WO2023157730A1

WO2023157730A1 - Biaxially oriented polyester film

Info

Publication number: WO2023157730A1
Application number: PCT/JP2023/004185
Authority: WO
Inventors: 考道後藤; 信之真鍋; 昇玉利
Original assignee: 東洋紡株式会社
Priority date: 2022-02-16
Filing date: 2023-02-08
Publication date: 2023-08-24
Also published as: TW202344582A; JPWO2023157730A1

Abstract

[Problem] To provide a polyester film which has excellent cold formability and which can suppress the occurrence of spring-back and curling after forming. [Solution] Provided is a biaxially oriented polyester film which has terephthalic acid and ethylene glycol as main components. The puncture strength is 0.45 N/μm to 0.80 N/μm; the thermal shrinkage at 150°C in both the MD direction and the TD direction is 2.5% or less; the dynamic friction coefficient μd between at least one surface of the film and a metal plate is 0.10 to 0.50; in a tensile stress relaxation test at 25°C, the stress decay rate indicated by formula (1) stress decay rate (%) = 100 × (σ0-σ1)/ σ0 in both the MD direction and the TD direction is 15.0% or more; and the content of radiocarbon (C14) with respect to the total carbon in the film is 10% to 20%.

Description

biaxially oriented polyester film

The present invention relates to a polyester film, having excellent cold formability, and particularly to a polyester film that can be suitably used for applications where molding is performed after laminating metal foil, such as battery exteriors and pharmaceutical packaging.

Aromatic polyesters, typified by polyethylene terephthalate (PET), have excellent mechanical properties and chemical resistance, and are widely used as molded products such as fibers and films. In particular, PET resin is inexpensive and excellent in terms of sanitation, so it is widely used as food containers and beverage containers.

In recent years, laminate-type lithium-ion battery outer packaging materials, press-through packs, and the like are obtained by cold forming laminates composed of resin films and metal foils.
Laminates for cold forming generally have a structure such as polyethylene terephthalate film/biaxially oriented nylon film/aluminum foil/polypropylene film. (See Patent Document 1, for example)

In addition, for pharmaceutical packaging, there is a growing need for a packaging form that uses metal foil such as aluminum to prevent deterioration of the contents, and there is a demand for improved formability of the metal foil to match the shape of the contents. there is

The flexibility of the resin film is one of the factors that affect the moldability during cold forming. If the resin film has low flexibility, a strong load is applied during elongation during cold forming, and pinholes and delamination may occur. Conversely, if the resin film has too high flexibility, the effect of protecting the laminate containing the metal foil as the base material is reduced, and the physical properties of the resulting laminate are deteriorated. Therefore, it is important that the resin film has flexibility that is neither too high nor too low.

As a means for solving these problems, for example, according to Patent Document 2, at least a substrate layer, an adhesive layer, a metal layer, and a sealant layer are laminated in order, and the substrate layer is formed in the MD direction. The sum of the stress value A at 50% elongation / stress at 5% elongation in the TD direction and the stress value B at 50% elongation / 5% elongation in the TD direction (A + B) as a specific range It is disclosed that good moldability can be obtained by

On the other hand, the above-described cold forming tends to pose a problem of so-called springback, a phenomenon in which a part of the formed product returns from the shape after forming to the shape before forming after drawing. Such springback may cause a problem that the dimensional accuracy of the shape after draw forming becomes insufficient. In addition, since the surrounding part is strongly pulled during the molding process, the surrounding base material layer that has been molded and processed tends to return to its original state, causing warping and lowering the yield in post-processing. I was afraid I might let it go.
On the other hand, as described in the above-mentioned Patent Document 2, although the molding depth can be improved only by controlling the F5 value and F50 value of the film, the deterioration of dimensional accuracy due to springback after molding, It was insufficient to improve the warpage resistance after molding.

Along with the growing demand for building a recycling-based society, there is a desire to break away from fossil fuels in the material field as well as energy, and the use of biomass is attracting attention. Biomass is an organic compound that is photosynthesised from carbon dioxide and water, and is a so-called carbon-neutral renewable energy that is regenerated into carbon dioxide and water by using it. In recent years, the practical use of biomass plastics using these biomass as raw materials has progressed rapidly, and attempts have been made to produce polyesters, which are general-purpose polymer materials, from these biomass raw materials.

JP 2008-053133 A International Publication No. 2015-125806

The present invention was made against the background of such problems of the prior art. That is, the object of the present invention is to provide a polyester film that not only has excellent cold formability, but also suppresses deterioration in dimensional accuracy after forming due to springback, and has excellent warpage resistance, and uses biomass-derived raw materials. To provide a carbon-neutral polyester film.

As a result of diligent studies by the present inventors, it was found that by selecting a specific range of stretching conditions and controlling the mechanical properties of the film within a predetermined range, it is possible to achieve excellent cold formability and prevent springback and curl after forming. We found that it can be suppressed, and arrived at the present invention.

