WO2020071315A1 - 低吸着性シーラントフィルム、積層体および包装袋 - Google Patents
低吸着性シーラントフィルム、積層体および包装袋Info
- Publication number
- WO2020071315A1 WO2020071315A1 PCT/JP2019/038525 JP2019038525W WO2020071315A1 WO 2020071315 A1 WO2020071315 A1 WO 2020071315A1 JP 2019038525 W JP2019038525 W JP 2019038525W WO 2020071315 A1 WO2020071315 A1 WO 2020071315A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- heat
- film
- less
- layer
- heat seal
- Prior art date
Links
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B65D31/00—Bags or like containers made of paper and having structural provision for thickness of contents
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Definitions
- the present invention relates to a sealant film having both excellent low adsorbability and heat sealability, and a laminate and a packaging bag using the same.
- sealant films have been used as packaging materials for many distribution articles represented by foods, pharmaceuticals, and industrial products.
- the innermost layer of the packaging material constituting the packaging bag, the lid material, and the like is provided with a heat sealing layer made of a polyolefin resin such as polyethylene or polypropylene, which exhibits high heat sealing strength, or a copolymer resin such as ionomer or EMMA.
- a non-stretched sealant film made of a polyolefin-based resin as described in Patent Literature 1 easily adsorbs components made of organic compounds such as oils and fats and fragrances.
- the packaging material that is in contact with the layer has the disadvantage that the scent and taste of the contents are easily changed.
- a sealant layer made of polyolefin resin is used as the innermost layer of packaging bags for chemicals, pharmaceuticals, foods, etc., it is not suitable because it requires measures such as including a large amount of the active ingredient in the contents in advance. There are many cases.
- Patent Document 3 discloses a polyester film having a non-adsorption property of an organic compound and used for a sealant.
- the polyester film of Patent Document 3 has a high heat-sealing strength of 100 ° C., the innermost heat-sealing layers are likely to stick to each other when the contents are used as a packaging bag and the contents are boiled with hot water and warmed. There was a problem that it was difficult to open the packaging bag.
- Patent Document 4 a polyester film having a non-adsorbing property for an organic compound and used for a sealant.
- the speed of automatic filling and packaging has been increased in order to increase productivity, but it has been found that the polyester film of Patent Document 4 cannot cope with high-speed automatic filling and packaging.
- the temperature of the heat seal bar is set to 140 ° C.
- the temperature of the sealant film rises only to around 120 ° C. because of the short heating time.
- the polyester-based film disclosed in Patent Document 4 does not have a sufficient heat seal strength at 120 ° C., and thus has a problem in that the seal portion peels off after heat seal processing.
- Patent No. 3817846 JP-A-7-132946 International Publication No. WO 2014/175313 JP-A-2017-165059
- the present invention provides a sealant film (A) which is less likely to adsorb components composed of various organic compounds and has excellent heat sealability at 140 ° C.
- the first invention of the present application provides the sealant film of (A), wherein the heat seal layers are less likely to stick to each other even when the contents are used as a packaging bag and the contents are boiled in hot water and are warmed. Is what you do.
- the second invention of the present application provides the sealant film (A) having a sufficient heat-sealing strength even in high-speed automatic filling and packaging, since the heat-sealing property at a low temperature of 120 ° C. is also excellent.
- Another object of the present invention is to provide a laminate including at least one of the sealant films according to the first and second aspects of the present invention and a packaging bag using the same.
- a low-adsorbent sealant film comprising at least one heat-sealing layer made of a polyester component and satisfying the following (1) to (3).
- Sealing strength between heat seal layers at 100 ° C. and 0.2 MPa for 2 seconds is 0 N / 15 mm or more and 5 N / 15 mm or less.
- Heat seal layers at 140 ° C. and 0.2 MPa for 2 seconds are referred to as a second invention of the present application.
- the density of the film including all the layers is 1.20 or more and less than 1.39, when the sealing strength is 8 N / 15 mm or more and 30 N / 15 mm or less.
- a low-adhesive sealant film comprising at least one heat-sealing layer made of a polyester component and satisfying the following (4) to (6).
- Sealing strength between heat seal layers at 120 ° C. and 0.2 MPa for 2 seconds is 4 N / 15 mm or more and 15 N / 15 mm or less.
- the oxygen atom abundance ratio determined by X-ray electron spectroscopy (ESCA) is 26.6% or more and 31.0% or less.
- the average length RSm of the element of the surface roughness obtained from the three-dimensional roughness meter is from 18 ⁇ m to 29 ⁇ m. Or 2.
- the coefficient of dynamic friction between the heat sealing surfaces is 0.30 or more and 0.80 or less.
- the component constituting the film is made of a polyester containing ethylene terephthalate as a main component. ⁇ 4.
- the polyester component constituting the heat-sealing layer contains a diol monomer component other than ethylene glycol, and the diol monomer component is neopentyl glycol, 1,4-cyclohexanedimethanol, 1,4-butanediol And at least one of diethylene glycol ⁇ 5.
- the heat shrinkage when treated in hot water at 80 ° C. for 10 seconds is 0% or more and 10% or less in both the longitudinal direction and the width direction. ⁇ 6.
- a low-absorbing sealant film according to any one of the above. 8. 1. ⁇ 7.
- a laminate comprising at least one layer of the sealant film according to any one of the above. 9. 1. ⁇ 7. 7.
- the sealant film of the present invention does not easily adsorb various organic compounds, it can hygienically package articles containing oils and fragrances, such as chemical products, pharmaceuticals, and foods, and has excellent heat sealability at 140 ° C. Since the sealant film of the first invention of the present application has a low heat seal strength at 100 ° C., when the contents are used as a packaging bag and the contents are boiled in hot water and are to be warmed, the innermost heat seal layers are less likely to stick to each other. .
- the second invention of the present application is excellent in heat sealability at 140 ° C. and also excellent in heat sealability at 120 ° C.
- the sealant film of the first invention of the present application is a low-adhesive sealant film having at least one heat-sealing layer made of a polyester component and satisfying the following (1) to (3). .
- Sealing strength between heat seal layers at 100 ° C. and 0.2 MPa for 2 seconds is 0 N / 15 mm or more and 5 N / 15 mm or less.
- the density of the film including all layers is 1.20 or more and less than 1.39 or less, and the properties, layer constitution, and layer of the sealant film of the present invention are as follows. The ratio, the raw material constituting the sealant film, the method for producing the sealant film, the type of contents, the configuration of the package, and the bag making method will be described in detail.
- the sealant film of the first invention of the present application is a heat seal layer obtained by heat sealing the heat sealing layers at a temperature of 100 ° C., a seal bar pressure of 0.2 MPa, and a sealing time of 2 seconds.
- the seal strength needs to be 0 N / 15 mm or more and 5 N / 15 mm or less. If the heat seal strength at 100 ° C. exceeds 5 N / 15 mm, the innermost heat seal layers are likely to stick to each other when the contents are to be used as a packaging bag to warm the contents, resulting in impaired openability. Not suitable as.
- the heat sealing strength at 100 ° C. is more preferably 4.5 N / 15 mm or less, and even more preferably 4.0 N / 15 mm or less.
- the sealant film of the second invention of the present application has a heat seal strength of 4 N when heat seal layers are heat sealed at a temperature of 120 ° C., a seal bar pressure of 0.2 MPa, and a seal time of 2 seconds. / 15 mm or more and 15 N / 15 mm or less.
- the heat seal strength at 120 ° C. is less than 4 N / 15 mm, the heat seal strength at the time of high-speed automatic filling and packaging is insufficient, so that the productivity of the packaging bag cannot be increased. It is preferable that the heat seal strength at 120 ° C. is large.
- the upper limit obtained at present is about 15 N / 15 mm, which is practically sufficient.
- the 120 ° C. heat seal strength is more preferably 5 N / 15 mm or more, and even more preferably 6 N / 15 mm or more.
- the sealant film of the present invention has a heat seal strength of 8 N / 15 mm or more when heat seal layers are heat-sealed at a temperature of 140 ° C., a seal bar pressure of 0.2 MPa, and a seal time of 2 seconds. It is necessary to be 30 N / 15 mm or less. When the heat sealing strength at 140 ° C. is less than 8 N / 15 mm, the sealing portion is easily peeled off, and thus it is difficult to use as a packaging bag. It is preferable that the heat sealing strength at 140 ° C. is large, but in the state of the art of the present invention, the currently obtainable upper limit is about 30 N / 15 mm.
- the 140 ° C. heat seal strength is more preferably 9 N / 15 mm or more, and even more preferably 10 N / 15 mm or more.
- the density of the film including all layers needs to be 1.20 or more and less than 1.39.
- the density of the film including all layers, the adsorptivity and heat resistance, and the heat sealing strength at 140 ° C. are correlated.
- the density is 1.39 or more, low adsorbability and heat resistance are excellent, but the heat sealability at 140 ° C. is impaired, so that it is not suitable as a sealant film.
- the density range is more preferably 1.25 or more and 1.38 or less, and even more preferably 1.30 or more and 1.37 or less.
- Average length RSm of surface roughness element of heat seal layer In the sealant film of the present invention, the average length RSm of the surface roughness element of the heat seal layer measured at a cutoff of 0.250 mm and a measurement speed of 0.2 mm / sec is 18 ⁇ m or more and 2 It is preferably 9 ⁇ m or less.
- the average length RSm of the element of the surface roughness of the heat seal layer is correlated with the heat seal strength at 100 ° C. and the coefficient of dynamic friction between the heat seal surfaces. The longer the average length RSm of the element of the surface roughness of the heat seal layer is, the less the unevenness of the heat seal surface becomes, and the smoother the surface becomes.
- the contact area becomes larger and the heat seal strength at 100 ° C. becomes higher. Also has a high dynamic friction coefficient.
- the average length RSm of the element of the surface roughness of the heat seal layer is 29 ⁇ m or more, the heat seal strength at 100 ° C. increases, and when the contents are used as a packaging bag to warm the contents, the heat seal of the innermost layer Since the layers easily stick to each other and the opening property is impaired, it is not suitable as a packaging bag.
- the average length RSm of the element of the surface roughness is less than 18 ⁇ m, the contact area between the heat-sealed surfaces becomes extremely small, so that the sealing strength at 140 ° C. becomes low, which is not suitable as a sealant film.
- the range of the average length RSm of the surface roughness element of the heat seal layer is more preferably 19 ⁇ m or more and 28 ⁇ m or less, and further preferably 20 ⁇ m or more and 27 ⁇ m or less.
- the sealant film of the present invention preferably has a dynamic friction coefficient between heat seal surfaces of 0.30 or more and 0.80 or less. If the coefficient of kinetic friction is less than 0.30, the film will slide too much, and the handling properties will deteriorate. On the other hand, when the coefficient of kinetic friction exceeds 0.80, wrinkles are likely to occur when the film is wound on a roll due to poor slipperiness, and the winding quality may be degraded.
- the range of the dynamic friction coefficient of the heat seal layer is more preferably 0.35 or more and 0.75 or less, and further preferably 0.40 or more and 0.70 or less.
- Non-Patent Document 1 introduces that by introducing an oxygen-containing group by surface treatment, the bias of the charge density is increased, the intermolecular force and the strength are increased, and the adhesive force can be improved. This is because it is said that adhesion centering on plastics occurs by bonding by intermolecular force.
- the sealant film of the present invention it is considered that the higher the abundance ratio of oxygen atoms on the surface of the heat seal layer, the larger the bias of the charge density, and thus the higher the heat seal strength at 120 ° C. Therefore, when the abundance ratio of oxygen atoms on the surface of the heat seal layer is less than 26.6%, the heat seal strength at 120 ° C. becomes small, and the heat seal strength becomes insufficient during high-speed automatic filling and packaging. Further, when the abundance ratio of oxygen atoms on the surface of the heat seal layer exceeds 31.0%, the bias of the charge density is large, and the film easily adheres at room temperature. Can not be rolled up.
- the range of the abundance ratio of oxygen atoms on the surface of the heat seal layer is more preferably 26.7% or more and 30.5% or less, further preferably 26.8% or more and 30.0% or less.
- wet tension of heat seal layer surface In the sealant film of the second invention of the present application, it is preferable that the wetting tension on the surface of the heat sealing layer is 38 mN / m or more and 55 mN / m or less. The higher the proportion of oxygen atoms present on the surface of the heat seal layer, the higher the wetting tension on the surface of the heat seal layer and the higher the heat seal strength at 120 ° C. When the wetting tension on the surface of the heat seal layer is less than 38 mN / m, the heat seal strength at 120 ° C. is low, and the heat seal strength is insufficient during high-speed automatic filling and packaging.
- the wetting tension on the surface of the heat sealing layer exceeds 55 mN / m, the films wound on the rolls are blocked from each other, and the film cannot be wound smoothly.
- the range of the wetting tension on the surface of the heat seal layer is more preferably from 39 mN / m to 54 mN / m, and further preferably from 40 mN / m to 53 mN / m.
