WO2017022742A1 - Polyester film - Google Patents
Polyester film Download PDFInfo
- Publication number
- WO2017022742A1 WO2017022742A1 PCT/JP2016/072608 JP2016072608W WO2017022742A1 WO 2017022742 A1 WO2017022742 A1 WO 2017022742A1 JP 2016072608 W JP2016072608 W JP 2016072608W WO 2017022742 A1 WO2017022742 A1 WO 2017022742A1
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- WIPO (PCT)
- Prior art keywords
- shrinkage
- film
- temperature
- heat
- main shrinkage
- Prior art date
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Classifications
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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
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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
- B29C61/00—Shaping by liberation of internal stresses; Making preforms having internal stresses; Apparatus therefor
- B29C61/02—Thermal shrinking
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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
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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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
Definitions
- the present invention relates to a polyester film having special thermal characteristics.
- Heat shrink films are widely used for packaging, labeling, etc., but recently, water-based inks, special inks, water-based coatings, special coatings, etc., such as coatings that involve heating processes in the coating and drying processes, etc.
- the original film has heat resistance that does not undergo deformation such as shrinkage at a low temperature of about 90 ° C. in the coating and drying process, and heat shrinkage that shrinks greatly at a high temperature in the subsequent shrinking process.
- packaging applications centering on bottle containers such as tea and soft drinks decorative applications that give high-design designs to members with complex shapes using film shrinkage, optical layers such as retardation forming layers
- optical layers such as retardation forming layers
- a heat-shrinkable film a uniaxially stretched film as typified by Patent Documents 1 and 2 for shrinking in a specific direction, and stretching in the transverse direction and then biaxially stretching in the longitudinal direction to cause heat shrinkage only in the specified direction Film is known.
- an object of the present invention is to provide a polyester film that does not shrink at a process temperature of about 90 ° C., such as a coating process or a drying process, or has a small shrinkage rate, and that shrinks greatly at the shrinking process temperature.
- the polyester film according to the present invention has a 150 ° C. heat shrinkage rate in the main shrinkage direction of 15% or more and a 150 ° C. heat shrinkage rate in a direction orthogonal to the main shrinkage direction of less than 15%.
- the 90 ° C. heat shrinkage rate in the shrinking direction is 14% or less.
- the 150 ° C. heat shrinkage rate in the main shrinkage direction is 15% or more and the 150 ° C. heat shrinkage rate in the direction orthogonal to the main shrinkage direction is less than 15%
- the glass transition temperature obtained from the temperature modulation DSC is 100 ° C. or more. It is characterized by being.
- the polyester film according to the present invention has special thermal properties that shrink at 15% or more in the main shrinkage direction at 150 ° C., less than 15% in the direction orthogonal to the main shrinkage direction, and less than 14% in the main shrinkage direction at 90 ° C.
- the polyester film according to the present invention has a 150 ° C. heat shrinkage rate in the main shrinkage direction of 15% or more and a 150 ° C. heat shrinkage rate in a direction orthogonal to the main shrinkage direction of less than 15%, and is obtained from temperature-modulated DSC. It has special thermal characteristics with a glass transition temperature of 100 ° C. or higher.
- the shrinkage rate is small at 90 ° C., and sufficient heating for spreading and drying of the coating agent is possible in the application process and drying process of various functional layers, and then 15% or more in the main shrink direction at 150 ° C.
- it exhibits a special heat shrinkage that shrinks in a specific direction that shrinks less than 15% in a direction perpendicular to the main shrinkage direction, and thus can be preferably used as a packaging application, a decoration application, or an optical application. .
- ethylene glycol is preferably 80 mol% or more.
- 1,2-propanediol, 1,3- Aliphatic dihydroxy compounds such as propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, poly Polyoxyalkylene glycols such as tetramethylene glycol, alicyclic dihydroxy compounds such as 1,4-cyclohexanedimethanol, aromatic dihydroxy compounds such as bisphenol A and bisphenol S, and It may include their derivatives.
- terephthalic acid is preferably 80 mol% or more, but as other components, for example, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic Aromatic dicarboxylic acids such as acid, diphenyldicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenoxyethanedicarboxylic acid, aliphatic dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, sebacic acid, dimer acid, maleic acid, fumaric acid, Examples thereof include alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, oxycarboxylic acids such as paraoxybenzoic acid, and derivatives thereof.
- dicarboxylic acid derivatives include dimethyl terephthalate, diethyl terephthalate, 2-hydroxyethyl methyl terephthalate, dimethyl 2,6-naphthalenedicarboxylate, dimethyl isophthalate, dimethyl adipate, diethyl maleate, and dimethyl dimer.
- An esterified product may be contained.
- the viewpoint of increasing the heat shrinkage rate in the main shrinkage direction at 150 ° C. and reducing the heat shrinkage rate in the main shrinkage direction at 90 ° C., and the glass transition temperature obtained by temperature modulation DSC is 100 ° C. or more.
- the higher the crystallinity of the polyester the more preferable that the ethylene glycol is 85 mol% or more as the glycol component. % Or more is more preferable.
- a dicarboxylic acid component it is preferable that a terephthalic acid is 85 mol% or more, and it is more preferable that it is 90 mol% or more.
- the copolymer component is contained in an amount of 3 mol% or more, more preferably 5 mol% or more, particularly preferably 10 mol% or more.
- any of the above-mentioned dicarboxylic acid components or glycol components may be used as the copolymerization component.
- 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedimethanol is preferably used.
- the polyester film of the present invention preferably has a glass transition temperature of 90 ° C. or higher obtained from temperature-modulated DSC from the viewpoint of achieving both heat resistance and heat shrinkability.
- the glass transition temperature can be obtained by the method described in (6) Temperature-modulated DSC glass transition temperature in the method for measuring characteristics described later.
- the polyester film of the present invention is intended to prevent shrinkage deformation at about 90 ° C., which is within the range of the application process temperature or the drying process temperature of various functional layers. For this reason, since it is preferable to make the molecular mobility in a film bulk low at 90 degreeC, it is preferable to make the glass transition temperature obtained from temperature modulation DSC into 90 degreeC or more.
- the film may be deformed in the drying step after the application of various functional layers and the like.
- the glass transition temperature obtained from the temperature-modulated DSC is preferably 95 ° C. or higher, and more preferably 100 ° C. or higher.
- the glass transition temperature obtained from the temperature modulation DSC needs to be 100 ° C. or higher, preferably 103 ° C. or higher and 120 ° C. or lower, and 105 ° C. or higher. It is more preferable that it is 115 degrees C or less. If the glass transition temperature obtained from the temperature modulation DSC is 120 ° C.
- the heat shrinkability at 150 ° C. may be lowered.
- the film may be deformed in the drying step after applying various functional layers and the like.
- the method for setting the glass transition temperature to 90 ° C. or higher can be controlled, for example, by copolymerizing rigid components. Further.
- the glass transition temperature can be raised to 100 ° C. or higher by selecting the copolymer component, controlling the amount of copolymerization, and adjusting the stretching conditions.