That is, the present invention consists of the following configurations.
[1] A biaxially oriented polyester film containing terephthalic acid and ethylene glycol as main components,
The puncture strength measured according to JIS Z 7102 is 0.45 N/μm or more and 0.80 N/μm or less,
The thermal shrinkage rate at 150 ° C. is 2.5% or less in both the MD direction and the TD direction,
A dynamic friction coefficient μd between at least one surface of the film and the metal plate is 0.10 or more and 0.50 or less,
In a tensile stress relaxation test at 25 ° C., the stress attenuation rate represented by the following formula (1) is 15.0% or more in both the MD direction and the TD direction,
Formula (1) Stress attenuation rate (%) = 100 × (σ0-σ1)/σ0
Here, σ0 represents the value of the tensile stress immediately after applying a tensile force to the film at a tensile speed of 200 mm / min and the 50% tensile strain is applied, and σ1 is the tensile stress from σ0 to 50%. Shows the value of tensile stress when the strain is held for 2 seconds,
A biaxially oriented polyester film in which the content of radioactive carbon C14 is 10% or more and 20% or less with respect to the total carbon in the film.
[2] At 25 ° C., the stress at 3% elongation in the MD and TD directions of the film is X (MD) and X (TD), respectively, and the stress at 30% elongation in the MD and TD directions is Y (MD) and When the values of Y(TD), Y(MD)/X(MD) and Y(MD)/X(MD) are respectively Z(MD) and Z(TD), the following formulas (2) to (5) The biaxially oriented polyester film according to [1], which satisfies both of the above.
Formula (2) 125 MPa ≤ Y(MD) ≤ 155 MPa
Formula (3) 140 MPa ≤ Y(TD) ≤ 190 MPa
Formula (4) 1.3≦Z(MD)≦1.6
Formula (5) 1.7≦Z(TD)≦2.2
[3] The biaxially oriented polyester film of [1] or [2], comprising a biomass polyester resin having a biomass-derived ethylene glycol as a diol unit and a fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit.
[4] The biaxially oriented polyester film according to any one of [1] to [3], which is used for cold forming applications.
[5] A laminate comprising the biaxially oriented polyester film of any one of [1] to [4], a gas barrier layer and a sealant layer.
[6] The laminate according to [5], wherein the gas barrier layer contains a metal foil.
[7] A battery exterior material comprising the laminate according to [5] or [6].

By using the biaxially oriented polyester film of the present invention as a substrate layer, the metal foil can appropriately conform to the shape of the mold during molding. Since it is excellent in springback and warpage resistance after molding, it is excellent in dimensional accuracy in molding and can contribute to improvement in productivity. In addition, by using a carbon-neutral polyester film using a biomass-derived raw material, it is possible to contribute to the reduction of the environmental load in that it does not affect the increase or decrease of carbon dioxide on the ground.

It is a schematic diagram showing a method of multi-stage stretching in the TD direction in the film manufacturing process.

The present invention will be described in detail below.

[Polyester resin composition]
The biaxially oriented polyester film in the present invention is a film formed from a polyester resin composition containing, as main constituents, terephthalic acid as a dicarboxylic acid component and ethylene glycol as a diol component. Here, "containing as a main component" means that the content of the component in the polyester resin composition is 80 mol% or more based on 100 mol% of the total constituent components of the polyester resin, and 90 mol. % or more, more preferably 95 mol % or more, most preferably 97 mol % or more.

In the present invention, a polyester resin containing biomass-derived ethylene glycol as a constituent can be used as a diol component. All of the ethylene glycol may be biomass-derived ethylene glycol, or a mixture of biomass-derived and fossil fuel-derived ethylene glycol may be used. By using biomass-derived ethylene glycol, the degree of biomass in the film can be increased, making it possible to obtain a carbon-neutral film.

As an example of biomass-derived ethylene glycol, ethanol produced from biomass (biomass ethanol) can be used as a raw material. Biomass-derived ethylene glycol can be obtained from biomass ethanol by a conventionally known method, such as a method of producing ethylene glycol via ethylene oxide.

In addition, these polyester resins may be copolymerized with other components as long as the object of the present invention is not impaired. Specifically, examples of copolymerizable components include dicarboxylic acid components such as isophthalic acid, naphthalenedicarboxylic acid, 4,4-diphenyldicarboxylic acid, adipic acid, sebacic acid and ester-forming derivatives thereof. Diol components include diethylene glycol, hexamethylene glycol, neopentyl glycol, and cyclohexanedimethanol. Also included are polyoxyalkylene glycols such as polyethylene glycol and polypropylene glycol. The amount of copolymerization is preferably 10 mol % or less, more preferably 5 mol % or less, most preferably 3 mol % or less per constituent repeating unit.

The polyester resin composition may contain a single polyester resin, or may contain a plurality of polyester resins. Moreover, resins other than polyester resin may be included.

The intrinsic viscosity of the polyester resin composition is preferably in the range of 0.50 to 0.90 dl/g, more preferably in the range of 0.55 to 0.80 dl/g, from the viewpoint of film-forming properties and recycling properties. is.

In addition to the polyester resin, the polyester resin composition may contain conventionally known additives such as lubricants, stabilizers, colorants, antioxidants, antistatic agents, and ultraviolet absorbers.

For example, the lubricant can adjust the dynamic friction coefficient of the film, and includes inorganic lubricants such as silica, calcium carbonate, and alumina, as well as organic lubricants. As the inorganic lubricant, silica and calcium carbonate are preferred, and porous silica is most preferred from the viewpoint of achieving both transparency and lubricity.

The lower limit of the lubricant content in the biaxially oriented polyester film of the present invention is preferably 400 mass ppm, more preferably 600 mass ppm. By making it 500 mass ppm or more, it is possible to improve the slipperiness of the film. The upper limit of the lubricant content is preferably 1500 mass ppm, more preferably 1200 mass ppm. By making it 1500 mass ppm or less, the transparency of the film can be improved.

In the biaxially oriented polyester film of the present invention, the content of biomass-derived carbon measured by radioactive carbon (C14) is preferably 10% or more and 20% or less based on the total carbon in the polyester film. Since carbon dioxide in the atmosphere contains a certain proportion of C14 (105.5 pMC), the C14 content in plants that grow by taking in carbon dioxide in the atmosphere, such as corn, is also about 105.5 pMC. It is known. It is also known that fossil fuels contain almost no C14. Therefore, by measuring the ratio of C14 contained in the total carbon atoms in the polyester, the ratio of biomass-derived carbon can be calculated.

