WO2015146496A1 - Film stratifie - Google Patents

Film stratifie Download PDF

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Publication number
WO2015146496A1
WO2015146496A1 PCT/JP2015/056050 JP2015056050W WO2015146496A1 WO 2015146496 A1 WO2015146496 A1 WO 2015146496A1 JP 2015056050 W JP2015056050 W JP 2015056050W WO 2015146496 A1 WO2015146496 A1 WO 2015146496A1
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Prior art keywords
film
thickness
inorganic thin
resin
less
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PCT/JP2015/056050
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English (en)
Japanese (ja)
Inventor
麻洋 中野
中谷　伊志
清水　敏之
池畠　良知
多保田　規
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東洋紡株式会社
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Priority to JP2015518681A priority Critical patent/JP6210242B2/ja
Publication of WO2015146496A1 publication Critical patent/WO2015146496A1/fr

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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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • 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
    • 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
    • B32B27/06—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
    • 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
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/048—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material made of particles
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • B32B2307/736—Shrinkable
    • 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
    • B32B2439/00—Containers; Receptacles
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/40—Closed containers
    • B32B2439/60—Bottles

Definitions

  • the present invention relates to a laminated film using a polyester resin recycled from a PET bottle. More specifically, good gas barrier properties when using a polyester resin recycled from PET bottles, having a low heat shrinkage, high laminate strength, and having a thin film with an inorganic thin film layer due to small thickness unevenness It is related with the laminated
  • the biaxially stretched film is heat-treated at a high temperature, but since the cooling to room temperature is rapid, there is unevenness in the relaxation of the film, and the thickness unevenness is poor. Become. Therefore, when an inorganic thin film is deposited using a polyester film having such a large thickness unevenness as a base material, there is a problem that the thickness of the inorganic thin film layer is not uniform and the gas barrier property is lowered.
  • the biaxially stretched film is heat-treated at a high temperature, but since the cooling to room temperature is rapid, there is unevenness in the relaxation of the film, and the thickness unevenness is poor. Become. Therefore, when an inorganic thin film is deposited using a polyester film having such a large thickness unevenness as a base material, there is a problem that the thickness of the inorganic thin film layer is not uniform and the gas barrier property is lowered.
  • Patent Document 3 there has been known a technique for improving the slit property and the shaving property in the calendar process for magnetic recording media by controlling the particles in the film and the film forming conditions.
  • this conventional technology is an example of polyethylene terephthalate that does not use polyester resin recycled from PET bottles, but when a film is made using a resin raw material having an intrinsic viscosity of 0.62 dl / g made of the recycled resin. Since the composition inside the film has variations, the occurrence of variations in the laminated surface and uneven thickness are poor.
  • the biaxially stretched film is heat-treated at a high temperature, but since the cooling to room temperature is rapid, there is unevenness in the relaxation of the film, and the thickness unevenness is poor. Become. Therefore, when an inorganic thin film is deposited using a polyester film having such a large thickness unevenness as a base material, there is a problem that the thickness of the inorganic thin film layer is not uniform and the gas barrier property is lowered.
  • the biaxially stretched film is heat-treated at a high temperature, and optionally a technical idea of cooling after the heat treatment is disclosed.
  • a film containing 0.5 to 5.0 mol% of isophthalic acid even if this technology is used as it is, the relaxation of the film is uneven in the surface, the thickness unevenness is poor, and the inorganic thin film is similarly deposited. In this case, the thickness of the inorganic thin film layer is not uniform, and the gas barrier property is lowered.
  • the planarity of the film is maintained by controlling the refractive index (Nz) in the thickness direction, but this document describes that when polyethylene terephthalate is 100% as a raw material and Nz is 1.493 or less. The case is envisaged. Films containing 0.5 to 5.0 mol% of isophthalic acid have the advantage of easier lamination strength than 0 mol% polyethylene terephthalate film, but Nz is the best way to improve both lamination strength and thickness unevenness. There is a problem that this technique cannot be used as it is because it is too expensive.
  • the object of the present invention is to provide a laminated film as follows.
  • Lamination of recycled resin obtained by recycling PET bottles containing 0.5 to 5.0 mol% isophthalic acid, high melt viscosity, solid phase polymerization, and often adding high crystallization nucleating agents Even if it is used as a raw material resin for a base film in a film, it is possible to stabilize the extrusion of the resin by optimizing the extrusion temperature, and to homogenize the resin, additives, particles, etc. in the film. To reduce the thickness unevenness of the laminate, eliminate the variation of the laminate, and improve the laminate strength. 2.