- preferable copolymerization components for polyethylene terephthalate include 2,6-naphthalenedicarboxylic acid and 1,4-cyclohexanedimethanol.
- it can achieve by adjusting the temperature of the extending
- the polyester film of the present invention preferably has a movable amorphous amount of 25% or more.
- the movable amorphous amount can be calculated from the specific heat difference at the glass transition temperature measured by the temperature modulation DSC as described in the measurement method (5) movable amorphous amount (fraction) described later. . If the amount of movable amorphous material is less than 25%, the amount of amorphous component that exhibits shrinkage behavior in the heat shrinking process is small, and at 150 ° C., it may be impossible to shrink 15% or more in the main shrinkage direction. Moreover, although an upper limit is not specifically limited, Since mechanical strength may fall when it exceeds 40%, it is preferable that it is 40% or less. In order to make the movable amorphous amount 25% or more, it can be achieved by adjusting the stretching method, the stretching ratio, the stretching and the temperature of the heat treatment during film formation.
- the polyester film of the present invention needs to have a heat shrinkage rate of 150 ° C. in the main shrinkage direction of 15% or more.
- a heat shrinkage rate of 150 ° C. thermal shrinkage rate in the main shrinkage direction is 20% or more, more preferably 25% or more, and most preferably 30% or more.
- it may be stretched in the shrinkage direction in the stretching step. For example, if it is intended to shrink 15%, it is necessary to stretch at least 1.15 times or more.
- the refractive index in the main shrinkage direction should be 1.6 or more. Is preferred.
- the refractive index in the main shrinkage direction exceeds 1.64, the 150 ° C. heat shrinkage rate in the direction orthogonal to the main shrinkage direction is set to less than 15%, and then the main shrinkage direction 150 ° C. heat shrinkage. The rate is difficult to be 15% or more. Therefore, the refractive index in the main shrinkage direction of the polyester film in the present invention is preferably 1.60 or more and 1.64 or less.
- the main shrinkage direction in the present invention refers to a direction in which any one direction of the film is 0 °, and the heat shrinkage rate is measured at 150 ° C. in each direction up to 180 ° at 5 ° intervals. Indicates the higher direction.
- the main shrinkage direction is preferably the film longitudinal direction, and the direction perpendicular to the main shrinkage direction is preferably the film width direction.
- the polyester film of the present invention needs to have a heat shrinkage at 150 ° C. in a direction orthogonal to the main shrinkage direction of less than 15%.
- a heat shrinkage at 150 ° C. in a direction orthogonal to the main shrinkage direction of less than 15%.
- the film is biaxially stretched sequentially in the order of length and width, or if it is a film that is simultaneously biaxially stretched with the same stretch ratio and stretch speed in the length and width directions, if the direction perpendicular to the main shrinkage direction is the film width direction, Will also shrink.
- a 150 ° C. heat shrinkage rate in a direction orthogonal to the main shrinkage direction is obtained by adopting a sequential biaxial stretching method including a step of stretching in the longitudinal direction, which is the orthogonal direction, after stretching in at least the width direction.
- amorphous component which is considered to be a shrinkage component, can be selectively distorted in the longitudinal direction by stretching in the longitudinal direction once oriented and crystallized in the width direction.
- a resin having a crystallinity it is preferable to use a resin having a crystallinity to such an extent that it can be oriented and crystallized.
- Orientation crystallization refers to what is defined by the refractive index and the plane orientation coefficient, and the plane orientation coefficient is preferably 0.1 or more, and is a plane orientation in that the amorphous component is distorted without crystallization.
- the coefficient is preferably 0.14 or less.
- the polyester film of the present invention preferably has a 90 ° C. thermal shrinkage in the main shrinkage direction of 14% or less.
- it is calculated
- it exceeds 14% it shrinks and deforms in the drying process after the application of various functional layers, so that it may not be able to withstand the process.
- the 90 ° C. thermal shrinkage rate in the main shrinkage direction is 14% or less. The 90 ° C.
- heat shrinkage rate in the main shrinkage direction is more preferably 10% or less, and further preferably 5% or less.
- the thermal shrinkage rate in the main shrinkage direction it can be achieved, for example, by setting the glass transition temperature obtained from the temperature modulation DSC of the film to 90 ° C. or more.
- the polyester film of the present invention preferably has a heat shrinkage stress of 1 MPa or less at 80 ° C. in the main shrinkage direction from the viewpoint of heat resistance. If the heat shrinkage stress at 80 ° C. is 1 MPa or less, shrinkage deformation at the process temperature of the application process or drying process of various functional layers can be suppressed to a very low level.
- the heat shrinkage stress at 80 ° C. in the main shrinkage direction is more preferably 0.9 MPa or less, further preferably 0.001 MPa or more and 0.8 MPa or less, and most preferably 0.01 MPa or more and 0.2 MPa or less.
- heat treatment is performed at 80 ° C. or more and 105 ° C. or less after stretching, and then heat treatment at a temperature higher than 105 ° C.
- the method of performing the step heat processing to perform is mentioned.
- the polyester film of the present invention preferably has a breaking elongation of 100% or more in the direction orthogonal to the main shrinkage direction from the viewpoint of high toughness. Moreover, it is preferable for the elongation at break in the main shrinkage direction to be 100% or more because the toughness of the film is increased and it is easy to suppress film breakage during processing.
- the breaking elongation in the direction orthogonal to the main shrinkage direction is more preferably 120% or more, and most preferably 150% or more.
- a method in which the elongation at break in the direction perpendicular to the main shrinkage direction is 100% or more is preferably a method in which the stretching temperature in the direction perpendicular to the main shrinkage direction is 90 ° C.
- the stretching temperature in the direction perpendicular to the main shrinkage direction is 95 ° C. or higher.
- the polyester film of the present invention preferably has a breaking elongation in the main shrinkage direction of 150% or higher and higher than the breaking elongation in the direction perpendicular to the main shrinkage direction.
- a breaking elongation in the main shrinkage direction of 150% or higher and higher than the breaking elongation in the direction perpendicular to the main shrinkage direction.
- the polyester film of the present invention has a hard coat property, self-healing property, antiglare property, and antireflection property on at least one surface for the purpose of surface smoothing such as when a fine scratch is attached to the film surface by biaxial stretching.
- the surface layer may have one or more functions selected from the group consisting of low reflectivity, ultraviolet shielding, and antistatic properties.
- the surface layer is preferably soft enough to follow the shrinkage and deform from the viewpoint of followability due to the original film shrinkage.
- polyester for example, polyethylene terephthalate is supplied to an extruder and melt extruded.
- the resin temperature is preferably controlled to 265 ° C. to 295 ° C.
- foreign matter is removed and the amount of extrusion is leveled through a filter and a gear pump, respectively, and discharged from a T-die onto a cooling drum in a sheet form.
- an electrostatic application method in which a cooling drum and the resin are brought into close contact with each other by static electricity using an electrode applied with a high voltage
- a casting method in which a water film is provided between the casting drum and the extruded polymer sheet, and the casting drum temperature is set to be equal to that of the polyester resin.
