WO2013035653A1 - 二軸延伸ポリエステルフィルムおよびその製造方法 - Google Patents
二軸延伸ポリエステルフィルムおよびその製造方法 Download PDFInfo
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- WO2013035653A1 WO2013035653A1 PCT/JP2012/072299 JP2012072299W WO2013035653A1 WO 2013035653 A1 WO2013035653 A1 WO 2013035653A1 JP 2012072299 W JP2012072299 W JP 2012072299W WO 2013035653 A1 WO2013035653 A1 WO 2013035653A1
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- biaxially stretched
- film
- polyester film
- modified pbt
- stretched polyester
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
- B29C51/04—Combined thermoforming and prestretching, e.g. biaxial stretching
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
- B29K2067/003—PET, i.e. poylethylene terephthalate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
- B29K2067/006—PBT, i.e. polybutylene terephthalate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0088—Blends of polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
Definitions
- the present invention relates to a polyester film having tear linearity suitable as a film used for packaging materials, electrical insulating materials, general industrial materials and the like.
- a packaging bag using a biaxially stretched polyester film has a problem that tear tearability is poor.
- the confectionery may break when opened, or if the contents are liquid, troubles such as soiling of clothes may occur.
- An easy-open material excellent in tear linearity that tears linearly when the film is torn is a laminate of a uniaxially stretched polyolefin film as an intermediate layer.
- a laminate of a uniaxially stretched polyolefin film as an intermediate layer As such, for example, there is a three-layer laminate film of biaxially stretched polyester film / uniaxially stretched polyolefin film / non-stretched polyolefin film, but it is necessary to provide an intermediate layer, which is problematic in terms of cost. Applications were limited.
- the present applicant has previously made a polybutylene terephthalate containing 5 to 20% of polytetramethylene glycol (PTMG) having a molecular weight of 600 to 4000 as a method for imparting tear linearity to the biaxially stretched polyester film itself.
- PTMG polytetramethylene glycol
- the present applicant has a high barrier property against oxygen and water vapor by depositing a metal compound such as aluminum oxide or silicon oxide on at least one surface of a biaxially stretched polyester film having tearing linearity.
- a metal compound such as aluminum oxide or silicon oxide
- biaxially stretched polyester films and laminates having tear linearity were proposed (Patent Documents 7 to 8).
- the biaxially stretched polyester film provided with this tear linearity has a larger amount of outgas remaining in the film than a normal polyester film. For this reason, this film could not be used as a film constituting a container or a package for storing electronic materials such as semiconductors that require high cleanliness.
- this film when this film is vapor-deposited in a vacuum atmosphere, the quality of the vapor-deposited layer tends to become unstable as the roll length increases.
- An object of the present invention is to provide a biaxially stretched polyester film having tearing linearity and a reduced amount of residual outgas in the film.
- outgas generated from a polyester film having tear linearity is particularly tetrahydrofuran (THF) compared to outgas generated from a general PET film. It has been clarified that it is contained in a large amount and that this THF is generated from PBT (modified PBT) containing polytetramethylene glycol (PTMG).
- PBT modified PBT
- PTMG polytetramethylene glycol
- the present inventors pay attention to the amount of THF remaining in the modified PBT, and after removing this significantly at the chip stage, the polyester has a tear linearity function by blending with PET resin and forming into a film.
- the inventors have found that a biaxially stretched polyester film having a small amount of residual outgas can be obtained, and reached the present invention.
- the gist of the present invention is as follows.
- a biaxially stretched film containing modified polybutylene terephthalate (modified PBT) and polyethylene terephthalate (PET), and the mass ratio of modified PBT to PET (modified PBT / PET) is 20/80 to 5 / 95, and the modified PBT is a PBT containing 5 to 20% by mass of a polytetramethylene glycol unit having a molecular weight of 600 to 4,000, and the biaxially stretched film is heat-treated at 180 ° C. for 30 minutes in a helium gas atmosphere.
- the biaxially stretched polyester film is characterized in that the amount of tetrahydrofuran (THF) generated by the above is 50 ⁇ g / g or less and has tear linearity in the longitudinal direction.