- the sealant film of the present invention preferably has a hot water heat shrinkage rate of 0% or more and 10% or less in a width direction and a longitudinal direction when treated in hot water of 80 ° C. for 10 seconds.
- a hot water heat shrinkage rate of 0% or more and 10% or less in a width direction and a longitudinal direction when treated in hot water of 80 ° C. for 10 seconds.
- the upper limit of the heat shrinkage is more preferably 9% or less, and further preferably 8% or less.
- the sealant film of the present invention preferably has a haze of 0% or more and less than 10%. If the haze is 10% or more, the transparency is impaired, and the content is difficult to visually recognize when used as a packaging bag, which is not preferable.
- the upper limit of the haze is more preferably 9% or less, and further preferably 8% or less.
- the thickness of the sealant film of the present invention is not particularly limited, but is preferably 3 ⁇ m or more and 200 ⁇ m or less. When the thickness of the film is less than 3 ⁇ m, it is not preferable because the heat sealing strength may be insufficient and processing such as printing may be difficult. Although the film thickness may be greater than 200 ⁇ m, it is not preferable because the use weight of the film increases and the chemical cost increases. The thickness of the film is more preferably 5 ⁇ m or more and 160 ⁇ m or less, and still more preferably 7 ⁇ m or more and 120 ⁇ m or less.
- the sealant film of the present invention may be a single layer consisting of only the heat-seal layer, or may be a laminate structure of two or more layers. However, since the heat sealability and the heat resistance have a trade-off relationship, in the first invention of the present application, a layer other than the heat seal layer (hereinafter referred to as a heat resistant layer) is maintained while maintaining the heat sealability of the heat seal layer at 140 ° C. In some cases, the heat-sealing property can be increased, so that the laminated structure is preferable. In the second invention of the present application, the heat-sealing layer is heated at 120 ° C.
- a laminated structure is preferable.
- a preferred lamination structure is a structure having a heat seal layer on at least a surface layer on one surface of the film, and examples thereof include a two-layer structure of a heat seal layer / a heat-resistant layer, and a three-layer structure of a heat seal layer / a heat-resistant layer / a heat seal layer. And a two-layer structure of a heat seal layer / a heat resistant layer is more preferable.
- the layer ratio of the heat seal layer is preferably 20% or more and 80% or less.
- the layer ratio of the heat seal layer is less than 20%, the heat seal strength of the film is undesirably reduced.
- the layer ratio of the heat sealing layer is higher than 80%, the heat sealing property of the film is improved, but the heat resistance is undesirably reduced.
- the layer ratio of the heat seal layer is more preferably 30% or more and 70% or less.
- the heat seal layer must be on at least one surface layer of the film surface.
- a Kochi method such as a method of forming an in-line film by coextrusion or a method of laminating by laminating after film formation can be used.
- the former method includes co-extrusion using a multi-manifold T-die or an inflation method, and the latter method includes extrusion lamination, wet or dry lamination, and adhesion by hot melt.
- dry lamination a commercially available adhesive for dry lamination can be used.
- the heat seal layer may be any of non-stretched, uniaxially stretched, and biaxially stretched, but is preferably stretched in at least one direction (uniaxially stretched) from the viewpoint of strength, and is preferably biaxially stretched. Is more preferred. A preferred production method for biaxial stretching will be described later.
- the sealant film of the first invention of the present application can be provided with a layer subjected to a coating treatment or a flame treatment, regardless of the heat seal layer or other layers. You can go. However, it is preferable that the corona treatment and the plasma treatment are not performed on the heat seal layer because there is a concern that the heat seal strength at 100 ° C. becomes 5 N / 15 mm or more.
- the sealant film of the second invention of the present application can be provided with a layer subjected to a corona treatment, a plasma treatment, a coating treatment, a flame treatment, etc., regardless of a heat seal layer or other layers, and the deposition of an inorganic substance or the like. You can go. Since the corona treatment and the plasma treatment can increase the abundance ratio of oxygen atoms on the surface, it is preferably performed on the surface of the heat seal layer. Particularly, corona treatment is preferable.
- the sealant film of the present invention may have a configuration of three or more layers having at least one inorganic thin film layer for the purpose of improving the barrier properties in addition to the heat seal layer and the heat resistant layer. Good.
- gas barrier properties can be imparted.
- the inorganic thin film layer and the heat-resistant layer may be located at any positions, but the heat-sealing layer needs to be the outermost layer in order to develop necessary heat-sealing strength.
- the preferred order of the layers is such that both outermost layers are a seal layer and an inorganic thin film layer, and a heat-resistant layer is provided in the middle.
- the layer configuration of the laminate may include one or more layers other than the heat seal layer, the heat resistant layer, and the inorganic thin film layer.
- Specific examples include an anchor coat layer provided below the inorganic thin film layer, an overcoat layer provided on the inorganic thin film layer, and a resin layer (film) other than the resin layer constituting the sealant film of the present invention.
- the thickness of the inorganic thin film layer is preferably 2 nm or more and 100 nm or less (the thickness ratio of the inorganic thin film layer to the total thickness of the laminate is so small as to be negligible). If the thickness of the inorganic thin film layer is less than 2 nm, it is difficult to satisfy the gas barrier property, which is not preferable. On the other hand, if the thickness of the inorganic thin film layer exceeds 100 nm, there is no effect of improving the gas barrier property corresponding thereto, and the production cost increases, which is not preferable.
- the thickness of the inorganic thin film layer is more preferably 5 nm or more and 97 nm or less, and even more preferably 8 nm or more and 94 nm or less.
- the sealant film of the present invention needs to have at least one heat-sealing layer made of a polyester-based component, and the polyester-based component of the heat-sealing layer contains oxygen per unit of ester unit. It is preferable that the number of atoms is 2 or more and 6 or less.
- a polyester raw material containing ethylene terephthalate as a main component is preferable.
- “to be a main constituent” means that the content is 50% by mole or more when the total amount of the constituents is 100% by mole.
- the polyester used in the present invention contains, as a component other than the ethylene terephthalate unit, at least one monomer component that can be an amorphous component (hereinafter simply referred to as an amorphous component).
- an amorphous component a monomer component that can be an amorphous component
- the monomer of the dicarboxylic acid component that can be an amorphous component include, for example, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid.
- Examples of the monomer of the diol component which can be an amorphous component include neopentyl glycol, 1,4-cyclohexanedimethanol, diethylene glycol, 2,2-diethyl-1,3-propanediol, 2-n-butyl-2-ethyl Examples thereof include 1,3-propanediol, 2,2-isopropyl-1,3-propanediol, 2,2-di-n-butyl-1,3-propanediol, and hexanediol.
- amorphous dicarboxylic acid components and diol components it is preferable to use isophthalic acid, neopentyl glycol, 1,4-cyclohexanedimethanol, and diethylene glycol. By using these components, the amorphous property of the film is increased, and the heat sealing strength is easily improved.
- components other than ethylene terephthalate and amorphous components may be contained.
- the dicarboxylic acid component constituting the polyester include aromatic dicarboxylic acids such as orthophthalic acid, adipic acid, azelaic acid, sebacic acid, aliphatic dicarboxylic acids such as decanedicarboxylic acid, and alicyclic dicarboxylic acids.
- aromatic dicarboxylic acids such as orthophthalic acid, adipic acid, azelaic acid, sebacic acid
- aliphatic dicarboxylic acids such as decanedicarboxylic acid
- alicyclic dicarboxylic acids alicyclic dicarboxylic acids.
- trivalent or higher polycarboxylic acids for example, trimellitic acid, pyromellitic acid and anhydrides thereof
- examples of the components constituting the polyester include long-chain diols such as 1,4-butanediol, aliphatic diols such as hexanediol, and aromatic diols such as bisphenol A. Among them, it is preferable to contain 1,4-butanediol. Further, as a component constituting the polyester, a polyester elastomer containing ⁇ -caprolactone, tetramethylene glycol, or the like may be included. Since these components have an effect of lowering the melting point of the film, they are preferable as components of the heat seal layer.
- a diol having 8 or more carbon atoms for example, octanediol
- a polyhydric alcohol having 3 or more valencies for example, trimethylolpropane, trimethylolethane, glycerin, diglycerin, etc.
- a diol having 8 or more carbon atoms for example, octanediol
- a polyhydric alcohol having 3 or more valencies for example, trimethylolpropane, trimethylolethane, glycerin, diglycerin, etc.
- various additives for example, waxes, antioxidants, antistatic agents, crystal nucleating agents, thickeners, heat stabilizers, coloring pigments, coloring prevention Agents, ultraviolet absorbers and the like can be added.
- fine particles as a lubricant for improving the slip property of the film to at least the surface layer of the film.
- Any fine particles can be selected.
- inorganic fine particles include silica, alumina, titanium dioxide, calcium carbonate, kaolin, barium sulfate and the like
- organic fine particles include acrylic resin particles, melamine resin particles, silicone resin particles, cross-linked polystyrene. And the like.
- the average particle diameter of the fine particles can be appropriately selected as needed within the range of 0.05 to 3.0 ⁇ m as measured by a Coulter counter.
- these fine particles it is preferable to add silica and calcium carbonate in order to achieve both slipperiness and transparency of the film, and silica is particularly preferable.
- the preferable addition amount varies depending on the type of the fine particles to be added, and cannot be uniquely determined.
- the addition amount is preferably 200 ppm or more and 1000 ppm or less, more preferably 300 ppm or more and 900 ppm or less, and more preferably 400 ppm or more. 800 ppm or less is more preferable. If the added amount of silica is less than 200 ppm, the sliding property cannot be sufficiently improved. On the other hand, if the amount of silica exceeds 1000 ppm, the haze is undesirably high.
- a method of blending particles in the sealant film of the present invention for example, it can be added at any stage of producing a polyester-based resin, but after the esterification stage or the end of the transesterification reaction, the polycondensation reaction starts. It is preferable to add as a slurry dispersed in ethylene glycol or the like in the previous step to advance the polycondensation reaction. Also, a method of blending a slurry of particles dispersed in ethylene glycol, water, or another solvent with a polyester resin raw material using a vented kneading extruder, or a method of kneading and extruding dried particles and a polyester resin raw material. And a method of blending using a machine.
- the same polyester as the heat seal layer can be used as a raw material type for layers other than the heat seal layer.
- a polyester having a composition different from that of the heat seal layer can be provided by using a polyester made of a suitable component for the heat seal layer.
- the polyester used for the heat seal layer of the present invention has a content of a dicarboxylic acid monomer and / or a diol monomer other than terephthalic acid and ethylene glycol constituting ethylene terephthalate of 20 mol% or more. Is preferably 25 mol% or more, and particularly preferably 30 mol% or more. As the amount of the amorphous component increases, the density decreases and the heat seal strength is easily improved. Further, the upper limit of the content of the monomer which is a component other than the ethylene terephthalate is 50 mol%.
- the monomer which is a component other than ethylene terephthalate contained in the heat seal layer is lower than 30 mol%, even if the molten resin is extruded from a die and solidified rapidly, it is crystallized in a subsequent stretching and heat fixing step. It is not preferable because it becomes difficult to make the heat seal strength at 140 ° C. 8 N / 15 mm or more.
- the amount of the monomer which is a component other than ethylene terephthalate contained in the heat seal layer is 50 mol% or more, the heat resistance of the heat seal layer becomes extremely low. (Phenomenon of sealing in a wider range than intended due to heat conduction from the heating member), which makes it difficult to perform appropriate heat sealing.
- the content of the monomer which is a component other than ethylene terephthalate is more preferably 48 mol% or less, and particularly preferably 46% or less.
- the polyester used for the heat resistant layer is a dicarboxylic acid monomer and / or a diol monomer which are components other than terephthalic acid and ethylene glycol constituting ethylene terephthalate.
- the content is preferably at least 9 mol%, more preferably at least 10 mol%, particularly preferably at least 11 mol%.
- the upper limit of the content of the monomer other than the ethylene terephthalate is 20 mol%.
- the monomer which is a component other than the ethylene terephthalate contained in the heat resistant layer is 20 mol% or more, heat resistance of the laminate is deteriorated such that holes are generated by heat applied at the time of heat sealing.
- the content of the monomer which is 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 the curl, in addition to the amount of each of the above-described layers alone, is such that the difference between the sealing layer and the heat-resistant layer is not less than 10 mol% and not more than 45 mol%. More preferably, it is 11 mol% or more and 44 mol% or less.
- the raw material type of the inorganic thin film layer is not particularly limited, and a conventionally known material can be used. In order to satisfy the above, it can be appropriately selected according to the purpose.
- the raw material species of the inorganic thin film layer include metals such as silicon, aluminum, tin, zinc, iron, and manganese, and inorganic compounds containing at least one of these metals. Materials, carbides, fluorides and the like. These inorganic substances or inorganic compounds may be used alone or in combination.