[Method for producing biaxially oriented polyester film]
The method for obtaining the biaxially oriented polyester film of the present invention is not particularly limited, and can be appropriately selected from a T-die method, an inflation method, and the like. Here, a representative manufacturing process of the T-die method will be described. In the T-die method, (1) a process of melt extruding a polyester resin composition into a sheet and cooling it on a cooling roll to form an unstretched sheet, (2) the unstretched sheet that has been molded is processed in the MD direction (longitudinal direction). ) and a stretching step of stretching in the TD direction (width direction) perpendicular to the MD direction, (3) a heat setting step of heating and crystallizing the film after the stretching, (4) the heat set film It includes a thermal relaxation step (sometimes referred to as a relaxation step) for removing residual strain, and (5) a cooling step for cooling the film after thermal relaxation.

The film of the present invention may have a single layer structure of at least one layer, or may have a laminated structure of two or more layers. It may be two layers, three layers, four layers, or five layers.

The upper limit of the cooling roll temperature is preferably 40°C, more preferably 20°C or less. When the temperature is 40° C. or higher, the degree of crystallinity does not become too high when the melted polyester resin composition cools and solidifies, and stretching becomes easier, and a decrease in transparency due to crystallization can be suppressed.
The lower limit of the chill roll temperature is preferably 0°C. When the temperature is 0°C or higher, the effect of suppressing crystallization when the molten polyester resin composition is cooled and solidified can be sufficiently exhibited. Further, when the cooling roll temperature is within the above range, it is preferable to lower the humidity of the environment around the cooling roll to prevent dew condensation.

The thickness of the unstretched sheet is preferably in the range of 15-2500 μm. It is more preferably 600 μm or less, and most preferably 400 μm or less.

Next, the stretching process will be explained. The stretching method may be simultaneous biaxial stretching or sequential biaxial stretching. The sequential biaxial stretching will be described below as an example.

The lower limit of the draw ratio in the MD direction is preferably 2.5 times, more preferably 2.8 times, and particularly preferably 3.1 times. If it is 2.5 times or more, not only will the mechanical strength of the film be good, but also the thickness unevenness will be good, leading to an improvement in the winding quality of the roll.
The upper limit of the draw ratio in the MD direction is preferably 5.0 times, more preferably 4.5 times, and particularly preferably 4.0 times. By setting the draw ratio in the MD direction to 5.0 times or less, it is possible to suppress the increase in springback and curl after molding due to excessive orientation of the film.

The temperature during stretching in the MD direction is preferably in the range of 80 to 130°C. If the stretching temperature in the MD direction is lower than 80° C., the orientation of the film becomes too high, which may increase springback and curl after molding. On the other hand, if the stretching temperature in the MD direction is higher than 130° C., the orientation in the MD direction will be low, so there is a possibility that the formability will deteriorate.

As a method of stretching in the MD direction, a method of stretching between rolls while heating a plurality of rolls or a method of heating and stretching with an infrared heater or the like is used. The method of heating and stretching with an infrared heater or the like is preferable from the viewpoint that a high temperature can be easily obtained, local heating can be easily performed, and flaws caused by rolls can be reduced. On the other hand, when a method of stretching between rolls while heating a plurality of rolls is used, a method of multistage stretching between a plurality of rolls is preferable. By using a method of multi-stage stretching between a plurality of rolls, it is possible to suppress an increase in the orientation in the MD direction even in stretching at a high magnification, and to suppress springback and curling after molding. The number of rolls for multistage stretching is preferably 2 or more, more preferably 3 or more.

In the stretching step, it is preferable that there is a relaxation step in the MD direction (hereinafter also referred to as MD relaxation) between the stretching step in the MD direction and the stretching step in the TD direction following the stretching step in the MD direction.
The lower limit of the MD relaxation rate is preferably 1%, more preferably 3%, particularly preferably 5%. When it is 1% or more, the amorphous component in the film is relaxed, and the stretching stress in the subsequent stretching step in the TD direction can be reduced, and as a result, it is possible to suppress the orientation of the film from becoming too high. , springback and curl after molding can be suppressed.
The upper limit of the MD relaxation rate is preferably 10%, more preferably 8%, particularly preferably 6%. When it is 10% or less, wrinkles due to shrinkage can be suppressed, and not only can the quality of the film be improved, but also a decrease in mechanical strength due to relaxation of orientation can be suppressed.
Although the method of MD relaxation is not particularly limited, for example, there is a method of applying relaxation treatment using a speed difference between rolls after heating with a hot air heater.

The lower limit of the stretching temperature in the TD direction is preferably 90°C, more preferably 100°C, and particularly preferably 110°C. When the temperature is 90° C. or higher, the stretching stress can be reduced, so that springback and curling after molding can be suppressed.
The upper limit of the stretching temperature in the TD direction is preferably 140°C, more preferably 130°C, and particularly preferably 120°C. If the stretching temperature in the TD exceeds 140° C., not only the film formability is lowered, but also the orientation of the obtained film in the TD direction is weakened, so that the moldability may be lowered.

The lower limit of the draw ratio in the TD direction is preferably 2.5 times, more preferably 3.0 times, and particularly preferably 3.5 times. When it is 2.5 times or more, not only the mechanical strength and thickness unevenness of the film are improved, but also the moldability is improved.
The upper limit of the draw ratio in the TD direction is preferably 5.0 times, more preferably 4.5 times, and particularly preferably 4.0 times. By making it 5.0 times or less, it is possible to suppress an increase in the orientation in the TD direction and suppress the occurrence of springback and curl after molding.

As for the stretching pattern in the TD direction, multistage stretching can be preferably used in addition to the generally used linear stretching pattern in which the stretching ratio increases linearly. Multi-stage drawing is a normal one-stage drawing, that is, a linear drawing pattern, as shown in FIG. can do. As a result, even if the draw ratio is the same, the orientation in the TD direction can be prevented from becoming too high, and springback and curling after molding can be suppressed.