  • the film can be stretched at a high magnification and reduced in thickness unevenness of the substrate film. 3. Even if the melt viscosity of the resin after extrusion is high, it is possible to perform lateral stretching at a high magnification and reduce the thickness unevenness of the base film by adopting lateral stretching at a high temperature. 4). Lowering the vertical and horizontal thermal shrinkage of the base film by performing high-temperature heat treatment. 5. To achieve a high laminate strength by adjusting the refractive index in the thickness direction of the base film through high-temperature, high-magnification stretching and high-temperature heat treatment. 6).
  • the thickness unevenness of the base film containing 0.5 mol% or more and 5.0 mol% or less of isophthalic acid as an acid component is reduced. Also, the laminate strength will not vary within the film. 7). Even when a gas barrier laminate film with an inorganic thin film layer is used, the thickness unevenness is small, the thickness of the inorganic thin film layer is uniform due to the low thermal shrinkage rate, and polyester resin recycled from PET bottles that exhibit good gas barrier properties is used. It is to provide an excellent laminated film.
  • this invention consists of the following structures.
  • a laminated film in which an inorganic thin film layer is laminated on one side of a base film, wherein the base film contains 50% to 95% by weight of a polyester resin recycled from a PET bottle and is biaxially stretched A laminated film characterized by satisfying the following requirements. (1) The content of the isophthalic acid component with respect to all dicarboxylic acid components in all the polyester resins constituting the base film is 0.5 mol% or more and 5.0 mol% or less.
  • the inorganic thin film layer is composed of two kinds of metals, two kinds of inorganic oxides, or one kind of metal and one kind of inorganic oxide.
  • a laminated film according to 1. Three types of inorganic oxides comprising silicon oxide and aluminum oxide. 2. The laminated film according to 2. 4). 1. The water vapor permeability is 5.0 g / m 2 ⁇ day or less and the oxygen permeability is 40.0 ml / m 2 ⁇ day ⁇ MPa or less. ⁇ 3.
  • the polyester film using the polyester resin recycled from the PET bottle according to the present invention has the following effects. 1. Lamination of recycled resin obtained by recycling PET bottles containing 0.5 to 5.0 mol% isophthalic acid, high melt viscosity, solid phase polymerization, and often adding high crystallization nucleating agents Even if it is used as a raw material resin for a base film in a film, the extrusion of the resin is stabilized by optimizing the extrusion temperature, and the resin, additives and particles in the film are made uniform, thereby making the base film To reduce the thickness unevenness of the laminate, eliminate the variation of the laminate, and improve the laminate strength. 2.
  • the film can be stretched at a high magnification and reduced in thickness unevenness of the substrate film. 3. Even if the melt viscosity of the resin after extrusion is high, it is possible to perform lateral stretching at a high magnification and reduce the thickness unevenness of the base film by adopting lateral stretching at a high temperature. 4). Lowering the vertical and horizontal thermal shrinkage of the base film by performing high-temperature heat treatment. 5. To achieve a high laminate strength by adjusting the refractive index in the thickness direction of the base film through high-temperature, high-magnification stretching and high-temperature heat treatment. 6).
  • the thickness unevenness of the base film containing 0.5 mol% or more and 5.0 mol% or less of isophthalic acid as an acid component is reduced. Also, the laminate strength will not vary within the film. 7). Even when a gas barrier laminate film with an inorganic thin film layer is used, the thickness unevenness is small, the thickness of the inorganic thin film layer is uniform due to the low thermal shrinkage rate, and polyester resin recycled from PET bottles that exhibit good gas barrier properties is used. It is to provide an excellent laminated film.
  • the biaxial stretching method is not particularly limited, and a tubular method, a simultaneous biaxial stretching method, or the like can be employed. A sequential biaxial stretching method is preferred.
  • the lower limit of the intrinsic viscosity of the resin constituting the film obtained by measuring the base film is preferably 0.58 dl / g, more preferably 0.60 dl / g.
  • the upper limit is preferably 0.70 dl / g, more preferably 0.68 dl / g. If it exceeds 0.70 dl / g, it is difficult to discharge the resin from the extruder and the productivity may be lowered.