- the sheet-like polymer is brought into close contact with the casting drum and solidified by cooling by a method of adhering the extruded polymer below the glass transition point or a combination of these methods to obtain an unstretched film.
- a method of applying an electrostatic force is preferably used from the viewpoint of productivity and flatness.
- the polyester film of the present invention has a 150 ° C. heat shrinkage rate in the main shrinkage direction of 15% or more and a 150 ° C. heat shrinkage rate in the direction perpendicular to the main shrinkage direction of less than 15%, The rate is 14% or less. Further, the 150 ° C. heat shrinkage rate in the main shrinkage direction is 15% or more and the 150 ° C. heat shrinkage rate in the direction orthogonal to the main shrinkage direction is less than 15%, and the glass transition temperature obtained from the temperature modulation DSC is 100 ° C. or more. It is characterized by being.
- the stretching method of the sheet obtained by the casting method includes, for example, sequential biaxial stretching in the film longitudinal direction-width direction-longitudinal direction, or sequential biaxial stretching in the film width direction-longitudinal direction.
- a method of heat treatment at 101 ° C. or more and 160 ° C. or less gripping the end in the film width direction, stretching in the longitudinal direction and the width direction, and stretching ratio in the longitudinal direction of 5% from the final point of all stretching steps
- a method of performing a heat treatment at a temperature of 101 ° C. or higher and 160 ° C. or lower, etc. is preferably used.
- the sheet when applied to an application in which high shrinkage in the main shrinkage direction is important, the sheet is stretched by successively biaxially stretching in the longitudinal direction-width direction-longitudinal direction and then at 101 ° C. or higher and 160 ° C.
- the first stretching ratio in the longitudinal direction is not more than the stretching ratio in the subsequent longitudinal direction.
- the first longitudinal stretching ratio is 1.01 to 3 times
- the subsequent longitudinal stretching ratio is 1.1 to 4 times
- the first longitudinal stretching is It is preferable that the magnification is not more than the subsequent draw ratio in the longitudinal direction.
- the sheet is stretched by sequentially biaxially stretching in the film width direction-longitudinal direction and then heat-treating at 101 ° C. or higher and 160 ° C. or lower.
- the film is stretched 1.5 to 6 times in the width direction, and then 1.1 to 4 times in the longitudinal direction.
- a cooling step of 100 ° C. or less, 101 ° C. to 160 ° C.
- a heat treatment step of less than or equal to ° C.
- the sheet stretching method is to hold the edge in the width direction of the sheet, stretch the longitudinal direction and the width direction, and set the stretch ratio in the longitudinal direction of 5% from the final point of the entire stretching process to the stretch ratio in the width direction.
- the stretching method when applying to a use in which both high shrinkage in the main shrinkage direction, mechanical strength, and handling properties are important, the stretching method is sequentially biaxially stretched in the longitudinal direction-width direction-longitudinal direction. Later, it is preferable that the heat treatment is performed at a temperature of 101 ° C. or higher and 160 ° C. or lower, and the first longitudinal stretch ratio is made higher than the subsequent longitudinal stretch ratio. Specifically, the first longitudinal stretch ratio is 1.11 times to 4 times, the subsequent longitudinal stretch ratio is 1.01 times to 3 times, and the first longitudinal stretch ratio is Is preferably higher than the subsequent stretching ratio in the longitudinal direction.
- the film width direction end is grasped, the film longitudinal direction and the width direction are stretched, and the longitudinal stretch ratio of the section of 5% from the final point of the entire stretching process is the width direction stretch ratio.
- the total lengthwise draw ratio higher than the total widthwise draw ratio and perform a heat treatment at 101 ° C. or higher and 160 ° C. or lower after drawing.
- the preferable heat treatment temperature indicates the highest temperature among the heat treatment temperatures performed after biaxial stretching.
- the heat treatment time can be any time within a range not deteriorating the characteristics, and is preferably 5 seconds to 60 seconds, more preferably 10 seconds to 40 seconds, and most preferably 15 seconds to 30 seconds. be able to.
- the thickness of the polyester film of the present invention is not particularly limited as long as it does not impair the object of the present invention, and may be about 3 ⁇ m to 300 ⁇ m that is generally used as a biaxially stretched film. Moreover, the thickness of a film can be selected according to a use, the ink to apply
- the polyester film of the present invention may be reinforced with a backing material or the like.
- the backing material include a biaxially oriented polyester film and a biaxially oriented polypropylene film.
- the polyester film of the present invention has a low heat shrinkage rate in a low temperature region and shows a uniform heat shrinkability in a high temperature region, it is preferably used as a packaging application. Because it has heat resistance that does not cause thermal shrinkage in the coating, forming and drying processes of various functional layers such as printed layers, weathering layers, adhesive layers, adhesive layers, and vapor-deposited layers, it is also compatible with coating agents for aqueous solvents, for example. Is possible. Furthermore, since it exhibits high heat shrinkability when heated at a high temperature, it is excellent in the ability to be attached to a container such as a bottle, and therefore is preferably used for various packaging applications mainly for labels.
- the polyester film of the present invention can be preferably used for decorative purposes. Since it has heat resistance that does not cause thermal shrinkage in the coating, forming process and drying process of various functional layers such as printed layers, weather resistant layers, adhesive layers, adhesive layers, vapor-deposited layers, scratch-resistant layers, fingerprint-resistant layers, etc. It can be applied to various coatings, has excellent heat resistance in the drying process after application of various functional layers, and exhibits high heat shrinkability when heated at high temperatures. Can be applied.
- the polyester film of the present invention is also preferably used for optical applications. It is excellent in heat resistance in the coating process and drying process of various functional layers such as a phase difference forming layer, and it is possible to form a phase difference layer by utilizing shrinkage characteristics during high temperature heating.
- the characteristic measuring method and the effect evaluating method in the present invention are as follows.
- (1) Composition of polyester A polyester film can be dissolved in hexafluoroisopropanol (HFIP), and the content of each monomer residue component and by-product diethylene glycol can be quantified using 1 H-NMR and 13 C-NMR.
- HFIP hexafluoroisopropanol
- the components constituting each layer can be collected and evaluated by scraping off each layer of the film according to the laminated thickness.
- the composition was computed by calculation from the mixing ratio at the time of film manufacture.
- Movable amorphous amount (fraction) Measurement was performed using a temperature modulated DSC manufactured by TA Instruments. A sample of 5 mg was measured in a nitrogen atmosphere from 0 ° C. to 150 ° C. at a rate of temperature increase of 2 ° C./min, a temperature modulation amplitude of ⁇ 1 ° C., and a temperature modulation period of 60 seconds. The specific heat difference at the glass transition temperature was determined and calculated from the following formula.
- Movable amorphous amount (%) (specific heat difference) / (theoretical value of specific heat difference of polyester completely amorphous) ⁇ 100
- Theoretical specific heat difference of polyethylene terephthalate completely amorphous material 0.40552 J / (g ° C.)
- those having a polyethylene terephthalate unit of 89 mol% or more were referred to the specific heat difference theoretical value of a completely amorphous polyethylene terephthalate.
- the glass transition temperature is measured by the method described in (6) below when the resin is in an amorphous state, and the specific heat difference before and after the glass transition temperature obtained at that time is measured.