- the component of the inorganic compound is a binary of silicon oxide and aluminum oxide
- the content of aluminum oxide is preferably from 20% by mass to 80% by mass, and more preferably from 25% by mass to 70% by mass.
- the content of aluminum oxide is 20% by mass or less, the density of the inorganic thin film layer is decreased, and the gas barrier property may be undesirably reduced.
- the content of aluminum oxide is 80% by mass or more, the flexibility of the inorganic thin film layer is reduced, and cracks are easily generated. As a result, the gas barrier property may be reduced, which is not preferable.
- the oxygen / metal element ratio of the metal oxide used in the inorganic thin film layer is preferably 1.3 or more and less than 1.8, since there is little variation in gas barrier properties and excellent gas barrier properties can always be obtained.
- the oxygen / metal element ratio can be determined by measuring the amounts of oxygen and metal elements by X-ray photoelectron spectroscopy (XPS) and calculating the oxygen / metal element ratio.
- the sealant film of the present invention is characterized in that the above-mentioned 3.
- the polyester raw material described in the “raw material constituting the sealant film” is melt-extruded with an extruder to form an unstretched laminated film, which is obtained by uniaxially or biaxially stretching the film by a predetermined method described below. be able to. Films obtained by biaxial stretching are more preferred.
- the polyester can be obtained by selecting the types and amounts of the dicarboxylic acid component and the diol component and subjecting them to polycondensation so as to contain an appropriate amount of a monomer that can be a component other than ethylene terephthalate.
- two or more kinds of polyester chips may be mixed and used as a raw material of the film.
- the raw material resin is melt-extruded, it is preferable to dry the polyester raw material of each layer using a drier such as a hopper drier or a paddle drier, or a vacuum drier. After the polyester raw material of each layer is dried as described above, it is melted at a temperature of 200 to 300 ° C. using an extruder and extruded as a film.
- a drier such as a hopper drier or a paddle drier, or a vacuum drier.
- the polyester raw material of each layer is dried as described above, it is melted at a temperature of 200 to 300 ° C. using an extruder and extruded as a film.
- any existing method such as a T-die method and a tubular method can be adopted.
- the film melted by extrusion is quenched to obtain an unstretched film.
- a method of rapidly cooling the molten resin a method of casting a molten resin from a die on a rotating drum and rapidly cooling and solidifying the molten resin to obtain a substantially unoriented resin sheet can be suitably adopted.
- the film is stretched in at least one of the longitudinal (longitudinal) direction and the transverse (width) direction, that is, uniaxial stretching or biaxial stretching.
- a sequential biaxial stretching method by longitudinal stretching in which longitudinal stretching is performed first, and then transverse stretching, followed by transverse stretching, will be described.
- transverse stretching in which the order is reversed
- the main orientation direction is not changed. It doesn't matter as it just changes.
- a simultaneous biaxial stretching method may be used.
- the longitudinal stretching may be performed by introducing a non-stretched film into a longitudinal stretching machine in which a plurality of roll groups are continuously arranged.
- the film temperature is lower than 65 ° C., it is difficult to stretch the film in the longitudinal direction, and the film is easily broken.
- the temperature is higher than 90 ° C., the film is likely to stick to the roll, and the film is easily wound around the roll and the roll is liable to be stained by continuous production, which is not preferable.
- longitudinal stretching is performed.
- the longitudinal stretching ratio is preferably from 1 to 5 times. Since 1 time means that the film is not stretched longitudinally, the longitudinal stretching ratio is 1 time in order to obtain a transversely uniaxially stretched film and 1.1 times or more in order to obtain a biaxially stretched film.
- the upper limit of the longitudinal stretching ratio may be any number. However, if the longitudinal stretching ratio is too high, transverse stretching becomes difficult and breakage easily occurs, so that the upper limit is preferably 5 times or less.
- the relaxation rate in the longitudinal direction is 0% or more and 70% or less (a relaxation rate of 0% indicates that relaxation is not performed). Since the upper limit of the relaxation rate in the longitudinal direction is determined by the raw material used and the longitudinal stretching conditions, relaxation cannot be performed beyond this.
- the upper limit of the relaxation rate in the longitudinal direction is 70%.
- Relaxation in the longitudinal direction can be performed by heating the longitudinally stretched film at a temperature of 65 ° C. to 100 ° C. or less and adjusting the difference in roll speed.
- the heating means any of a roll, near-infrared ray, far-infrared ray, hot air heater, and the like can be used.
- the relaxation in the longitudinal direction can be performed not only immediately after the longitudinal stretching but also in the transverse stretching (including the preheating zone) or the final heat treatment by narrowing the clip interval in the longitudinal direction (in this case, both ends in the film width direction). Is also relaxed in the longitudinal direction, thereby reducing the bowing distortion), and can be performed at any timing.
- Lateral Stretching After longitudinal stretching, it is preferable to carry out lateral stretching at 65 ° C. to 110 ° C. with a stretching ratio of about 3 to 5 times while holding both ends in the width direction of the film in a tenter with clips. It is preferable to perform preheating before stretching in the transverse direction, and it is preferable to perform preheating until the film surface temperature becomes 75 to 120 ° C.
- the film after the transverse stretching is passed through an intermediate zone in which no active heating operation is performed. Since the temperature is higher in the final heat treatment zone next to the transverse stretching zone of the tenter, if no intermediate zone is provided, the heat of the final heat treatment zone (hot air itself or radiant heat) flows into the transverse stretching step. In this case, since the temperature in the transverse stretching zone is not stable, not only the thickness accuracy of the film is deteriorated, but also the physical properties such as the heat seal strength and the shrinkage ratio vary. Therefore, it is preferable that the film after the transverse stretching is passed through the intermediate zone and a predetermined time has elapsed, and then subjected to the final heat treatment.
- the intermediate zone when a strip-shaped piece of paper is hung in a state where the film is not passed through, the wrapping flow accompanying the film running, the lateral stretching zone and the final stretching so that the piece of paper dangles almost completely in the vertical direction. It is important to block out hot air from the heat treatment zone. A transit time of about 1 second to 5 seconds is sufficient. If it is shorter than 1 second, the length of the intermediate zone will be insufficient, and the heat blocking effect will be insufficient. On the other hand, it is preferable that the intermediate zone is long, but if it is too long, the equipment becomes large, so that about 5 seconds is sufficient.
- heat treatment is preferably performed in the final heat treatment zone at a stretching temperature or higher and 250 ° C. or lower.
- the heat shrinkage of the film can be reduced by performing the heat treatment, the effect as the heat treatment is not exhibited unless the film is at or above the stretching temperature.
- the shrinkage ratio of the film in hot water at 80 ° C. becomes higher than 10%, and wrinkles are likely to be formed during heat sealing, which is not preferable.
- the higher the heat treatment temperature the lower the shrinkage of the film, but if it is higher than 250 ° C., the haze of the film will be higher than 15%, or the film will melt and fall into the tenter during the final heat treatment step. Therefore, it is not preferable.
- the range of the heat treatment temperature is more preferably from 120 ° C to 240 ° C, and particularly preferably from 150 ° C to 220 ° C.
- the melting of the heat sealing layer smoothes the surface and increases the average length RSm of the element of the surface roughness of the heat sealing layer. Therefore, as the heat treatment temperature increases, the heat seal strength at 100 ° C. increases, and the slip property deteriorates.
- the average length RSm of the elements of the 140 ° C. heat seal strength and the surface roughness of the heat seal layer is determined not only by the heat treatment temperature but also by the component amount of the raw material of the heat seal layer, the longitudinal stretching conditions, and the transverse stretching conditions. Therefore, the preferable range of the heat treatment temperature cannot be unambiguously determined.
- the heat treatment temperature is preferably 170 ° C. or more and 210 ° C. or less, and 180 ° C. or more and 200 ° C. The following is more preferred. If the heat treatment temperature is lower than 170 ° C., the heat seal strength at 140 ° C. becomes insufficient, which is not preferable. On the other hand, when the heat treatment temperature exceeds 210 ° C., the heat seal strength at 100 ° C. becomes high, and the slipperiness is deteriorated.
- the shrinkage in the width direction can be reduced by reducing the distance between the clips of the tenter by an arbitrary magnification (relaxation in the width direction). Therefore, in the final heat treatment, it is preferable to perform relaxation in the width direction in a range of 0% or more and 10% or less (a relaxation rate of 0% indicates that relaxation is not performed).
- a relaxation rate of 0% indicates that relaxation is not performed.
- the upper limit of the relaxation rate in the width direction is 10%.
- the passage time of the final heat treatment zone is preferably 2 seconds or more and 20 seconds or less. If the passage time is less than 2 seconds, the film passes through the heat treatment zone without reaching the set temperature, so that the heat treatment becomes meaningless. Since the effect of the heat treatment increases as the passage time increases, it is preferably at least 2 seconds, more preferably at least 5 seconds. However, if the transit time is to be lengthened, the equipment becomes huge, so that practically 20 seconds or less is sufficient.
- the film is preferably cooled in a cooling zone with a cooling air having a temperature of 10 ° C or more and 30 ° C or less. At this time, it is preferable to improve the cooling efficiency by lowering the temperature of the cooling air or increasing the wind speed so that the actual temperature of the film at the exit of the tenter is lower than the glass transition temperature of the heat seal layer.
- the actual temperature is a film surface temperature measured by a non-contact radiation thermometer. If the actual temperature of the film at the exit of the tenter exceeds the glass transition temperature, the film shrinks when both ends of the film held by the clip are released, which is not preferable.
- the passage time of the cooling zone is preferably from 2 seconds to 20 seconds. If the passage time is less than 2 seconds, the film passes through the cooling zone without reaching the glass transition temperature. The longer the passage time, the more the cooling effect increases. Therefore, the passage time is preferably 2 seconds or more, and more preferably 5 seconds or more. However, if the transit time is to be lengthened, the equipment becomes huge, so that practically 20 seconds or less is sufficient. Thereafter, if the film is wound up while cutting and removing both ends of the film, a sealant film roll is obtained.
- Corona treatment In the second invention of the present application, it is preferable that after cooling, the surface of the heat seal layer is subjected to corona treatment by a corona treatment device.
- the degree of corona treatment is determined by the line speed of the sealant film, the corona treatment voltage, and the roll temperature. Therefore, these preferable condition ranges cannot be unambiguously determined.
- the oxygen atom abundance ratio on the heat seal layer surface is reduced to 26 mN / m. It can be higher than 0.5%.
- the corona treatment is preferably performed in air.
- the sealant film of the present invention has a feature of hardly adsorbing organic compounds contained in chemical products, pharmaceuticals, foods, and the like, and is preferable for packaging of contents described later.
- the contents include d-limonene, citral, citronellal, p-menthane, pinene, terpinene, myrcene, caren, geraniol, nerol, citronellal, terpineol, l-menthol, nerolidol, borneol, dl-camphor, lycopene, Carotene, trans-2- Hexenal, cis-3-hexenol, ⁇ -ionone, selinene, 1-octen-3-ol, Aroma components and medicinal components such as benzyl alcohol, octal tulobuterol hydrochloride, and tocopherol acetate are exemplified.
- the sealant film of the present invention has a heat seal layer made of a polyester component, and the polyester component of the heat seal layer contains 2 to 6 oxygen atoms per ester unit, In the contents having a similar chemical structure containing many oxygen atoms, the adsorptivity tends to increase.
- the ratio of the number of oxygen atoms / carbon atoms in the contents is proportional to the amount of adsorption of the sealant film of the present invention, and the contents in which the ratio of oxygen atoms / carbon atoms in the contents is 0.2 or more, such as eugenol
- the sealant film of the present invention is not suitable for packaging of contents such as methyl salicylate and the like.
- the preferred range of adsorption is in 10 [mu] g / cm 2 or less, more preferably 6 [mu] g / cm 2 or less, 2 [mu] g / cm 2 or less is more preferred.
- the sealant film of the present invention can be suitably used as a package.
- the sealant of the present invention can be made into a bag alone, it may be made into a laminate in which other materials are laminated.
- a non-stretched film containing polyethylene terephthalate as a component a non-stretched film containing another amorphous polyester as a component, a uniaxially or biaxially stretched film, and nylon as a component.
- examples include, but are not limited to, non-stretched, uniaxially or biaxially stretched films, and non-stretched, monoaxially or biaxially stretched films containing polypropylene as a component.
- the method of using the sealant for the package is not particularly limited, and a conventionally known manufacturing method such as a coating method, a laminating method, or a heat sealing method can be employed.
- At least a part of the package may be made of the sealant according to the present invention, but a structure in which the above-described sealant is present in the entire package is preferable. Further, the package may have the sealant of the present invention in any layer.However, in consideration of the non-adhesiveness to the contents and the sealing strength at the time of bag making, the heat seal layer of the sealant of the present invention Is preferably the innermost layer.
- the package having the sealant of the present invention can be suitably used as a packaging material for various articles such as foods, pharmaceuticals, and industrial products.