  • the lower limit of the thickness of the base film is preferably 8 ⁇ m, more preferably 10 ⁇ m, and even more preferably 12 ⁇ m. If it is less than 8 ⁇ m, the film strength may be insufficient, which is not preferable.
  • the upper limit is preferably 200 ⁇ m, more preferably 50 ⁇ m, and even more preferably 30 ⁇ m. If it exceeds 200 ⁇ m, it may be too thick and difficult to process.
  • the lower limit of the heat shrinkage rate by treatment at 150 ° C. for 30 minutes in the longitudinal direction (may be described as MD) and lateral direction (may be described as TD) of the base film is preferably 0.1%, more preferably Is 0.3%. If it is less than 0.1%, the improvement effect is saturated, and it may become mechanically brittle, which is not preferable.
  • the upper limit is preferably 1.5%, more preferably 1.2%. If it exceeds 1.5%, it is not preferable because pitch deviation may occur due to dimensional changes during processing such as printing. On the other hand, if it exceeds 1.5%, shrinkage or the like in the width direction may occur due to dimensional changes during processing such as printing.
  • the lower limit of the refractive index in the thickness direction of the base film is preferably 1.4930, and more preferably 1.4940. If it is less than 1.4930, since the orientation is not sufficient, the laminate strength may not be obtained.
  • the upper limit is preferably 1.4995, more preferably 1.4980. If it exceeds 1.4995, the orientation of the surface is broken and the mechanical properties may be insufficient.
  • the lower limit of the laminate strength when a polyolefin film is laminated on the side opposite to the laminated surface of the inorganic thin film layer of the base film is preferably 4.0 N / 15 mm, more preferably 4.5 N / 15 mm, still more preferably 5.0 N / 15mm. If it is less than 4.0 N / 15 mm, it is not preferable since the laminate part may be easily peeled off when used as a bag.
  • the upper limit is preferably 20.0 N / 15 mm, more preferably 15.0 N / 15 mm, and even more preferably 10.0 N / 15 mm. If it exceeds 20.0 N / 15 mm, the film may be substantially destroyed at the time of peeling, which is not preferable.
  • ⁇ ⁇ Appearance evaluation after lamination is done by visually observing the sample after peeling. In order to facilitate visual observation, it is preferable to dye the adhesive. The evaluation is as follows. ⁇ Level means that there is no minute removal of the adhesive on the surface after peeling, ⁇ level means that minute removal is 10% or less of the total peeled area, and ⁇ level means that there is no minute removal. It exceeds 10% of the peeled area. Preferably it is (triangle
  • a recycled polyester resin comprising a PET bottle containing an isophthalic acid component as an acid component as a raw material for the base film.
  • Polyester used in PET bottles is controlled for crystallinity in order to improve the appearance of the bottle.
  • polyester containing 10 mol% or less of isophthalic acid component may be used.
  • a material containing an isophthalic acid component may be used.
  • the lower limit of the amount of the terephthalic acid component in the total dicarboxylic acid component constituting the polyester resin contained in the base film is preferably 95.0 mol%, more preferably 96.0 mol%, still more preferably 96.5 mol%. Particularly preferably 97.0 mol%. If it is less than 95.0 mol%, the crystallinity is lowered, and the thermal shrinkage rate may be increased, which is not preferable.
  • the upper limit of the amount of the terephthalic acid component of the polyester resin contained in the film is preferably 99.5 mol%, more preferably 99.0 mol%. Recycled polyester resins made of PET bottles often have dicarboxylic acid components other than terephthalic acid typified by isophthalic acid. Therefore, the content of terephthalic acid components constituting the polyester resin in the film exceeds 99.5 mol%. As a result, it is difficult to produce a polyester film having a high resin ratio, which is not preferable.
  • the lower limit of the amount of the isophthalic acid component in the total dicarboxylic acid component constituting the polyester resin contained in the base film is preferably 0.5 mol%, more preferably 0.7 mol%, still more preferably 0.9 mol%. It is particularly preferably 1.0 mol%.
  • Recycled polyester resins made of PET bottles contain many isophthalic acid components. Therefore, the content of the isophthalic acid component constituting the polyester resin in the film is less than 0.5 mol%. Manufacturing becomes difficult as a result, which is less preferred.