- the resin can be brought into an amorphous state by, for example, a method in which the resin is heated to a melting point or higher and melted, and then rapidly cooled to 20 ° C. or lower within 3 seconds.
- any other means can be used as long as it is generally a non-crystalline state.
- the polycarbonate laminated film prepared in (ii) was finely stretched in the direction perpendicular to the main shrinkage direction while shrinking in the main shrinkage direction in an oven at 150 ° C. to form a retardation layer.
- the toughness was evaluated according to the following criteria.
- C The film was stretched 1.05 times or more and less than 1.1 times in a direction orthogonal to the main shrinkage direction.
- D The film could not be stretched 1.05 times in the direction orthogonal to the main shrinkage direction. It was evaluated that the film could be stretched when the film did not break even when stretched to a predetermined magnification.
- A, B, and C are acceptable levels.
- the polyester resin used for film formation was prepared as follows.
- Polyethylene terephthalate resin (intrinsic viscosity 0.65) in which the terephthalic acid component is 100 mol% as the dicarboxylic acid component and the ethylene glycol component is 100 mol% as the glycol component.
- polyester B A polyester resin (intrinsic viscosity 0.65) in which the terephthalic acid component is 90 mol% as the dicarboxylic acid component, the isophthalic acid component is 10 mol%, and the ethylene glycol component is 100 mol% as the glycol component.
- polyester C A polyester resin (intrinsic viscosity 0.65) in which the terephthalic acid component is 100 mol% as the dicarboxylic acid component, the ethylene glycol component is 90 mol%, and the 1,4-cyclohexanedimethanol component is 10 mol% as the glycol component.
- particle Master A Polyethylene terephthalate particle master (intrinsic viscosity 0.63) containing agglomerated silica having a number average particle size of 0.2 ⁇ m in polyester A at a particle concentration of 5 mass%.
- Examples 1 to 11, Comparative Examples 1 and 2 The composition of the polyester and particle master used was as shown in Table 1, and the raw materials were supplied to the extruder, the extruder cylinder temperature was melted at 270 ° C, the short tube temperature was 275 ° C, the die temperature was 280 ° C, and the T-die The sheet was discharged in the form of a sheet on a cooling drum whose temperature was controlled to 25 ° C. At that time, a wire electrode having a diameter of 0.1 mm was applied electrostatically and adhered to the cooling drum to obtain an unstretched sheet.
- Tables 2 and 3 show the physical properties, measurement of properties, and evaluation results of the obtained films.
- the 90 ° C. heat shrinkage rate was less than 15%
- the 150 ° C. heat shrinkage rate was 25% or more
- the heat shrinkage characteristics were excellent in suitability for use.
- the examples were excellent in drying suitability after application of various functional layers, and thereafter suitable for shrinking properties that greatly shrink at 150 ° C.
- Example 11 was unsatisfactory in the practicality required in the decoration application, but since the heat shrinkage stress at 80 ° C. was less than 1 MPa, it was a practically no problem level in packaging and optical applications. Met.
- the polyester film of the present invention has a special heat shrink property that does not shrink at about 90 ° C. and shrinks greatly at about 150 ° C. Thereby, drying after application of various functional layers can be performed without contraction and deformation at about 90 ° C., and thereafter, it can be used in applications that need to be largely contracted at about 150 ° C.
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Abstract
Description
本発明に係るポリエステルフィルムに用いるポリエステルを与えるグリコールあるいはその誘導体としては、エチレングリコールが80モル%以上であることが好ましいが、その他の成分として、例えば、1,2-プロパンジオール、1,3-プロパンジオール、1,3-ブタンジオール、1,4-ブタンジオール、1,5-ペンタンジオール、1,6-ヘキサンジオール、ネオペンチルグリコールなどの脂肪族ジヒドロキシ化合物、ジエチレングリコール、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコールなどのポリオキシアルキレングリコール、1,4-シクロヘキサンジメタノールなどの脂環族ジヒドロキシ化合物、ビスフェノールA、ビスフェノールSなどの芳香族ジヒドロキシ化合物、並びに、それらの誘導体を含んでいてもよい。 Hereinafter, the polyester film of the present invention will be described in detail together with embodiments.
As the glycol or derivative thereof that gives the polyester used in the polyester film according to the present invention, ethylene glycol is preferably 80 mol% or more. As other components, for example, 1,2-propanediol, 1,3- Aliphatic dihydroxy compounds such as propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, poly Polyoxyalkylene glycols such as tetramethylene glycol, alicyclic dihydroxy compounds such as 1,4-cyclohexanedimethanol, aromatic dihydroxy compounds such as bisphenol A and bisphenol S, and It may include their derivatives.
本発明における特性の測定方法、および効果の評価方法は次のとおりである。
(1)ポリエステルの組成
ポリエステルフィルムをヘキサフルオロイソプロパノール(HFIP)に溶解し、1H-NMRおよび13C-NMRを用いて各モノマー残基成分や副生ジエチレングリコールについて含有量を定量することができる。積層フィルムの場合は、積層厚みに応じて、フィルムの各層を削り取ることで、各層単体を構成する成分を採取し、評価することができる。なお、本発明のフィルムについては、フィルム製造時の混合比率から計算により、組成を算出した。 (Characteristic measurement method and effect evaluation method)
The characteristic measuring method and the effect evaluating method in the present invention are as follows.
(1) Composition of polyester A polyester film can be dissolved in hexafluoroisopropanol (HFIP), and the content of each monomer residue component and by-product diethylene glycol can be quantified using 1 H-NMR and 13 C-NMR. In the case of a laminated film, the components constituting each layer can be collected and evaluated by scraping off each layer of the film according to the laminated thickness. In addition, about the film of this invention, the composition was computed by calculation from the mixing ratio at the time of film manufacture.
フィルムの任意の1方向を0°として、そこから5°間隔にて180°までの方向について150mm(測定方向)×幅10mm(測定方向に直交する方向)のサイズに切り出したサンプルに、100mm(L0)の間隔の両端位置にマーク(標線)を入れ、3gの錘を吊して150℃に加熱した熱風オーブン内に30分間設置し加熱処理を行った。熱処理後の標線間距離(L1)を測定し、加熱前後の標線間距離の変化から下記式にて熱収縮率を算出した。
熱収縮率(%) = 100×(L0-L1)/L0
測定は各方向とも5回ずつ行い、最も熱収縮率の高い方向を主収縮方向とした。 (2) Film main shrinkage direction Any one direction of the film is defined as 0 °, and a size of 150 mm (measurement direction) × width 10 mm (a direction perpendicular to the measurement direction) in a direction from there to 180 ° at intervals of 5 °. Marks (marked lines) were placed at both end positions with an interval of 100 mm (L0) in the cut out sample, and a heat treatment was performed by placing in a hot air oven heated to 150 ° C. by hanging a 3 g weight for 30 minutes. The distance between marked lines (L1) after heat treatment was measured, and the heat shrinkage rate was calculated by the following formula from the change in the distance between marked lines before and after heating.