- THF tetrahydrofuran
- a method for producing the biaxially stretched polyester film described in (1) above comprising 5 to 20% by mass of a polytetramethylene glycol unit having a molecular weight of 600 to 4,000, and in a helium gas atmosphere
- a modified polybutylene terephthalate (modified PBT) in which the amount of tetrahydrofuran (THF) generated by heat treatment at 180 ° C. for 30 minutes is 800 ⁇ g / g or less and polyethylene terephthalate (PET) is a mass ratio of the modified PBT and PET
- a biaxially stretched polyester film having durability, moisture resistance, mechanical properties, heat resistance, oil resistance, tear linearity in the longitudinal direction, and low residual outgas amount.
- the film of the present invention since the film of the present invention generates a small amount of outgas, it is suitable for a packaging bag in a field that requires particularly cleanliness, and can form a deposited layer stably even in a vacuum state.
- the shape of the test piece used for tearing linearity evaluation of a film is shown. It is a figure which shows the shape of the test piece after tear in a tear test, (a) shows the example of the test piece after tearing of the sample with favorable tear linearity, (b) shows the sample with poor tear linearity The example of the test piece after tearing is shown.
- the biaxially stretched polyester film of the present invention contains modified polybutylene terephthalate (modified PBT) and polyethylene terephthalate (PET).
- modified PBT modified polybutylene terephthalate
- PET polyethylene terephthalate
- PET contains terephthalic acid and ethylene glycol as polymerization components, and other components may be copolymerized as long as the effects of the present invention are not impaired.
- copolymer components include isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 5-sodium sulfoisophthalic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, maleic anhydride, maleic Acids, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, dicarboxylic acids such as cyclohexanedicarboxylic acid, 4-hydroxybenzoic acid, ⁇ -caprolactone, oxycarboxylic acids such as lactic acid, 1,3-propanediol, 1,6- Examples thereof include glycols such as hexanediol and cyclohexanedimethanol, and polyfunctional compounds
- PET is obtained by a known production method, that is, an ester exchange reaction method from dimethyl terephthalate and ethylene glycol, or a direct esterification method from terephthalic acid and ethylene glycol, followed by melt polymerization or further solidification. It can be obtained by phase polymerization.
- the modified polybutylene terephthalate is polybutylene terephthalate (PBT) containing 5 to 20% by mass of a polytetramethylene glycol (PTMG) unit having a molecular weight of 600 to 4,000.
- PBT polybutylene terephthalate
- PTMG polytetramethylene glycol
- the molecular weight of PTMG constituting the modified PBT needs to be 600 to 4,000, preferably 1,000 to 3,000, and preferably 1,000 to 2,000. Is more preferable.
- the molecular weight of PTMG is less than 600, the tear linearity of the resulting film cannot be obtained, and when it exceeds 4,000, the mechanical strength, dimensional stability, haze and other performance of the resulting film are degraded. In addition, stable tear linearity does not appear.
- the content of the PTMG unit in the modified PBT is required to be 5 to 20% by mass, preferably 10 to 20% by mass, and more preferably 10 to 15% by mass.
- the content of PTMG is less than 5% by mass, the tearing linearity of the obtained film does not appear, and when it exceeds 20% by mass, the mechanical strength, dimensional stability, haze, etc. of the obtained film The performance deteriorates, and it becomes difficult to obtain a stable tear linearity of the film.
- a phenomenon in which the film pulsates during extrusion may be manifested particularly when produced on a mass production scale, and the thickness unevenness of the film increases. May occur.
- Modified PBT can be obtained by polycondensation by adding PTMG in the polymerization process of PBT.
- it can be obtained by a polycondensation reaction between a transesterification product of dimethyl terephthalate and 1,4-butanediol and PTMG having a molecular weight of 600 to 4,000.
- the mass ratio of the modified PBT to PET (modified PBT / PET) needs to be 20/80 to 5/95, and is 15/85 to 10/90. Is preferred.
- the mass ratio of the modified PBT is less than 5% by mass, it is difficult to obtain the tear linearity of the film.
- it exceeds 20% by mass the variation in the thickness of the film becomes large and the tearing linearity of the resulting film decreases, and the outgas generation amount specified in the present invention may be exceeded. That is, in order to impart tearing linearity to the film and reduce the outgas generation amount, the mixing ratio of the modified PBT and PET needs to be within the above range.
- the biaxially stretched polyester film of the present invention can contain other polymers such as polyethylene naphthalate and polycyclohexylenedimethylene terephthalate as long as the effects of the present invention are not impaired.