- the evaluation method of the film is as follows. In the case where the longitudinal direction and the width direction cannot be immediately specified due to a small area of the film or the like, the longitudinal direction and the width direction may be temporarily determined and the measurement may be performed. A difference of 90 degrees does not cause any problem.
- the heat seal strength was measured according to JIS Z1707. The specific procedure will be briefly described. Using a heat sealer, the heat-sealed surfaces of the samples that had not been subjected to a coating process or the like were bonded to each other. The heat sealing conditions were a heat seal width of 10 mm, an upper bar temperature of 100 ° C., a lower bar temperature of 30 ° C., a pressure of 0.2 MPa, and a time of 2 seconds. The bonded sample was cut out so as to have a seal width of 15 mm. The peel strength was measured using a universal tensile tester “DSS-100” manufactured by Shimadzu Corporation at a tensile speed of 200 mm / min. The peel strength is shown as a strength per 15 mm (N / 15 mm).
- the film was cut into a square of 10 cm ⁇ 10 cm, and two sheets were overlapped with the heat-sealed surface facing inside, and a position 1 cm from the end of the film was heat-sealed to form a bag.
- An aluminum cup containing 0.5 ml of the contents was placed in the bag, and a position 1 cm from the end of the film was heat-sealed to close and close the bag.
- D-limonene manufactured by Tokyo Chemical Industry Co., Ltd.
- D-camphor manufactured by Nakarai Tesque Co., Ltd.
- the gas chromatograph uses "GC-14A Glass ID 2.6 ⁇ x1.1m PET-HT 5% Uniport HP 80/100 (manufactured by GL Sciences)" for the column, FID for the detector, and N 2 for the carrier gas.
- the amount was determined by the area percentage method at a carrier gas flow rate of 35 ml / min and an injection amount of 1 ⁇ l.
- the amount of adsorption was indicated by the amount of adsorption ( ⁇ g / cm 2 ) per 1 cm 2 of the heat-sealed surface, and the low adsorbability was determined as follows.
- Polyester (A) was obtained.
- This polyester (A) is polyethylene terephthalate.
- Table 1 shows the composition of the polyester (A).
- Polyesters (B) to (G) in which the monomer was changed were obtained in the same procedure as in Synthesis Example 1.
- Table 1 shows the composition of each polyester.
- TPA is terephthalic acid
- IPA is isophthalic acid
- EG is ethylene glycol
- BD is 1,4-butanediol
- NPG is neopentyl glycol
- CHDM is 1,4-cyclohexanedimethanol
- DEG diethylene glycol.
- SiO 2 SiO 2 (Silicia 266 manufactured by Fuji Silysia Ltd.) was added as a lubricant at a ratio of 7,000 ppm to the polyester.
- Each polyester was appropriately formed into a chip.
- the intrinsic viscosities of the respective polyesters are B: 0.73 dl / g, C: 0.69 dl / g, D: 0.73 dl / g, E: 0.74 dl / g, F: 0.80 dl / g, and G, respectively. : 0.75 dl / g.
- Table 1 shows the compositions of the polyesters (B) to (G).
- Polyester A, polyester B, polyester F, and polyester G are mixed at a mass ratio of 10: 60: 24: 6 as a raw material of the heat sealing layer, and polyester A, polyester B, polyester F, and polyester G are mixed as raw materials of the heat-resistant layer.
- the mixture was mixed at 51: 37: 6: 6.
- the mixed raw materials of the heat seal layer and the heat resistant layer were respectively charged into separate twin screw extruders, and were all melted at 270 ° 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. to obtain an unstretched laminated film.
- the flow path of the molten resin is set so that the laminated film has a heat-sealing layer on one side and a heat-resistant layer on the other side (a two-layer structure consisting of a heat-sealing layer and a heat-resistant layer), and the thickness ratio between the heat-sealing layer and the heat-resistant layer.
- 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 a preheating roll until the film temperature reaches 80 ° C., and then stretched 4.1 times. did.
- the film immediately after the longitudinal stretching was passed through a heating furnace set at 90 ° C.
- the film after the relaxation treatment was guided to a transverse stretching machine (tenter) and preheated for 5 seconds until the surface temperature reached 95 ° C., and then stretched 4.0 times in the width direction (lateral direction).
- the film after the transverse stretching was led to the intermediate zone as it was and passed in 1.0 second.
- hot air from the final heat treatment zone and the horizontal stretching zone are used so that when a strip of paper is hung in a state where the film is not passed, the paper hung almost completely in the vertical direction. From the hot air. Thereafter, the film passed through the intermediate zone was led to a final heat treatment zone, where it was heat-treated at 180 ° C. for 5 seconds.
- the film after passing through the final heat treatment zone is cooled and subjected to corona discharge treatment at room temperature by an in-line corona treatment device (manufactured by Kasuga Electric Co., Ltd.) at room temperature so that the wetting tension of the heat seal layer surface becomes 38 mN / m or more.
- the corona treatment power at that time was 1.8 kW.
- both edges were cut off and wound into a roll having a width of 500 mm, thereby continuously producing a biaxially stretched film having a thickness of 30 ⁇ m over a predetermined length.
- This film was used as Example 7.
- the properties of the obtained film were evaluated by the above methods.
- the production conditions and evaluation results are shown in Tables 2 and 3.
- Example 2 to 5 Comparative Examples 1 and 2
- a heat-sealing layer and a heat-resistant layer were laminated in the same manner as in Example 1, and a polyester-based sealant in which the mixing ratio of raw materials and final heat treatment conditions were variously changed was formed. evaluated.
- Table 2 shows film production conditions and evaluation results of each of the examples and comparative examples.
- Example 8 to 11 and Comparative Example 8 a heat seal layer and a heat-resistant layer were laminated in the same manner as in Example 7, and the mixing ratio of the raw materials, final heat treatment conditions, and corona treatment conditions (Comparative Example 8 without corona treatment) were used. Various modified polyester sealants were formed and evaluated. Table 3 shows film production conditions and evaluation results of each of the examples and comparative examples.
- Example 6 Polyester A, polyester B, polyester F, and polyester G were mixed at a mass ratio of 10: 60: 24: 6 as the raw material of the heat seal layer, and the subsequent steps were performed in the same manner as in Example 1 except that the final heat treatment temperature was reduced to 200 ° C. A 15 ⁇ m-thick polyester-based sealant film of only the changed layer A was formed. In addition, polyester A and polyester G were mixed at a mass ratio of 94: 6 as raw materials for the heat-resistant layer, and the subsequent steps were performed in the same manner as in Example 1 except that only the final heat treatment temperature was changed to 230 ° C. Was formed.
- the polyester-based sealant film of only the layer A is used as a heat-sealing layer
- the polyester-based film of only the layer B is used as a heat-resistant layer
- two films are used as an adhesive for dry lamination (Takelac (registered trademark) A-950, manufactured by Mitsui Chemicals, Inc.). And glued.
- Table 2 shows the manufacturing conditions and the evaluation results.
- Example 12 Polyester A, polyester B, polyester F, and polyester G are mixed at a mass ratio of 10: 60: 24: 6 as raw materials for the heat seal layer, and the subsequent steps are performed in the same manner as in Example 1 except that the final heat treatment temperature is 200 ° C. A polyester sealant film having only the layer A with the corona treatment power changed to 2.7 kW was formed. Polyester A and polyester G were mixed at a mass ratio of 94: 6 as raw materials for the heat-resistant layer, and the subsequent steps were the same as in Example 1 except that the final heat treatment temperature was changed to 230 ° C. Was formed.
- the polyester-based sealant film of only the layer A is used as a heat-sealing layer
- the polyester-based film of only the layer B is used as a heat-resistant layer
- two films are used as an adhesive for dry lamination (Takelac (registered trademark) A-950, manufactured by Mitsui Chemicals, Inc.). And glued.
- Table 3 shows the manufacturing conditions and evaluation results.
- Polyester A, polyester B, polyester F, and polyester G were mixed at a mass ratio of 5: 66: 24: 5 as a raw material of the heat seal layer, and the subsequent steps were performed in the same manner as in Example 1 except that the final heat treatment temperature was raised to 170 ° C.
- the changed polyester-based sealant having only the layer A was formed and evaluated. Table 2 shows the manufacturing conditions and the evaluation results.
- Polyester A and polyester G were mixed at a mass ratio of 94: 6 as a raw material of the heat seal layer, and the subsequent steps were performed in the same manner as in Example 1 except that only the final heat treatment temperature was changed to 230 ° C. A film was formed and evaluated. Table 2 shows the manufacturing conditions and the evaluation results.
- Comparative Example 5 Rix Film (registered trademark) L4102-25 ⁇ m manufactured by Toyobo Co., Ltd. was used. Table 2 shows the evaluation results.
- Comparative Example 6 Pyren Film-CT (registered trademark) P1128-25 ⁇ m manufactured by Toyobo Co., Ltd. was used. Table 2 shows the evaluation results.
- Polyester A, polyester B, polyester F, and polyester G are mixed at a mass ratio of 9: 75: 10: 6 as a raw material of the heat seal layer, and polyester A, polyester B, polyester F, and polyester G are mixed as a heat resistant material.
- the mixture was mixed at 47: 37: 10: 6.
- the flow path of the molten resin is set so that the surface of the laminated film becomes a heat-sealing layer and the inner layer becomes a heat-resistant layer (a heat-sealing layer / a heat-resistant layer / a heat-sealing layer).
- the polyester-based sealant in the same manner as in Example 1 except that the final heat treatment temperature was changed to 115 ° C. and the corona treatment was not performed by adjusting the discharge amount so that the ratio became 25:50:25. Films were evaluated. Table 3 shows the manufacturing conditions and evaluation results.
- Comparative Example 10 Rix Film (registered trademark) L4102-25 ⁇ m manufactured by Toyobo Co., Ltd. was used. Table 3 shows the evaluation results.
- Comparative Example 11 Pyrene Film-CT (registered trademark) P1128-25 ⁇ m manufactured by Toyobo Co., Ltd. was used. Table 3 shows the evaluation results.
- the surface is smoothed due to the melting of the heat seal layer during the final heat treatment, and the average length RSm of the surface roughness elements of the heat seal layer is increased. Therefore, the sealing strength at 100 ° C. is high, and the suitability for boiling in a packaging bag is poor.
- the coefficient of dynamic friction of the heat seal layer is high, wrinkles are likely to be generated when the film is wound around a roll, and the winding quality may be reduced.
- the film of Comparative Example 4 has a large density of 1.394 and low heat seal strength at 140 ° C., and thus is not suitable as a sealant film. Since the films of Comparative Examples 5 and 6 use olefin films, they are inferior in low adsorptivity.
- the film of Comparative Example 5 also has a low heat seal strength at 140 ° C.
- the films of Examples 7 to 12 all have a predetermined range of the oxygen atom abundance ratio on the surface of the heat seal layer, and have a heat seal strength of 120 ° C. and a heat seal strength of 140 ° C., a dynamic friction coefficient of the heat seal layer, It was excellent in haze, hot water shrinkage ratio at 80 ° C., and low adsorptivity, and the results of blocking evaluation and bag dropping evaluation were also good.
- the film of Comparative Example 7 is excellent in the heat seal strength at 140 ° C., the coefficient of kinetic friction of the heat seal layer, the haze, the shrinkage ratio of hot water at 80 ° C., the low adsorption property, and the suitability for boiling in a packaging bag. Since the abundance ratio of oxygen atoms on the surface was 26.5% or less, the heat seal strength at 120 ° C. was low, and the bag was easily broken in the dropping bag evaluation.
- the film of Comparative Example 8 has a low heat seal strength of 120 ° C. and a low heat seal strength of 140 ° C. since the abundance ratio of oxygen atoms on the surface of the heat seal layer is 26.5% or less, and thus is suitable as a sealant film. Absent.
- the film of Comparative Example 9 was excellent in heat seal strength at 120 ° C. because the abundance ratio of oxygen atoms on the surface of the heat seal layer was 31.0% or more, but the films blocked each other.
- the films of Comparative Examples 10 and 11 use olefin films, they are inferior in low adsorptivity.
- the film of Comparative Example 10 has a low heat seal strength of 140 ° C.
- the film of Comparative Example 11 has a low heat seal strength of 120 ° C.
- the first invention of the present application is a method in which components composed of various organic compounds are hardly adsorbed and have excellent heat sealing properties at 140 ° C., while having low heat sealing strength at 100 ° C. and used as a packaging bag to boil the contents in hot water. It is possible to provide a sealant film in which the heat seal layers are less likely to stick to each other even when warming.
- the second invention of the present application hardly adsorbs various organic compounds, is excellent in heat sealability at 140 ° C., and is also excellent in heat sealability at 120 ° C. at low temperature, so that it has sufficient heat seal strength even in high-speed automatic filling packaging.
- a sealant film can be provided.