  • the upper limit of the amount of the isophthalic acid component in the total dicarboxylic acid component constituting the polyester resin contained in the film is preferably 5.0 mol%, more preferably 4.0 mol%, still more preferably 3.5 mol%. It is particularly preferably 3.0 mol%. If it exceeds 5.0 mol%, the crystallinity is lowered, and the thermal shrinkage rate may be increased, which is not preferable. In addition, it is preferable that the content of the isophthalic acid component is within the above range because a film excellent in laminate strength, shrinkage rate, and thickness unevenness can be easily produced.
  • the upper limit of the intrinsic viscosity of the recycled resin made of PET bottles is preferably 0.90 dl / g, more preferably 0.80 dl / g, still more preferably 0.77 dl / g, and particularly preferably 0.75 dl / g. . If it exceeds 0.9 dl / g, the resin from the extruder is difficult to be discharged and the productivity may be lowered, which is not preferable.
  • the lower limit of the content of the polyester resin recycled from the PET bottle to the film is preferably 50% by weight, more preferably 65% by weight, and further preferably 75% by weight. When the content is less than 50% by weight, the content of recycled resin is poor, which is not preferable in terms of contribution to environmental protection.
  • the upper limit of the content of the polyester resin recycled from the PET bottle is preferably 95% by weight, more preferably 90% by weight, and still more preferably 85% by weight. If it exceeds 95% by weight, a lubricant and additives such as inorganic particles may not be sufficiently added to improve the function of the film, which is not preferable.
  • the polyester resin recycled from the PET bottle can also be used as a masterbatch (high concentration containing resin) used when adding lubricants and additives such as inorganic particles for the purpose of improving the function of the film.
  • lubricant type in addition to inorganic lubricants such as silica, calcium carbonate, and alumina, organic lubricants are preferable, and silica and calcium carbonate are more preferable. By these, transparency and slipperiness can be expressed.
  • the lower limit of the lubricant content in the base film is preferably 0.01% by weight, more preferably 0.015% by weight, and still more preferably 0.02% by weight. If it is less than 0.01% by weight, the slipperiness may be lowered.
  • the upper limit is preferably 1% by weight, more preferably 0.2% by weight, and still more preferably 0.1% by weight. If it exceeds 1% by weight, the transparency may be lowered, which is not preferable.
  • the manufacturing method of the base film used for the laminated film of the present invention is not particularly limited, for example, the following manufacturing method is recommended.
  • the temperature setting for melting and extruding the resin in the extruder is important.
  • the basic idea is that (1) polyester resin used in PET bottles contains an isophthalic acid component, so (2) limiting viscosity and fine high crystals while suppressing deterioration by extruding at the lowest possible temperature. In order to sufficiently and uniformly melt the sex part, it has a part that melts at a high temperature or high pressure. Inclusion of the isophthalic acid component reduces the stereoregularity of the polyester, leading to a decrease in the melting point.
  • melt viscosity is greatly reduced or deteriorated due to heat, and the mechanical strength is reduced or deteriorated foreign matters are increased. Further, if the extrusion temperature is simply lowered, sufficient melt-kneading cannot be performed, and foreign matter such as an increase in thickness unevenness and fish eyes may become a problem.
  • a recommended manufacturing method for example, there are a method of using two extruders in tandem, a method of increasing the pressure in the filter section, a method of using a screw having a strong shearing force as a part of the screw configuration, and the like. Can be mentioned. The following is an example of temperature control using a single extruder.
  • FIG. 1 shows one aspect of the inside of the extruder of the film forming equipment in the present invention.
  • the screw 1 having the flight 2 between the barrels 3, there are a supply unit 4, a compression unit 5, and a measurement unit 6 from the screw base to the tip.
  • the compression unit 5 is a region where the space between the screw 1 and the barrel 3 becomes narrower.
  • the set temperature of the supply unit 4 and the measuring unit 6 is made as low as possible and the set temperature of the compression unit 5 is made high. It is preferable that the compression unit 5 having high shear is sufficiently melt-kneaded, and the supply unit 4 and the metering unit 6 are devised to prevent thermal deterioration.
  • the lower limit of the set temperature of the resin melting part in the extruder (excluding the highest set temperature of the compression part of the screw in the extruder) is preferably 270 ° C, and the upper limit is preferably 290 ° C. Extrusion is difficult at temperatures below 270 ° C, and resin degradation may occur at temperatures above 290 ° C, which is not preferred.