- the amount of tetrahydrofuran (THF) generated when heat treatment at 180 ° C. for 30 minutes in a helium gas atmosphere is required to be 50 ⁇ g / g or less, and 30 ⁇ g / g g or less is preferable, and 20 ⁇ g / g or less is more preferable.
- the reason why the generation amount of THF is particularly defined among the generated components is that THF is a volatile (low boiling point) component. When the amount of THF generated exceeds 50 ⁇ g / g, the packaged contents may be contaminated by the generated THF.
- THF is generated from the film during the vapor deposition treatment, which adversely affects the formation of the deposited film, and the gas barrier of the film.
- Property and water vapor gas barrier property may not be stably improved.
- the amount of THF generated from the modified PBT chip used in film production is set to 800 ⁇ g / g or less. It is preferably 500 ⁇ g / g or less, more preferably 300 ⁇ g / g or less.
- the amount of THF generated from the film may be larger than the value specified in the present invention depending on the blending ratio of the modified PBT and PET.
- the temperature is preferably 80 to 180 ° C.
- the time is preferably 12 hours or more, and more preferably 24 hours or more.
- the degree of reduced pressure is preferably 10 Pa or less in addition to the above temperature and time.
- the biaxially stretched polyester film of the present invention In order to produce the biaxially stretched polyester film of the present invention, first, for example, a mixture of modified PBT and PET is put into an extruder, heated and melted, and then extruded into a sheet form from a die orifice of a T die. A stretched sheet is produced.
- the sheet extruded from the die orifice of the T-die is cooled by being tightly wound around a cooling drum by an electrostatic application casting method or the like, and then at a temperature of 90 to 140 ° C., 3.0 to 5.
- the film is stretched at a magnification of 0 and further heat treated at a temperature of 210 to 245 ° C. to obtain a biaxially stretched film.
- the stretching temperature is less than 90 ° C, a homogeneous stretched film may not be obtained.
- the stretching temperature exceeds 140 ° C, crystallization of PET is promoted and transparency may be deteriorated.
- the draw ratio is less than 3.0 times, the strength of the obtained stretched film is low, and pinholes are likely to occur when formed into a bag.
- the draw ratio exceeds 5.0 times, stretching becomes difficult. There is a case.
- the heat treatment temperature is lower than 210 ° C, the heat shrinkage rate of the stretched film obtained is increased, and the bag after bag making may be deformed.
- the heat treatment temperature is higher than 245 ° C, the film is blown out. There is a case.
- the biaxial stretching method may be either a tenter simultaneous biaxial stretching method or a sequential biaxial stretching method using a roll and a tenter. Moreover, you may manufacture a biaxially stretched film with a tubular method.
- the biaxially stretched polyester film of the present invention obtained as described above is composed of aluminum, silicon oxide, aluminum oxide, or a combination of two or more of these components such as silicon oxide and aluminum oxide.
- the oxygen gas barrier property and water vapor barrier property of the film can be enhanced.
- a vacuum deposition method, an EB deposition method, a sputtering method, an ion plating method, or the like can be used as a method for producing the deposited thin film, but the vacuum deposition method is most preferable from the viewpoint of productivity and cost.
- the vacuum deposition method is a method in which after a film is evacuated in a chamber, components to be deposited are melted and then evaporated to adhere to the film to form a film.
- this method if there is a large amount of outgas in the film, the problem arises that the degree of vacuum in the chamber is not stable due to the outgas diffusion, the formation of the deposited film becomes unstable, and the desired oxygen barrier and water vapor barrier properties are achieved. It can be difficult to obtain.
- vacuum deposition is performed on a roll film, since the roll surface is continuously updated, even if a stable deposition film can be formed at the start of deposition, if outgas remains in the film, deposition is performed. As the process proceeds, the formation of the deposited film may become unstable.
- the biaxially stretched polyester film of the present invention has a small amount of residual outgas, even a roll film can stably form a deposited layer.
- the surface of the biaxially stretched polyester film of the present invention is pretreated by a method such as applying a corona discharge treatment or applying an anchor coating agent in advance in order to improve adhesion to a deposited film such as aluminum. Is preferred.
- the biaxially stretched polyester film of the present invention can be treated on the surface by corona discharge treatment, surface hardening treatment, plating treatment, coloring treatment, or various coating treatments depending on the application.
- the outgas component is identified by accurately weighing about 15 mg of a biaxially stretched polyester film or modified PBT chip and filling it in a sample cup.