- the present invention can be a laminate including at least one of the above-mentioned sealant films, and can be a packaging bag from such a laminate.
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Abstract
Description
しかし、特許文献1に記されているようなポリオレフィン系樹脂からなる無延伸のシーラントフィルムは、油脂や香料等の有機化合物からなる成分を吸着しやすいため、シーラントフィルムを最内層、すなわち内容物と接する層としている包装材は内容物の香りや味覚を変化させやすいという欠点を持っている。化成品、医薬品、食品等の包装袋の最内層としてポリオレフィン系樹脂からなるシーラント層を使用する場合、あらかじめ内容物の有効成分を多めに含ませる等の対策が必要であるため、使用に適さないケースが多い。
このような問題に鑑みて、特許文献3には有機化合物の非吸着性をもったシーラント用途のポリエステル系フィルムが開示されている。しかし、特許文献3のポリエステル系フィルムは100℃ヒートシール強度が高いため、包装袋として使用して内容物をお湯で茹でて温めようとした際に、最内層のヒートシール層同士が粘着しやすく包装袋を開封しにくくなる問題があった。
本願第一の発明は、100℃ヒートシール強度が低く包装袋として使用して内容物をお湯で茹でて温めようとした際もヒートシール層同士が粘着しにくい前記(A)のシーラントフィルムを提供するものである。
本願第二の発明は、低温の120℃ヒートシール性にも優れるため、高速自動充填包装でも十分なヒートシール強度を有する前記(A)のシーラントフィルムを提供するものである。
また、本発明は、前記の本願第一の発明又は本願第二の発明のシーラントフィルムを少なくとも一層として含む積層体、及びそれを用いた包装袋を提供しようとするものである。
本発明は、以下の構成よりなる。
1.少なくとも1層のポリエステル系成分からなるヒートシール層を有しており、以下(1)~(3)を満たすことを特徴とする低吸着性シーラントフィルム。
(1)ヒートシール層同士を100℃、0.2MPa、2秒間でシールしたときのシール強度が0N/15mm以上5N/15mm以下
(2)ヒートシール層同士を140℃、0.2MPa、2秒間でシールしたときのシール強度が8N/15mm以上30N/15mm以下
(3)全層を含んだフィルムの密度が1.20以上1.39未満
2.少なくとも1層のポリエステル系成分からなるヒートシール層を有しており、以下(4)~(6)を満たすことを特徴とする低吸着性シーラントフィルム。
(4)ヒートシール層同士を120℃、0.2MPa、2秒間でシールしたときのシール強度が4N/15mm以上15N/15mm以下
(5)ヒートシール層同士を140℃、0.2MPa、2秒間でシールしたときのシール強度が8N/15mm以上30N/15mm以下
(6)ヒートシール層において、X線電子分光法(ESCA)で求めた酸素原子の存在比率が26.6%以上31.0%以下
3.三次元粗さ計から求めた表面粗さの要素の平均長さRSmが18μm以上29μm以下である1.又は2.のいずれかに記載の低吸着性シーラントフィルム。
4.前記ヒートシール面同士の動摩擦係数が0.30以上0.80以下である1.~3.のいずれかに記載の低吸着性シーラントフィルム。
5.フィルムを構成する成分が、エチレンテレフタレートを主たる構成成分とするポリエステルからなる1.~4.のいずれかに記載の低吸着性シーラントフィルム。
6.ヒートシール層を構成するポリエステル系成分を構成するモノマーのうち、エチレングリコール以外のジオールモノマー成分を含有し、該ジオールモノマー成分がネオペンチルグリコール、1,4-シクロヘキサンジメタノール、1,4-ブタンジオール、ジエチレングリコールのいずれか1つ以上である1.~5.のいずれかに記載の低吸着性シーラントフィルム。
7.80℃温湯中で10秒間にわたって処理したときの熱収縮率が長手方向、幅方向いずれも0%以上10%以下である1.~6.のいずれかに記載の低吸着性シーラントフィルム。
8.前記1.~7.のいずれかに記載のシーラントフィルムを少なくとも1層は含むことを特徴とする積層体。
9.前記1.~7.のいずれかに記載のシーラントフィルム、又は8.に記載の積層体を少なくとも一部に用いたことを特徴とする包装袋。
さらに、前記の本願第一の発明又は第二の発明のシーラントフィルムを少なくとも一層として含む積層体と、それを用いた包装袋を提供できる。
(1)ヒートシール層同士を100℃、0.2MPa、2秒間でシールしたときのシール強度が0N/15mm以上5N/15mm以下
(2)ヒートシール層同士を140℃、0.2MPa、2秒間でシールしたときのシール強度が8N/15mm以上30N/15mm以下
(3)全層を含んだフィルムの密度が1.20以上1.39未満
以下、本発明のシーラントフィルムの特性、層構成、層比率、シーラントフィルムを構成する原料、シーラントフィルムの製造方法、内容物の種類、及び包装体の構成、製袋方法について詳述する。
1.1.100℃ヒートシール強度
本願第一の発明のシーラントフィルムは、ヒートシール層同士を温度100℃、シールバー圧力0.2MPa、シール時間2秒でヒートシールした際のヒートシール強度が0N/15mm以上5N/15mm以下である必要がある。
100℃ヒートシール強度が5N/15mmを超えると、包装袋として使用して内容物を温めようとした際に、最内層のヒートシール層同士が粘着しやすく、開封性が損なわれるため、包装袋として適さない。100℃ヒートシール強度は4.5N/15mm以下であるとより好ましく、4.0N/15mm以下であるとさらに好ましい。
本願第二の発明のシーラントフィルムは、ヒートシール層同士を温度120℃、シールバー圧力0.2MPa、シール時間2秒でヒートシールした際のヒートシール強度が4N/15mm以上15N/15mm以下である必要がある。
120℃ヒートシール強度が4N/15mm未満であると、高速自動充填包装時にヒートシール強度が不足するため、包装袋の生産性を高めることができない。120℃ヒートシール強度は大きいことが好ましいが、本発明の技術水準では現状得られる上限は15N/15mm程度であるが、実用上は十分である。120℃ヒートシール強度は5N/15mm以上であるとより好ましく、6N/15mm以上であるとさらに好ましい。
本発明のシーラントフィルムは、ヒートシール層同士を温度140℃、シールバー圧力0.2MPa、シール時間2秒でヒートシールした際のヒートシール強度が8N/15mm以上30N/15mm以下である必要がある。
140℃ヒートシール強度が8N/15mm未満であると、シール部分が容易に剥離されるため、包装袋として用いることが困難である。140℃ヒートシール強度は大きいことが好ましいが、本発明の技術水準では現状得られる上限は30N/15mm程度である。140℃ヒートシール強度は9N/15mm以上であるとより好ましく、10N/15mm以上であるとさらに好ましい。
本願第一の発明のシーラントフィルムは、全層を含んだフィルムの密度が1.20以上1.39未満である必要がある。全層を含んだフィルムの密度と吸着性および耐熱性、140℃ヒートシール強度は相関している。密度が高いほど低吸着性および耐熱性に優れたシーラントフィルムとなる。これは密度が高いほど結晶性が高い傾向にあり、結晶性が高いほど耐薬品性および耐熱性が高くなるためである。そのため、全層を含んだフィルムの密度が1.20未満であると、耐薬品性が悪くなるために吸着性が高くなり、かつ耐熱性が低くなってヒートシール時にフィルムに穴あきがしやすくなるため、包装袋として適さない。
また、密度が1.39以上となると低吸着性や耐熱性には優れるが、140℃のヒートシール性が損なわれるため、シーラントフィルムとして適さない。密度の範囲は1.25以上1.38以下であるとより好ましく、1.30以上1.37以下であるとさらに好ましい。
本発明のシーラントフィルムは、カットオフ0.250mm、測定速度0.2mm/秒
の条件で測定したヒートシール層の表面粗さの要素の平均長さRSmが18μm以上2
9μm以下であることが好ましい。ヒートシール層の表面粗さの要素の平均長さRSmは、100℃ヒートシール強度およびヒートシール面同士の動摩擦係数と相関している。ヒートシール層の表面粗さの要素の平均長さRSmが長いほど、ヒートシール面の凹凸が少なくなり平滑化するため、接触面積が大きくなって100℃ヒートシール強度が高くなり、ヒートシール面同士の動摩擦係数も高くなる。
ヒートシール層の表面粗さの要素の平均長さRSmが29μm以上であると、100℃ヒートシール強度が高くなり包装袋として使用して内容物を温めようとした際に、最内層のヒートシール層同士が粘着しやすく、開封性が損なわれるため、包装袋として適さない。一方、表面粗さの要素の平均長さRSmが18μm未満であると、ヒートシール面同士の接触面積が極端に小さくなるため、140℃シール強度が低くなり、シーラントフィルムとして適さない。ヒートシール層の表面粗さの要素の平均長さRSmの範囲は19μm以上28μm以下であるとより好ましく、20μm以上27μm以下であるとさらに好ましい。
本発明のシーラントフィルムは、ヒートシール面同士の動摩擦係数が0.30以上0.80以下であることが好ましい。
動摩擦係数が0.30未満であるとフィルムが滑りすぎてしまいハンドリング性が悪化する。一方、動摩擦係数が0.80を超えると、滑り性が悪いためにフィルムをロールに巻き取る際にシワが生じやすくなり巻き品質が下がるおそれがある。ヒートシール層の動摩擦係数の範囲は0.35以上0.75以下であるとより好ましく、0.40以上0.70以下であるとさらに好ましい。
本願第二の発明のシーラントフィルムは、ヒートシール層において、X線電子分光法(ESCA)で求めた酸素原子の存在比率が26.6%以上31.0%以下である必要がある。非特許文献1には表面処理で酸素含有基を導入することで、電荷密度の偏りが大きくなって分子間力や強くなり、接着力を向上させられることが紹介されている。これは、プラスチックを中心とした接着は分子間力による結合により起こるとされているためである。本発明のシーラントフィルムにおいても、ヒートシール層表面の酸素原子の存在比率が高いほど電荷密度の偏りも大きくなるため、120℃ヒートシール強度も強くなると考えられる。そのため、ヒートシール層表面の酸素原子の存在比率が26.6%未満であると、120℃ヒートシール強度が小さくなり、高速自動充填包装時にヒートシール強度が不足する。また、ヒートシール層表面の酸素原子の存在比率が31.0%を超えると、電荷密度の偏りが大きく常温下で密着しやすくなるため、ロールに巻き取ったフィルム同士がブロッキングし、フィルムをスムーズに巻きだせなくなる。ヒートシール層表面の酸素原子の存在比率の範囲は26.7%以上30.5%以下であるとより好ましく、26.8%以上30.0%以下であるとさらに好ましい。
本願第二の発明のシーラントフィルムは、ヒートシール層表面のぬれ張力が38mN/m以上55mN/m以下であることが好ましい。ヒートシール層表面の酸素原子の存在比率が高いほどヒートシール層表面のぬれ張力も高くなり、120℃ヒートシール強度が大きくなる。ヒートシール層表面のぬれ張力が38mN/m未満であると、120℃ヒートシール強度が小さくなり、高速自動充填包装時にヒートシール強度が不足する。一方、ヒートシール層表面のぬれ張力が55mN/mを超えると、ロールに巻き取ったフィルム同士がブロッキングし、フィルムをスムーズに巻きだせなくなる。ヒートシール層表面のぬれ張力の範囲は39mN/m以上54mN/m以下であるとより好ましく、40mN/m以上53mN/m以下であるとさらに好ましい。
本発明のシーラントフィルムは、80℃の温湯中に10秒間に亘って処理した場合における幅方向、長手方向の温湯熱収縮率がいずれも0%以上10%以下であることが好ましい。
熱収縮率が10%を超えると、フィルムをヒートシールしたときに収縮が大きくなり、シール後の平面性が悪化してしまう。一方、熱収縮率がゼロを下回る場合、フィルムが伸びることを意味しており、収縮率が高い場合と同様にフィルムが元の形状を維持できにくくなるため好ましくない。熱収縮率の上限は9%以下であるとより好ましく、8%以下であるとさらに好ましい。
本発明のシーラントフィルムは、ヘイズが0%以上10%未満であることが好ましい。ヘイズが10%以上であると、透明性が損なわれて包装袋として使用した際に内容物が視認しにくくなるため好ましくない。ヘイズの上限は9%以下であるとより好ましく、8%以下であるとさらに好ましい。
本発明のシーラントフィルムの厚みは特に限定されないが、3μm以上200μm以下が好ましい。
フィルムの厚みが3μmより薄いとヒートシール強度の不足や印刷等の加工が困難になるおそれがあるためあまり好ましくない。また、フィルム厚みが200μmより厚くても構わないが、フィルムの使用重量が増えてケミカルコストが高くなるので好ましくない。フィルムの厚みは5μm以上160μm以下であるとより好ましく、7μm以上120μm以下であるとさらに好ましい。
2.1.シーラントフィルムの層構成・ヒートシール層比率
