resin and the filler and additionally using a raw resin having the same components and contents as the co-polyester-based resin can be further improved.
  • the raw material resin may include a diol and a dicarboxylic acid.
  • the diol and dicarboxylic acid of the raw resin may have the same type and content as the diol and dicarboxylic acid of the co-polyester-based resin.
  • the quality of the produced polyester-based film can be further improved.
  • the content of the co-polyester-based resin added in the first mixing step may be 95% by weight or more or 97% by weight or more, 95% to 99.5% by weight, 95% to 99% by weight or 97% by weight. % to 99% by weight.
  • the content of the filler added in the mixing step may be 5% by weight or less, 4% by weight or less, or 3% by weight or less, 0.5% to 5% by weight, 0.5% to 4% by weight, or 1% to 3% by weight. weight percent.
  • the first mixture may be mixed in an amount of 1 part by weight to 10 parts by weight.
  • 1 part by weight to 10 parts by weight, 1 part by weight to 8 parts by weight, 1.5 parts by weight to 6 parts by weight, or 2 parts by weight to 5 parts by weight may be introduced and mixed.
  • the resin composition is melt-extruded to prepare an unstretched sheet .
  • cooling may be performed to prepare an unstretched sheet.
  • the melt-extruding step may be performed at a temperature of Tm+5°C to Tm+70°C, Tm+5°C to Tm+50°C or Tm+7°C to Tm+35°C, and the cooling step is Tg-120°C. to Tg+20°C, Tg-110°C to Tg+10°C, Tg-105°C to Tg-30°C, Tg-105°C to Tg-50°C, Tg-105°C to Tg-65°C, Tg-105°C to Tg-80 °C.
  • the melt extrusion temperature may be 260 ° C to 320 ° C, 270 ° C to 310 ° C or 270 ° C to 295 ° C
  • the cooling temperature may be -20 ° C to 100 ° C, 0 ° C to 90 ° C, 5 ° C to 75°C, 10°C to 60°C, 10°C to 50°C or 15°C to 45°C.
  • the melt-extrusion temperature satisfies the above range, the viscosity of the extrudate may be appropriately maintained while melting is smooth.
  • a stretched sheet is prepared by first stretching the unstretched sheet in a first direction and secondarily stretching it in a second direction perpendicular to the first direction.
  • the primary stretching may be performed at a stretching rate of 2 to 5 times at a temperature of 60° C. to 120° C.
  • the first stretching step is 2 to 5 times, 2.5 times at a temperature of 60 ° C to 120 ° C, 70 ° C to 110 ° C, 75 ° C to 105 ° C, 80 ° C to 100 ° C or 85 ° C to 100 ° C. to 4.5 times, 2.5 times to 4 times, or 2.9 times to 3.5 times.
  • the temperature and elongation rate of the primary stretching satisfy the above ranges, heat resistance, durability and hydrolysis resistance can be improved.
  • secondary stretching is performed in a second direction perpendicular to the first direction.
  • the secondary stretching may be performed at a stretching rate of 2 to 5 times.
  • the secondary stretching is 2 to 5 times, 2.5 times to 2.5 times at a temperature of 70 °C to 140 °C, 80 °C to 140 °C, 90 °C to 135 °C, 100 °C to 130 °C or 115 °C to 125 °C. It may be performed at a stretch rate of 5x, 3x to 4.5x or 3.5x to 4.5x.
  • a preheating step or a coating step may be additionally performed before the second stretching.
  • the preheating step may be performed at 70 °C to 120 °C for 0.01 to 1 minute.
  • the preheating temperature may be 70°C to 120°C, 75°C to 115°C, or 80°C to 110°C
  • the preheating time may be 0.01 to 1 minute, 0.05 minutes to 0.5 minutes, or 0.08 minutes to 0.2 minutes. there is.
  • the coating step is a step capable of imparting functionality such as antistatic to the polyester film, and may be performed by spin coating or in-line coating, but is not limited thereto.
  • a ratio (d1/d2) of the stretching ratio d1 in the first direction and the stretching ratio d2 in the second direction may be 0.5 to 1.
  • the ratio (d1/d2) of the stretching ratio d1 in the first direction and the stretching ratio d2 in the second direction may be 0.5 to 0.95, 0.65 to 0.95, or 0.7 to 0.9.
  • the stretched sheet is heat-set at 200° C. to 260° C. to prepare a polyester-based film .
  • the heat setting may be annealing, and may be performed at 200° C. to 260° C. for 0.01 minute to 1 minute.
  • the heat setting temperature may be 200 ° C to 260 ° C, 210 ° C to 250 ° C, 225 ° C to 250 ° C, or 235 ° C to 245 ° C
  • the heat setting time is 0.05 to 0.5 minutes or 0.08 minutes to 0.08 minutes. It may be 0.2 minutes, but is not limited thereto.
  • a step of relaxing the heat-set sheet in a first direction or in a second direction perpendicular to the first direction may be further performed.