- Helium gas in a pyrolyzer PY-2020iD
- GC tetrahydrofuran
- BD 1,4-butanediol
- EG ethylene glycol
- the amount of each outgas generated was measured using the following standard sample and internal standard. That is, as a standard sample, a solution in which 100 ppm each of hexadecane, THF, BD, and EG was dissolved in hexane was prepared, and this was subjected to GC / MS measurement under the same conditions as the sample, and the peak area ratio of each component to hexadecane was determined. Calculated.
- Sampling was performed at 100 m, 2000 m, 4000 m, and 7500 m from the surface layer (the core side of the charged biaxially stretched polyester film) of this deposited film, and the oxygen permeability and water vapor permeability were measured.
- Oxygen permeability is less than 20 ml / (m 2 ⁇ day ⁇ MPa)
- Oxygen permeability is 20 or more and less than 30 ml / (m 2 ⁇ day ⁇ MPa)
- an evaluation of ⁇ or more was regarded as acceptable.
- Evaluation ⁇ Water vapor transmission rate is less than 2 g / (m 2 ⁇ day) Evaluation ⁇ : Water vapor transmission rate is 2 or more and less than 5 g / (m 2 ⁇ day) Evaluation ⁇ : Water vapor transmission rate is 5 or more and 10 g / (m 2) -Day) Less than evaluation x: Water vapor permeability is 10 g / (m 2 ⁇ day) or more In the present invention, evaluation ⁇ or more was regarded as acceptable.
- Example 1 Manufacture of modified PBT> While heating 194 parts by weight of dimethyl terephthalate, 108 parts by weight of 1,4-butanediol, and 80 ppm of tetrabutyl titanate (value converted to the weight of titanium metal with respect to the polymer) from 150 ° C. to 210 ° C., 2 The transesterification reaction was carried out for 5 hours.
- the modified PBT produced by the above method was dried in a vacuum dryer at 120 ° C. and 5 Pa for 72 hours.
- the amount of outgas generated from the modified PBT after drying was THF 280 ⁇ g / g and BD 5 ⁇ g / g.
- This modified PBT and PET (relative viscosity: 1.38) mixed with a simple chip at a mass ratio of 15/85 were used with a 200 mm ⁇ extruder equipped with a coat hanger type T die and a resin temperature of 280 ° C. Then, the cast roll heated to 20 ° C.
- the biaxially stretched polyester film having a thickness of 12 ⁇ m was obtained.
- the amount of outgas generated from the produced biaxially stretched polyester was THF 8 ⁇ g / g, BD 1 ⁇ g / g, and ethylene glycol (EG) 70 ⁇ g / g.
- Examples 2-3 and Comparative Example 1 A biaxially stretched polyester film was obtained in the same manner as in Example 1 except that the drying time of the modified PBT chip was changed as shown in Table 1.
- Example 4 Put modified PBT chip dryer 5 m 3, under a 120 ° C. atmosphere, nitrogen dried 24 hours while flowing at a flow rate of 5 m 3 / s to dryer.
- the amount of outgas generated from the modified PBT after drying was THF 480 ⁇ g / g and BD 8 ⁇ g / g.
- a biaxially stretched polyester film was obtained in the same manner as in Example 1 using this modified PBT chip.
- Example 5 Comparative Example 2 A biaxially stretched polyester film was obtained in the same manner as in Example 4 except that the drying time of the modified PBT chip was changed as shown in Table 1.
- Example 6 The modified PBT chip was dried in a hot air dryer at 120 ° C. for 72 hours. The amount of outgas generated from the modified PBT after drying was 1200 ⁇ g / g of THF and 9 ⁇ g / g of BD. A biaxially stretched polyester film was obtained in the same manner as in Example 1 using this modified PBT chip.
- Comparative Example 3 A biaxially stretched polyester film was obtained in the same manner as in Example 6 except that the drying time of the modified PBT chip was changed as shown in Table 1.
- Examples 10-12, Comparative Examples 6-7 A biaxially stretched polyester film was obtained in the same manner as in Example 1 except that the blending ratio of the modified PBT and PET was changed as shown in Table 1.
- Examples 13 to 15 and Comparative Examples 8 to 9 A biaxially stretched polyester film was obtained in the same manner as in Example 1 except that the molecular weight of PTMG used for the modified PBT was changed as shown in Table 1.