本発明のシーラントフィルムは、ヒートシール層だけの単層であっても構わないし、2層以上の積層構成であっても構わない。ただし、ヒートシール性と耐熱性は二律背反の関係にあるため、本願第一の発明においてはヒートシール層の140℃ヒートシール性は保持したまま、ヒートシール層以外の層(以下、耐熱層と称する場合がある)で耐熱性を高めることができるので積層構成が好ましく、本願第二の発明においてはヒートシール層の120℃ヒートシール性は保持したまま、ヒートシール層以外の層で耐熱性を高めることができるので積層構成が好ましい。
好ましい積層構成は、ヒートシール層を少なくともフィルム片面の表層に有する構成であり、ヒートシール層/耐熱層の2層構成、ヒートシール層/耐熱層/ヒートシール層の3層構成等が挙げられるが、ヒートシール層/耐熱層の2層構成がより好ましい。
本発明のシーラントフィルムを積層構成にする場合は、ヒートシール層の層比率は、20%以上80%以下であることが好ましい。ヒートシール層の層比率が20%より少ない場合、フィルムのヒートシール強度が低下してしまうため好ましくない。ヒートシール層の層比率が80%よりも高くなると、フィルムのヒートシール性が向上するが、耐熱性が低下してしまうため好ましくない。ヒートシール層の層比率は、30%以上70%以下がより好ましい。
本発明のシーラントフィルムを積層構成とする場合は、ヒートシール層がフィルム面の少なくともどちらか一方の表層になければならない。フィルムを原料が樹脂である層(樹脂層)と積層するには、共押出しでインライン製膜する方法、製膜後に貼りあわせて積層する等、高知の方法を用いることができる。前者の方法にはマルチマニホールドTダイやインフレーション法による共押出し、後者の方法には押出ラミネート、ウェットまたはドライラミネート、ホットメルトによる接着等がある。ドライラミネートの場合は市販のドライラミネーション用接着剤を用いることができる。代表例としては、DIC社製ディックドライ(登録商標)LX-703VL、DIC社製KR-90、三井化学社製タケネート(登録商標)A-4、三井化学社製タケラック(登録商標)A-905などである。ヒートシール層は無延伸、一軸延伸、二軸延伸のいずれであっても構わないが、強度の観点からは少なくとも一方向に延伸されていること(一軸延伸)が好ましく、ニ軸延伸であることがより好ましい。ニ軸延伸の場合の好適な製造方法は後述する。
本願第一の発明のシーラントフィルムは、ヒートシール層、それ以外の層に関わらず、コーティング処理や火炎処理などを施した層を設けることが可能であり、無機物の蒸着等を行っても構わない。ただし、コロナ処理やプラズマ処理は100℃ヒートシール強度が5N/15mm以上となる懸念があるため、ヒートシール層には実施しないのが好ましい。
本願第二の発明のシーラントフィルムは、ヒートシール層、それ以外の層に関わらず、コロナ処理やプラズマ処理、コーティング処理、火炎処理などを施した層を設けることが可能であり、無機物の蒸着等を行っても構わない。コロナ処理とプラズマ処理は表面の酸素原子の存在比率を高めることが可能なため、ヒートシール層表面に実施するのが好ましい。特にコロナ処理が好ましい。
本発明のシーラントフィルムは、ヒートシール層と耐熱層以外にバリア性を向上させることを目的として、無機薄膜層を少なくとも1層は有した、3層以上の構成としてもよい。無機薄膜層を有することでガスバリア性を付与することができる。無機薄膜層と耐熱層は、どの位置にあっても構わないが、必要なヒートシール強度を発現させるためには、ヒートシール層を最外層にする必要がある。好ましい層の順番は、両最外層をシール層と無機薄膜層とし、耐熱層を中間に有した構成である。
また、積層体の層構成は、ヒートシール層と耐熱層と無機薄膜層以外の層を1つ以上有していても構わない。具体的には、無機薄膜層の下に設けるアンカーコート層、無機薄膜層の上に設けるオーバーコート層や、本発明のシーラントフィルムを構成する樹脂層以外の樹脂層(フィルム)等である。
3.1.シーラントを構成する原料の種類
本発明のシーラントフィルムは少なくとも1層のポリエステル系成分からなるヒートシール層を有している必要があり、前記ヒートシール層のポリエステル系成分はエステルユニット1単位あたりの酸素原子数が2個以上6個以下であることが好ましい。特にエチレンテレフタレートを主たる構成成分とするポリエステル原料が好ましい。ここで、「主たる構成成分とする」とは、全構成成分量を100モル%としたとき、50モル%以上含有することを指す。本発明に用いるポリエステルにエチレンテレフタレートユニット以外の成分として、非晶成分となりうる1種以上のモノマー成分(以下、単に非晶成分と記載する)を含むことが好ましい。これは、非晶成分の存在によりヒートシール強度が向上するためである。
非晶成分となりうるジカルボン酸成分のモノマーとしては、例えばイソフタル酸、1,4-シクロヘキサンジカルボン酸、2,6-ナフタレンジカルボン酸が挙げられる。
これらの非晶性ジカルボン酸成分、ジオール成分のうち、イソフタル酸、ネオペンチルグリコール、1,4-シクロヘキサンジメタノール、ジエチレングリコールを用いることが好ましい。これらの成分を用いることでフィルムの非晶性が高まり、ヒートシール強度を向上させやすくなる。
本発明のヒートシール層に用いるポリエステルは、エチレンテレフタレートを構成するテレフタル酸およびエチレングリコール以外の成分となるジカルボン酸モノマーおよび/又はジオールモノマーの含有量が20モル%以上であることが好ましく、25モル%以上がより好ましく、30モル%以上が特に好ましい。非晶成分が多いほど密度が低下し、ヒートシール強度を向上させやすくなる。また、前記エチレンテレフタレート以外の成分となるモノマー含有量の上限は50モル%である。
本発明のシーラントフィルムにおいて耐熱層を設ける場合、耐熱層に用いるポリエステルは、エチレンテレフタレートを構成するテレフタル酸およびエチレングリコール以外の成分となるジカルボン酸モノマーおよび/又はジオールモノマーの含有量が9モル%以上であることが好ましく、10モル%以上がより好ましく、11モル%以上が特に好ましい。また、前記エチレンテレフタレート以外の成分となるモノマー含有量の上限は20モル%である。
また、カールを制御するための前記エチレンテレフタレート以外の成分となるモノマー含有量は、上記の各層単体での量に加えて、シール層と耐熱層との差が10モル%以上45モル%以下であるとより好ましく、11モル%以上44モル%以下であるとさらに好ましい。
本発明のシーラントフィルムにおいて無機薄膜層を設ける場合、無機薄膜層の原料種は特に限定されず、従来から公知の材料を使用することができ、所望のガスバリア性等を満たすために目的に合わせて適宜選択することができる。無機薄膜層の原料種としては、例えば、ケイ素、アルミニウム、スズ、亜鉛、鉄、マンガン等の金属、これら金属の1種以上を含む無機化合物があり、該当する無機化合物としては、酸化物、窒化物、炭化物、フッ化物等が挙げられる。これらの無機物または無機化合物は単体で用いてもよいし、複数で用いてもよい。特に、酸化ケイ素、酸化アルミニウムを単体(一元体)または併用(二元体)で使用することにより、積層体の透明性を向上させることができるため好ましい。無機化合物の成分が酸化ケイ素と酸化アルミニウムの二元体からなる場合、酸化アルミニウムの含有量は20質量%以上80質量%以下であると好ましく、25質量%以上70質量%以下であるとより好ましい。酸化アルミニウムの含有量が20質量%以下の場合、無機薄膜層の密度が下がり、ガスバリア性が低下する恐れがあるため好ましくない。また、酸化アルミニウムの含有量が80質量%以上であると、無機薄膜層の柔軟性が低下してクラックが発生しやすくなり、結果としてガスバリア性が低下する恐れが生じるため好ましくない。
4.1.溶融押し出し
本発明のシーラントフィルムは、上記3.「シーラントフィルムを構成する原料」で記載したポリエステル原料を、押出機により溶融押し出しして未延伸の積層フィルムを形成し、それを以下に示す所定の方法により一軸延伸または二軸延伸することによって得ることができる。二軸延伸により得られたフィルムがより好ましい。なお、ポリエステルは、前記のように、エチレンテレフタレート以外の成分となり得るモノマーを適量含有するように、ジカルボン酸成分とジオール成分の種類と量を選定して重縮合させることで得ることができる。また、チップ状のポリエステルを2種以上混合してフィルムの原料として使用することもできる。
縦方向の延伸は、無延伸フィルムを複数のロール群を連続的に配置した縦延伸機へと導入するとよい。縦延伸にあたっては、予熱ロールでフィルム温度が65℃~90℃になるまで予備加熱することが好ましい。フィルム温度が65℃より低いと、縦方向に延伸する際に延伸しにくくなり、破断が生じやすくなるため好ましくない。また90℃より高いとロールにフィルムが粘着しやすくなり、ロールへのフィルムの巻き付きや連続生産によるロールの汚れやすくなるため好ましくない。
フィルム温度が65℃~90℃になったら縦延伸を行う。縦延伸倍率は、1倍以上5倍以下とすると良い。1倍は縦延伸をしていないということなので、横一軸延伸フィルムを得るには縦の延伸倍率を1倍に、二軸延伸フィルムを得るには1.1倍以上の縦延伸となる。また縦延伸倍率の上限は何倍でも構わないが、あまりに高い縦延伸倍率だと横延伸しにくくなって破断が生じやすくなるので5倍以下であることが好ましい。
縦延伸の後、テンター内でフィルムの幅方向の両端際をクリップによって把持した状態で、65℃~110℃で3~5倍程度の延伸倍率で横延伸を行うことが好ましい。横方向の延伸を行う前には、予備加熱を行っておくことが好ましく、予備加熱はフィルム表面温度が75℃~120℃になるまで行うとよい。
中間ゾーンの通過後は最終熱処理ゾーンにて、延伸温度以上250℃以下で熱処理を行うことが好ましい。熱処理を行うことでフィルムの熱収縮率を小さくすることができるが、延伸温度以上でなければ熱処理としての効果を発揮しない。この場合、フィルムの80℃温湯収縮率が10%よりも高くなり、ヒートシールを行う際にシワが入りやすくなってしまうため好ましくない。熱処理温度が高くなるほどフィルムの収縮率は低下するが、250℃よりも高くなるとフィルムのヘイズが15%よりも高くなったり、最終熱処理工程中にフィルムが融けてテンター内に落下してしまったりするため好ましくない。熱処理温度の範囲は120℃以上240℃以下がより好ましく、150℃以上220℃以下が特に好ましい。
最終熱処理通過後は冷却ゾーンにて、10℃以上30℃以下の冷却風でフィルムを冷却することが好ましい。このとき、テンター出口のフィルムの実温度が、ヒートシール層のガラス転移温度より低い温度になるよう、冷却風の温度を下げたり風速を上げたりして冷却効率を向上させることが好ましい。なお実温度とは、非接触の放射温度計で測定したフィルム表面温度のことである。テンター出口のフィルムの実温度がガラス転移温度を上回ると、クリップで把持していたフィルム両端部が解放されたときにフィルムが熱収縮するため好ましくない。
後は、フィルム両端部を裁断除去しながら巻き取れば、シーラントフィルムロールが得られる。
本願第二の発明において、冷却後はコロナ処理装置により、ヒートシール層表面をコロナ処理することが好ましい。コロナ処理度は、シーラントフィルムのライン速度やコロナ処理電圧、ロール温度によって決まる。そのため、これらの好ましい条件範囲を一義的に決めることはできないが、コロナ処理後のヒートシール層表面のぬれ張力を38mN/m以上とすることで、ヒートシール層表面の酸素原子の存在比率を26.5%よりも高くすることができる。また、コロナ処理は空気中で行うのが好ましい。
本発明のシーラントフィルムは化成品、医薬品、食品等に含まれる有機化合物を吸着しにくい特徴があり、後述する内容物の包装に好ましい。前記内容物としては、例えばd-リモネン、シトラール、シトロネラール、p-メンタン、ピネン、テルピネン、ミルセン、カレン、ゲラニオール、ネロール、シトロネラール、テルピネオール、l-メントール、ネロリドール、ボルネオール、dl-カンファー、リコピン、カロテン、トランス-2-
ヘキセナール、シス-3-ヘキセノール、β-イオノン、セリネン、1-オクテン-3-オール、
ベンジルアルコール、オクタールツロブテロール塩酸塩、酢酸トコフェロールなどの香気成分や薬効成分が挙げられる。
本発明のシーラントフィルムは、包装体として好適に使用することができる。本発明のシーラントは単独で袋にすることもできるが、他の材料を積層した積層体としてもよい。シーラントを構成する他の層としては、例えば、ポリエチレンテレフタレートを構成成分に含む無延伸フィルム、他の非晶性ポリエステルを構成成分に含む無延伸、一軸延伸または二軸延伸フィルム、ナイロンを構成成分に含む無延伸、一軸延伸または二軸延伸フィルム、ポリプロピレンを構成成分に含む無延伸、一軸延伸または二軸延伸フィルム等が挙げられるが、これらに限定されるものではない。包装体にシーラントを用いる方法は特に限定されず、塗布形成法、ラミネート法、ヒートシール法といった従来公知の製造方法を採用することができる。
本発明のシーラントを有する包装体は、食品、医薬品、工業製品等の様々な物品の包装材料として好適に使用することができる。
フィルムの評価方法は以下の通りである。なお、フィルムの面積が小さいなどの理由で長手方向と幅方向が直ちに特定できない場合は、仮に長手方向と幅方向を定めて測定すればよく、仮に定めた長手方向と幅方向が真の方向に対して90度違っているからといって、とくに問題を生ずることはない。
[密度]