The multi-stage stretching in the TD direction is preferably 2-stage stretching or more and 5-stage stretching or less. Multi-stage stretching is preferable because it is possible to change the stretching stress by changing each stretching temperature, and the stretching stress during stretching in the TD direction can be reduced. If the stretching is two-stage or more, the stretching stress can be reduced, and even if the stretching ratio is the same, it is possible to suppress the orientation in the TD direction from becoming too high, and it is possible to suppress springback and curling after molding. . If the drawing is 5 stages or less, it is possible to prevent the equipment from becoming too large. In the multi-stage stretching, it is preferable to adopt a temperature pattern in which a temperature difference of 2° C. or more is provided in each stage of stretching, and the temperature is lowered from the first stage of stretching to the final stage of stretching.
In the case of multi-stage stretching, a zone having a fixed length can be appropriately provided after each stretching step. By providing a fixed-length zone after each drawing step, the internal stress generated during drawing is relieved in the fixed-length zone, so that the drawing stress in the next drawing can be further reduced, and the same draw ratio can be used. Even if there is, it is possible to suppress the orientation in the TD direction from becoming too high, and it is possible to suppress springback and curling after molding.

The lower limit of the heat setting temperature in the heat setting step is preferably 170°C, more preferably 180°C, and particularly preferably 190°C. A heat shrinkage rate can be made small as it is 170 degreeC or more. The upper limit of the heat setting temperature is preferably 230°C, more preferably 220°C, and particularly preferably 210°C. When the temperature is 230° C. or less, it is possible to suppress a decrease in mechanical strength due to brittleness of the biaxially oriented polyester film.

The lower limit of the relaxation rate in the TD direction in the thermal relaxation step is preferably 0.5%, more preferably 1.0%, and particularly preferably 2.0%. When it is 0.5% or more, the heat shrinkage rate in the TD direction can be kept low. The upper limit of the relaxation rate in the TD direction is preferably 10%, more preferably 8%, particularly preferably 6%. If it is 10% or less, it is possible to prevent the occurrence of slackness and the like, and it is possible to improve the flatness.

[Structure and properties of biaxially oriented polyester film]
The lower limit of the thickness of the biaxially oriented polyester film of the present invention is preferably 5 μm, more preferably 10 μm. By setting the thickness to 5 μm or more, good mechanical properties and moldability can be obtained. The upper limit of the thickness of the biaxially oriented polyester film of the present invention is preferably 100 µm, more preferably 70 µm, and particularly preferably 40 µm.

The lower limit of the puncture strength of the biaxially oriented polyester film of the present invention is preferably 0.45 N/μm, more preferably 0.50 N/μm. Good moldability can be obtained when the puncture strength is 0.45 N/μm or more. The upper limit of the puncture strength of the biaxially oriented polyester film of the present invention is 0.80 N/μm. When the puncture strength exceeds 0.80 N/μm, the effect of improving the formability is saturated. Here, the piercing strength (unit: N/μm) in the present invention means the strength (unit: N ) divided by the film thickness (unit μm).

The lower limit of the heat shrinkage rate in the MD and TD directions of the biaxially oriented polyester film of the present invention is preferably 0.1%, more preferably 0.2%, and particularly preferably 0.3%. . The upper limit of the heat shrinkage rate in the MD and TD directions is preferably 2.5%, more preferably 2.0%, and particularly preferably 1.8%. When it is 2.5% or less, it is possible to suppress the dimensional change when heated in the secondary processing step and reduce the occurrence of wrinkles.

The thickness unevenness in the TD direction of the biaxially oriented polyester film of the present invention is preferably 18% or less, more preferably 16% or less, still more preferably 14% or less. When it is 18% or less, the winding quality of the roll becomes good.

The haze of the biaxially oriented polyester film of the present invention is preferably 5.0% or less, more preferably 3.0% or less, still more preferably 2.5% or less. A content of 5.0% or less is preferable because the print looks beautiful.

Next, springback during molding will be described.
When molding for applications such as battery packaging and pharmaceutical packaging, the film is pressed into a mold of a predetermined shape, held in the pressed state for a certain period of time, and then lifted out of the mold to produce a molded body. However, if the mold is pulled up while the internal stress in the film is not sufficiently relieved during the holding time, the film will exert a force to return to its original shape, resulting in increased springback, resulting in a molded body. There is a risk that the dimensional accuracy of the The present inventors found that the springback can be reduced by setting the stress reduction rate after holding for 2 seconds within a specific range in a tensile stress relaxation test of the obtained biaxially oriented polyester film.

In the tensile stress relaxation test at 25°C of the biaxially oriented polyester film of the present invention, the stress attenuation rate represented by the following formula (1) is preferably 15% or more in both the MD direction and the TD direction. % or more is more preferable.
Formula (1) Stress decay rate (%) after holding for 2 seconds = 100 x (σ0-σ1)/σ0
Here, σ0 represents the value of the tensile stress of the film immediately after applying a tensile force to the film at a tensile speed of 200 mm / min and the 50% tensile strain is applied, and σ1 is σ0 to 50 % tensile strain is shown for 2 seconds.

In the biaxially oriented polyester film of the present invention, the stress at 30% elongation (F30 value) in the MD direction of the film at 25 ° C. is Y (MD), and the stress at 30% elongation in the TD direction (F30 value) is Y (TD ), it is preferable to satisfy the following formulas (2) and (3).
Formula (2) 125 MPa ≤ Y(MD) ≤ 155 MPa
Formula (3) 140 MPa ≤ Y(TD) ≤ 190 MPa

By setting the value of Y (MD) to 125 MPa or more, excellent moldability can be obtained. On the other hand, by setting the value of Y (MD) to 155 MPa or less, the stress of the film after molding is suppressed from becoming too large, the springback and warpage resistance after molding are reduced, and good moldability is achieved. Obtainable. Similarly, by setting the Y(TD) value to 140 MPa or more, excellent moldability can be obtained. By setting the value of Y(TD) to 190 MPa or less, the stress of the film after molding is suppressed from becoming too large, the springback and warpage resistance after molding are reduced, and good moldability is obtained. can be done.