- Example 16 A biaxially stretched polyester film was obtained in the same manner as in Example 6 except that the blending ratio of the modified PBT and PET was changed as shown in Table 1.
- Comparative Example 10 A biaxially stretched polyester film was obtained in the same manner as in Comparative Example 1 except that the blending ratio of the modified PBT and PET was changed as shown in Table 1.
- the amount of PTMG contained in the modified PBT and its molecular weight, the blending ratio of the modified PBT and PET, and the amount of THF generated from the biaxially stretched polyester film are defined in the present invention.
- the comparative example has the following problems.
- Comparative Examples 1 to 3 although the PTMG amount and the molecular weight contained in the modified PBT and the blending ratio of the modified PBT and PET satisfy the range defined in the present invention, a film having linear tearability was obtained.
- the vapor deposition film had unstable oxygen permeability and water vapor permeability.
- Comparative Example 4 since the ratio of PTMG contained in the modified PBT was larger than the range defined in the present invention, it was difficult to form a film and a biaxially stretched polyester film could not be collected. Further, in Comparative Example 5, since the THF generation amount specified in the present invention is satisfied, the ratio of PTMG contained in the modified PBT is within the range specified in the present invention, although the oxygen permeability and water vapor permeability of the deposited film are stable. Since there were few, the film which has favorable tear linearity was not able to be obtained.
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Abstract
Description
プラスチックフィルムのなかでも、二軸延伸ポリエステルフィルムは、耐久性、防湿性、力学的強度、耐熱性、耐油性が優れており、チューブラー法、フラット式同時二軸延伸法、フラット式逐次二軸延伸法などを用いて製造され、食品包装分野などにおいて幅広く使用されている。
(1)変性ポリブチレンテレフタレート(変性PBT)と、ポリエチレンテレフタレート(PET)とを含有する二軸延伸フィルムであり、変性PBTとPETとの質量比(変性PBT/PET)が20/80~5/95であり、変性PBTが、分子量600~4,000のポリテトラメチレングリコール単位5~20質量%を含有するPBTであり、二軸延伸フィルムをヘリウムガス雰囲気下で180℃、30分間熱処理することにより発生するテトラヒドロフラン(THF)量が50μg/g以下であり、長手方向に引裂直線性を有することを特徴とする二軸延伸ポリエステルフィルム。