Thermal contraction rate (%) = 100 × (L0−L1) / L0
The measurement was performed five times in each direction, and the direction with the highest thermal shrinkage was defined as the main shrinkage direction.
フィルムの主収縮方向および主収縮方向と直交する方向について測定を行った。150mm(測定方向)×幅10mm(測定方向に直交する方向)のサイズに切り出したサンプルに、100mm(L0)の間隔の両端位置にマーク(標線)を入れ、3gの錘を吊して測定温度に加熱した熱風オーブン内に30分間設置し加熱処理を行った。熱処理後の標線間距離(L1)を測定し、加熱前後の標線間距離の変化から下記式にて熱収縮率を算出した。測定は各方向とも5サンプル実施して平均値で評価を行った。
熱収縮率(%) = 100×(L0-L1)/L0 (3) 90 degreeC and 150 degreeC heat shrinkage rate It measured about the main shrinkage direction of a film, and the direction orthogonal to the main shrinkage direction. A sample cut into a size of 150 mm (measurement direction) x 10 mm width (direction perpendicular to the measurement direction) is marked with a mark (marked line) at both end positions with an interval of 100 mm (L0), and a 3 g weight is suspended and measured. It heat-processed by installing for 30 minutes in the hot-air oven heated to temperature. The distance between marked lines (L1) after heat treatment was measured, and the heat shrinkage rate was calculated by the following formula from the change in the distance between marked lines before and after heating. Measurement was carried out with 5 samples in each direction, and the average value was evaluated.
Thermal contraction rate (%) = 100 × (L0−L1) / L0
フィルムの主収縮方向および主収縮方向と直交する方向について測定を行った。引張試験機(オリエンテック社製テンシロンUCT-100)を用いて、幅10mmのサンプルフィルムを測定方向にチャック間長さ50mm(初期試験長)となるようにセットし、温度25℃、湿度65%RHの条件下で、引張速度300mm/分で引張試験を行い、破断したときの伸度を破断伸度とした。各測定はそれぞれ5回ずつ行い、その平均値を用いた。 (4) Elongation at break The film was measured in the main shrinkage direction and the direction perpendicular to the main shrinkage direction. Using a tensile tester (Tensilon UCT-100 manufactured by Orientec Co., Ltd.), set a sample film with a width of 10 mm in the measurement direction so that the length between chucks is 50 mm (initial test length), temperature 25 ° C., humidity 65% Under the condition of RH, a tensile test was performed at a tensile speed of 300 mm / min, and the elongation at break was defined as the elongation at break. Each measurement was performed 5 times, and the average value was used.
TA Instruments社製温度変調DSCを用いて測定した。試料5mgを窒素雰囲気下、0℃から150℃まで2℃/minの昇温速度、温度変調振幅±1℃、温度変調周期60秒で測定した。ガラス転移温度での比熱差を求め、以下の式より算出した。
可動非晶量(%)=(比熱差)/(ポリエステル完全非晶物の比熱差理論値)×100
ポリエチレンテレフタレート完全非晶物の比熱差理論値=0.4052J/(g℃)
また、本発明ではポリエチレンテレフタレートユニットが89モル%以上であるものについては、ポリエチレンテレフタレートの完全非晶物の比熱差理論値を参照した。また、ポリエチレンテレフタレートユニットが89モル%未満の場合は、該樹脂が非晶状態において下記(6)記載の方法によりガラス転移温度を測定し、その際に得られたガラス転移温度前後での比熱差を該樹脂における完全非晶物の比熱差理論値とした。尚、樹脂を非晶状態とするには、例えば、該樹脂を融点以上に加熱して溶融させた後、3秒以内に20℃以下に急冷することで得るなどの方法が挙げられる。その他、一般的に非晶状態とする手段であれば上記方法に限らず、用いることができる。 (5) Movable amorphous amount (fraction)
Measurement was performed using a temperature modulated DSC manufactured by TA Instruments. A sample of 5 mg was measured in a nitrogen atmosphere from 0 ° C. to 150 ° C. at a rate of temperature increase of 2 ° C./min, a temperature modulation amplitude of ± 1 ° C., and a temperature modulation period of 60 seconds. The specific heat difference at the glass transition temperature was determined and calculated from the following formula.
Movable amorphous amount (%) = (specific heat difference) / (theoretical value of specific heat difference of polyester completely amorphous) × 100
Theoretical specific heat difference of polyethylene terephthalate completely amorphous material = 0.40552 J / (g ° C.)
In the present invention, those having a polyethylene terephthalate unit of 89 mol% or more were referred to the specific heat difference theoretical value of a completely amorphous polyethylene terephthalate. When the polyethylene terephthalate unit is less than 89 mol%, the glass transition temperature is measured by the method described in (6) below when the resin is in an amorphous state, and the specific heat difference before and after the glass transition temperature obtained at that time is measured. Was the theoretical value of the specific heat difference of a completely amorphous material in the resin. The resin can be brought into an amorphous state by, for example, a method in which the resin is heated to a melting point or higher and melted, and then rapidly cooled to 20 ° C. or lower within 3 seconds. Other than the above method, any other means can be used as long as it is generally a non-crystalline state.
TA Instrument社製温度変調DSCを用いて下記条件にて測定を行った。
加熱温度:270~570K(RCS冷却法)
温度校正:高純度インジウムおよび錫の融点
温度変調振幅:±1K
温度変調周期:60秒
温度ステップ:5K
試料重量:5mg
試料容器:アルミニウム製開放型容器(22mg)
参照容器:アルミニウム製開放型容器(18mg)
なお、ガラス転移点は下記式より算出した。
ガラス転移温度=(補外ガラス転移開始温度+補外ガラス転移終了温度)/2 (6) Temperature-modulated DSC glass transition temperature Measurement was performed under the following conditions using a temperature-modulated DSC manufactured by TA Instrument.
Heating temperature: 270-570K (RCS cooling method)
Temperature calibration: Melting point of high purity indium and tin Temperature modulation amplitude: ± 1K
Temperature modulation period: 60 seconds Temperature step: 5K
Sample weight: 5mg
Sample container: Aluminum open container (22 mg)
Reference container: Aluminum open container (18mg)
The glass transition point was calculated from the following formula.