JIS K7112に従って、フィルムを密度勾配液(硝酸カルシウム水溶液)に浸して求めた。
JIS B0601:2013に従って、小坂研究所社製の三次元微細形状測定器「ET4000A」を使用し、測定速度0.2mm/秒、カットオフ0.25mmの条件でヒートシール面を測定した。
JIS Z1707に準拠してヒートシール強度を測定した。具体的な手順を簡単に示
す。ヒートシーラーにて、サンプルのコート処理等を実施していないヒートシール面同士を接着した。ヒートシール条件は、ヒートシール幅10mm、上バー温度100℃、下バー温度30℃、圧力0.2MPa、時間2秒とした。接着サンプルは、シール幅が15mmとなるように切り出した。剥離強度は、島津製作所社製の万能引張試験機「DSS-100」を用いて引張速度200mm/分で測定した。剥離強度は、15mmあたりの強度(N/15mm)で示す。
上バー温度を120℃に変更した以外は100℃ヒートシール強度評価方法と同様に評価した。
上バー温度を140℃に変更した以外は100℃ヒートシール強度評価方法と同様に評価した。
JIS K7125に準拠し、引張試験機(ORIENTEC社製テンシロン)を用い
、23℃・65%RH環境下で、ヒートシール面同士を接合させた場合の動摩擦係数μdを求めた。なお、上側のフィルムを巻き付けたスレッド(錘)の重量は、1.5kgであり、スレッドの底面積の大きさは、縦63mm×横63mmであった。また、摩擦測定の際の引張速度は、200mm/min.であった。
Thermo Fisher Scientific社製のXPS分光計「K-Alpha+」を用いて、炭素、窒素、酸素、ケイ素のナロースキャンを行い、ヒートシール層表面の酸素原子の存在比率を評価した。励起X線にはモノクロ化AlKα線を用い、X線出力12kV、6mA、光電子脱出角度90°、スポットサイズ400μmφ、パスエネルギー50eV(ナロースキャン)、ステップ0.1eV(ナロースキャン)で評価した。
JIS K6768:1999に従って、ヒートシール層表面のぬれ張力を評価した。
JIS-K-7136に準拠し、ヘイズメータ(日本電色工業株式会社製、300A)を用いて測定した。なお、測定は2回行い、その平均値を求めた。
フィルムを10cm×10cmの正方形に裁断し、80±0.5℃の温水中に無荷重状態で10秒間浸漬して収縮させた後、25℃±0.5℃の水中に10秒間浸漬し、水中から出した。その後、フィルムの縦および横方向の寸法を測定し、下式1にしたがって各方向の収縮率を求めた。なお、測定は2回行い、その平均値を求めた。
収縮率={(収縮前の長さ-収縮後の長さ)/収縮前の長さ}×100(%) 式1
フィルムを10cm×10cmの正方形に裁断し、ヒートシール面を内側にした状態で2枚を重ね、フィルム端部より1cmの位置をヒートシールして袋を作成した。袋に内容物0.5mlの入ったアルミカップを入れ、フィルム端部より1cmの位置をヒートシールして袋を閉じて密閉した。前記内容物にはD-リモネン(東京化成工業株式会社製)、D-カンファー(ナカライテスク株式会社製)を使用した。30℃環境下で20時間保持した後、フィルム袋のアルミカップの口部に接する面より5cm×5cmの正方形を切り取り、切り取ったフィルムを抽出溶媒4mlに浸した状態で、超音波で30分間抽出した。D-リモネンの抽出溶媒には99.8%エタノール(富士フイルム和光純薬株式会社製)を、D-カンファーの抽出溶媒には99.8%メタノール(富士フイルム和光純薬株式会社製)を用いた。島津製作所社製のガスクロマトグラフ「GC-14B」を用いて抽出溶液中の内容物の濃度を定量した。ガスクロマトグラフは、カラムに「GC-14A Glass I.D.2.6φx1.1m PET-HT 5% Uniport HP 80/100(ジーエルサイエンス社製)」、検出器にFID,キャリアガスにN2を用い、キャリアガス流量35ml/分、注入量1μlにて面積百分率法で定量した。吸着量はヒートシール面1cm2あたりの吸着量(μg/cm2)で示し、低吸着性を以下のように判定した。
判定○ 0μg/cm2以上、2μg/cm2未満
判定△ 2μg/cm2以上、10μg/cm2未満
判定× 10μg/cm2以上
フィルムを10cm×10cmの正方形に裁断し、ヒートシール面と非ヒートシール面が接する状態で5枚を重ね、その上に5kgの重りを載せて40℃環境下で2時間静置した。静置後、重りを外し、手でフィルムを1枚ずつ取り出したときのフィルムの状態に応じて、以下のように判定した。
判定○ 5枚すべてのフィルムでブロッキング痕やフィルム破れなし
判定× 5枚中、1枚以上のフィルムにブロッキング痕やフィルム破れあり
フィルムを12cm×12cmの正方形に裁断し、ヒートシール面を内側にした状態で2枚を重ね、袋の内径が10cm×10cmとなるようにヒートシールして袋を作成した。ヒートシール条件は、ヒートシール幅10mm、上バー温度140℃、下バー温度30℃、圧力0.2MPa、時間2秒とした。作成した袋を100℃の沸騰水で30分間加熱して冷却した。ハサミで袋の一辺を切り取って袋内面の状態を確認して以下のように判定した。
判定○ 袋内面同士の粘着がなく、容易に袋を開封できる。
判定× 袋内面同士が粘着しており、袋を開封することができない。
フィルムを20cm×20cmの正方形に裁断し、ヒートシール面を内側にした状態で2枚を重ね、フィルム端部より1cmの位置をヒートシールして袋を作成した。ヒートシール条件は、ヒートシール幅10mm、上バー温度120℃、下バー温度30℃、圧力0.2MPa、時間2秒とした。袋に水を吸わせて重量を100gに調整したキムタオル(日本製紙クレシア製)2枚を丸めて袋に入れ、袋開放部の端部より1cmの位置を製袋時と同じヒートシール条件でヒートシールして袋を閉じて密閉した。
作製した密閉袋を1mの高さから繰り返し5回落下させ、以下に示すように、袋が破れるまでの回数を落袋スコアとして求めた。なお、落袋スコアは5回試行後の和として算出した(最高4点×5回=20点満点)。
1回目で破袋 0点
2回目で破袋 1点
3回目で破袋 2点
4回目で破袋 3点
5回目で破袋 4点
また、落袋スコアの点数により以下のように判定した。
判定○ 落袋スコア10点以上
判定× 落袋スコア9点以下
[合成例1]
撹拌機、温度計および部分環流式冷却器を備えたステンレススチール製オートクレーブに、ジカルボン酸成分としてジメチルテレフタレート(DMT)100モル%と、多価アルコール成分としてエチレングリコール(EG)100モル%とを、エチレングリコールがモル比でジメチルテレフタレートの2.2倍になるように仕込み、エステル交換触媒として酢酸亜鉛を0.05モル%(酸成分に対して)用いて、生成するメタノールを系外へ留去しながらエステル交換反応を行った。その後、重縮合触媒として三酸化アンチモン0.225モル%(酸成分に対して)を添加し、280℃で26.7Paの減圧条件下、重縮合反応を行い、固有粘度0.75dl/gのポリエステル(A)を得た。このポリエステル(A)は、ポリエチレンテレフタレートである。ポリエステル(A)の組成を表1に示す。
合成例1と同様の手順でモノマーを変更したポリエステル(B)~(G)を得た。各ポリエステルの組成を表1に示す。表1において、TPAはテレフタル酸、IPAはイソフタル酸、EGはエチレングリコール、BDは1,4-ブタンジオール、NPGはネオペンチルグリコール、CHDMは1,4-シクロヘキサンジメタノール、DEGはジエチレングリコールである。なお、ポリエステル(G)の製造の際には、滑剤としてSiO2(富士シリシア社製サイリシア266)をポリエステルに対して7,000ppmの割合で添加した。各ポリエステルは、適宜チップ状にした。各ポリエステルの固有粘度は、それぞれ、B:0.73dl/g,C:0.69dl/g,D:0.73dl/g,E:0.74dl/g,F:0.80dl/g、G:0.75dl/gであった。ポリエステル(B)~(G)の組成を表1に示す。
ヒートシール層の原料としてポリエステルAとポリエステルBとポリエステルFとポリエステルGを質量比10:60:24:6で混合し、耐熱層の原料としてポリエステルAとポリエステルBとポリエステルFとポリエステルGを質量比51:37:6:6で混合した。
ヒートシール層及び耐熱層の混合原料はそれぞれ別々の二軸スクリュー押出機に投入し、いずれも270℃で溶融させた。それぞれの溶融樹脂は、流路の途中でフィードブロックによって接合させてTダイより吐出し、表面温度30℃に設定したチルロール上で冷却することによって未延伸の積層フィルムを得た。積層フィルムは片側がヒートシール層、もう片側が耐熱層(ヒートシール層/耐熱層の2種2層構成)となるように溶融樹脂の流路を設定し、ヒートシール層と耐熱層の厚み比率が50:50となるように吐出量を調整した。
冷却固化して得た未延伸の積層フィルムを複数のロール群を連続的に配置した縦延伸機へ導き、予熱ロール上でフィルム温度が80℃になるまで予備加熱した後に4.1倍に延伸した。縦延伸直後のフィルムを熱風ヒータで90℃に設定された加熱炉へ通し、加熱炉の入口と出口のロール間の速度差を利用して、長手方向に20%リラックス処理を行った。その後、縦延伸したフィルムを、表面温度25℃に設定された冷却ロールによって強制的に冷却した。
その後、中間ゾーンを通過したフィルムを最終熱処理ゾーンに導き、180℃で5秒間熱処理した。このとき、熱処理を行うと同時にフィルム幅方向のクリップ間隔を狭めることにより、幅方向に3%リラックス処理を行った。最終熱処理ゾーンを通過後はフィルムを冷却し、両縁部を裁断除去して幅500mmでロール状に巻き取ることによって、厚さ30μmの二軸延伸フィルムを所定の長さにわたって連続的に製造した。このフィルムを実施例1とした。
得られたフィルムの特性は上記の方法によって評価した。製造条件および評価結果を表2及び表3に示す。
実施例2~5、比較例1、2も実施例1と同様の方法でヒートシール層と耐熱層を積層させ、原料の配合比率、最終熱処理条件を種々変更したポリエステル系シーラントを製膜し、評価した。各実施例および比較例のフィルム製造条件と評価結果を表2に示す。
実施例8~11、比較例8も実施例7と同様の方法でヒートシール層と耐熱層を積層させ、原料の配合比率、最終熱処理条件、コロナ処理条件(比較例8はコロナ処理なし)を種々変更したポリエステル系シーラントを製膜し、評価した。各実施例および比較例のフィルム製造条件と評価結果を表3に示す。
ヒートシール層の原料としてポリエステルAとポリエステルBとポリエステルFとポリエステルGを質量比10:60:24:6で混合し、後の工程は実施例1と同様の方法で最終熱処理温度のみ200℃に変更したA層のみの厚さ15μmのポリエステル系シーラントフィルムを製膜した。また、耐熱層の原料としてポリエステルAとポリエステルGを質量比94:6で混合し、後の工程は実施例1と同様の方法で最終熱処理温度のみ230℃に変更したB層のみの厚さ45μmのポリエステル系フィルムを製膜した。前記A層のみのポリエステル系シーラントフィルムをヒートシール層とし、前記B層のみのポリエステル系フィルムを耐熱層として2つのフィルムをドライラミネーション用接着剤(三井化学社製タケラック(登録商標)A-950)で接着させた。製造条件と評価結果を表2に示す。
ヒートシール層の原料としてポリエステルAとポリエステルBとポリエステルFとポリエステルGを質量比10:60:24:6で混合し、後の工程は実施例1と同様の方法で最終熱処理温度を200℃、コロナ処理電力を2.7kWに変更したA層のみのポリエステル系シーラントフィルムを製膜した。また、耐熱層の原料としてポリエステルAとポリエステルGを質量比94:6で混合し、後の工程は実施例1と同様の方法で最終熱処理温度を230℃に変更したB層のみのポリエステル系フィルムを製膜した。前記A層のみのポリエステル系シーラントフィルムをヒートシール層とし、前記B層のみのポリエステル系フィルムを耐熱層として2つのフィルムをドライラミネーション用接着剤(三井化学社製タケラック(登録商標)A-950)で接着させた。製造条件と評価結果を表3に示す。
ヒートシール層の原料としてポリエステルAとポリエステルBとポリエステルFとポリエステルGを質量比5:66:24:5で混合し、後の工程は実施例1と同様の方法で最終熱処理温度のみ170℃に変更したA層のみのポリエステル系シーラントを製膜し、評価した。製造条件と評価結果を表2に示す。
ヒートシール層の原料としてポリエステルAとポリエステルGを質量比94:6で混合し、後の工程は実施例1と同様の方法で最終熱処理温度のみ230℃に変更したA層のみのポリエステル系シーラントを製膜し、評価した。製造条件と評価結果を表2に示す。
比較例4は、東洋紡株式会社製リックスフィルム(登録商標)L4102-25μmを用いた。評価結果を表2に示す。
比較例5は、東洋紡株式会社製パイレンフィルム-CT(登録商標)P1128-25μmを用いた。評価結果を表2に示す。
ヒートシール層の原料としてポリエステルAとポリエステルBとポリエステルFとポリエステルGを質量比9:75:10:6で混合し、耐熱層の原料としてポリエステルAとポリエステルBとポリエステルFとポリエステルGを質量比47:37:10:6で混合した。積層フィルムは表面がヒートシール層、内側の層が耐熱層(ヒートシール層/耐熱層/ヒートシール層の2種3層構成)となるように溶融樹脂の流路を設定し、各層の厚み比率が25:50:25となるように吐出量を調整して最終熱処理温度を115℃に変更し、コロナ処理を行わなかった以外の工程は実施例1と同様の方法で、ポリエステル系シーラントを製膜し、評価した。製造条件と評価結果を表3に示す。