(2)上記(1)記載の二軸延伸ポリエステルフィルムの少なくとも片面に、アルミニウム、酸化アルミニウム、酸化珪素の少なくとも一種が蒸着され、ガスバリア性と引裂直線性とを有することを特徴とする二軸延伸ポリエステルフィルム。
(3)上記(1)記載の二軸延伸ポリエステルフィルムを製造するための方法であって、分子量600~4,000のポリテトラメチレングリコール単位5~20質量%を含有し、ヘリウムガス雰囲気下で180℃、30分間熱処理することにより発生するテトラヒドロフラン(THF)量が800μg/g以下である変性ポリブチレンテレフタレート(変性PBT)と、ポリエチレンテレフタレート(PET)とを、変性PBTとPETとの質量比(変性PBT/PET)が20/80~5/95となるように配合して、製膜、延伸することを特徴とする二軸延伸ポリエステルフィルムの製造方法。
他の共重合成分としては、イソフタル酸、フタル酸、2,6-ナフタレンジカルボン酸、5-ナトリウムスルホイソフタル酸、コハク酸、アジピン酸、セバシン酸、ドデカン二酸、ダイマー酸、無水マレイン酸、マレイン酸、フマール酸、イタコン酸、シトラコン酸、メサコン酸、シクロヘキサンジカルボン酸などのジカルボン酸、4-ヒドロキシ安息香酸、ε-カプロラクトン、乳酸などのオキシカルボン酸、1,3-プロパンジオール、1,6-ヘキサンジオール、シクロヘキサンジメタノールなどのグリコールや、トリメリット酸、トリメシン酸、ピロメリット酸、トリメチロールプロパン、グリセリン、ペンタエリスリトールなどの多官能化合物が挙げられる。
PETは、公知の製法、すなわち、テレフタル酸ジメチルとエチレングリコールとからのエステル交換反応法、あるいは、テレフタル酸とエチレングリコールとからの直接エステル化法によりオリゴマーを得た後、溶融重合、あるいはさらに固相重合して得ることができる。
THF発生量が50μg/gを超える場合、発生したTHFによって、包装された内容物を汚染してしまう恐れがある。また、ガスバリア性、水蒸気ガスバリア性向上を目的として二軸延伸ポリエステルフィルム上に蒸着加工が施されても、蒸着処理中にフィルムからTHFが発生して蒸着膜の形成に悪影響を及ぼし、フィルムのガスバリア性、水蒸気ガスバリア性が安定して向上しない恐れがある。
これらの方法で乾燥させる場合、温度は80~180℃が好ましく、時間は12時間以上が好ましく、24時間以上がより好ましい。また減圧環境下で乾燥させる場合は、上記温度、時間に加えて、減圧度は10Pa以下が好ましい。
延伸温度が90℃未満の場合には、均質な延伸フィルムを得ることができない場合があり、140℃を超えると、PETの結晶化が促進されて、透明性が悪くなる場合がある。延伸倍率が3.0倍未満の場合には、得られる延伸フィルムの強度が低く、袋にしたときにピンホールが発生しやすくなり、延伸倍率が5.0倍を超えると延伸が困難となる場合がある。また、熱処理温度が210℃より低いと、得られる延伸フィルムの熱収縮率が大きくなり、製袋後の袋が変形する場合があり、また、熱処理温度が245℃より高いとフィルムの溶断が発生する場合がある。
二軸延伸ポリエステルフィルムより長手方向(MD)に205mm、巾方向(TD)に20mmの短冊状のフィルム片を採取し、このフィルム片の一方のTD辺の中央部に長さ5mmの切り込み(ノッチ)を入れた試料を10本作製し、次にノッチよりMD方向に手で引き裂き、引裂伝播端がノッチを入れた辺に向かい合うTD辺に到達した試料本数を評価した。
評価基準を下記に示す。
評価◎:到達した試料片が9~10本
評価○:到達した試料片が7~8本
評価△:到達した試料片が5~6本
評価×:到達した試料片が4本以下
本発明においては評価○以上を合格とした。
アウトガス成分の特定は、二軸延伸ポリエステルフィルムまたは変成PBTチップ約15mgを精秤して試料カップに詰め、パイロライザー(PY-2020iD)中、ヘリウムガス雰囲気下で180℃×30分間加熱し、発生した揮発成分についてGC/MS(GC:Agilent 6890N、MS:Agilent 5975C)測定により行った。この際、発生したアウトガスは、テトラヒドロフラン(THF)、1,4-ブタンジオール(BD)、水であり、二軸延伸ポリエステルフィルムからは、エチレングリコール(EG)も発生した。
各アウトガスの発生量については、以下の標準試料と内部標準を用いて測定した。すなわち、標準試料として、ヘキサン中に、ヘキサデカン、THF、BDおよびEGが各100ppm溶解した溶液を調製し、これを試料と同じ条件でGC/MS測定を行い、ヘキサデカンに対する各成分のピーク面積比を算出した。次に内部標準としてヘキサデカン濃度が100ppmのヘキサン溶液を調製し、二軸延伸ポリエステルフィルムまたは変成PBTチップ約15mgを精秤した試料に、この内部標準5μl添加してGC/MS測定を行うことにより、各アウトガス成分の発生量を定量した。