Glass transition temperature = (extrapolated glass transition start temperature + extrapolated glass transition end temperature) / 2
ナトリウムD線(波長589nm)を光源とし、マウント液としてヨウ化メチレンを用い、25℃にてアッベ屈折計を用いてフィルム長手方向、幅方向および厚み方向の屈折率(各々、nMD、nTD、nZD)を求めた。求めた屈折率から下記の式により、面配向係数(fn)を算出した。
fn=(nMD+nTD)/2-nZD (7) Film refractive index and plane orientation coefficient Using sodium D line (wavelength 589 nm) as a light source, using methylene iodide as a mounting solution, and using an Abbe refractometer at 25 ° C. Refractive indices (nMD, nTD, and nZD, respectively) were determined. The plane orientation coefficient (fn) was calculated from the obtained refractive index according to the following formula.
fn = (nMD + nTD) / 2−nZD
(i)乾燥耐熱性
フィルム表面に、スクリーン印刷を行った。印刷は、ミノグループ(株)製インキU-PET(517)、スクリーンSX270Tを用いて、スキージスピード300mm/sec、スキージ角度45°の条件で行い、次いで90℃条件下の熱風オーブン中で5分間乾燥して、印刷層積層フィルムを得た。得られた印刷層積層フィルムについての外観について、下記の基準で評価を行った。
A:乾燥後もシワの発生は確認されず、良好な外観であった。
B:乾燥後に若干のシワが確認されたが、良好な外観であった。
C:乾燥後にシワが確認されたが、実用上問題ないレベルであった。
D:乾燥後にシワが確認され、実用レベルではなかった。
A、B、Cが合格レベルである。 (8) Suitability for packaging applications (i) Drying heat resistance Screen printing was performed on the film surface. Printing was performed using Mino Group's ink U-PET (517) and screen SX270T under conditions of a squeegee speed of 300 mm / sec and a squeegee angle of 45 °, and then in a hot air oven at 90 ° C. for 5 minutes. It dried and obtained the printing layer laminated | multilayer film. The appearance of the obtained printed layer laminated film was evaluated according to the following criteria.
A: Generation of wrinkles was not confirmed even after drying, and the appearance was good.
B: Although slight wrinkles were confirmed after drying, the appearance was good.
C: Although wrinkles were confirmed after drying, it was a level with no practical problem.
D: Wrinkles were confirmed after drying and were not at a practical level.
A, B, and C are acceptable levels.
(i)で作成した印刷層積層フィルムについて、フィルム両端部を溶断シールで接着し、円筒状のラベルを作成した。該ラベルを円筒形のアルミボトルの胴部(底面直径150mm)に被せ、150℃雰囲気下のトンネルオーブンに、通過時間3秒で通過させて、ボトルに装着し、収縮外観を下記基準で評価した。
A:シワ、ゆがみ、収縮不足が発生せず、意匠性に優れた外観であった。
B:シワ、ゆがみ、収縮不足の少なくともいずれかが確認できるが、意匠性に優れた外観であった。
C:シワ、ゆがみ、収縮不足の少なくともいずれかが確認できるが実用上問題なかった。
D:シワ、ゆがみ、収縮不足の少なくともいずれかが確認でき、実用レベルではなかった。
A、B、Cが合格レベルである。 (Ii) Heat shrinkability About the printed layer laminated film created in (i), both ends of the film were bonded with a fusing seal to create a cylindrical label. The label was placed on the body of a cylindrical aluminum bottle (bottom diameter: 150 mm), passed through a tunnel oven in a 150 ° C. atmosphere at a passage time of 3 seconds, attached to the bottle, and the shrink appearance was evaluated according to the following criteria. .
A: Wrinkles, distortion, and insufficient shrinkage did not occur, and the appearance was excellent in design.
B: Although at least one of wrinkles, distortion, and insufficient shrinkage can be confirmed, the appearance was excellent in design.
C: At least one of wrinkles, distortion, and insufficient shrinkage could be confirmed, but there was no practical problem.
D: At least one of wrinkles, distortion, and insufficient shrinkage could be confirmed, which was not a practical level.
A, B, and C are acceptable levels.
(i)乾燥耐熱性
フィルム表面に、アプリケーターを用いて、日本ケミカル社製892Lを塗工し、90℃で5分間乾燥を行い、接着層を形成した。接着層積層フィルムについての外観について、下記の基準で評価を行った。
A:乾燥後もシワの発生は確認されず、良好な外観であった。
B:乾燥後に若干のシワが確認されたが、良好な外観であった。
C:乾燥後にシワが確認されたが、実用上問題ないレベルであった。
D:乾燥後にシワが確認され、実用レベルではなかった。
A、B、Cが合格レベルである。 (9) Suitability for decoration use (i) Drying heat resistance 892L made by Nippon Chemical Co., Ltd. was applied to the film surface using an applicator and dried at 90 ° C. for 5 minutes to form an adhesive layer. The appearance of the adhesive layer laminated film was evaluated according to the following criteria.
A: Generation of wrinkles was not confirmed even after drying, and the appearance was good.
B: Although slight wrinkles were confirmed after drying, the appearance was good.
C: Although wrinkles were confirmed after drying, it was a level with no practical problem.
D: Wrinkles were confirmed after drying and were not at a practical level.
A, B, and C are acceptable levels.
(i)で作成した接着層積層フィルムについて、接着層積層フィルムを80℃に加熱したマグネシウム筐体(底面200mm×100mm×高さ30mmの直方体)に被せ、150℃雰囲気下のトンネルオーブンに通過時間10秒で通過させて、形状追従させ、収縮外観について下記の基準で評価した。
A:高さ30mmまで追従できた。
B:高さ25mm以上30mm未満まで追従できた。
C:高さ20mm以上25mm未満まで追従できた
D:追従性が低く、高さ20mmまで追従できなかった。
A、B、Cが合格レベルである。 (Ii) Shape followability About the adhesive layer laminated film prepared in (i), the adhesive layer laminated film is covered with a magnesium case (a rectangular parallelepiped having a bottom surface of 200 mm × 100 mm × height of 30 mm) heated to 80 ° C., and in an atmosphere of 150 ° C. Were passed through the tunnel oven with a passage time of 10 seconds, followed by shape follow-up, and the shrinkage appearance was evaluated according to the following criteria.
A: Followed up to a height of 30 mm.
B: The height could be tracked to 25 mm or more and less than 30 mm.
C: The height was able to follow 20 mm or more and less than 25 mm. D: The followability was low, and the height could not be followed up to 20 mm.
A, B, and C are acceptable levels.
(i)ハンドリング性
実施例及び比較例で得られた熱収縮性フィルムの端部を切り落としたフィルムロールについて、巻出張力を100N/mとして、巻取張力を100N/m、200N/m、250N/m、300N/mとして搬送し、ハンドリング性について、下記の基準で評価を行った。
A:巻取張力300N/mにて、1000m巻取ができた。
B:巻取張力250N/mでは1000m巻取ができたが、300N/mでは1000m巻取る前にフィルム破断が発生した。
C:巻取張力200N/mでは1000m巻取ができたが、250N/mでは1000m巻取る前にフィルム破断が発生した。
D:巻取張力100N/mでも1000m巻取る前にフィルム破断が発生した
A、B、Cが合格レベルである。 (10) Suitability for optical use (i) Handling property For the film roll obtained by cutting off the end of the heat-shrinkable film obtained in Examples and Comparative Examples, the unwinding tension is 100 N / m and the winding tension is 100 N / m. , 200 N / m, 250 N / m, and 300 N / m, and the handling property was evaluated according to the following criteria.
A: 1000 m winding was possible at a winding tension of 300 N / m.
B: Although the film was wound up to 1000 m at a winding tension of 250 N / m, the film was broken before being wound up to 1000 m at 300 N / m.
C: Although the film was wound up to 1000 m at a winding tension of 200 N / m, the film was broken before it was wound up to 1000 m at 250 N / m.