  • the lower limit of the maximum set temperature of the compression part of the screw in the extruder is preferably 295 ° C.
  • Polyester resins used in PET bottles often have high melting point crystals (260 ° C. to 290 ° C.) from the viewpoint of transparency.
  • additives, crystallization nucleating agents, and the like are added, and the fine melting behavior in the resin material varies. If it is less than 295 ° C., it is difficult to sufficiently melt them, which is not preferable.
  • the upper limit of the maximum set temperature of the compression part of the screw in the extruder is preferably 310 ° C. If it exceeds 310 ° C, the resin may deteriorate, which is not preferable.
  • the lower limit of the time for the resin to pass through the region of the maximum set temperature of the compression part of the screw in the extruder is preferably 10 seconds, more preferably 15 seconds. If it is less than 10 seconds, the polyester resin used in the PET bottle cannot be sufficiently melted, which is not preferable.
  • the upper limit is preferably 60 seconds, more preferably 50 seconds. If it exceeds 60 seconds, the resin tends to deteriorate, which is not preferable.
  • the resin melted in this manner is extruded into a sheet on a cooling roll and then biaxially stretched.
  • the stretching method may be a simultaneous biaxial stretching method, but a sequential biaxial stretching method is particularly preferable. These make it easy to meet productivity and quality required for the present invention.
  • the method for stretching the film is not particularly limited, but the following points are important.
  • MD machine direction
  • TD transverse direction
  • the ratio and temperature of machine direction (MD) stretching and transverse direction (TD) stretching are important. If the MD stretch ratio and temperature are not appropriate, the stretching force is not applied uniformly, the molecular orientation is insufficient, and the thickness unevenness and mechanical properties may be insufficient. Further, the film may be broken in the next TD stretching step, or an extreme increase in thickness unevenness may occur. If the TD draw ratio and temperature are not appropriate, the film may not be drawn uniformly, resulting in poor vertical / horizontal orientation balance and insufficient mechanical properties.
  • the longitudinal direction (MD) stretching method is preferably a roll stretching method or an IR heating method.
  • the lower limit of the MD stretching temperature is preferably 100 ° C, more preferably 110 ° C, and further preferably 120 ° C.
  • the upper limit is preferably 140 ° C, more preferably 135 ° C, and even more preferably 130 ° C. If it exceeds 140 ° C, the orientation of the molecular chain becomes insufficient, and the mechanical properties may be insufficient.
  • the lower limit of the MD draw ratio is preferably 2.5 times, more preferably 3.5 times, and further preferably 4 times. If it is less than 2.5 times, even if a polyester resin having an intrinsic viscosity of 0.64 dl / g or more is stretched and molecularly oriented in the longitudinal direction, the film will break in the next transverse stretching process or an extreme thickness defect will occur. This is not preferable.
  • the upper limit is preferably 5 times, more preferably 4.8 times, and even more preferably 4.5 times. If it exceeds 5 times, the effect of improving mechanical strength and thickness unevenness may be saturated, which is not so meaningful.
  • the MD stretching method may be the above-mentioned one-stage stretching, but it is more preferable to divide the stretching into two or more stages. By dividing into two or more stages, it is possible to satisfactorily stretch a polyester resin having a high intrinsic viscosity and made of a recycled resin containing isophthalic acid, and the thickness unevenness, laminate strength, mechanical properties, etc. are improved.
  • the lower limit of the preferred first stage MD stretching temperature is 110 ° C, more preferably 115 ° C. If it is less than 110 ° C., heat is insufficient, and sufficient longitudinal stretching cannot be achieved, resulting in poor flatness.
  • the upper limit of the preferred first stage MD stretching temperature is 125 ° C, more preferably 120 ° C. If the temperature exceeds 125 ° C., the orientation of the molecular chain becomes insufficient, and the mechanical properties may be deteriorated.
  • the lower limit of the preferred first stage MD stretch ratio is 1.1 times, more preferably 1.3 times.
  • the upper limit of the preferred first stage MD stretch ratio is 2 times, more preferably 1.6 times. If it exceeds 2 times, the orientation of the molecular chains in the longitudinal direction becomes too high, which makes it difficult to stretch in the second and subsequent stages and results in a film with poor thickness unevenness.
  • the lower limit of the preferred second stage (or final stage) MD stretching temperature is preferably 110 ° C., more preferably 115 ° C.
