WO2020213471A1 - ポリエステル系シーラントフィルムおよびそれを用いた包装体 - Google Patents

ポリエステル系シーラントフィルムおよびそれを用いた包装体 Download PDF

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Publication number
WO2020213471A1
WO2020213471A1 PCT/JP2020/015644 JP2020015644W WO2020213471A1 WO 2020213471 A1 WO2020213471 A1 WO 2020213471A1 JP 2020015644 W JP2020015644 W JP 2020015644W WO 2020213471 A1 WO2020213471 A1 WO 2020213471A1
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Prior art keywords
heat
film
layer
polyester
gas barrier
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PCT/JP2020/015644
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English (en)
French (fr)
Japanese (ja)
Inventor
慎太郎 石丸
雅幸 春田
尚郎 奥
遼平 山根
明莉 小林
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Toyobo Co Ltd
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Toyobo Co Ltd
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Priority to JP2021514893A priority Critical patent/JP7392715B2/ja
Publication of WO2020213471A1 publication Critical patent/WO2020213471A1/ja
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes

Definitions

  • the present invention relates to a polyester-based sealant film preferably used as a lid material for packaging containers, and is particularly excellent in heat-sealing strength for polyester-based containers. Further, since the lid material using the polyester-based sealant film of the present invention has an appropriate heat shrinkage property, the appearance of the container can be improved by heating after heat-sealing the container. Furthermore, the present invention also relates to a package using the lid material.
  • packaging has been used for many of the distribution articles represented by foods, pharmaceuticals and industrial products.
  • a container formed by molding a plastic film or a sheet.
  • a sealant film made of plastic is often used as a lid material.
  • the lid material is adhered to the flange portion of the container by a heat seal to complete the package, which has functions such as protection of the contents and prevention of leakage.
  • a container made of polyester-based material such as polyethylene terephthalate (PET) is widely used in consideration of not only the beautiful appearance such as transparency and luster but also the recyclable material. ..
  • PET polyethylene terephthalate
  • the lid material is often made of the same polyester-based material. This is due to the technical problem that it is difficult to establish a heat seal between different materials.
  • a sealant made of a polyolefin-based material such as polypropylene or polyethylene has been widely used as a lid material from the viewpoint of sealing performance and cost (for example, Patent Document 1).
  • a sealant made of a polyolefin-based material such as polypropylene or polyethylene
  • Patent Document 1 a sealant made of a polyolefin-based material
  • the use of polyester-based containers has become widespread, and the number of cases where polyester-based sealants are used as lid materials is increasing.
  • the polyolefin-based sealant has a drawback that it easily adsorbs and permeates the components of the contents (organic compounds such as fats and oils and aroma components), and improvement has been desired.
  • Patent Document 2 discloses a aroma-retaining film having a heat-sealing layer and a resin layer composed of a cyclic polyolefin.
  • the heat-sealing layer that comes into direct contact with the contents uses a polyolefin-based resin that is used as a heat-sealing layer for packaging materials such as foods (that is, general), there is a problem of adsorbing the contents. Has not been resolved.
  • the polyester-based sealant is not only easy to adhere to the polyester-based container, but also has a feature that it is difficult to adsorb and permeate the components of the contents.
  • a polyester-based sealant for example, Patent Document 3 discloses a laminated material composed of a PET resin layer extruded and laminated on one side or both sides of a biaxially stretched PET film.
  • Patent Document 4 discloses a transparent release polyester film composed of a base layer made of a biaxially stretched polyester film and at least one releaseable coating layer formed offline on the base layer.
  • Patent Document 5 discloses an unstretched sealant film containing a polyester resin having a solubility parameter of 9 or more.
  • the sealant of Patent Document 5 is unstretched and has a problem due to the fact that the molecules are not substantially oriented.
  • unstretched film since unstretched film has low mechanical strength, there is a problem that it is inferior in workability because it is easily stretched and broken by the tension received from the pass line when unwinding on the production line during secondary processing such as printing, vapor deposition, and laminating. there were.
  • Patent Document 6 discloses a uniaxially or biaxially stretched sealant film using an amorphous polyester raw material.
  • the sealant film of Patent Document 6 has excellent mechanical strength, it has a large heat shrinkage rate, so that not only the sealant is thermally deformed when heat-sealed, but also it cannot be used for a package that requires high temperature treatment such as boiling treatment. was there. Since the stretched film has a molecular orientation, it has been one of the technically important issues to suppress the heat shrinkage caused by the stretched film.
  • Patent Document 7 a polyester-based lid material having at least one heat-sealing layer and one base material layer and suppressing heat shrinkage stress.
  • the lid material of Patent Document 7 can be heat-sealed with an unstretched polyethylene terephthalate sheet, but in the examples, it is necessary to laminate the heat-sealing layer and the base material layer, and as in Patent Documents 3 and 4, the productivity is improved. There was room for improvement.
  • each layer of the heat seal layer and the base material layer has at least one layer, and these layers are laminated and film-formed in the same manufacturing process.
  • the system sealant film is disclosed.
  • the film of Patent Document 8 has a high heat seal strength and a low heat shrinkage rate, and solves the problems conventionally seen.
  • the 140 ° C. heat seal strength in the examples of Patent Document 8 is 16 N / 15 mm at the maximum (Example 6), and further improvement is desired.
  • the film of Example 6 of Patent Document 8 has extremely poor slipperiness of the heat seal layer, problems such as winding misalignment, unevenness, and blocking occur when the film is wound as a roll.
  • Japanese Patent No. 60033080 Japanese Unexamined Patent Publication No. 2016-117227 Japanese Patent No. 6009500 JP-A-2018-75835 Japanese Unexamined Patent Publication No. 2017-165871 Japanese Patent No. 6384324 JP-A-2018-114992 International Publication No. 2018/150997
  • An object of the present invention is to solve the above-mentioned problems of the prior art. That is, an object of the present invention is to provide a sealant film which has less adsorption of components of the contents, is excellent in mechanical strength and heat seal strength in a low temperature range, and is less likely to cause winding failure when wound as a roll. It is a thing. At the same time, an object of the present invention is to give an appropriate tension to the sealant film by appropriately heat-shrinking the sealant film by heating after heat-sealing the container and the lid material when used as the lid material of the container. Is trying to provide a beautiful sealant film.
  • the present invention has the following configuration.
  • 1. A polyester system having at least one heat-sealing layer, the heat-sealing layer being formed of polyester containing ethylene terephthalate as a main component, and satisfying the following requirements (1) to (4). Sealant film.
  • the sealing strength when the heat-sealing layers are sealed at 140 ° C., 0.2 MPa, and 2 seconds is 5 N / 15 mm or more and 10 N / 15 mm or less per 10 ⁇ m film thickness.
  • the maximum heat shrinkage stress in at least one direction in the longitudinal direction or the width direction is 0.2 MPa or more and 3 MPa or less.
  • the dynamic friction coefficient between the heat seal layers is 0.1 or more and 0.9 or less.
  • the peak intensity ratio of 1340 cm -1 and 1410 cm -1 in the infrared in the spectrum measured in the polarizing ATR method is 0.05 to 0.6 It is characterized by 1.
  • the heat-sealed layer was measured by 1 H-NMR, and the transesterification degree of ethylene glycol and butanediol was 8% or more and 25% or less. Or 2.
  • a print layer is provided.
  • ⁇ 6. The polyester sealant film according to any one.
  • ⁇ 7. A gas-barrier laminate characterized in that a gas-barrier layer is provided on the polyester-based sealant film according to any one of them.
  • the above 1. ⁇ 7. The polyester sealant film according to any one of the above or 8. ⁇ 12.
  • the above 1. ⁇ 7. 8. The polyester sealant film according to any one of. ⁇ 12.
  • the gas barrier laminate according to 1. A packaging body characterized in that any one of the laminates described in the above is used for at least a part thereof. 15.
  • the polyester sealant film according to any one of. ⁇ 12. The gas barrier laminate according to 1.
  • a packaging body characterized in that any one of the laminates described in the above is used as at least a part of a lid material. 16.
  • the gas barrier laminate according to 1. A method for producing a package in which any of the laminates described in the above is used as at least a part of a lid material, and the lid material is heat-shrinked by heat treatment after heat-sealing the container
  • the polyester-based sealant film of the present invention has little adsorption of components of the contents and is excellent in mechanical strength and heat-sealing strength in a low temperature range, it has excellent suitability when used as a packaging material such as a lid material. Have. In addition, it has an appropriate heat shrinkage property so that it can have a feeling of tension when used as a lid material for a container.
  • the polyester-based sealant film of the present invention has at least one heat-sealing layer, and has the following preferable properties and a preferable composition.
  • sealant film 1.
  • Heat-seal strength per 10 ⁇ m film thickness The polyester-based sealant film of the present invention (hereinafter, may be simply referred to as “film”) has a heat-seal layer at a temperature of 140 ° C., a seal bar pressure of 0.2 MPa, and a seal time of 2 seconds.
  • the heat seal strength when heat-sealing each other needs to be 5.0 N / 15 mm or more and 10.0 N / 15 mm or less per 10 ⁇ m film thickness.
  • the heat-sealing strength is the tensile strength of the film.
  • the heat seal strength also increases as the thickness of the film increases. If the heat seal strength per film thickness of 10 ⁇ m is less than 5 N / 15 mm, the seal portion is easily broken and cannot be used as a package.
  • the heat seal strength per film thickness of 10 ⁇ m is more preferably 5.2 N / 15 mm or more, further preferably 5.4 N / 15 mm or more.
  • the polyester-based sealant film of the present invention has a film thickness of 10 ⁇ m when a heat-sealing layer and an unstretched polyethylene terephthalate (APET) sheet are heat-sealed at a temperature of 140 ° C., a seal bar pressure of 0.2 MPa, and a sealing time of 2 seconds.
  • the heat seal strength of the above is preferably 3.0 N / 15 mm or more and 10.0 N / 15 mm or less. If the heat seal strength is less than 3.0 N / 15 mm, the seal portion is easily broken and cannot be used as a package.