D: A, B, and C in which film breakage occurred before winding 1000 m even at a winding tension of 100 N / m are acceptable levels.
フィルム表面にポリカーボネート/トルエン分散体をダイコーターにて塗工・乾燥を行った(乾燥温度:90℃、乾燥時間:1分、巻出張力:200N/m、巻取張力:100N/m)。得られたポリカーボネート積層フィルムの外観について、下記の基準で評価を行った。
A:乾燥後もシワの発生は確認されず、良好な外観であった。
B:乾燥後に若干のシワが確認されたが、良好な外観であった。
C:乾燥後にシワが確認されたが、実用上問題ないレベルであった。
D:乾燥後にシワが確認され、実用レベルではなかった。
A、B、Cが合格レベルである。 (Ii) Drying heat resistance A polycarbonate / toluene dispersion was applied to the film surface with a die coater and dried (drying temperature: 90 ° C., drying time: 1 minute, unwinding tension: 200 N / m, winding tension). : 100 N / m). The appearance of the obtained polycarbonate laminated film was evaluated according to the following criteria.
A: Generation of wrinkles was not confirmed even after drying, and the appearance was good.
B: Although slight wrinkles were confirmed after drying, the appearance was good.
C: Although wrinkles were confirmed after drying, it was a level with no practical problem.
D: Wrinkles were confirmed after drying and were not at a practical level.
A, B, and C are acceptable levels.
(ii)で作成したポリカーボネート積層フィルムについて、150℃のオーブン中で主収縮方向に収縮させながら、主収縮方向と直交する方向に微延伸して位相差層を形成した。その際、靱性について、下記の基準で評価を行った。
A:主収縮方向と直交する方向に1.2倍以上延伸できた。
B:主収縮方向と直交する方向に1.1倍以上1.2倍未満延伸できた。
C:主収縮方向と直交する方向に1.05倍以上1.1倍未満延伸できた。
D:主収縮方向と直交する方向に1.05倍延伸ができなかった。
所定の倍率まで延伸してもフィルムが破断しない場合に、延伸できたと評価した。
A、B、Cが合格レベルである。 (Iii) Toughness The polycarbonate laminated film prepared in (ii) was finely stretched in the direction perpendicular to the main shrinkage direction while shrinking in the main shrinkage direction in an oven at 150 ° C. to form a retardation layer. At that time, the toughness was evaluated according to the following criteria.
A: The film was stretched 1.2 times or more in the direction orthogonal to the main shrinkage direction.
B: The film was stretched 1.1 times or more and less than 1.2 times in the direction orthogonal to the main shrinkage direction.
C: The film was stretched 1.05 times or more and less than 1.1 times in a direction orthogonal to the main shrinkage direction.
D: The film could not be stretched 1.05 times in the direction orthogonal to the main shrinkage direction.
It was evaluated that the film could be stretched when the film did not break even when stretched to a predetermined magnification.
A, B, and C are acceptable levels.
(iii)と同様にして、150℃のオーブン中で主収縮方向に収縮させたフィルムの熱収縮性について、下記の基準で評価した。
A:主収縮方向の熱収縮率が30%以上であり、収縮後のフィルム外観にシワがみられなかった。
B:主収縮方向の熱収縮率が20%以上30%未満収縮であり、収縮後のフィルム外観にシワがみられなかった。
C:主収縮方向の熱収縮率が15%以上20%未満であり、収縮後のフィルム外観にシワがみられなかった。
D:主収縮方向の熱収縮率が15%未満であるか、もしくはフィルム外観にシワがみられた。
A、B、Cが合格レベルである。 (Iv) Heat shrinkability In the same manner as in (iii), the heat shrinkability of a film shrunk in the main shrink direction in an oven at 150 ° C. was evaluated according to the following criteria.
A: The heat shrinkage rate in the main shrinkage direction was 30% or more, and no wrinkle was observed in the film appearance after shrinkage.
B: The thermal shrinkage in the main shrinkage direction was 20% or more and less than 30%, and no wrinkle was observed in the film appearance after shrinkage.
C: The heat shrinkage rate in the main shrinkage direction was 15% or more and less than 20%, and no wrinkle was observed in the film appearance after shrinkage.
D: The heat shrinkage rate in the main shrinkage direction was less than 15%, or wrinkles were observed in the film appearance.
A, B, and C are acceptable levels.
温度23℃、相対湿度65%に24時間静置させたフィルムをTMA/SS6000(セイコーインスツルメンツ社製)を用いて、サンプルの初期長20mm、幅2mmとして、23℃から170℃まで昇温速度5℃/分で測定し、得られた熱収縮力曲線より80℃における熱収縮力[N]を読みとり、フィルムの厚みと測定幅より求められる断面積にて割り返して、熱収縮応力[MPa]を算出した。 (11) Thermal shrinkage stress at 80 ° C. Using a TMA / SS6000 (manufactured by Seiko Instruments Co., Ltd.), a film that was allowed to stand at a temperature of 23 ° C. and a relative humidity of 65% for 24 hours, the sample had an initial length of 20 mm and a width of 2 mm. The heat shrinkage force [N] at 80 ° C. is read from the obtained heat shrinkage force curve, and divided by the cross-sectional area obtained from the film thickness and measurement width. In return, the heat shrinkage stress [MPa] was calculated.
製膜に供したポリエステル樹脂は以下のように準備した。 (Manufacture of polyester)
The polyester resin used for film formation was prepared as follows.
ジカルボン酸成分としてテレフタル酸成分が100モル%、グリコール成分としてエチレングリコール成分が100モル%であるポリエチレンテレフタレート樹脂(固有粘度0.65)。 (Polyester A)
Polyethylene terephthalate resin (intrinsic viscosity 0.65) in which the terephthalic acid component is 100 mol% as the dicarboxylic acid component and the ethylene glycol component is 100 mol% as the glycol component.
ジカルボン酸成分としてテレフタル酸成分が90モル%、イソフタル酸成分が10モル%、グリコール成分としてエチレングリコール成分が100モル%であるポリエステル樹脂(固有粘度0.65)。 (Polyester B)
A polyester resin (intrinsic viscosity 0.65) in which the terephthalic acid component is 90 mol% as the dicarboxylic acid component, the isophthalic acid component is 10 mol%, and the ethylene glycol component is 100 mol% as the glycol component.
ジカルボン酸成分としてテレフタル酸成分が100モル%、グリコール成分としてエチレングリコール成分が90モル%、1,4-シクロヘキサンジメタノール成分が10モル%であるポリエステル樹脂(固有粘度0.65)。 (Polyester C)
A polyester resin (intrinsic viscosity 0.65) in which the terephthalic acid component is 100 mol% as the dicarboxylic acid component, the ethylene glycol component is 90 mol%, and the 1,4-cyclohexanedimethanol component is 10 mol% as the glycol component.
(粒子マスターA)
ポリエステルA中に数平均粒子径0.2μmの凝集シリカを粒子濃度5質量%で含有したポリエチレンテレフタレート粒子マスター(固有粘度0.63)。 (Manufacture of particle master)
(Particle Master A)
Polyethylene terephthalate particle master (intrinsic viscosity 0.63) containing agglomerated silica having a number average particle size of 0.2 μm in polyester A at a particle concentration of 5 mass%.