In the biaxially oriented polyester film of the present invention, the stress at 3% elongation (F3 value) in the MD direction of the film at 25 ° C. is X (MD), and the stress at 3% elongation (F3 value) in the TD direction is X (TD ), the value of Y (MD) / X (MD) is Z (MD), and the value of Y (TD) / X (TD) is Z (TD), the following formulas (4) and (5) is preferably satisfied.
Formula (4) 1.3≦Z(MD)≦1.6
Formula (5) 1.7≦Z(TD)≦2.2

By setting the value of Z(MD) to 1.3 or more, excellent moldability can be obtained. On the other hand, by setting the value of Z (MD) to 1.6 or less, the stress of the film after molding is suppressed from becoming too large, and the springback and warpage resistance after molding are reduced, resulting in good molding. You can get sex. Similarly, by setting the value of Z(TD) to 11.7 or more, excellent moldability can be obtained. By setting the value of Z (TD) to 2.2 or less, the stress of the film after molding is suppressed from becoming too large, and the springback and warpage resistance after molding are reduced, resulting in good moldability. Obtainable.

From the standpoint of formability, the biaxially oriented polyester film of the present invention preferably has a coefficient of dynamic friction μd with a metal surface of 0.10 or more and 0.50 or less. When the polyester film of the present invention is used for battery packaging or pharmaceutical packaging, these structures are molded by male-female press molding, and the coefficient of dynamic friction μd between the film and metal is 0.10. As described above, by making it 0.50 or less, it becomes possible to perform molding smoothly because the slipperiness with the press mold is improved. It is more preferably 0.20 or more and 0.50 or less, and still more preferably 0.25 or more and 0.40 or less. In the present invention, the coefficient of dynamic friction with metal indicates the coefficient of dynamic friction between any surface of the film and SUS304-#400 mirror-finished material. The dynamic friction coefficient can be controlled by the content of the lubricant added to the film.

A printed layer may be laminated on the biaxially oriented polyester film of the present invention. As the printing ink for forming the printing layer, water-based and solvent-based resin-containing printing inks can be preferably used. Resins used in printing inks include acrylic resins, urethane resins, polyester resins, vinyl chloride resins, vinyl acetate copolymer resins, and mixtures thereof. Known additives such as antistatic agents, light blocking agents, ultraviolet absorbers, plasticizers, lubricants, fillers, colorants, stabilizers, lubricants, antifoaming agents, cross-linking agents, anti-blocking agents, and antioxidants are added to printing inks. agents may be included.

The printing method for providing the printed layer is not particularly limited, and known printing methods such as offset printing, gravure printing, and screen printing can be used. For drying the solvent after printing, a known drying method such as hot air drying, hot roll drying, or infrared drying can be used.

The present invention further provides a laminate in which a biaxially oriented polyester film is provided with an inorganic thin film layer or a gas barrier layer such as a metal foil.

The inorganic thin film layer is a thin film made of metal or inorganic oxide. The material for forming the inorganic thin film layer is not particularly limited as long as it can be formed into a thin film. Oxides are preferred. In particular, a composite oxide of silicon oxide and aluminum oxide is preferable from the viewpoint of achieving both flexibility and denseness of the thin film layer.

In this composite oxide, the mixing ratio of silicon oxide and aluminum oxide is preferably in the range of 20 to 70% by mass of Al in terms of the metal content. On the other hand, if it is 70% or less, the inorganic thin film layer can be softened, and it is possible to suppress deterioration of the gas barrier properties due to destruction of the thin film during secondary processing such as printing and lamination. Here, silicon oxide means various silicon oxides such as SiO and SiO ₂ or mixtures thereof, and aluminum oxide means various aluminum oxides such as AlO and AL ₂ O ₃ or mixtures thereof.

The film thickness of the inorganic thin film layer is usually 1 to 100 nm, preferably 5 to 50 nm. When the film thickness of the inorganic thin film layer is 1 nm or less, it becomes easier to obtain more satisfactory gas barrier properties. On the other hand, when it is 100 nm or less, it is advantageous in terms of bending resistance and manufacturing cost.

The method for forming the inorganic thin film layer is not particularly limited. Laws should be adopted accordingly. A typical method for forming an inorganic thin film layer will be described below using a silicon oxide/aluminum oxide thin film as an example. For example, when a vacuum deposition method is employed, a mixture of SiO ₂ and Al ₂ O ₃ or a mixture of SiO ₂ and Al is preferably used as the deposition raw material. Particles are usually used as these vapor deposition raw materials, and the size of each particle is preferably such that the pressure during vapor deposition does not change, and the preferred particle diameter is 1 to 5 mm. Methods such as resistance heating, high-frequency induction heating, electron beam heating, and laser heating can be employed for heating. It is also possible to introduce oxygen, nitrogen, hydrogen, argon, carbon dioxide gas, water vapor, etc. as reaction gases, or adopt reactive vapor deposition using means such as addition of ozone and ion assist. Furthermore, film formation conditions can be arbitrarily changed, such as applying a bias to the object to be vapor-deposited (laminated film to be vapor-deposited) or heating or cooling the object to be vapor-deposited. Such vapor deposition material, reaction gas, bias of the object to be vapor-deposited, heating/cooling, etc. can be similarly changed when adopting the sputtering method or the CVD method. Furthermore, a printed layer may be laminated on the inorganic thin film layer.