  • the heat-set sheet is firstly relaxed in a first direction and then secondarily relaxed in a second direction, or the heat-set sheet is firstly relaxed in a second direction and then the first direction
  • a second relaxation step may be additionally performed.
  • the heat-set sheet may be first relaxed in the TD direction and then secondarily relaxed in the MD direction.
  • the relaxation step is 0.5% to 5%, 0.8% at a temperature of 100 ° C to 180 ° C or 110 ° C to 175 ° C. % to 4% or 0.8% to 3.5% relaxation rate.
  • the first relaxation may be performed at an elongation rate of 1% to 10% in the second direction
  • the second relaxation may be performed at an elongation rate of 0.5% or more to less than 2% in the first direction.
  • the first relaxation step may be performed at a relaxation rate of 0.5% or more to less than 2% at a temperature of 150 ° C to 200 ° C
  • the second relaxation step may be performed at a relaxation rate of 0.5% to 5% at a temperature of 110°C to 190°C.
  • the first relaxation step is 1% to 10%, 1% to 9%, 1.5% at a temperature of 150 ° C to 200 ° C, 155 ° C to 200 ° C, 160 ° C to 180 ° C or 165 ° C to 175 ° C. to 8%, 1.5% to 7%, 2% to 6%, or 2% to 5% relaxation rate
  • the second relaxation step is 110°C to 190°C, 110°C to 180°C, 110°C 0.5% to less than 2%, 0.5% to 1.95%, 0.7% to 1.8% or 0.9% to 1.6% at a temperature of from 170 ° C, 115 ° C to 150 ° C, 115 ° C to 140 ° C or 115 ° C to 130 ° C. It can be done with a relaxation rate.
  • the first relaxation rate: the second relaxation rate may be 1:0.1 to 1.0.
  • the first relaxation rate: the second relaxation rate may be 1:0.1 to 0.9, 1:0.1 to 0.8, 1:0.2 to 0.7, or 1:0.25 to 0.65.
  • the second relaxation step may be performed in two or more sections, and the second relaxation rate may be the total sum of the relaxation rates of each section.
  • the second relaxation rate is 2 %am.
  • the transport speed of the film in the second relaxation step may be 1% to 10% slower than the transport speed of the film in the first relaxation step.
  • the transport speed of the film in the secondary relaxation step may be 2% to 10% or 2% to 8% slower than the transport speed of the film in the first relaxation step.
  • tetrabutyl titanate based on 100 parts by weight of the dicarboxylic acid was added as a polymerization catalyst and stirred for 10 minutes. Thereafter, the reactants were transferred to a separate reactor equipped with a vacuum facility, and a polymerization reaction was performed at 300 ° C. for 180 minutes to prepare a copolymerized polyester-based resin (polycyclohexanedimethylene terephthalate (PCT) resin).
  • PCT polycyclohexanedimethylene terephthalate
  • a resin composition was prepared by secondarily mixing 4 parts by weight of the primary mixture with 96 parts by weight of a base resin.
  • the raw material resin contained 100 mol% of cyclohexanedimethanol (CHDM) as a diol, and 96 mol% of terephthalic acid (TPA) and 4 mol% of isophthalic acid (IPA) as dicarboxylic acids.
  • the content of the silica beads in the resin composition prepared by the secondary mixing was 1,000 ppm.
  • a resin composition was prepared in the same manner as in Preparation Example 2-1, except that blocky silica beads (D sem : 3.5 ⁇ m) were used.
  • a polyester-based film was prepared in the same manner as in Example 1, except that process conditions were applied as shown in Table 1 below.
  • Example 1 Preparation Example 2-1 3.0 4.0 90 120 240
  • Example 2 Preparation Example 2-1 3.2 3.9 90 120 240
  • Example 3 Preparation Example 2-1 3.4 4.0 90 120 240 Comparative Example 1 Preparation Example 2-2 3.0 3.9 90 120 240 Comparative Example 2
  • the 10-point average roughness (R z ) is a surface roughness according to KS B 0161, and when the surface is first cut with a plane perpendicular to the surface of the film, a section appearing on the cut surface is enlarged and recorded by a reference length in the cross-sectional curve was collected, and an arbitrary straight line parallel to the average line of the cross-sectional curve was set as the reference line. At this time, the difference between the average value of the distance from the baseline for the five highest peaks and the average value for the distance from the baseline for the five lowest valleys was calculated.
  • the center line average roughness (R a ) is a surface roughness according to KS B 0161, and a straight line generated when a mountain is cut from a roughness curve to fill a valley is called a center line, and a measured length is taken in the direction of the center line, and from the center line It was calculated by dividing the area of the upper part obtained by folding the lower part upward by the measured length.
  • the maximum height roughness (R max ) is a surface roughness according to KS B 0161, a reference length is taken from a cross-sectional curve, and the distance between two parallel lines that are parallel to the center line of the cross-sectional curve and touch the highest peak and the deepest valley was calculated. .
  • R d was calculated according to Equation 1 below.
  • R max is the maximum height roughness ( ⁇ m) of the polyester-based film
  • R a is the center line average roughness ( ⁇ m) of the polyester-based film.