用いたポリエステルおよび粒子マスターの組成を表1の通りとして、原料を押出機に供給し、押出機シリンダー温度を270℃で溶融し、短管温度を275℃、口金温度を280℃で、Tダイより25℃に温度制御した冷却ドラム上にシート状に吐出した。その際、直径0.1mmのワイヤー状電極を使用して静電印加し、冷却ドラムに密着させ未延伸シートを得た。1縦延伸、1横延伸、熱処理、2縦延伸、2横延伸、熱処理を順に行い、それぞれ表1に示した延伸倍率、延伸温度、熱処理温度としてポリエステルフィルムを得た。なお、延伸倍率1.0倍は延伸を行わずに、表1に記載の温度にて熱処理を行ったことを示す。 (Examples 1 to 11, Comparative Examples 1 and 2)
The composition of the polyester and particle master used was as shown in Table 1, and the raw materials were supplied to the extruder, the extruder cylinder temperature was melted at 270 ° C, the short tube temperature was 275 ° C, the die temperature was 280 ° C, and the T-die The sheet was discharged in the form of a sheet on a cooling drum whose temperature was controlled to 25 ° C. At that time, a wire electrode having a diameter of 0.1 mm was applied electrostatically and adhered to the cooling drum to obtain an unstretched sheet. 1 longitudinal stretching, 1 lateral stretching, heat treatment, 2 longitudinal stretching, 2 lateral stretching, and heat treatment were sequentially performed to obtain a polyester film as the stretching ratio, stretching temperature, and heat treatment temperature shown in Table 1, respectively. In addition, the draw ratio of 1.0 indicates that heat treatment was performed at the temperature shown in Table 1 without performing the drawing.
Claims (9)
- 主収縮方向の150℃熱収縮率が15%以上かつ主収縮方向と直交する方向の150℃熱収縮率が15%未満、主収縮方向の90℃熱収縮率が14%以下であることを特徴とするポリエステルフィルム。 150 ° C. thermal shrinkage in the main shrinkage direction is 15% or more, 150 ° C. heat shrinkage in the direction perpendicular to the main shrinkage direction is less than 15%, and 90 ° C. heat shrinkage in the main shrinkage direction is 14% or less. A polyester film.
- 温度変調DSCより得られるガラス転移温度が90℃以上である請求項1に記載のポリエステルフィルム。 The polyester film according to claim 1, wherein the glass transition temperature obtained from the temperature modulation DSC is 90 ° C or higher.
- 温度変調DSCより得られるガラス転移温度が100℃以上である請求項1に記載のポリエステルフィルム。 The polyester film according to claim 1, wherein the glass transition temperature obtained from the temperature modulation DSC is 100 ° C. or higher.
- 主収縮方向の150℃熱収縮率が15%以上かつ主収縮方向と直交する方向の150℃熱収縮率が15%未満であって、温度変調DSCより得られるガラス転移温度が100℃以上であることを特徴とするポリエステルフィルム。 The 150 ° C. heat shrinkage rate in the main shrinkage direction is 15% or more and the 150 ° C. heat shrinkage rate in the direction orthogonal to the main shrinkage direction is less than 15%, and the glass transition temperature obtained from the temperature modulation DSC is 100 ° C. or more. A polyester film characterized by that.
- 主収縮方向の90℃熱収縮率が14%以下である、請求項4に記載のポリエステルフィルム。 The polyester film according to claim 4, wherein the 90 ° C. heat shrinkage in the main shrinkage direction is 14% or less.
- 主収縮方向の屈折率が1.6以上1.64以下かつ、主収縮方向と直交する方向の屈折率が主収縮方向の屈折率よりも大きく、かつ面配向係数が0.1以上0.14以下である請求項1または4に記載のポリエステルフィルム。 The refractive index in the main shrinkage direction is 1.6 or more and 1.64 or less, the refractive index in the direction orthogonal to the main shrinkage direction is larger than the refractive index in the main shrinkage direction, and the plane orientation coefficient is 0.1 or more and 0.14. The polyester film according to claim 1 or 4, wherein:
- 温度変調DSCより得られる可動非晶量(分率)が25%以上である請求項1または4に記載のポリエステルフィルム。 The polyester film according to claim 1 or 4, wherein the movable amorphous amount (fraction) obtained from the temperature modulation DSC is 25% or more.
- 破断伸度が主収縮方向、主収縮方向と直交する方向ともに100%以上である請求項1または4に記載のポリエステルフィルム。 The polyester film according to claim 1 or 4, wherein the elongation at break is 100% or more in both the main shrinkage direction and the direction perpendicular to the main shrinkage direction.
- 主収縮方向の80℃における熱収縮応力が1MPa以下である請求項1または4に記載のポリエステルフィルム。 The polyester film according to claim 1 or 4, wherein the heat shrinkage stress at 80 ° C in the main shrinkage direction is 1 MPa or less.
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CN201680040931.1A CN107848193B (en) | 2015-08-06 | 2016-08-02 | Polyester film |
JP2016560834A JP6789821B2 (en) | 2015-08-06 | 2016-08-02 | Polyester film |
KR1020187001935A KR102538384B1 (en) | 2015-08-06 | 2016-08-02 | polyester film |
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KR (1) | KR102538384B1 (en) |
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Cited By (3)
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WO2018021212A1 (en) * | 2016-07-27 | 2018-02-01 | 東洋紡株式会社 | Heat-shrinkable film, heat shrink label, and packaging body |
CN114206999A (en) * | 2019-07-26 | 2022-03-18 | 东洋纺株式会社 | Heat-shrinkable polyester film |
JP7537094B2 (en) | 2020-02-18 | 2024-08-21 | 東レ株式会社 | Polyester Film |
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CN109401212B (en) * | 2017-08-16 | 2022-12-13 | 中国石油化工股份有限公司 | Polyester composition, heat-shrinkable film and process for producing the same |
CN108665810A (en) * | 2018-05-31 | 2018-10-16 | 昆山国显光电有限公司 | Metal wire, display screen, metal wire production method and metal wire restorative procedure |
CA3169101C (en) * | 2020-03-11 | 2024-04-30 | Yuya Kawai | Resin-coated metal sheet for containers |
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- 2016-08-02 WO PCT/JP2016/072608 patent/WO2017022742A1/en active Application Filing
- 2016-08-02 KR KR1020187001935A patent/KR102538384B1/en active IP Right Grant
- 2016-08-02 CN CN201680040931.1A patent/CN107848193B/en active Active
- 2016-08-05 TW TW105124892A patent/TWI720006B/en active
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KR20180037181A (en) | 2018-04-11 |
JPWO2017022742A1 (en) | 2018-05-24 |
JP6789821B2 (en) | 2020-11-25 |
TWI720006B (en) | 2021-03-01 |
KR102538384B1 (en) | 2023-05-31 |
CN107848193A (en) | 2018-03-27 |
TW201714730A (en) | 2017-05-01 |
CN107848193B (en) | 2020-01-10 |
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