  • the heat seal strength per film thickness of 10 ⁇ m is more preferably 3.5 N / 15 mm or more, further preferably 4.0 N / 15 mm or more.
  • the heat-sealing layers of the film itself are sealed unless otherwise specified.
  • the film of the present invention has a maximum heat shrinkage rate of 1 when the temperature is raised from 30 ° C. to 220 ° C. at 10 ° C./min using thermomechanical analysis (TMA) in either the longitudinal direction or the width direction. It needs to be% or more and 12% or less.
  • TMA thermomechanical analysis
  • the maximum heat shrinkage rate in the present invention mainly affects the appearance when used as a lid material. That is, after heat-sealing the container with the film of the present invention as a lid material, the heat shrinkage generated by heating eliminates the slack of the lid material to give a feeling of tension, and the appearance becomes beautiful.
  • the maximum heat shrinkage rate is less than 1%, heat shrinkage due to heating hardly occurs, so that the slack of the lid material cannot be eliminated.
  • the maximum heat shrinkage rate exceeds 12%, not only is it easy to be thermally deformed during high temperature treatment such as heat sealing and boiling treatment, but also the lid material is excessively used in the heat treatment after heat sealing the container. It is not preferable because it shrinks and easily deforms the container.
  • the maximum heat shrinkage rate is more preferably 2% or more and 11% or less, and further preferably 3% or more and 10% or less.
  • the film of the present invention preferably has a maximum heat shrinkage rate within the above range in both the longitudinal direction and the width direction.
  • the film of the present invention has a maximum heat shrinkage stress of 0.2 MPa or more and 3 MPa or less when the temperature is raised from 30 ° C. to 220 ° C. at 10 ° C./min using TMA in either the longitudinal direction or the width direction. Must be.
  • the maximum heat shrinkage stress of the present invention like the maximum heat shrinkage rate described above, affects the appearance when heated by using it as a lid material. The smaller the maximum heat shrinkage stress is, the more the deformation of the container due to the excessive heat shrinkage of the lid material can be suppressed, which is preferable. However, if it is less than 0.2 MPa, the maximum heat shrinkage rate tends to be less than 1%, which is not preferable.
  • the maximum heat shrinkage stress exceeds 3 MPa, the heat deformation of the lid material caused by heating after heat-sealing the container becomes excessive, and the container is easily deformed, which is not preferable.
  • the maximum heat shrinkage stress is more preferably 0.3 MPa or more and 2.9 MPa or less, and further preferably 0.4 MPa or more and 2.8 MPa or less.
  • the film of the present invention preferably has a maximum heat shrinkage stress within the above range in both the longitudinal direction and the width direction.
  • the dynamic friction coefficient of the heat seal layer of the present invention needs to be 0.1 or more and 0.9 or less. If the coefficient of kinetic friction is less than 0.1, the film slips too much, so that the position may easily shift when, for example, the heat-sealing layers are overlapped and heat-sealed, or when the films are laminated on a single sheet. On the other hand, if the coefficient of kinetic friction exceeds 0.9, the film becomes less slippery, and problems such as winding misalignment, unevenness, and blocking are likely to occur when the film is wound as a roll.
  • the coefficient of kinetic friction is more preferably 0.2 or more and 0.8 or less, and further preferably 0.3 or more and 0.7 or less.
  • Heat seal layer of the infrared peak intensity ratio invention the heat sealing layer, the peak intensity ratio peak of 1340 cm -1 and 1410 cm -1 in the infrared in the spectrum measured in the polarizing ATR method (hereinafter, an infrared peak intensity ratio Although it may be described), it is preferably 0.05 or more and 0.6 or less in the longer of the longitudinal direction and the width direction.
  • the infrared peak of 1340 cm -1 indicates the trans conformation of ethylene glycol.
  • the infrared peak of 1410 cm -1 is a peak used for normalization, which is not affected by the thickness of the film and the like.
  • the peak intensity ratio of 1340 cm -1 and 1410 cm -1 indicates the relative amount of the trans conformation, and it can be said that the higher the peak intensity ratio, the more the molecular main chain is oriented.
  • the reason why the heat seal strength is developed will be described while considering the change in the molecular structure that occurs when the film is heat-sealed and during the film forming process.
  • the polymers that make up the film undergo glass transition or melting. It is considered that these phenomena cause the molecular chains to move and bite or entangle with each other to complete the heat seal. That is, it can be said that it is necessary to move the molecular chain of the heat seal layer by heat energy in order to develop the heat seal strength.
  • the degree of orientation of the molecular chains that make up the heat seal layer the higher the degree of orientation (the molecular chains are regularly aligned), the higher the intermolecular force, which is necessary to develop the heat seal strength. It is considered that the amount of heat is relatively high (the molecular chain is difficult to move).
  • the degree of orientation of the molecular chain indicated by this infrared peak intensity ratio is determined by the degree of transesterification described later, stretching during film formation, and process conditions of intermediate and final heat treatment.
  • the molecular chains of the heat seal layer are oriented in the stretching step prior to the final heat treatment, but the molecular orientation generated by partially melting the heat seal layer in the final heat treatment step is disrupted. Can be done. The detailed conditions of the final heat treatment step will be described later.
  • the infrared peak intensity ratio of the heat seal layer exceeds 0.6, the degree of orientation of the molecules constituting this layer is high, so that the mechanical strength of the film is improved, but the heat seal strength of 140 ° C. per 10 ⁇ m of film thickness is increased. It becomes difficult to make it 5.0 N / 15 mm or more.
  • the infrared peak intensity ratio is less than 0.05, the 140 ° C. heat seal strength per 10 ⁇ m film thickness is likely to be 5.0 N / 15 mm or more, but the dynamic friction coefficient of the heat seal layer should be suppressed to 0.9 or less. Becomes difficult.
  • the infrared peak intensity ratio is more preferably 0.1 or more and 0.55 or less, and further preferably 0.15 or more and 0.5 or less.
  • the heat-sealed layer of the film of the present invention has a transesterification degree of 5% or more calculated from the peak area obtained from the proton nuclear magnetic resonance ( 1 H-NMR, hereinafter simply referred to as NMR) spectrum. It is preferably 25% or less. It is generally known that when two or more different polyesters are mixed and melted by heating, a transesterification reaction occurs to form a block copolymer.
  • the transesterification degree in the present invention means how much of the sequence of three consecutive diol monomers (sandwiching two carboxylic acids) in the ester unit, the three chains of butanediol (BB) are replaced with ethylene glycol.
  • the peak on the highest magnetic field side of orthochlorophenol is 6.6 ppm
  • the peak group of 4.54 to 4.62 ppm is BBB, BBE in order from the low magnetic field side. It is attributed to the chain-derived peaks of (BD side) and BBE (EG side).
  • the transesterification degree can be obtained by obtaining (taking a ratio) the ratio of the integrated value of the BBE peak to the total integrated value of the peak group of 4.54 to 4.62 ppm.
  • the melting point of the heat seal layer decreases. It is considered that this is because the ratio of different diol monomers present in one polymer chain increases due to transesterification, which makes it difficult for the molecular chains to be uniformly aligned, and as a result, the melting point is lowered. This is the above 1.4. It is considered to be related to the trans conformation of ethylene glycol indicated by the "infrared peak intensity ratio". When the transesterification between ethylene glycol and butanediol is promoted, the number of molecular chains in which EE is arranged is relatively small, so that the infrared peak intensity ratio tends to decrease to 0.6 or less.
  • the infrared peak intensity ratio exceeds 0.6, and the heat seal strength at 140 ° C. per 10 ⁇ m film thickness is less than 5.0 N / 15 mm, which is not preferable.
  • the infrared peak intensity ratio tends to be 0.6 or less, and the heat seal strength at 140 ° C. per 10 ⁇ m film thickness tends to be 5.0 N / 15 mm or more, but the heat is as described above.
  • the average length of the surface (RSm: described later) may exceed 29 ⁇ m, and the dynamic friction coefficient may exceed 0.9.
  • the final heat treatment temperature is lowered below the melting point -10 ° C to avoid melting of the heat seal layer (the preferable range of the final heat treatment temperature will be described later)
  • the maximum heat shrinkage rate and the maximum heat shrink stress exceed the predetermined ranges. There is a risk.
  • the transesterification degree is more preferably 6% or more and 24% or less, and further preferably 7% or more and 23% or less.
  • the film of the present invention preferably has a tensile breaking strength of 80 MPa or more and 200 MPa in either the longitudinal direction or the width direction. If the tensile breaking strength is less than 80 MPa, it is not preferable because it is easily broken by the tension received from the pass line when unwinding on the production line during secondary processing such as printing, vapor deposition, and laminating. On the other hand, the higher the tensile breaking strength, the higher the mechanical strength of the film, which is preferable. However, at the technical level of the present invention, 200 MPa is the upper limit. For practical purposes, an upper limit of 190 MPa is sufficient.
  • the film of the present invention preferably has a melting point of 195 ° C. or higher and 230 ° C. or lower obtained from a non-reverse heat flow when the heat sealed layer is measured by a temperature-modulated differential scanning calorimeter (temperature-modulated DSC). ..
  • the melting point is affected not only by the transesterification degree described above, but also by the raw material composition.
  • the preferred raw material composition will be described later.
  • the detailed measurement method of the melting point will be described in Examples described later, but when two or more melting peaks are observed, the peak appearing on the lowest temperature side is defined as the melting point.
  • the melting point of the heat-sealing layer is less than 195 ° C.
  • the heat-sealing layer is easily melted in the final heat treatment step, so that the heat shrinkage characteristics of the film and the slipperiness cannot be compatible.
  • the coefficient of dynamic friction of the heat-sealing layer exceeds 0.9 by the mechanism described in "1.2. Transesterification degree of the heat-sealing layer" above. There is a risk.