  • R max is the maximum height roughness ( ⁇ m) of the polyester-based film
  • F d is the kinetic friction coefficient of the polyester-based film.
  • Samples were prepared by cutting the films prepared in Examples 1 to 3 and Comparative Examples 1 to 3 into a size of 150 mm in width and 100 mm in length, and in accordance with ASTM D 882, an INSTRON universal testing machine (4206 -001, manufacturer: UTM) at a test speed of 200 mm/min, the tensile strength was measured three times for the same sample, and the average value was calculated.
  • Samples were prepared by cutting the films prepared in Examples 1 to 3 and Comparative Examples 1 to 3 into a size of 150 mm in width and 100 mm in length, and in accordance with ASTM D 882, an INSTRON universal testing machine (4206 -001, manufacturer: UTM) at a test speed of 200 mm/min, the elongation at break was measured three times for the same sample, and the average value was calculated.
  • ASTM D 882 an INSTRON universal testing machine (4206 -001, manufacturer: UTM) at a test speed of 200 mm/min
  • Modulus of the films prepared in Examples 1 to 3 and Comparative Examples 1 to 3 was measured according to KS B 5521.
  • the haze of the films prepared in Examples 1 to 3 and Comparative Examples 1 to 3 was measured using a haze meter (SEP-H, manufactured by Nihon Semitsu Kogaku).
  • the light transmittance at 380 nm was measured using UltraScan PRO (manufacturer: Hunterlab).
  • FIGS. 1 to 3 show scanning electron microscope (SEM) images of the polyester films of Examples 1 to 3
  • FIGS. 4 to 6 are scanning electron microscope images of the polyester films of Comparative Examples 1 to 3 ( SEM) images are shown.
  • polyester films of Examples 1 to 3 had better dispersibility than the films of Comparative Examples 1 to 3, so that the surface roughness was effectively controlled while having excellent surface properties.
  • polyester films of Examples 1 to 3 exhibited superior optical properties and mechanical properties compared to the films of Comparative Examples 1 to 3.
  • the 10-point average roughness (R z ), the center line average roughness (R a ), and the maximum height roughness (R max ) are all controlled within a specific range, thereby increasing the friction coefficient and tensile strength.
  • optical properties such as haze and light transmittance were all excellent without degradation of mechanical properties such as elongation at break and modulus.
  • the 10-point average roughness (R z ), the center line average roughness (R a ), and the maximum height roughness (R max ) do not satisfy desirable ranges, and thus have poor optical properties such as haze and light transmittance. has been lowered

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

Un mode de réalisation concerne : un film à base de polyester qui comprend une charge et une résine à base de polyester copolymérisée formée par copolymérisation d'un diol et d'un acide dicarboxylique et qui a un Rd, selon la formule 1 pour la rugosité arithmétique moyenne (Ra) et la rugosité maximale (Rmax), d'au maximum 2,5 ; et un procédé de production s'y rapportant. Le film à base de polyester comprend une charge spécifique et ainsi la rugosité de surface du film à base de polyester peut être réglée et par conséquent, l'aptitude au traitement, notamment les performances d'enroulement et d'avancée, est améliorée et de plus, les propriétés mécaniques et optiques sont améliorées et ainsi le film à base de polyester a une excellente qualité.
PCT/KR2022/015165 2021-12-03 2022-10-07 Film à base de polyester et procédé de production s'y rapportant WO2023101191A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4939232A (en) * 1988-07-05 1990-07-03 Diafoil Company, Ltd. Shrinkable polyester film
US6372326B1 (en) * 1998-04-13 2002-04-16 Teijin Limited Biaxially oriented polyester film to be molded and laminated on metal sheet
KR20150075471A (ko) * 2013-12-26 2015-07-06 코오롱인더스트리 주식회사 폴리에스테르 수지 조성물 및 이를 이용한 폴리에스테르 필름
KR20150094992A (ko) * 2014-02-12 2015-08-20 에스케이씨 주식회사 고내열성을 가지는 폴리에스테르 필름
KR20170080025A (ko) * 2015-12-31 2017-07-10 코오롱인더스트리 주식회사 폴리사이클로헥실렌디메틸렌 테레프탈레이트 필름 및 이의 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4939232A (en) * 1988-07-05 1990-07-03 Diafoil Company, Ltd. Shrinkable polyester film
US6372326B1 (en) * 1998-04-13 2002-04-16 Teijin Limited Biaxially oriented polyester film to be molded and laminated on metal sheet
KR20150075471A (ko) * 2013-12-26 2015-07-06 코오롱인더스트리 주식회사 폴리에스테르 수지 조성물 및 이를 이용한 폴리에스테르 필름
KR20150094992A (ko) * 2014-02-12 2015-08-20 에스케이씨 주식회사 고내열성을 가지는 폴리에스테르 필름
KR20170080025A (ko) * 2015-12-31 2017-07-10 코오롱인더스트리 주식회사 폴리사이클로헥실렌디메틸렌 테레프탈레이트 필름 및 이의 제조방법

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