比較例10は、東洋紡株式会社製リックスフィルム(登録商標)L4102-25μmを用いた。評価結果を表3に示す。
比較例11は、東洋紡株式会社製パイレンフィルム-CT(登録商標)P1128-25μmを用いた。評価結果を表3に示す。
表2より、実施例1から6までのフィルムはいずれも密度とヒートシール層の表面粗さの要素の平均長さRSmが所定の範囲となり、100℃ヒートシール強度および140℃ヒートシール強度、ヒートシール層の動摩擦係数、ヘイズ、80℃温湯収縮率、低吸着性、包装袋でのボイル適性に優れており、良好な評価結果が得られた。
一方、比較例1のフィルムは、100℃ヒートシール強度、ヒートシール層の動摩擦係数、ヘイズ、80℃温湯収縮率、低吸着性、包装袋でのボイル適性には優れているが、最終熱処理温度が低いために140℃ヒートシール強度が低かった。
比較例4のフィルムは密度が1.394と大きく、140℃ヒートシール強度が低いため、シーラントフィルムとして適さない。
比較例5および6のフィルムはオレフィン系フィルムを使用しているため、低吸着性に劣る。また、比較例5のフィルムは140℃ヒートシール強度も低い。
一方、比較例7のフィルムは、140℃ヒートシール強度、ヒートシール層の動摩擦係数、ヘイズ、80℃温湯収縮率、低吸着性、包装袋でのボイル適性には優れているが、ヒートシール層表面の酸素原子の存在比率が26.5%以下であるために120℃ヒートシール強度が低く、落袋評価において破袋しやすい結果であった。
比較例9のフィルムは、ヒートシール層表面の酸素原子の存在比率が31.0%以上であるため、120℃ヒートシール強度に優れているが、フィルム同士がブロッキングした。
本願第二の発明は、種々の有機化合物を吸着しにくく、140℃のヒートシール性に優れ、さらに低温の120℃ヒートシール性にも優れるため、高速自動充填包装でも十分なヒートシール強度を有するシーラントフィルムを提供することができる。
また、本発明は、前記のシーラントフィルムを少なくとも一層として含む積層体とすることもでき、そのような積層体から包装袋とすることもできる。
Claims (9)
- 少なくとも1層のポリエステル系成分からなるヒートシール層を有しており、以下(1)~(3)を満たすことを特徴とする低吸着性シーラントフィルム。
(1)ヒートシール層同士を100℃、0.2MPa、2秒間でシールしたときのシール強度が0N/15mm以上5N/15mm以下
(2)ヒートシール層同士を140℃、0.2MPa、2秒間でシールしたときのシール強度が8N/15mm以上30N/15mm以下
(3)全層を含んだフィルムの密度が1.20以上1.39未満 - 少なくとも1層のポリエステル系成分からなるヒートシール層を有しており、以下(4)~(6)を満たすことを特徴とする低吸着性シーラントフィルム。
(4)ヒートシール層同士を120℃、0.2MPa、2秒間でシールしたときのシール強度が4N/15mm以上15N/15mm以下
(5)ヒートシール層同士を140℃、0.2MPa、2秒間でシールしたときのシール強度が8N/15mm以上30N/15mm以下
(6)ヒートシール層において、X線電子分光法(ESCA)で求めた酸素原子の存在比率が26.6%以上31.0%以下 - 三次元粗さ計から求めた表面粗さの要素の平均長さRSmが18μm以上29μm以下である請求項1又は2のいずれかに記載の低吸着性シーラントフィルム。
- 前記ヒートシール面同士の動摩擦係数が0.30以上0.80以下である請求項1~3のいずれかに記載の低吸着性シーラントフィルム。
- フィルムを構成する成分が、エチレンテレフタレートを主たる構成成分とするポリエステルからなる請求項1~4のいずれかに記載の低吸着性シーラントフィルム。
- ヒートシール層を構成するポリエステル系成分を構成するモノマーのうち、エチレングリコール以外のジオールモノマー成分を含有し、該ジオールモノマー成分がネオペンチルグリコール、1,4-シクロヘキサンジメタノール、1,4-ブタンジオール、ジエチレングリコールのいずれか1つ以上である請求項1~5のいずれかに記載の低吸着性シーラントフィルム。
- 80℃温湯中で10秒間にわたって処理したときの熱収縮率が長手方向、幅方向いずれも0%以上10%以下である請求項1~6のいずれかに記載の低吸着性シーラントフィルム。
- 請求項1~7のいずれかに記載のシーラントフィルムを少なくとも1層は含むことを特徴とする積層体。
- 請求項1~7のいずれかに記載のシーラントフィルム、又は請求項8に記載の積層体を少なくとも一部に用いたことを特徴とする包装袋。
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EP19869230.3A EP3862381A4 (en) | 2018-10-03 | 2019-09-30 | Low adsorption sealant film, layered body, and packaging bag |
US17/279,577 US11548271B2 (en) | 2018-10-03 | 2019-09-30 | Low adsorption sealant film, laminated body, and packaging bag |
CN201980064811.9A CN112805319B (zh) | 2018-10-03 | 2019-09-30 | 低吸附性密封剂薄膜、层叠体和包装袋 |
KR1020217011628A KR20210069658A (ko) | 2018-10-03 | 2019-09-30 | 저흡착성 실란트 필름, 적층체 및 포장봉지 |
JP2020550420A JPWO2020071315A1 (ja) | 2018-10-03 | 2019-09-30 | 低吸着性シーラントフィルム、積層体および包装袋 |
MX2021003789A MX2021003789A (es) | 2018-10-03 | 2019-09-30 | Pelicula selladora de baja adsorcion, cuerpo laminado y bolsa de empaquetado. |
JP2024017081A JP2024040295A (ja) | 2018-10-03 | 2024-02-07 | 低吸着性シーラントフィルム、積層体および包装袋 |
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WO2022071046A1 (ja) * | 2020-10-01 | 2022-04-07 | 東洋紡株式会社 | 熱収縮性ポリエステル系フィルム |
JP2023166720A (ja) * | 2022-05-10 | 2023-11-22 | 株式会社メタルカラー | 積層体、ptp包装体、積層体の製造方法 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07132946A (ja) | 1993-11-08 | 1995-05-23 | Seisan Nipponsha Kk | 揮発性成分を内蔵する被包装物の包装用チヤツク付き袋体 |
JPH07196899A (ja) * | 1993-12-28 | 1995-08-01 | Mitsui Petrochem Ind Ltd | ラミネート用ポリエステル樹脂組成物とその製造方法およびその積層体 |
JPH0817846B2 (ja) | 1989-04-05 | 1996-02-28 | 株式会社マルホン | パチンコ遊技機用電動役物装置 |
JPH10193547A (ja) * | 1996-12-20 | 1998-07-28 | Hoechst Diafoil Gmbh | ヒートシール性ポリエステルフィルム及びその製造方法ならびに使用方法 |
JP2003528746A (ja) * | 2000-02-19 | 2003-09-30 | ミツビシ ポリエステル フィルム ジーエムビーエイチ | シール性および難燃性を有する二軸延伸白色フィルムおよびその使用ならびにその製造方法 |
WO2014175313A1 (ja) | 2013-04-26 | 2014-10-30 | 東洋紡株式会社 | シーラント用途のポリエステル系フィルム、積層体及び包装袋 |
WO2017159582A1 (ja) * | 2016-03-18 | 2017-09-21 | 東洋紡株式会社 | ポリエステル系フィルム、積層体及び包装体 |
JP2017165059A (ja) | 2016-03-18 | 2017-09-21 | 東洋紡株式会社 | シーラント用途のポリエステルフィルム、積層体及び包装体 |
WO2018150997A1 (ja) * | 2017-02-15 | 2018-08-23 | 東洋紡株式会社 | ポリエステル系シーラントフィルム、積層体及び包装体 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3817846B2 (ja) | 1997-07-09 | 2006-09-06 | 住友化学株式会社 | 複合フィルム |
JP6635119B2 (ja) * | 2016-07-27 | 2020-01-22 | 東洋紡株式会社 | 白色ポリエステル系フィルム、積層体及び包装袋 |
-
2019
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Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0817846B2 (ja) | 1989-04-05 | 1996-02-28 | 株式会社マルホン | パチンコ遊技機用電動役物装置 |
JPH07132946A (ja) | 1993-11-08 | 1995-05-23 | Seisan Nipponsha Kk | 揮発性成分を内蔵する被包装物の包装用チヤツク付き袋体 |
JPH07196899A (ja) * | 1993-12-28 | 1995-08-01 | Mitsui Petrochem Ind Ltd | ラミネート用ポリエステル樹脂組成物とその製造方法およびその積層体 |
JPH10193547A (ja) * | 1996-12-20 | 1998-07-28 | Hoechst Diafoil Gmbh | ヒートシール性ポリエステルフィルム及びその製造方法ならびに使用方法 |
JP2003528746A (ja) * | 2000-02-19 | 2003-09-30 | ミツビシ ポリエステル フィルム ジーエムビーエイチ | シール性および難燃性を有する二軸延伸白色フィルムおよびその使用ならびにその製造方法 |
WO2014175313A1 (ja) | 2013-04-26 | 2014-10-30 | 東洋紡株式会社 | シーラント用途のポリエステル系フィルム、積層体及び包装袋 |
WO2017159582A1 (ja) * | 2016-03-18 | 2017-09-21 | 東洋紡株式会社 | ポリエステル系フィルム、積層体及び包装体 |
JP2017165059A (ja) | 2016-03-18 | 2017-09-21 | 東洋紡株式会社 | シーラント用途のポリエステルフィルム、積層体及び包装体 |
WO2018150997A1 (ja) * | 2017-02-15 | 2018-08-23 | 東洋紡株式会社 | ポリエステル系シーラントフィルム、積層体及び包装体 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3862381A4 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022071046A1 (ja) * | 2020-10-01 | 2022-04-07 | 東洋紡株式会社 | 熱収縮性ポリエステル系フィルム |
JP2023166720A (ja) * | 2022-05-10 | 2023-11-22 | 株式会社メタルカラー | 積層体、ptp包装体、積層体の製造方法 |
JP7446575B2 (ja) | 2022-05-10 | 2024-03-11 | 株式会社メタルカラー | 積層体、ptp包装体、積層体の製造方法 |
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CN112805319B (zh) | 2023-06-13 |
TWI822870B (zh) | 2023-11-21 |
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MX2021003789A (es) | 2021-05-27 |
US11548271B2 (en) | 2023-01-10 |
KR20210069658A (ko) | 2021-06-11 |
JPWO2020071315A1 (ja) | 2021-09-24 |
CN112805319A (zh) | 2021-05-14 |
EP3862381A1 (en) | 2021-08-11 |
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