  • the melting point of the heat seal layer exceeds 235 ° C, melting of the heat seal layer is less likely to occur in the final heat treatment step. Therefore, the infrared peak intensity ratio is 0.6 or less and the heat seal strength is 140 ° C. per 10 ⁇ m film thickness. It becomes difficult to set the value to 5 N / 15 mm or more.
  • the melting point of the heat seal layer is more preferably 193 ° C. or higher and 228 ° C. or lower, and further preferably 191 ° C. or higher and 226 ° C. or lower.
  • Average length (RSm) of the surface roughness element of the heat seal layer In the heat seal layer of the present invention, the average length (RSm) of the surface roughness elements of the heat seal layer measured at a cutoff of 0.25 mm and a measurement speed of 0.2 mm / sec is preferably 18 ⁇ m or more and 35 ⁇ m or less.
  • the larger the RSm of the heat seal layer the smaller the unevenness (smoothing), so that when the heat seal layers are brought into contact with each other, the contact area with each other tends to increase. Therefore, if the RSm of the heat seal layer exceeds 35 ⁇ m, the coefficient of kinetic friction tends to exceed 0.9, which is not preferable.
  • the RSm of the heat seal layer is more preferably 19 ⁇ m or more and 34 ⁇ m or less, and further preferably 20 ⁇ m or more and 33 ⁇ m or less.
  • Intrinsic viscosity of heat seal layer (IV)
  • the heat-sealed layer of the present invention preferably has an intrinsic viscosity (IV) of 0.55 dL / g or more and 0.9 dL / g. If the IV of the heat seal layer is less than 0.55 dL / g, not only is it difficult to set the tensile fracture strength of the film to 80 MPa or more, but also the possibility of breakage during the stretching step during film formation increases. Therefore, it is not preferable.
  • the IV of the heat seal layer is more preferably 0.57 dL / g or more and 0.88 dL / g or less, and further preferably 0.59 dL / g or more and 0.86 dL / g or less.
  • the film of the present invention preferably has a haze of 1% or more and 15% or less. If the haze exceeds 15%, the transparency of the film deteriorates, so that the visibility of the contents becomes poor when it is used as a package.
  • the upper limit of haze is more preferably 13% or less, and further preferably 11% or less. The lower the haze, the higher the transparency, which is preferable. However, at the current state of the art, 1% is the lower limit, and even 2% or more is sufficient for practical use.
  • the thickness of the film of the present invention is not particularly limited, but is preferably 3 ⁇ m or more and 200 ⁇ m or less. If the thickness of the film is thinner than 3 ⁇ m, the heat seal strength may be insufficient and processing such as printing may become difficult, which is not preferable. Further, the film thickness may be thicker than 200 ⁇ m, but this is not preferable because the weight of the film used increases and the chemical cost increases.
  • the thickness of the film is more preferably 5 ⁇ m or more and 160 ⁇ m or less, and further preferably 7 ⁇ m or more and 120 ⁇ m or less.
  • the film of the present invention is characterized in that it does not easily adsorb organic compounds contained in chemical products, pharmaceuticals, foods, and the like.
  • the organic compound include d-limonene, citral, citronellal, p-menthane, pinen, terpinen, myrcene, carotene, geraniol, nerol, citronellal, terpineol, l-menthol, nerolidol, borneol, dl-campar and lycopene.
  • the amount adsorbed on the sealant varies depending on the adsorption conditions (concentration of adsorbed substance, storage period, temperature, etc.), but the amount adsorbed when stored for 1 week by the method shown in Examples described later is 0 ⁇ g / cm 2 or more and 2 ⁇ g / cm. It is preferably 2 .
  • the adsorption amount of 0 ⁇ g / cm 2 indicates that the contents are not adsorbed on the sealant at all.
  • Adsorption amount is more preferable to be 1.8 ⁇ g / cm 2 or less and further preferably 1.6 [mu] g / cm 2 or less. Since the film of the present invention has a heat-sealing layer made of a polyester-based component, the adsorption amount may be high for an organic compound having a similar chemical structure.
  • the polyester-based component constituting the heat-seal layer has four oxygen atoms, as the chemical structure of the organic compound, the larger the number of oxygen atoms (closer to four), the more the organic compound with respect to the heat-seal layer Solubility tends to increase and the amount of adsorption tends to increase.
  • packaging a content containing eugenol having two oxygen atoms or methyl salicylate having three oxygen atoms is not preferable because the adsorption amount tends to exceed 2 ⁇ g / cm 2 .
  • the film of the present invention needs to have at least one heat-sealing layer made of polyester containing ethylene terephthalate as a main component. It is preferable to provide a base material layer separately from the heat seal layer because the heat resistance and mechanical strength of the film are improved. In this case, the layer having the highest ethylene terephthalate component content is the base material layer.
  • a three-layer structure in which a gas barrier layer is provided in addition to the above two layers is more preferable because the gas barrier property as a film is improved and the shelf life of the contents is improved when used as a package.
  • the gas barrier layer is preferably composed of an inorganic thin film containing a metal or a metal oxide as a main component, and may be located on either the outermost layer or the intermediate layer. Further, the gas barrier layer is preferably transparent. Further, the present invention may have an anchor coat layer provided below the inorganic thin film layer and an overcoat layer provided above the inorganic thin film layer, in addition to the above three layers. By providing these layers, it is expected that the adhesion between the gas barrier layer and the film layer is improved, the gas barrier property is improved, and the like, which is more preferable. The configuration requirements for each layer will be described later.
  • the film of the present invention may be provided with a printing layer on which characters and patterns are described in order to improve the design as a package.
  • a printing layer on which characters and patterns are described in order to improve the design as a package.
  • known materials such as ink for gravure printing and ink for flexographic printing can be used.
  • the number of printing layers may be one layer or a plurality of layers.
  • the print layer may be located on either the outermost layer or the intermediate layer. However, if the print layer is provided on the heat seal layer, the print layer may hinder the heat seal and it may be difficult to increase the heat seal strength at 140 ° C. to 15 N / 15 mm or more, which is not preferable.
  • the ratio of the heat seal layer to the total thickness of the film is preferably 20% or more and 80% or less. If the layer ratio of the heat seal layer is less than 20%, the heat seal strength is lowered, which is not preferable. If the layer ratio of the heat seal layer exceeds 80%, the heat seal strength is improved, but the heat resistance and the mechanical strength are lowered, which is not preferable.
  • the layer ratio of the heat seal layer is more preferably 30% or more and 70% or less.
  • the outermost layer (including the heat seal layer) of the film of the present invention may be provided with a layer subjected to corona treatment, coating treatment, flame treatment, etc. in order to improve the printability and slipperiness of the film surface. It is possible and can be arbitrarily provided as long as the requirements of the present invention are not deviated.
  • polyester raw materials that make up the film of the present invention are mainly composed of ethylene terephthalate units.
  • "to be the main constituent component” means that the content is 50 mol% or more when the total amount of the constituent component is 100 mol%. Since the ethylene terephthalate unit contains a benzene ring derived from a carboxylic acid, the rigidity of the molecule is improved, and as a result, the tensile strength at break is 80 MPa or more and the maximum heat shrinkage is 12% or less.
  • the polyester used in the polyester-based resin layer of the present invention preferably contains at least one component other than ethylene terephthalate.
  • the presence of a component other than ethylene terephthalate improves the heat seal strength (the heat seal fracture mode is likely to be cut off).
  • the amount of components other than ethylene terephthalate is small, but by containing components other than ethylene terephthalate, the difference in shrinkage rate from the heat seal layer can be reduced, and the curl of the laminate can be reduced. effective. Since the content of each component differs between the heat seal layer and the base material layer, it will be described later.
  • dicarboxylic acid monomer that can be a component other than terephthalic acid constituting ethylene terephthalate
  • dicarboxylic acid monomer that can be a component other than terephthalic acid constituting ethylene terephthalate
  • isophthalic acid 1,4-cyclohexanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, aromatic dicarboxylic acid such as orthophthalic acid, adipic acid, and the like.
  • aromatic dicarboxylic acid such as orthophthalic acid, adipic acid, and the like.
  • examples thereof include aliphatic dicarboxylic acids such as adipic acid, sebacic acid and decandicarboxylic acid, and alicyclic dicarboxylic acids.
  • the polyvalent carboxylic acid having a valence of 3 or more (for example, trimellitic acid, pyromellitic acid and anhydrides thereof) is not contained in the polyester.
  • the polyvalent carboxylic acid having a valence of 3 or more for example, trimellitic acid, pyromellitic acid and anhydrides thereof.
  • isophthalic acid because the heat seal strength at 140 ° C. per 10 ⁇ m film thickness can be easily set to 5.0 N / 15 mm or more.
  • the polyester may not contain a diol having 8 or more carbon atoms (for example, octane diol) or a polyhydric alcohol having 3 or more valences (for example, trimethylolpropane, trimethylolethane, glycerin, diglycerin, etc.). preferable.
  • a polyester elastomer containing ⁇ -caprolactone, tetramethylene glycol or the like may be contained. Since the polyester elastomer has the effect of lowering the melting point of the polyester resin layer, it can be particularly preferably used for the heat seal layer.
  • polyester raw material listed above a plurality of types of homopolyester in which a carboxylic acid monomer and a diol monomer are polymerized in a one-to-one ratio may be mixed (dry blended), or two or more types of carboxylics may be used.
  • An acid monomer or two or more kinds of diol monomers may be copolymerized and used.
  • the homopolyester and the copolymerized polyester may be mixed and used.
  • the homopolyester and / and the copolymerized polyester may be dry-blended, heated and melted to cool and solidify the mixed (melt-blended) polyester, which may be used as a raw material.
  • a raw material in which two or more different polyesters are melt-blended is one of the preferred embodiments because the transesterification of each monomer is promoted and the transesterification degree is easily increased to 5% or more.
  • the method of melt blending two or more different polyesters is not particularly limited, and a known method such as an extruder or a heating type stirrer can be used. Among these, a method using an extruder equipped with a barrel and a screw is preferable.
  • a method using an extruder equipped with a barrel and a screw is preferable.