ポリエステル系樹脂(ユニチカ社製エリーテルUE-3200、Tg:65℃)とイソシアネート系硬化剤(東洋モートン社製CAT-10)とを、10/1(質量比)の配合比で混合して塗料を調製した。得られた塗料をアンカーコート剤として、厚みが0.1μmとなるように、巻長8000mの二軸延伸ポリエステルフィルム上に塗布したのち、連続式真空蒸着装置を用いて、蒸着厚みが40~50nmとなるように、酸化アルミニウム層を蒸着した。この蒸着フィルムの表層(投入した二軸延伸ポリエステルフィルムの巻芯側)から100m、2000m、4000m、7500mの部分でサンプリングを行い酸素透過度、水蒸気透過度の測定を行った。
JIS K-7129に準じて、モダンコントロール社製、OX-TRAN100型を用いて、温度20℃、湿度100%RHの条件下で測定した。
評価基準を下記に示す。
評価◎:酸素透過度が20ml/(m2・day・MPa)未満
評価○:酸素透過度が20以上、30ml/(m2・day・MPa)未満
評価△:酸素透過度が30以上、50ml/(m2・day・MPa)未満
評価×:酸素透過度が50ml/(m2・day・MPa)以上
本発明においては評価○以上を合格とした。
JIS K-7129に準じて、モダンコントロール社製、PARMATRAN W3/31を用いて温度40℃、湿度90%RHの条件下で測定した。
評価基準を下記に示す。
評価◎:水蒸気透過度が2g/(m2・day)未満
評価○:水蒸気透過度が2以上、5g/(m2・day)未満
評価△:水蒸気透過度が5以上、10g/(m2・day)未満
評価×:水蒸気透過度が10g/(m2・day)以上
本発明においては評価○以上を合格とした。
<変性PBTの製造>
ジメチルテレフタレート194質量部と、1,4-ブタンジオール108質量部と、テトラブチルチタネート80ppm(ポリマーに対するチタン金属の質量に換算した数値)とを、150℃から210℃に加熱昇温しながら、2.5時間エステル交換反応を行った。得られたエステル交換反応生成物85質量部を重合缶に移送し、テトラブチルチタネートを40ppm添加した後、分子量1,100のPTMGを15質量部添加して、減圧を開始し、最終的に1hPaの減圧下、210℃から昇温し最終的に245℃の温度で2時間溶融重合し、相対粘度1.62の変性PBTを製造した。
製造された変成PBTから発生したアウトガス量は、THF3000μg/g、1,4-ブタンジオール(BD)10μg/gであった。
上記方法で製造された変性PBTを、減圧乾燥機内で120℃、5Pa条件下で72時間乾燥させた。乾燥後の変成PBTから発生したアウトガス量は、THF280μg/g、BD5μg/gであった。
<二軸延伸ポリエステルフィルムの製造>
この変成PBTとPET(相対粘度:1.38)とを、質量比15/85で単純チップ混合したものを、コートハンガータイプのTダイを具備した200mmφ押出機を使用して、樹脂温度280℃で溶融押出し、20℃に温調されたキャストロールにピニングワイヤーに7kVの印加電圧をかけて密着急冷し、厚さ約190μmの未延伸シートを得た。
得られた未延伸シートを、ロール縦延伸機で90℃で3.5倍、テンター横延伸機で120℃で4.5倍に延伸した後、横方向の弛緩率を3%として、235℃で熱処理を施し、室温まで徐冷し、厚さ12μmの二軸延伸ポリエステルフィルムを得た。
製造された二軸延伸ポリエステルから発生したアウトガス量はTHF8μg/g、BD1μg/g、エチレングリコール(EG)70μg/gであった。
変成PBTチップの乾燥時間を表1に示すように変更した以外は実施例1と同様にして二軸延伸ポリエステルフィルムを得た。
変成PBTチップを5m3の乾燥機に入れ、120℃雰囲気下にて、乾燥機内に窒素を5m3/sの流量で流しつつ24時間乾燥させた。乾燥後の変成PBTから発生したアウトガス量はTHF480μg/g、BD8μg/gであった。この変成PBTチップを用いて実施例1と同様にして二軸延伸ポリエステルフィルムを得た。
変成PBTチップの乾燥時間を表1に示すように変更した以外は実施例4と同様にして二軸延伸ポリエステルフィルムを得た。
変成PBTチップを、120℃の熱風乾燥機にて72時間乾燥させた。乾燥後の変成PBTから発生したアウトガス量はTHF1200μg/g、BD9μg/gであった。この変成PBTチップを用いて実施例1と同様にして二軸延伸ポリエステルフィルムを得た。
変成PBTチップの乾燥時間を表1に示すように変更した以外は実施例6と同様にして二軸延伸ポリエステルフィルムを得た。
変成PBTチップ中のPTMGの割合を表1に示すように変更した以外は実施例1と同様にして二軸延伸ポリエステルフィルムを得た。
変成PBTとPETの配合割合を表1に示すように変更した以外は実施例1と同様にして二軸延伸ポリエステルフィルムを得た。
変成PBTに用いるPTMGの分子量を表1に示すように変更した以外は実施例1と同様にして二軸延伸ポリエステルフィルムを得た。
変成PBTとPETの配合割合を表1に示すように変更した以外は実施例6と同様にして二軸延伸ポリエステルフィルムを得た。