When providing an inorganic thin film layer on the biaxially oriented polyester film of the present invention, it is preferable to provide a protective layer on the inorganic thin film layer. A gas barrier layer made of a metal oxide is not a completely dense film, and is dotted with minute defects. By forming a protective layer by applying a specific resin composition for a protective layer to be described later on the metal oxide layer, the resin in the protective compatible resin composition penetrates into the defective portions of the metal oxide layer, As a result, the effect of stabilizing the gas barrier property is obtained. In addition, by using a material with gas barrier properties for the protective layer itself, the gas barrier properties of the laminated film are greatly improved.

Examples of the protective layer include resins such as urethane, polyester, acrylic, titanium, isocyanate, imine, and polybutadiene to which curing agents such as epoxy, isocyanate, and melamine are added. . Examples of the solvent (solvent) used for forming the protective layer include aromatic solvents such as benzene and toluene; alcohol solvents such as methanol and ethanol; ketone solvents such as acetone and methyl ethyl ketone; ethyl acetate and butyl acetate. ester-based solvents such as ethylene glycol monomethyl ether; and polyhydric alcohol derivatives such as ethylene glycol monomethyl ether.

As the metal foil used for the gas barrier layer, various metal foils such as aluminum and stainless steel can be used, and aluminum foil is preferable in terms of workability such as moisture resistance and extensibility, and cost. A general soft aluminum foil can be used as the aluminum foil. Among them, aluminum foil containing iron is preferable from the viewpoint of excellent pinhole resistance and extensibility during molding. The iron content in the iron-containing aluminum foil (100% by mass) is preferably 0.1 to 9.0% by mass, more preferably 0.5 to 2.0% by mass. If the iron content is at least the lower limit, the pinhole resistance and spreadability are excellent. If the iron content is 9.0% by mass or less, the flexibility is excellent. The thickness of the metal foil is preferably 9 to 200 μm, more preferably 15 to 100 μm, from the viewpoints of barrier properties, pinhole resistance and workability.

The laminate of the present invention may be laminated with layers of other materials. As the method, a method of laminating the biaxially oriented polyester film after film formation and a method of laminating the film during film formation can be employed.

The laminate of the present invention can be used as a packaging material for cold molding by further forming a heat-sealable resin layer called a sealant (also called a sealant layer) on the biaxially oriented polyester film and the gas barrier layer. Formation of the sealant layer is usually carried out by an extrusion lamination method or a dry lamination method.

Examples of the sealant layer include resin films made of acid-modified polyolefin resin obtained by graft-modifying polyolefin resin or acid such as maleic anhydride to polyolefin resin. Examples of the polyolefin-based resins include low-, medium-, and high-density polyethylene; ethylene-α-olefin copolymers; homo-, block-, or random polypropylene; and propylene-α-olefin copolymers. These polyolefin-based resins may be used alone or in combination of two or more.

The sealant layer may be a single layer film or a multilayer film, and may be selected according to the required functions. For example, from the viewpoint of imparting moisture resistance, a multilayer film in which a resin such as an ethylene-cyclic olefin copolymer or polymethylpentene is interposed can be used. In addition, the sealant layer may contain various additives such as flame retardants, slip agents, antiblocking agents, antioxidants, light stabilizers and tackifiers. The thickness of the sealant layer is preferably 10-100 μm, more preferably 20-60 μm.

The laminate of the present invention can also be constructed by providing an adhesive layer, a printed layer, etc. between the biaxially oriented polyester film and the gas barrier layer and/or between the gas barrier layer and the sealant layer.

The present invention provides a battery exterior material including a laminate containing a biaxially oriented polyester film, a gas barrier layer and a sealant layer. In particular, it is suitably used for battery outer packaging materials for laminated lithium ion batteries. In another aspect, the invention provides a pharmaceutical packaging material.

　Films and laminates were evaluated by the following measurement methods. Unless otherwise specified, measurements were carried out in a measurement room at 23° C. and a relative humidity of 65%.

[Film thickness]
It was measured using a dial gauge in accordance with JIS K7130-1999 A method.

[Evaluation of thickness unevenness in the TD direction]
A sample of 800 mm in the TD direction and 40 mm in the longitudinal direction was sampled from the film roll, and the thickness in the width direction was continuously measured at 5 m/sec using a film tester continuous thickness measuring device (manufactured by Fujiwork). The maximum thickness at the time of measurement is Tmax. , the minimum thickness is Tmin. , the average thickness of Tave. , and the thickness unevenness in the film width direction was calculated from the following formula (6).
Equation (6) Thickness unevenness = {(Tmax.-Tmin.)/Tave. }×100(%)

[Thermal shrinkage of film]
The heat shrinkage rate was measured by the dimensional change test method according to JIS-C-2318 except that the test temperature was 150° C. and the heating time was 15 minutes. Samples were cut out from the MD direction and the TD direction, respectively, and measured.

[Measurement of film biomass]
The degree of film biomass obtained was determined by radiocarbon (C14) measurement given in ASTM D6866-16 Method B (AMS).

[Puncture strength]
It was measured in accordance with "2. Test methods for strength, etc." of "Standards and Standards for Foods, Additives, etc. No. 3: Utensils and Containers and Packages" (Ministry of Health and Welfare Notification No. 20, 1982) in the Food Sanitation Law. A needle with a tip radius of 0.5 mm was pierced into the film at a piercing speed of 50 mm/min, and the strength (N) when the needle penetrated the film was divided by the film thickness (μm) to obtain the piercing strength. . The measurement is performed at normal temperature (23° C.), and the unit is [N/μm].