  • two or more types of polyester are charged, melt-blended by heating from the inside of the barrel and heating by friction between the barrel wall and the screw wall, and then through a discharge device such as a melt line and a strand die. It is possible to obtain a single polyester raw material. Before heating and melting the polyester, it is preferable to dry the polyester to a moisture content of 100 ppm or less using a dryer such as a hopper dryer or a paddle dryer, or a vacuum dryer.
  • the water content of the polyester exceeds 100 ppm, hydrolysis proceeds during the melting of the polyester, making it difficult to maintain IV at 0.55 dL / g or more, which is not preferable.
  • the water content is more preferably 90 ppm or less, and even more preferably 80 ppm or less.
  • the lower limit of the water content is 0 ppm, and the lower the water content, the more preferable, but the practical lower limit of about 30 ppm is sufficient.
  • the heating temperature at the time of melt blending is preferably 200 ° C. or higher and 300 ° C. or lower.
  • the heating temperature is less than 200 ° C., not only the transesterification does not proceed sufficiently, but also the melt viscosity of the polyester becomes too high, the resin pressure increases, and the filter in the melt line is deformed, which is not preferable.
  • the heating temperature exceeds 300 ° C., transesterification is promoted, which is preferable, but the thermal decomposition of the polyester proceeds and it becomes difficult to set IV to 0.55 dL / g or more.
  • the heating temperature is more preferably 210 ° C. or higher and 290 ° C. or lower, and further preferably 220 ° C. or higher and 280 ° C. or lower.
  • the residence time in the melt line is preferably 1 minute or more and 15 minutes or less.
  • the residence time is less than 1 minute, the transesterification will not proceed sufficiently, which is not preferable. If the residence time exceeds 15 minutes, the thermal decomposition of the polyester proceeds and the IV tends to be less than 0.55 dL / g, which is not preferable.
  • the operation of melting two or more kinds of polyesters to proceed with transesterification as described above may be carried out not only once but also twice or more, with a transesterification degree of 25% or less and an IV of 0.55 dL / g or more. It can be freely provided using the range as a guide.
  • the polyester resin constituting the film of the present invention contains various additives such as waxes, antioxidants, antistatic agents, crystal nucleating agents, thickeners, heat stabilizers, and coloring agents, if necessary. Pigments, color inhibitors, UV absorbers and the like can be added. Further, it is preferable to add fine particles as a lubricant for improving the slipperiness of the film to at least the outermost layer of the film. Any fine particles can be selected.
  • examples of the inorganic fine particles include silica, alumina, titanium dioxide, calcium carbonate, kaolin, barium sulfate, and the like
  • examples of the organic fine particles include acrylic resin particles, melamine resin particles, silicone resin particles, and crosslinked polystyrene.
  • the average particle size of the fine particles can be appropriately selected within the range of 0.05 to 3.0 ⁇ m when measured with a Coulter counter, if necessary.
  • the lower limit of the fine particle content in the film is preferably 0.01% by weight, more preferably 0.015% by weight, and even more preferably 0.02% by weight. If it is less than 0.01% by weight, the slipperiness may decrease.
  • the upper limit is preferably 1% by weight, more preferably 0.2% by weight, and even more preferably 0.1% by weight. If it exceeds 1% by weight, the transparency may decrease, which is not very preferable.
  • a method of blending particles into the polyester resin constituting the film of the present invention for example, it can be added at any stage of producing a polyester resin, but it is heavy at the stage of esterification or after the completion of the transesterification reaction. It is preferable to add it as a slurry dispersed in ethylene glycol or the like at a stage before the start of the condensation reaction to proceed with the polycondensation reaction.
  • a method of blending a slurry of particles dispersed in ethylene glycol, water, or other solvent with a polyester resin raw material using a kneading extruder with a vent, or using a kneading extruder of dried particles and polyester There is also a method of blending.
  • Polyester used in heat seal layer contains 30 mol% or more of dicarboxylic acid monomer and / or diol monomer which are components other than terephthalic acid and ethylene glycol constituting ethylene terephthalate. Is more preferable, 32 mol% or more is more preferable, and 34 mol% or more is particularly preferable. Further, the upper limit of the monomer content as a component other than the ethylene terephthalate is 50 mol%.
  • the amount of the monomer other than the ethylene terephthalate contained in the heat seal layer is less than 30 mol%, even if the molten resin is extruded from the die and then rapidly cooled and solidified, it will crystallize in the subsequent stretching and heat fixing steps. Therefore, it is difficult to set the 140 ° C. heat seal strength per 10 ⁇ m film thickness to 5.0 N / 15 mm or more, which is not preferable.
  • the amount of the monomer other than the ethylene terephthalate contained in the heat seal layer is 50 mol% or more, the heat seal strength of the film can be increased, but the heat resistance of the heat seal layer becomes extremely low.
  • the content of the monomer as a component other than ethylene terephthalate is more preferably 48 mol% or less, and particularly preferably 46 mol% or less.
  • polyester used in the base layer contains 9 mol% or more of dicarboxylic acid monomer and / or diol monomer which are components other than terephthalic acid and ethylene glycol constituting ethylene terephthalate. Is more preferable, and 10 mol% or more is more preferable, and 11 mol% or more is particularly preferable. Further, the upper limit of the monomer content as a component other than the ethylene terephthalate is 20 mol%.
  • the difference in heat shrinkage with the heat seal layer becomes large, and the curl of the film becomes large, which is not preferable. If the difference in the monomer content of the base material layer and the heat seal layer, which is a component other than the ethylene terephthalate, becomes large, the difference in the heat shrinkage rate between the layers during the heat treatment becomes large, and even if the cooling after the heat treatment is strengthened. However, the shrinkage to the heat seal layer side becomes large, and the curl becomes large.
  • the amount of the monomer which is a component other than the ethylene terephthalate contained in the base material layer is 20 mol% or more, it becomes difficult to set the maximum heat shrinkage rate to 12% or less, which is not preferable.
  • the content of the monomer as a component other than the ethylene terephthalate is more preferably 19 mol% or less, and particularly preferably 18% or less.
  • the monomer content as a component other than the ethylene terephthalate for controlling curl is 10 mol% or more and 45 mol% in the difference between the heat seal layer and the base material layer in addition to the amount of each layer alone. It is more preferably 11 mol% or more and 44 mol% or less.
  • the film of the present invention has the above 3.1. It can be obtained by melt-extruding the polyester raw material described in "Types of polyester raw material” with an extruder to form an unstretched film, and stretching the unstretched film by a predetermined method shown below.
  • the timing of laminating each layer may be before or after stretching.
  • laminating before stretching it is preferable to adopt a method in which the resins used as raw materials for each layer are melt-extruded by separate extruders and joined using a feed block or the like in the middle of the resin flow path.
  • laminating after stretching it is preferable to employ laminating in which films formed separately are bonded together with an adhesive, or extrusion laminating in which a molten polyester resin is poured and laminated on the surface layer of a single or laminated film. From the viewpoint of productivity, a method of laminating each layer before stretching is preferable.
  • the polyester resin can be obtained by polycondensing by selecting the type and amount of the dicarboxylic acid component and the diol component so as to contain an appropriate amount of a monomer that can be a component other than ethylene terephthalate.
  • two or more types of chip-shaped polyester can be mixed and used as a raw material for the polyester-based resin layer.
  • the above 3.1 As a method of melt extrusion of the raw material resin, the above 3.1. A known method can be used in the same manner as described in "Types of polyester raw material", and a method using an extruder equipped with a barrel and a screw is preferable.
  • the polyester raw material of each layer is preferably dried in advance using a dryer such as a hopper dryer or a paddle dryer, or a vacuum dryer until the moisture content is 100 ppm or less, more preferably 90 ppm or less, and further preferably 80 ppm or less. After the polyester raw material of each layer is dried in this way, it is melted at a temperature of 200 to 300 ° C. by an extruder and extruded as a laminated film.
  • the extrusion temperature is preferably 200 ° C. or higher and 300 ° C. or lower. If the extrusion temperature is less than 200 ° C., not only the transesterification does not proceed sufficiently, but also the melt viscosity of the polyester resin becomes too high, the extrusion pressure increases, and the filter in the melt line is deformed, which is not preferable. When the heating temperature exceeds 300 ° C., transesterification is promoted, which is preferable, but thermal decomposition of the resin proceeds, and it becomes difficult to set IV to 0.55 dL / g or more.
  • the extrusion temperature is more preferably 210 ° C.
  • the residence time in the melt line is preferably 1 minute or more and 15 minutes or less. If the residence time is less than 1 minute, the transesterification will not proceed sufficiently, which is not preferable. If the residence time exceeds 15 minutes, the thermal decomposition of the polyester resin proceeds and the IV tends to be less than 0.55 dL / g, which is not preferable.
  • the unstretched film can be obtained by quenching the film melted by extrusion.
  • a method for rapidly cooling the molten resin a method of casting the molten resin from a base onto a rotary drum and quenching and solidifying the molten resin to obtain a substantially unoriented resin sheet can be preferably adopted.
  • the film may be formed by any method of non-stretching, uniaxial stretching (stretching in at least one of the longitudinal (longitudinal) direction and the lateral (width) direction), and biaxial stretching. From the viewpoint of mechanical strength and productivity, uniaxial stretching is preferable, and biaxial stretching is more preferable.
  • First (longitudinal) stretching For stretching in the first direction (longitudinal or longitudinal direction), it is preferable to introduce the unstretched film into a longitudinal stretching machine in which a plurality of roll groups are continuously arranged. In the longitudinal stretching, it is preferable to preheat the film with a preheating roll until the film temperature reaches 65 ° C. to 90 ° C. If the film temperature is lower than 65 ° C., it becomes difficult to stretch the film when it is stretched in the vertical direction, and breakage is likely to occur, which is not preferable. Further, if the temperature is higher than 90 ° C., the film tends to adhere to the roll, and the film is easily wrapped around the roll or the roll is easily soiled due to continuous production, which is not preferable.