  • the upper limit is preferably 130 ° C, more preferably 125 ° C. If the temperature exceeds 130 ° C., crystallization is promoted and transverse stretching becomes difficult and thickness unevenness may increase, which is not preferable.
  • the lower limit of the MD stretch ratio of the second stage (or final stage) is preferably 2.1 times, more preferably 2.5 times. If it is less than 2.1 times, a polyester resin with an intrinsic viscosity of 0.64 dl / g or more will be stretched and molecular orientation will occur in the longitudinal direction. This is not preferable.
  • the upper limit is preferably 3.5 times, more preferably 3.1 times. If it exceeds 3.5 times, the longitudinal orientation becomes too high, so that the second and subsequent stretches may not be possible, and the film may have a large thickness unevenness, which is not preferable.
  • the lower limit of the TD stretching temperature is preferably 110 ° C, more preferably 120 ° C, and further preferably 125 ° C. If it is less than 110 ° C., the stretching stress in the transverse direction becomes high, and the film may be broken or the thickness unevenness may become extremely large.
  • the upper limit is preferably 150 ° C, more preferably 145 ° C, and even more preferably 140 ° C. If the temperature exceeds 150 ° C., the orientation of the molecular chain does not increase, and the mechanical properties may be deteriorated.
  • the lower limit of the transverse direction (TD) stretch ratio is preferably 3.5 times, more preferably 3.9 times. If it is less than 3.5 times, the molecular orientation is weak and the mechanical strength may be insufficient, which is not preferable. In addition, since the orientation of molecular chains in the vertical direction is large and the vertical and horizontal balance is deteriorated, thickness unevenness is increased, which is not preferable.
  • the upper limit is preferably 5.5 times, more preferably 4.5 times. If it exceeds 5.5 times, it may break, which is not preferable.
  • Polyester film containing recycled resin made from PET bottles containing isophthalic acid has lower crystallinity than ordinary polyethylene terephthalate film not containing isophthalic acid, and is easy to melt extremely finely, and also has mechanical strength. Low. Therefore, if the film is exposed to high temperature under tension suddenly after the end of stretching, or if it is cooled rapidly under tension after the completion of high-temperature heat setting, the tension balance in the width direction is disturbed due to the inevitable temperature difference in the width direction of the film. , Thickness unevenness and mechanical properties are poor.
  • a sufficient laminate strength may not be obtained.
  • a slightly low temperature heat setting 1 and a sufficiently high temperature heat setting 2 heat setting 3 if necessary
  • a slow cooling step to lower the temperature to room temperature.
  • it is not limited to this method for example, a method of controlling the film tension according to the speed of hot air in the tenter or the temperature of each zone, a heat treatment at a relatively low temperature with a sufficient furnace length after stretching. And a method of relaxing with a heating roll after completion of heat setting.
  • the lower limit of the temperature of heat setting 1 is preferably 160 ° C, more preferably 170 ° C. When the temperature is lower than 160 ° C., the thermal shrinkage rate is finally increased, and a shift or shrinkage at the time of processing may occur.
  • the upper limit is preferably 215 ° C, more preferably 210 ° C. If the temperature exceeds 215 ° C., a high temperature is suddenly applied to the film, and thickness unevenness may be increased or the film may be broken.
  • the lower limit of the time for heat fixation 1 is preferably 0.5 seconds, and more preferably 2 seconds. If it is less than 0.5 seconds, the film temperature may be insufficiently increased.
  • the upper limit is preferably 10 seconds, and more preferably 8 seconds. If it exceeds 10 seconds, the productivity may decrease, which is not preferable.
  • the lower limit of the temperature of heat setting 2 is preferably 220 ° C, more preferably 227 ° C. When the temperature is less than 220 ° C., the thermal shrinkage rate is increased, which may cause displacement or shrinkage during processing, which is not preferable.
  • the upper limit is preferably 240 ° C, more preferably 237 ° C. If it exceeds 240 ° C., the film may melt, and if it does not melt, it may become brittle, which is not preferable.
  • the lower limit of the time for heat fixation 2 is preferably 0.5 seconds, and more preferably 3 seconds. If it is less than 0.5 seconds, breakage tends to occur during heat setting, which is not preferable.
  • the upper limit is preferably 10 seconds, and more preferably 8 seconds. If it exceeds 10 seconds, sagging may occur and thickness unevenness may occur, which is not preferable.