[Dynamic Friction Coefficient]
In accordance with JIS K-7125, using a tensile tester (Tensilon manufactured by ORIENTEC), under an environment of 23 ° C. and 65% RH, the surface of the film not subjected to corona treatment and SUS304-#400 mirror finish material A dynamic friction coefficient μd was obtained when the were joined. The weight of the SUS304-#400 mirror-finished material was 1.5 kg, and the size of the bottom area of the SUS304-#400 mirror-finished material was 63 mm long×63 mm wide. Moreover, the tensile speed during the friction measurement was 200 mm/min. Met.

[Haze]
The sample was measured at three different locations using a haze meter (NDH2000, manufactured by Nippon Denshoku Co., Ltd.) in accordance with JIS-K-7105, and the average value was taken as the haze. The unit is [%].

[Strength and elongation of biaxially oriented film]
Based on JIS K 7127, a test sample of 15 mm width and 100 mm length was cut out in the MD direction of the film. The test sample was subjected to a tensile test using a tensile tester (Autograph AG-I manufactured by Shimadzu Corporation) under the conditions of a gauge length of 50 mm and a tensile speed of 200 mm/min. The obtained stress-strain curve was used to calculate the stress at 3% elongation (F3 value) and the stress at 30% elongation (F30 value) of the test sample.

[Stress decay rate of biaxially oriented film]
A test sample with a width of 15 mm and a length of 100 mm was cut in the MD direction of the film. With a tensile tester (Autograph AG-I manufactured by Shimadzu Corporation), a tensile strain of 50% is applied under the conditions of a gauge length of 50 mm and a tensile speed of 200 mm / min, and the 50% tensile strain is applied. The tensile strain was maintained for 100 seconds after the application, and the change in stress during that time was recorded.
From the obtained holding time-stress graph, the stress value after holding for 2 seconds from immediately after application of 50% strain was read, and the stress decay rate after holding for 2 seconds was determined by the following formula (1).

Formula (1) Stress decay rate (%) after holding for 2 seconds = 100 x (σ0-σ1)/σ0

Here, σ0 represents the tensile stress of the film immediately after the 50% tensile strain was applied by applying a tensile force to the film at a tensile speed of 200 mm/min, and σ1 is the tensile stress of 50% from σ0. The stress value when the tensile strain is held for 2 seconds is shown.

[Cold formability]
Biaxially oriented polyester film, biaxially oriented polyamide film (manufactured by Toyobo, N1102, thickness 15 μm), aluminum foil (material 8079, thickness 40 μm), and unstretched polypropylene film as a sealant layer (manufactured by Toyobo, P1146, thickness 70 μm) is dry laminated using a urethane-based adhesive (dry laminate adhesive manufactured by Toyo-Morton Co., Ltd., TM-509, CAT10L, ethyl acetate compounding ratio of 33.6: 4.0: 62.4 (mass ratio)) Then, a laminate was produced in which biaxially oriented polyester film//biaxially oriented polyamide film//aluminum foil//sealant layer were laminated in this order. The obtained laminate was placed in a die set mold (protrusion shape: 90 mm×50 mm) and pressurized at 23° C. by a pressing machine to carry out draw forming. The depth of drawing during molding was increased in units of 0.2 mm, and the maximum depth of drawing at which the laminate was not damaged was defined as the depth of drawing.
A: Drawing depth is 8mm or more
B: Drawing depth is less than 6mm to 8mm
C: The drawing depth is less than 4 mm to 6 mm
D: Drawing depth is less than 4mm

[Springback after molding]
The laminate was placed in a die set mold (protrusion shape: 90 mm×50 mm) and pressurized at 23° C. by a pressing machine to perform draw forming. In addition, the pushing speed of the mold during draw forming was set to 200 mm/min, and the holding time after pushing was set to 2 seconds. After removing the mold, the depth of the container was measured, and the retention rate (ratio of container depth to molding depth) was calculated and evaluated as follows.
A: Retention rate is 90% or more
B: Retention rate is 80% or more and less than 90%
C: Retention rate is 70% or more and less than 80%
D: Retention rate is less than 70%

[Curl after molding]
A test piece that was molded without being damaged in the cold formability evaluation was placed on a horizontal table so that the convex portion faced upward. The average value of the heights of the four corners of the test piece after molding, starting from the base, was defined as the average warpage height, and evaluation was performed according to the following criteria.
A: Average warpage height is less than 3mm
B: The average warpage height is 3 mm or more and less than 5 mm
C: The average warpage height is 5 mm or more and less than 10 mm
D: Warp height average value is 10 mm or more

[Manufacturing example]
Polyester resins used in Examples and Comparative Examples are as follows.

(Polyester resin A)
A biomass-containing PET resin of terephthalic acid//biomass-derived ethylene glycol=100//100 (mol %) (intrinsic viscosity of 0.80 dl/g) was used. The biomass-derived ethylene glycol is a raw material manufactured by Indian Glycol, and the biomass degree of the PET resin is 18%.

(Polyester resin B)
A fossil fuel-derived PET resin containing terephthalic acid//ethylene glycol=100//100 (mol %) and a porous silica particle content of 0.72 mass % (intrinsic viscosity of 0.62 dl/g) was used.

(polyester resin C)
A fossil fuel-derived PET resin with terephthalic acid//ethylene glycol=100//100 (mol %) (intrinsic viscosity of 0.62 dl/g) was used.

[Example 1]
Polyester resin A and polyester resin B were charged into the extruder at the ratio shown in Table 1. After the resin was melted at 280° C. in an extruder, it was cast from a T-die and brought into close contact with a cooling roll at 10° C. by an electrostatic adhesion method to obtain an unstretched sheet. Next, the obtained unstretched film was preheated with rolls heated to a temperature of 80° C., heated to 120° C. with an infrared heater, and stretched in the MD direction at a draw ratio of 3.7 times.
Subsequently, the film was stretched in the TD direction at a preheating temperature of 120°C, a stretching temperature of 140°C, and a stretching ratio of 4.6 times using a tenter-type transverse stretching machine. After that, it is heat-set at 210°C, subjected to a 5% relaxation treatment in the TD direction, subjected to a corona treatment at 40 W min/m2 on the surface layer (A) on the side in contact with the chill roll, and wound into a roll with a winder. A biaxially oriented polyester film having a thickness of 12 μm was produced by removing the film.
Table 1 shows the raw material composition and film-forming conditions of the obtained film, the physical properties of the obtained film, and the evaluation results.