  • the longitudinal stretching ratio is preferably 1 to 5 times or less. Since 1x is not longitudinally stretched, the longitudinal stretching ratio is 1x to obtain a horizontally uniaxially stretched film, and 1.1 times or more is required to obtain a biaxially stretched film. By setting the longitudinal stretching ratio to 1.1 times or more, molecular orientation can be given in the longitudinal direction of the film to increase the mechanical strength, so that the tensile breaking strength can be easily set to 80 MPa or more. Further, the upper limit of the longitudinal stretching ratio may be any number, but if the longitudinal stretching ratio is too high, it becomes difficult to laterally stretch and fracture is likely to occur, so it is preferably 5 times or less.
  • Intermediate heat treatment After the first (longitudinal) stretching, it is preferable that there is a step of heating the film (intermediate heat treatment) in order to reduce the shrinkage rate of the film caused by the stretching.
  • intermediate heat treatment constant length heating in which the length of the film is kept constant, or relaxation treatment in which the film is heated while relaxing in the longitudinal direction can be adopted.
  • relaxation treatment in order to reduce the shrinkage rate in the longitudinal direction of the film caused by longitudinal stretching, it is a preferable embodiment to adopt a relaxing treatment.
  • the relaxation rate in the longitudinal direction is preferably 0% or more and 70% or less (a relaxation rate of 0% means that relaxation is not performed). Since the upper limit of the relaxation rate in the longitudinal direction is determined by the raw materials used and the longitudinal stretching conditions, relaxation cannot be performed beyond this. In the present invention, the relaxation rate in the longitudinal direction is limited to 70%.
  • the film after longitudinal stretching is heated at a temperature of 65 ° C to 100 ° C or less to adjust the roll speed difference (decrease the roll speed on the downstream side) or reduce the distance between clips (to reduce the distance between clips). It can be carried out by slowing down the moving speed on the downstream side).
  • the heating means any of roll, near infrared ray, far infrared ray, hot air heater and the like can be used.
  • relaxation in the longitudinal direction can be performed not immediately after longitudinal stretching, but also in lateral stretching (including preheating zone) and final heat treatment by narrowing the clip interval in the longitudinal direction (in this case, both ends in the film width direction). (Because it is relaxed in the longitudinal direction, Boeing distortion is reduced), it can be performed at any time. After relaxing in the longitudinal direction (longitudinal stretching if not relaxing), it is preferable to cool the film once, and it is preferable to cool it with a cooling roll having a surface temperature of 20 to 40 ° C.
  • Second (horizontal) stretching After the first (longitudinal) stretching, the film is gripped by clips at both ends in the width direction (direction orthogonal to the longitudinal direction) in the tenter, and 3 to 5 at 65 ° C to 110 ° C. It is preferable to perform transverse stretching at a stretching ratio of about twice. Preheating is preferably performed before stretching in the lateral direction, and the preheating is preferably performed until the film surface temperature reaches 75 ° C. to 120 ° C.
  • the film after the transverse stretching is passed through an intermediate zone where no active heating operation is performed. Since the temperature is higher in the next final heat treatment zone than in the transverse stretching zone of the tenter, the heat of the final heat treatment zone (hot air itself or radiant heat) will flow into the transverse stretching process unless the intermediate zone is provided. In this case, since the temperature of the laterally stretched zone is not stable, not only the thickness accuracy of the film deteriorates, but also the physical properties such as heat seal strength and heat shrinkage rate vary. Therefore, it is preferable that the film after the transverse stretching is passed through the intermediate zone and a predetermined time has passed, and then the final heat treatment is performed.
  • the accompanying flow accompanying the running of the film, the transverse stretching zone, and the final so that when the strip-shaped piece of paper is hung down without passing through the film, the piece of paper hangs down almost completely in the vertical direction. It is important to block hot air from the heat treatment zone.
  • the transit time of the intermediate zone is sufficient to be about 1 second to 5 seconds. If it is shorter than 1 second, the length of the intermediate zone becomes insufficient and the heat blocking effect is insufficient. On the other hand, it is preferable that the intermediate zone is long, but if it is too long, the equipment will become large, so about 5 seconds is sufficient.
  • the final heat treatment process has two main roles. That is, (1) reduction of the maximum heat shrinkage rate and maximum heat shrinkage stress caused by stretching, and (2) melting of the heat seal layer. Regarding the former, the maximum heat shrinkage rate and the maximum heat shrinkage stress decrease as the amount of heat received by the film (the sum of the products of temperature and residence time) in the final heat treatment step increases.
  • the maximum heat shrinkage rate In order to set the maximum heat shrinkage rate to 1% or more and 12% or less and the maximum heat shrinkage stress to 0.2 MPa or more and 3 MPa or less, it is necessary to adjust the amount of heat in the final heat treatment step. Regarding the latter, melting of the heat-sealed layer begins with the melting point of the heat-sealed layer at ⁇ 30 ° C. as a guide. In order to develop the heat seal strength in the present invention, it is necessary to appropriately disintegrate the molecular orientation of the heat seal layer generated by stretching as described in the series of "1. Characteristics of sealant film" above. If the final heat treatment temperature is less than the melting point of the heat seal of -30 ° C, the heat seal layer does not melt.
  • the infrared peak intensity ratio is 0.6 or less, and the heat seal strength of 140 ° C per film thickness of 10 ⁇ m is 5. It becomes difficult to make it 0 N / 15 mm or more.
  • the final heat treatment temperature exceeds the melting point of the heat seal layer of -10 ° C, melting is promoted too much, the infrared peak intensity ratio is 0.05 or more, the RSm of the heat seal layer is 29 ⁇ m or more, and the dynamic friction coefficient is 0. It becomes difficult to make it 9 or less.
  • the final heat treatment temperature is more preferably ⁇ 29 ° C. or higher and -11 ° C. or lower, and further preferably ⁇ 28 ° C. or higher and ⁇ 12 ° C. or lower.
  • the heat shrinkage in the width direction can be reduced by reducing the distance between the clips of the tenter at an arbitrary magnification (relaxation in the width direction). Therefore, in the final heat treatment, it is preferable to relax in the width direction in the range of 0% or more and 10% or less (a relaxation rate of 0% means that relaxation is not performed).
  • a relaxation rate of 0% means that relaxation is not performed.
  • the higher the relaxation rate in the width direction, the lower the shrinkage rate in the width direction, but the upper limit of the relaxation rate (shrinkage rate in the width direction of the film immediately after lateral stretching) is the raw material used, the stretching conditions in the width direction, and the heat treatment temperature. It is not possible to carry out relaxation beyond this, as it is determined by.
  • the relaxation rate in the width direction is limited to 10%. Further, at the time of the final heat treatment, as described above, the distance between the clips of the tenter can be shortened by an arbitrary magnification (relaxation in the longitudinal direction) in the longitudinal direction.
  • the passage time of the final heat treatment zone is preferably 2 seconds or more and 20 seconds or less. If the passing time is 2 seconds or less, the surface temperature of the film passes through the heat treatment zone without reaching the set temperature, which makes the heat treatment meaningless. The longer the transit time, the higher the effect of the heat treatment. Therefore, it is preferably 2 seconds or longer, and more preferably 5 seconds or longer. However, if the transit time is to be lengthened, the equipment will become huge, so 20 seconds or less is sufficient for practical use.
  • Cooling After passing through the final heat treatment zone, it is preferable to cool the film with cooling air of 10 ° C. or higher and 30 ° C. or lower in the cooling zone. At this time, the cooling efficiency is improved by lowering the cooling air temperature or increasing the wind speed so that the actual temperature of the film at the outlet of the tenter becomes lower than the glass transition temperature of the heat seal layer or the base material layer, whichever is lower. It is preferable to improve.
  • the actual temperature is the film surface temperature measured by a non-contact radiation thermometer. If the actual temperature of the film at the outlet of the tenter exceeds the glass transition temperature, the film will heat shrink when both ends of the film gripped by the clips are released. At this time, the film is not preferable because it curls to the heat seal layer having a large heat shrinkage rate.
  • the passage time of the cooling zone is preferably 2 seconds or more and 20 seconds or less. If the passing time is 2 seconds or less, the surface temperature of the film passes through the cooling zone without reaching the glass transition temperature, so that the curl becomes large. The longer the transit time, the higher the cooling effect. Therefore, it is preferably 2 seconds or longer, and more preferably 5 seconds or longer. However, if the transit time is to be lengthened, the equipment will become huge, so 20 seconds or less is sufficient for practical use. After that, a film roll can be obtained by winding while cutting and removing both ends of the film.
  • Gas barrier layer The film of the present invention may be provided with a gas barrier layer mainly composed of an inorganic thin film.
  • the sealant of the present invention provided with the gas barrier layer is simply referred to as a "laminate” or a "gas barrier layer laminate”.
  • the laminate using the film of the present invention has a water vapor permeability of 0.05 [g / (m 2 ⁇ d)] or more and 4 [g / () under a temperature of 40 ° C. and a relative humidity of 90% RH. m 2 ⁇ d)] or less is preferable. If the water vapor permeability exceeds 4 [g / (m 2 ⁇ d)], the shelf life of the contents will be shortened when used as a package containing the contents, which is not preferable.
  • the water vapor permeability is smaller than 0.05 [g / (m 2 ⁇ d)]
  • the gas barrier property is enhanced and the shelf life of the contents is extended, which is preferable, but the current technical level is 0.05 [g].
  • / (M 2 ⁇ d)] is the lower limit. Even if the lower limit of water vapor permeability is 0.05 [g / (m 2 ⁇ d)], it can be said that it is practically sufficient.
  • the upper limit of the water vapor permeability is preferably 3.8 [g / (m 2 ⁇ d)], more preferably 3.6 [g / (m 2 ⁇ d)].
  • the laminate using the film of the present invention has an oxygen permeability of 0.05 [cc / (m 2 ⁇ d ⁇ atm)] or more and 4 [cc] under a temperature of 23 ° C. and a relative humidity of 65% RH. / (M 2 ⁇ d ⁇ atm)] or less is preferable. If the oxygen permeability exceeds 4 [cc / (m 2 ⁇ d ⁇ atm)], the shelf life of the contents will be shortened, which is not preferable.