変成PBTとPETの配合割合を表1に示すように変更した以外は比較例1と同様にして二軸延伸ポリエステルフィルムを得た。
これに対し、比較例では、次のような問題があった。
比較例1~3では、変成PBTに含まれるPTMG量とその分子量や、変成PBTとPETの配合割合が、本発明で規定する範囲を満たすので、直線引裂性を有するフィルムが得られたものの、THF発生量が本発明で規定した範囲を超えていたために、蒸着フィルムは、酸素透過度・水蒸気透過度が不安定となった。
比較例4では、変成PBT中に含まれるPTMGの割合が本発明で規定する範囲より多かったため、製膜が困難となり、二軸延伸ポリエステルフィルムを採取することができなかった。また比較例5では、本発明で規定するTHF発生量を満たすので、蒸着フィルムの酸素透過度・水蒸気透過度は安定したものの、変成PBT中に含まれるPTMGの割合が本発明で規定する範囲より少なかったため、良好な引裂直線性を有するフィルムを得ることができなかった。
比較例6~7では、本発明で規定するTHF発生量を満たすので、蒸着フィルムの酸素透過度・水蒸気透過度は安定したものの、変成PBTとPETの割合が本発明で規定する範囲外であるために、良好な引裂直線性を有するフィルムを得ることはできなかった。
比較例8~9では、本発明で規定するTHF発生量を満たすので、蒸着フィルムの酸素透過度・水蒸気透過度は安定したものの、変成PBTチップに含まれるPTMGの分子量が本発明で規定する範囲外であるために、良好な引裂直線性を有するフィルムを得ることはできなかった。
比較例10では、二軸延伸ポリエステルフィルム中から発生するTHF量が本発明で規定した範囲を超えていたために、蒸着フィルムの酸素透過度・水蒸気透過度が不安定となった。さらに変成PBTとPETの割合が本発明で規定する範囲外であるために、良好な引裂直線性を有するフィルムを得ることはできなかった。
Claims (3)
- 変性ポリブチレンテレフタレート(変性PBT)と、ポリエチレンテレフタレート(PET)とを含有する二軸延伸フィルムであり、変性PBTとPETとの質量比(変性PBT/PET)が20/80~5/95であり、変性PBTが、分子量600~4,000のポリテトラメチレングリコール単位5~20質量%を含有するPBTであり、二軸延伸フィルムをヘリウムガス雰囲気下で180℃、30分間熱処理することにより発生するテトラヒドロフラン(THF)量が50μg/g以下であり、長手方向に引裂直線性を有することを特徴とする二軸延伸ポリエステルフィルム。
- 請求項1記載の二軸延伸ポリエステルフィルムの少なくとも片面に、アルミニウム、酸化アルミニウム、酸化珪素の少なくとも一種が蒸着され、ガスバリア性と引裂直線性とを有することを特徴とする二軸延伸ポリエステルフィルム。
- 請求項1記載の二軸延伸ポリエステルフィルムを製造するための方法であって、分子量600~4,000のポリテトラメチレングリコール単位5~20質量%を含有し、ヘリウムガス雰囲気下で180℃、30分間熱処理することにより発生するテトラヒドロフラン(THF)量が800μg/g以下である変性ポリブチレンテレフタレート(変性PBT)と、ポリエチレンテレフタレート(PET)とを、変性PBTとPETとの質量比(変性PBT/PET)が20/80~5/95となるように配合して、製膜、延伸することを特徴とする二軸延伸ポリエステルフィルムの製造方法。
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KR20140057268A (ko) | 2014-05-12 |
JP2013053258A (ja) | 2013-03-21 |
TWI552855B (zh) | 2016-10-11 |
US9518195B2 (en) | 2016-12-13 |
KR101896302B1 (ko) | 2018-09-07 |
JP5822611B2 (ja) | 2015-11-24 |
CA2847117A1 (en) | 2013-03-14 |
AU2012305417B2 (en) | 2016-03-17 |
EP2754686B1 (en) | 2022-11-09 |
MY168299A (en) | 2018-10-25 |
US20140193648A1 (en) | 2014-07-10 |
EP2754686A4 (en) | 2015-03-18 |
CA2847117C (en) | 2020-03-24 |
CN109333983A (zh) | 2019-02-15 |
EP2754686A1 (en) | 2014-07-16 |
CN103781827A (zh) | 2014-05-07 |
TW201317115A (zh) | 2013-05-01 |
NZ621873A (en) | 2015-07-31 |
AU2012305417A1 (en) | 2014-03-20 |
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