[Examples 2-3]
A biaxially oriented polyester film having a thickness of 12 μm was obtained in the same manner as in Example 1 except that the longitudinal draw ratio was changed to the ratio shown in Table 1. Table 1 shows physical properties and evaluation results.

[Example 4]
The longitudinal stretching method is 3-stage roll stretching, the roll heating temperature is 115 ° C., and the 1st stage is 1.24 times, the 2nd stage is 1.4 times, and the 3rd stage is 2.6 times. A biaxially oriented polyester film having a thickness of 12 μm was obtained in the same manner as in Example 1 except that the film was stretched in the longitudinal direction at a total stretching ratio of 4.5 times. Table 1 shows physical properties and evaluation results.

[Example 5]
Polyester resin A and polyester resin B were charged into the extruder at the ratio shown in Table 1. After the resin was melted at 280° C. in an extruder, it was cast from a T-die and brought into close contact with a cooling roll at 10° C. by an electrostatic adhesion method to obtain an unstretched sheet. Next, the obtained unstretched film was preheated with rolls heated to a temperature of 80° C., heated to 120° C. with an infrared heater, and stretched in the MD direction at a draw ratio of 5.0 times.
The film immediately after MD stretching was passed through a heating furnace set at 95° C. with a hot air heater, and subjected to 3% relaxation treatment in the MD direction using the speed difference between rolls at the entrance and exit of the heating furnace.
Next, the stretching method in the tenter-type transverse stretching machine was changed to three-stage stretching, and the film was stretched by providing a constant-length region of 1 m between the first and second stages and between the second and third stages. Table 1 shows the stretching temperature and the stretching ratio at each stage. After that, it is heat-set at 210°C, subjected to 5% heat relaxation treatment in the width direction, corona-treated at 40 W min/m2 on the surface of the side in contact with the chill roll, and wound into a roll with a winder. , a biaxially oriented polyester film having a thickness of 12 μm was produced.
Table 1 shows the raw material composition and film-forming conditions of the obtained film, the physical properties of the obtained film, and the evaluation results.

[Examples 6-7]
A biaxially oriented polyester film having a thickness of 12 μm was obtained in the same manner as in Example 1 except that the ratio of polyester resin A and polyester resin B was changed to the ratio shown in Table 1. Table 1 shows physical properties and evaluation results.

[Comparative Examples 1 to 4]
A biaxially oriented polyester film having a thickness of 12 μm was obtained in the same manner as in Example 1 except that the longitudinal stretching conditions and transverse stretching conditions were changed to the conditions shown in Table 2. Table 2 shows physical properties and evaluation results.

[Comparative Examples 5-6]
A biaxially oriented polyester film having a thickness of 12 μm was obtained in the same manner as in Example 1 except that the ratio of polyester resin A and polyester resin B was changed to the ratio shown in Table 2. Table 2 shows physical properties and evaluation results.

[Comparative Example 7]
A biaxially oriented polyester film having a thickness of 12 μm was obtained in the same manner as in Example 1, except that the polyester resin A was replaced with a polyethylene terephthalate resin (polyester resin C) derived from a fossil fuel. Table 2 shows physical properties and evaluation results.

Claims

A biaxially oriented polyester film comprising terephthalic acid and ethylene glycol as main components,
The puncture strength measured according to JIS Z 7102 is 0.45 N/μm or more and 0.80 N/μm or less,
The thermal shrinkage rate at 150 ° C. is 2.5% or less in both the MD direction and the TD direction,
A dynamic friction coefficient μd between at least one surface of the film and the metal plate is 0.10 or more and 0.50 or less,
In a tensile stress relaxation test at 25 ° C., the stress attenuation rate represented by the following formula (1) is 15.0% or more in both the MD direction and the TD direction,
Formula (1) Stress attenuation rate (%) = 100 × (σ0-σ1)/σ0
Here, σ0 represents the value of the tensile stress immediately after applying a tensile force to the film at a tensile speed of 200 mm / min and the 50% tensile strain is applied, and σ1 is the tensile stress from σ0 to 50%. Shows the value of tensile stress when the strain is held for 2 seconds,
A biaxially oriented polyester film in which the content of radioactive carbon C14 is 10% or more and 20% or less with respect to the total carbon in the film.
The stress at 3% elongation in the MD and TD of the film at 25° C. is X(MD) and X(TD), respectively; TD), Y(MD)/X(MD) and Y(MD)/X(MD) are Z(MD) and Z(TD), respectively, any of the following formulas (2) to (5) The biaxially oriented polyester film of claim 1, which also satisfies
Formula (2) 125 MPa ≤ Y(MD) ≤ 155 MPa
Formula (3) 140 MPa ≤ Y(TD) ≤ 190 MPa
Formula (4) 1.3≦Z(MD)≦1.6
Formula (5) 1.7≦Z(TD)≦2.2
The biaxially oriented polyester film according to claim 1 or 2, comprising a biomass polyester resin having a biomass-derived ethylene glycol as a diol unit and a fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit.
The biaxially oriented polyester film according to any one of claims 1 to 3, which is used for cold forming applications.
A laminate comprising the biaxially oriented polyester film according to any one of claims 1 to 4, a gas barrier layer and a sealant layer.
The laminate according to claim 5, wherein the gas barrier layer contains a metal foil.
A battery exterior material comprising the laminate according to claim 5 or 6.