  • the oxygen permeability is smaller than 0.05 [cc / (m 2 ⁇ d ⁇ atm)]
  • the gas barrier property is enhanced and the shelf life of the contents is extended, which is preferable.
  • the oxygen permeability is preferable at the current technical level. Is 0.05 [cc / (m 2 ⁇ d ⁇ atm)] is the lower limit. Even if the lower limit of oxygen permeability is 0.05 [cc / (m 2 ⁇ d ⁇ atm)], it can be said that it is practically sufficient.
  • the upper limit of oxygen permeability is preferably 3.8 [cc / (m 2 ⁇ d ⁇ atm)], more preferably 3.6 [cc / (m 2 ⁇ d ⁇ atm)].
  • raw material species of the gas barrier layer are not particularly limited, and conventionally known materials can be used, and can be appropriately selected according to the purpose in order to satisfy desired gas barrier properties and the like.
  • raw material species for the gas barrier layer include metals such as silicon, aluminum, tin, zinc, iron, and manganese, and inorganic compounds containing one or more of these metals.
  • Applicable inorganic compounds include oxides and nitrides. , Carbide, fluoride and the like. These inorganic substances or inorganic compounds may be used alone or in combination of two or more.
  • the component of the inorganic compound is a binary product of silicon oxide and aluminum oxide
  • the content of aluminum oxide is preferably 20% by mass or more and 80% by mass or less, and more preferably 25% by mass or more and 70% by mass or less. ..
  • the content of aluminum oxide is 20% by mass or less, the density of the gas barrier layer is lowered and the gas barrier property may be lowered, which is not preferable.
  • the content of aluminum oxide is 80% by mass or more, the flexibility of the gas barrier layer is lowered and cracks are likely to occur, and as a result, the gas barrier property may be lowered, which is not preferable.
  • the oxygen / metal element ratio of the metal oxide used for the gas barrier layer is 1.3 or more and less than 1.8, there is little variation in the gas barrier property, and it is preferable that excellent gas barrier property can always be obtained.
  • the element ratio of oxygen / metal can be obtained by measuring the amounts of each element of oxygen and metal by X-ray photoelectron spectroscopy (XPS) and calculating the element ratio of oxygen / metal.
  • Method for forming a gas barrier layer is not particularly limited, and a known production method can be adopted as long as the object of the present invention is not impaired.
  • the known production methods it is preferable to adopt the vapor deposition method.
  • the vapor deposition method include a vacuum vapor deposition method, a sputtering method, a PVD method (physical vapor deposition method) such as ion plating, a CVD method (chemical vapor deposition method), and the like.
  • the vacuum vapor deposition method and the physical vapor deposition method are preferable, and the vacuum vapor deposition method is particularly preferable from the viewpoint of production speed and stability.
  • the heating method in the vacuum vapor deposition method resistance heating, high frequency induction heating, electron beam heating and the like can be used.
  • the reactive gas oxygen, nitrogen, water vapor or the like may be introduced, or reactive vapor deposition using means such as ozone addition and ion assist may be used.
  • the film forming conditions may be changed as long as the object of the present invention is not impaired, such as applying a bias to the substrate or raising or cooling the substrate temperature.
  • the film of the present invention is conveyed to the gas barrier layer manufacturing apparatus via a metal roll.
  • An example of the configuration of the gas barrier layer manufacturing apparatus includes a winding roll, a coating drum, a winding roll, an electron beam gun, a crucible, and a vacuum pump.
  • the film is set on a take-up roll and is taken up on a take-up roll via a coating drum.
  • the film pass line (inside the gas barrier layer manufacturing equipment) is depressurized by a vacuum pump, and the inorganic material set in the crucible is evaporated by the beam emitted from the electron gun and deposited on the film passing through the coating drum. ..
  • the film is heated and tension is also applied between the unwinding rolls. If the temperature applied to the film is too high, not only the heat shrinkage of the film becomes large, but also the softening progresses, so that elongation deformation due to tension is likely to occur.
  • the temperature applied to the film is preferably 100 ° C. or higher and 180 ° C. or lower, more preferably 110 ° C.
  • Tension per unit cross-sectional area according to the film (width ⁇ thickness), preferable to be 0.2 N / mm 2 or more 3N / mm 2 or less, if it is 0.6 N / mm 2 or more 2.6 N / mm 2 or less more preferably, further preferably a 1N / mm 2 or more 2.2 N / mm 2 or less.
  • Overcoat layer 6.1 Types of Overcoat Layer
  • the film of the present invention or the gas barrier laminate using the film of the present invention (in this section 6., these are collectively referred to as a base film) is described in "5. Gas barrier layer" above.
  • an overcoat layer may be provided for the purpose of improving scratch resistance and further gas barrier property.
  • the type of the overcoat layer is not particularly limited, but conventionally, a composition composed of a urethane resin and a silane coupling agent, a compound composed of an organosilicon and a hydrolyzate thereof, a water-soluble polymer having a hydroxyl group or a carboxyl group, and the like have been conventionally used.
  • a known material can be used and can be appropriately selected according to the purpose in order to satisfy the desired gas barrier property and the like.
  • one or more kinds of various additives are added for the purpose of imparting antistatic property, ultraviolet absorption, coloring, thermal stability, slipperiness, etc., as long as the object of the present invention is not impaired.
  • the type and amount of the various additives may be appropriately selected according to the desired purpose.
  • Method of forming an overcoat layer When forming an overcoat layer, the base film is conveyed to a coating facility via a metal roll.
  • equipment configurations include unwinding rolls, coating processes, drying processes, and winding processes.
  • the laminate set on the unwinding roll is passed through the metal roll through the coating step and the drying step, and finally led to the winding roll.
  • the coating method is not particularly limited, and the gravure coating method, reverse coating method, dipping method, low coating method, air knife coating method, comma coating method, screen printing method, spray coating method, gravure offset method, die coating method, bar coating method, etc.
  • a conventionally known method can be adopted, and can be appropriately selected according to a desired purpose.
  • the gravure coating method, the reverse coating method, and the bar coating method are preferable from the viewpoint of productivity.
  • the drying method one or a combination of two or more heating methods such as hot air drying, hot roll drying, high frequency irradiation, infrared irradiation, and UV irradiation can be used.
  • the substrate film is heated and tension is also applied between the metal rolls. If the temperature at which the base film is heated in the drying process is too high, not only the heat shrinkage of the base film becomes large, but also the softening progresses, so that elongation deformation due to tension is likely to occur, and the gas barrier layer of the base film becomes Cracks are likely to occur. Furthermore, after leaving the drying process, the temperature drop (cooling) of the laminate increases, and the amount of shrinkage after expansion (different from heat shrinkage) increases accordingly, causing cracks in the gas barrier layer and overcoat layer. It is not preferable because it becomes difficult to satisfy the desired gas barrier property.
  • the temperature at which the base film is heated is preferably 60 ° C. or higher and 200 ° C. or lower, more preferably 80 ° C. or higher and 180 ° C. or lower, and further preferably 100 ° C. or higher and 160 ° C. or lower. Further, if the tension applied to the base film is too high, the base film is easily stretched and deformed, which is not preferable.
  • Tension per unit cross-sectional area according to the substrate film (width ⁇ thickness), preferable to be 0.2 N / mm 2 or more 3N / mm 2 or less, 0.6 N / mm 2 or more 2.6 N / mm 2 or less more preferable to be, further preferably a 1N / mm 2 or more 2.2 N / mm 2 or less.
  • the film of the present invention can be made into a bag by itself, but other materials may be laminated.
  • the other layer include a non-stretched film containing polyethylene terephthalate as a component, a non-stretched film containing another amorphous polyester as a component, a uniaxially stretched or biaxially stretched film, and a non-stretched film containing nylon as a component.
  • Examples thereof include, but are not limited to, uniaxially stretched or biaxially stretched films, non-stretched films containing polypropylene as constituents, uniaxially stretched or biaxially stretched films, and the like.
  • the method of using the sealant for the package is not particularly limited, and conventionally known manufacturing methods such as a coating forming method, a laminating method, and a heat sealing method can be adopted.
  • the package may be at least partially composed of the film of the present invention. Further, in the package, the film of the present invention may come in any layer, but in consideration of non-adhesiveness to the contents and the sealing strength when making the bag, the heat-sealing layer of the present invention is the most suitable for the bag.
  • the structure that becomes the inner layer is preferable.
  • the method for producing the package having the film of the present invention is not particularly limited, and conventionally known production methods such as heat sealing using a heat bar (heat jaw), adhesion using a hot melt, and center sealing using a solvent are adopted. be able to.
  • the lid material is heat-shrinked after being adhered to the container by the manufacturing method described above, because a feeling of tension is created and the appearance is beautiful.
  • the method of heat-shrinking the lid material is not particularly limited, and known methods such as blowing hot air and / or steam using a heating tunnel, immersion in hot water, contact with a hot plate, atmospheric heating, microwaves, etc. are adopted. can do. Among these methods, in consideration of the influence on the contents, blowing hot air, contacting with a hot plate, and heating the atmosphere are preferable. Further, when the lid material is heat-shrinked, it is preferable to use a transport device such as a belt conveyor in combination because the productivity is improved.
  • the conditions for blowing hot air are not particularly limited, and can be freely changed as long as the container is not deformed.
  • the temperature of the hot air needs to be set in consideration of the heat shrinkage characteristics of the film.
  • the temperature of the hot air is preferably 100 ° C. or higher and 220 ° C. or lower. If the temperature of the hot air is less than 100 ° C., it may not reach a temperature sufficient for the lid material to shrink.
  • the temperature of the hot air is more preferably 110 ° C. or higher and 210 ° C. or lower, and further preferably 120 ° C. or higher and 200 ° C. or lower.
  • the wind speed of hot air is preferably 1 m / sec or more and 20 m / sec or less. If the wind speed of the hot air is less than 1 m / sec, the temperature may not reach a sufficient temperature for the lid material to shrink.
  • the wind speed of the hot air is more preferably 2 m / sec or more and 19 m / sec or less, and further preferably 3 m / sec or more and 18 m / sec or less.
  • the residence time in the heating tunnel is preferably 2 seconds or more and 50 seconds or less. If the residence time is less than 2 seconds, the temperature may not reach sufficient for the lid material to shrink.
  • the residence time is more preferably 3 seconds or more and 49 seconds or less, and further preferably 4 seconds or more and 48 seconds or less.
  • the packaging body having the film of the present invention can be suitably used as a packaging material for various articles such as foods, pharmaceuticals, and industrial products.
  • polyester A was obtained.
  • This polyester (A) is polyethylene terephthalate.
  • the composition of polyester A is shown in Table 1.
  • Polyesters B to F in which the monomers were changed were obtained in the same procedure as in Synthesis Example 1.
  • the composition of each polyester is shown in Table 1.
  • TPA is terephthalic acid
  • IPA is isophthalic acid
  • BD is 1,4-butanediol
  • NPG is neopentyl glycol
  • CHDM is 1,4-cyclohexanedimethanol
  • DEG diethylene glycol.
  • SiO2 Siliconicia 266 manufactured by Fuji Silysia Chemical Ltd.
  • Each polyester was appropriately formed into chips.
  • the intrinsic viscosity IV of each polyester is (B) 0.73 dL / g, (C) 0.72 dL / g, (D) 0.73 dL / g, (E) 0.8 dL / g, and (F) 0. It was .75 dL / g.
  • the composition of polyesters B to F is shown in Table 1.
  • Polyester A, polyester B, polyester E, and polyester F were mixed (dry blended) at a mass ratio of 28:49:15: 8, put into a screw extruder, and heated at 275 ° C. to melt and mix them. This molten resin was continuously discharged from a strand die in a columnar shape and cut with a strand cutter to obtain a chip-shaped polyester G.
  • the intrinsic viscosity IV of polyester G was 0.63 dL / g.
  • the composition of polyester G is shown in Table 1.
  • Polyester A, polyester B, polyester E, and polyester F were dry-blended at a mass ratio of 2: 66: 24: 8 and then melted and mixed to obtain polyester H in the same manner as in Mixing Example 1.
  • the intrinsic viscosity IV of polyester H was 0.65 dL / g.
  • the composition of polyester H is shown in Table 1.
  • Polyester B, polyester E, polyester F, and polyester G are mixed as raw materials for the heat seal layer (A layer) at a mass ratio of 46: 19: 5: 30, and polyester A and polyester B are used as raw materials for the base material layer (B layer). And polyester E and polyester F were mixed at a mass ratio of 48:38: 6: 8.
  • the mixed raw materials of the A layer and the B layer were put into separate screw extruders, and the A layer was melted at 272 ° C. and the B layer was melted at 283 ° C.
  • Each molten resin was joined by a feed block in the middle of the flow path, discharged from a T-die, and cooled on a chill roll set to a surface temperature of 30 ° C.
  • the flow path of the molten resin is set so that one side is the A layer and the other side is the B layer (two types of two layers of A layer / B layer), and the thickness ratio of the A layer and the B layer is 50 /.
  • the discharge amount was adjusted to 50.
  • the unstretched laminated film obtained by cooling and solidifying is guided to a longitudinal stretching machine in which a plurality of roll groups are continuously arranged, preheated on preheating rolls until the film temperature reaches 82 ° C., and then stretched 4.1 times. did.
  • the film immediately after longitudinal stretching was passed through a heating furnace set at 100 ° C. with a hot air heater, and a 20% relaxation treatment was performed in the longitudinal direction by utilizing the speed difference between the rolls at the inlet and the outlet of the heating furnace. Then, the vertically stretched film was forcibly cooled by a cooling roll set to a surface temperature of 25 ° C.
  • the film after the relaxation treatment was guided to a transverse stretching machine (tenter), preheated for 5 seconds until the surface temperature reached 115 ° C., and then stretched 4.1 times in the width direction (lateral direction).
  • the film after the transverse stretching was directly led to the intermediate zone and passed in 1.0 second.
  • the hot air from the final heat treatment zone and the lateral stretching zone so that when the strip-shaped piece of paper hangs down without passing through the film, the piece of paper hangs down almost completely in the vertical direction. The hot air from was cut off.
  • the film that passed through the intermediate zone was led to the final heat treatment zone and heat-treated at 198 ° C. for 7 seconds.
  • the heat treatment was performed and at the same time, the clip interval in the film width direction was narrowed to perform a 3% relaxation treatment in the width direction.
  • the film was cooled with cooling air at 30 ° C. for 5 seconds.
  • the actual film temperature at the outlet of the tenter was 45 ° C.
  • Examples 2 to 6 In Examples 2 to 6 as in Example 1, polyester films in which the mixing ratio of raw materials, first stretching, intermediate heat treatment, second stretching, and final heat treatment conditions were variously changed were continuously produced. Similar to Example 1, these films are wound into a roll having a width of 600 mm and a length of 1000 m. Tables 2 and 3 show the production conditions and evaluation results of each film.
  • Examples 4 to 6 are simultaneous biaxially stretched films stretched simultaneously in the longitudinal direction and the lateral direction (for convenience, the stretching conditions are described in the columns of longitudinal stretching and transverse stretching for Examples 4 to 6 in Table 2. However, these are simultaneously stretched under the same conditions).
  • Example 7 In Example 7, in the same manner as in Example 1, polyester films in which the mixing ratio of raw materials, first stretching, intermediate heat treatment, second stretching, and final heat treatment conditions were variously changed were continuously formed. Similar to Example 1, this film is wound into a roll having a width of 600 mm and a length of 1000 m. A gas barrier laminate is formed by laminating a gas barrier layer made of aluminum oxide (AlOx) on the base material layer side of this film roll by a vacuum vapor deposition method while introducing oxygen gas with a vacuum vapor deposition machine using aluminum as a vapor deposition source. Was continuously produced to obtain a roll having a width of 600 mm and a length of 1000 m. The thickness of the gas barrier layer was 10 nm. The characteristics of the obtained laminate were evaluated by the evaluation method described later. The manufacturing conditions and evaluation results are shown in Tables 2 and 3.
  • AlOx aluminum oxide
  • Example 8 polyester films in which the mixing ratio of raw materials, the first stretching, the intermediate heat treatment, the second stretching, and the final heat treatment conditions were variously changed were continuously formed. Similar to Example 1, this film is wound into a roll having a width of 600 mm and a length of 1000 m.
  • a gas barrier layer made of aluminum oxide (AlOx) and silicon oxide (SiOx) was laminated on the base material layer side of the film roll to continuously prepare a gas barrier laminate having a width of 600 mm. , A roll having a length of 1000 m was obtained. The thickness of the gas barrier layer was 30 nm.
  • the overcoat layer was continuously formed.
  • the thickness of the overcoat layer was 300 nm.
  • Comparative Examples 1 to 4 In Comparative Examples 1 to 4, in the same manner as in Example 1, polyester films in which the blending ratio of raw materials, first stretching, intermediate heat treatment, second stretching, and final heat treatment conditions were variously changed were continuously formed. Similar to Example 1, these films are wound into a roll having a width of 600 mm and a length of 1000 m. Tables 2 and 3 show the production conditions and evaluation results of each film.
  • Polyester A and polyester F were mixed as raw materials for the heat seal layer (layer A) at a mass ratio of 92: 8, and the mixed raw materials were put into a screw extruder and melted at 285 ° C.
  • This molten resin is discharged alone from a T-die, cooled on a chill roll set to a surface temperature of 30 ° C., and then both edges are cut and removed and wound into a roll with a width of 600 mm to have a thickness of 50 ⁇ m.
  • Stretched films were continuously produced over a predetermined length.
  • polyester A and polyester F were mixed as raw materials for the base material layer (B layer) at a mass ratio of 92: 8, and the mixed raw materials were put into a screw extruder and melted at 285 ° C.
  • This molten resin was discharged alone from a T-die and cooled on a chill roll set to a surface temperature of 30 ° C. to obtain an unstretched single-layer film.
  • the unstretched single-layer film obtained by cooling and solidifying is guided to a longitudinal stretching machine in which a plurality of roll groups are continuously arranged, preheated on preheating rolls until the film temperature reaches 90 ° C., and then increased 3.5 times. It was stretched. Then, the vertically stretched film was forcibly cooled by a cooling roll set to a surface temperature of 25 ° C. The cooled film was guided to a transverse stretching machine (tenter) and preheated for 5 seconds until the surface temperature reached 115 ° C., and then stretched 3.9 times in the width direction (lateral direction). The film after the transverse stretching was directly led to the intermediate zone and passed in 1.0 second.
  • a longitudinal stretching machine in which a plurality of roll groups are continuously arranged, preheated on preheating rolls until the film temperature reaches 90 ° C., and then increased 3.5 times. It was stretched. Then, the vertically stretched film was forcibly cooled by a cooling roll set to a surface temperature of 25 ° C. The
  • the hot air from the final heat treatment zone and the lateral stretching zone so that when the strip-shaped piece of paper hangs down without passing through the film, the piece of paper hangs down almost completely in the vertical direction.
  • the hot air from was cut off.
  • the film that passed through the intermediate zone was led to the final heat treatment zone and heat-treated at 230 ° C. for 7 seconds.
  • the heat treatment was performed and at the same time, the clip interval in the film width direction was narrowed to perform a 2% relaxation treatment in the width direction.
  • the film was cooled with cooling air at 30 ° C. for 5 seconds.
  • the actual film temperature at the outlet of the tenter was 45 ° C.
  • a two-layer film was prepared by laminating the obtained A layer and B layer using an adhesive for dry lamination (Takelac (registered trademark) A-950 manufactured by Mitsui Chemicals, Inc.). The total thickness of this film was 62 ⁇ m. The properties of the obtained film were evaluated by the above method. The manufacturing conditions and evaluation results are shown in Tables 2 and 3.
  • Comparative Example 6 a pipe wrench film-CT (registered trademark) P1128-30 ⁇ m manufactured by Toyobo Co., Ltd. was used. The evaluation results are shown in Tables 2 and 3.
  • the evaluation method of the film is as follows. If the longitudinal direction and the width direction cannot be specified immediately because the area of the film is small, the longitudinal direction and the width direction may be determined and the measurement may be performed, and the temporarily determined longitudinal direction and the width direction become the true direction. On the other hand, the difference of 90 degrees does not cause any particular problem.
  • the transesterification degree, melting point, and intrinsic viscosity (IV) of the heat seal layer shown below only the heat seal layer was scraped from the surface layer of the film with a feather blade and sampled. The cross section of the film sample after scraping was observed with an electron scanning microscope (SEM) to confirm that layers other than the heat seal layer were not scraped.
  • Transesterification degree (heat seal layer) Transesterification of the heat seal layer, a proton-type nuclear magnetic resonance spectroscopy measurement of the resonance frequency 600MHz in (1 H-NMR), was determined from Homodekappuru measurements 2, 3-position methylene protons of BD.
  • an NMR device AVANCE-NEO manufactured by BRUKER was used, and the number of integrations was 32 times.
  • Deuterated chloroform / orthochlorophenol 25/75 (weight ratio) was used as the solvent.
  • the melting point of the heat seal layer was determined using a temperature-modulated differential scanning calorimeter (DSC) "DSC250" (manufactured by TA instruments). The sample was weighed in a T-zero® pan at 2.0 ⁇ 0.2 mg and measured in MDSC® heat-only mode with an average heating rate of 2 ° C./min and a modulation cycle of 40 seconds. A chart of non-reverse heat flow was obtained. In the reverse heat flow chart, the temperature indicating the minimum value of the endothermic peak that appears was defined as the melting point. The endothermic peak here refers to one that appears in the temperature range of 160 to 280 ° C.
  • As the measurement solvent a mixture of phenol and 1,1,2,2-tetrachloroethane at 60/40 (wt%) was used.
  • the infrared peak intensity ratio of the heat seal layer was determined by an FT-IR apparatus "FTS 60A / 896" (manufactured by Varian). Using a diamond gate, the infrared absorption spectrum was measured by applying polarization in the measured wavenumber region of 650 to 4000 cm -1 , the number of integrations of 128 times, and the ATR method. From the obtained infrared absorption spectrum, and the ratio A1 / A2 of an infrared peak intensity A2 of the infrared peak intensity A1 and 1410 cm -1 in 1340 cm -1 and an infrared peak intensity ratio. The polarization direction at the time of measurement was set to be the longitudinal direction or the width direction of the film, and the measurements were taken separately.
  • Heat seal strength (heat seal layers)
  • the heat seal strength between the heat seal layers was measured according to JIS Z1707. The specific procedure is shown. The heat seal layers of the samples were adhered to each other with a heat sealer. The heat sealing conditions were an upper bar temperature of 140 ° C., a lower bar temperature of 30 ° C., a pressure of 0.2 MPa, and a time of 2 seconds. The adhesive sample was cut out so that the seal width was 15 mm.
  • the peel strength (heat seal strength) was measured at a tensile speed of 200 mm / min using a universal tensile tester "Autograph AG-Xplus" (manufactured by Shimadzu Corporation). The peel strength is indicated by the strength per 15 mm (N / 15 mm). The value of the peel strength converted per 10 ⁇ m of the sealant film was also determined.
  • Heat seal strength (heat seal layer vs. A-PET)
  • the heat seal strength of the heat seal layer and A-PET was measured according to JIS Z1707. The specific procedure is briefly shown.
  • the heat seal layer of the sample and a non-stretched polyethylene terephthalate (A-PET) sheet (200 ⁇ m, no surface treatment such as coating treatment or corona treatment) were adhered with a heat sealer.
  • the heat sealing conditions were an upper bar temperature of 140 ° C., a lower bar temperature of 30 ° C., a pressure of 0.2 MPa, and a time of 2 seconds.
  • the adhesive sample was cut out so that the seal width was 15 mm.
  • the peel strength (heat seal strength) was measured at a tensile speed of 200 mm / min using a universal tensile tester "Autograph AG-Xplus” (manufactured by Shimadzu Corporation). The peel strength is indicated by the strength per 15 mm (N / 15 mm). The value of the peel strength converted per 10 ⁇ m of the sealant film was also determined.
  • Maximum heat shrinkage stress A sample having a size of 30 mm ⁇ 4 mm was cut out, and the maximum heat shrinkage stress was measured using TMA.
  • the measurement direction was both the longitudinal direction and the width direction so that the measurement direction was 30 mm.
  • the distance between the chucks was 20 mm, and the sample was attached to the probe using a dedicated chuck. After setting the sample, the heat shrinkage stress when the temperature in the furnace was raised from 30 ° C. to 220 ° C. at 10 ° C./min was recorded, and the peak stress was taken as the maximum heat shrinkage stress.
  • the water vapor permeability was measured according to the JIS K7126 B method. Using a water vapor permeability measuring device (PERMATRAN-W3 / 33MG MOCON), measure the water vapor permeability in the direction in which the humidity control gas permeates from the heat seal layer side in an atmosphere of temperature 40 ° C. and humidity 90% RH. did. Before the measurement, the sample was left for 4 hours in a humidity of 65% RH environment to control the humidity.
  • PERMATRAN-W3 / 33MG MOCON PERMATRAN-W3 / 33MG MOCON
  • Oxygen permeability was measured according to the JIS K7126-2 method. Using an oxygen permeation measuring device (OX-TRAN 2/20 MOCON), the oxygen permeation was measured in the direction in which oxygen permeates from the heat seal layer side in an atmosphere of a temperature of 23 degrees and a humidity of 65% RH. .. Before the measurement, the sample was left for 4 hours in a humidity of 65% RH environment to control the humidity.
  • OX-TRAN 2/20 MOCON oxygen permeation measuring device
  • the film was cut into a square of 10 cm ⁇ 10 cm, two sheets were stacked with the heat seal layer inside, and the bag was prepared by heat sealing at a position 1 cm from the edge of the film.
  • An aluminum cup containing 0.5 ml of the contents was placed in a bag, and a position 1 cm from the end of the film was heat-sealed, and the bag was closed and sealed.
  • D-limonene manufactured by Tokyo Chemical Industry Co., Ltd.
  • L-menthol manufactured by Nacalai Tesque Co., Ltd.
  • a 5 cm ⁇ 5 cm square is cut out from the surface of the film bag in contact with the mouth of the aluminum cup, and the cut film is immersed in 4 ml of an extraction solvent and extracted with ultrasonic waves for 30 minutes. did. 99.8% ethanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used as the extraction solvent. The concentration of the contents in the extraction solution was quantified using a gas chromatograph "GC-14B" manufactured by Shimadzu Corporation.
  • the heat sealing conditions were a temperature of 140 ° C., a sealing pressure of 0.2 MPa, and a sealing time of 2 seconds.
  • the iron Toshiba Sewing Iron TA-A20 manufactured by Toshiba Lifestyle Products & Services Co., Ltd. was set to the output "high" and applied to the film for 3 seconds to heat shrink the film.
  • ⁇ Evaluation of film slack> The amount of slack in the film (produced through the above ⁇ Evaluation sample preparation method> and ⁇ Container deformation evaluation>) after heat-sealing the container is measured by the universal tensile tester Autograph "AG-Xplus" (Shimadzu Corporation). It was evaluated by the compression test mode of (manufactured by). A fixed platen was used for the jig attached to the test part of the autograph, and the lower part had a diameter of 200 mm ⁇ and the upper part had a diameter of 50 mm ⁇ .
  • the top surface (film surface) of the evaluation sample was placed in the center of the lower platen so as to face the upper platen, and the distance between the film surface and the upper platen was 10 mm (the distance between the upper and lower plateaus was 150 mm). .. After placing the evaluation sample prepared above, the upper platen was lowered toward the film surface at a speed of 50 mm / min, and the displacement when the test force generated after hitting the film surface exceeded 0.5 N was determined. .. The value obtained by subtracting 10 mm (distance between the film surface and the upper platen) from the obtained displacement was defined as the amount of slack, and was determined according to the following criteria.
  • the compression test results of Example 1 and Comparative Example 5 are shown in FIG. Judgment ⁇ Sag amount less than 2 mm Judgment ⁇ Sag amount 2 mm or more
  • Comparative Example 3 since the infrared peak intensity ratio of the heat seal layer was lower than the predetermined range and the dynamic friction coefficient exceeded 0.9, a large number of irregularities were generated on the roll around which this film was wound. Further, in Comparative Example 3, since the maximum heat shrinkage rate and the maximum heat shrinkage stress were extremely low, the amount of slack increased even when the container was heat-sealed and then heated, and the appearance (appearance) was compared with Examples 1 to 8. ) Was inferior. In Comparative Example 4, since the maximum heat shrinkage rate and the maximum heat shrinkage stress were too high, when the container was heat-sealed and heated, the container was deformed due to the heat shrinkage of the film.
  • the polyester-based sealant film of the present invention has little adsorption of components of the contents, has excellent mechanical strength, has high heat-sealing strength in a low temperature range, has excellent gas barrier properties when a gas barrier layer is provided, and is a film. Since it has excellent roll-windability and appropriate heat shrinkage, it can be suitably used as a sealant film as a lid material. Further, it is possible to provide a laminate and a package having at least one layer of the polyester-based sealant film of the present invention.

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CN114801391A (zh) * 2021-01-20 2022-07-29 内蒙古蒙牛乳业（集团）股份有限公司 一种复合片材及其制备方法
WO2025187417A1 (ja) * 2024-03-08 2025-09-12 東洋紡株式会社 ポリエステル系シーラントフィルム

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