  • the lower limit of the temperature when the heat fixing 3 is provided is preferably 205 ° C, more preferably 220 ° C.
  • the upper limit is preferably 240 ° C, more preferably 237 ° C. If it exceeds 240 ° C, the film will melt, and even if it does not melt, it may become brittle, which is not preferable.
  • the lower limit of the time when the heat fixing 3 is provided is preferably 0.5 seconds, and more preferably 3 seconds. If it is less than 0.5 seconds, breakage tends to occur during heat setting, which is not preferable.
  • the upper limit is preferably 10 seconds, and more preferably 8 seconds. If it exceeds 10 seconds, sagging may occur and thickness unevenness may occur, which is not preferable.
  • TD Relax can be performed at any place where heat fixation is performed.
  • the lower limit is preferably 0.5%, more preferably 3%. If it is less than 0.5%, the thermal shrinkage rate in the lateral direction is particularly large, which may cause a shift or shrinkage during processing, which is not preferable.
  • the upper limit is preferably 10%, more preferably 8%. If it exceeds 10%, sagging may occur and thickness unevenness may occur, which is not preferable.
  • the lower limit of the slow cooling temperature after TD heat setting is preferably 90 ° C, more preferably 100 ° C. If it is less than 90 ° C., it is a film containing isophthalic acid, so that thickness unevenness may increase due to shrinkage due to a rapid temperature change or breakage may occur.
  • the upper limit of the annealing temperature is preferably 150 ° C, more preferably 140 ° C. If it exceeds 150 ° C., a sufficient cooling effect may not be obtained, which is not preferable.
  • the lower limit of the slow cooling time after heat setting is preferably 2 seconds, more preferably 4 seconds. If it is less than 2 seconds, a sufficient slow cooling effect may not be obtained, which is not preferable.
  • the upper limit is preferably 20 seconds, and more preferably 15 seconds. If it exceeds 20 seconds, it tends to be disadvantageous in terms of productivity, which is not preferable.
  • the laminated film of the present invention takes an embodiment in which an inorganic thin film layer is laminated on the polyester film. That is, the laminated film of the present invention is used for a gas barrier laminated film having an inorganic thin film layer, and takes an aspect in which the inorganic thin film layer is laminated in advance.
  • the inorganic thin film layer is a thin film made of a metal or an inorganic oxide.
  • the material for forming the inorganic thin film layer is not particularly limited as long as it can be a thin film, but it is preferable to use a material containing aluminum from the viewpoint of workability and gas barrier properties.
  • the material containing aluminum include high-purity aluminum (99.9 mol% or more), aluminum alloys containing other additive elements, inorganic oxides such as aluminum oxide, and the like. Or a combination of a plurality of inorganic oxides.
  • the combination of materials for forming the inorganic thin film layer is not particularly limited.
  • high-purity aluminum and an aluminum alloy two kinds of aluminum alloys having different additive elements (additive elements such as magnesium, silicon, titanium, calcium, and manganese), Aluminum alloy and aluminum oxide, aluminum oxide and titanium oxide, silicon oxide and aluminum oxide, etc. are mentioned. From the viewpoint that both flexibility and denseness of the thin film layer can be achieved, silicon oxide (silica) and aluminum oxide (alumina) The composite oxide is preferable.
  • the mixing ratio of silicon oxide and aluminum oxide is preferably such that Al is in the range of 20% to 70% by mass ratio of metal. If the Al concentration is less than 20%, the water vapor barrier property may be lowered. On the other hand, if the Al concentration exceeds 70%, the inorganic thin film layer tends to be hard, and the film is formed during secondary processing such as printing or lamination. There is a possibility that the barrier property is lowered due to the destruction.
  • the silicon oxide referred to here is various silicon oxides such as SiO and SiO 2 or a mixture thereof
  • the aluminum oxide is various aluminum oxides such as AlO and Al 2 O 3 or a mixture thereof.
  • the film thickness of the inorganic thin film layer is usually 1 nm to 800 nm, preferably 5 nm to 500 nm. If the film thickness of the inorganic thin film layer is less than 1 nm, satisfactory gas barrier properties may be difficult to obtain. On the other hand, even if the thickness exceeds 800 nm, the corresponding gas barrier property improvement effect is obtained. However, it is disadvantageous in terms of bending resistance and manufacturing cost.
  • the water vapor permeability (g / m 2 ⁇ day) of the laminated film provided with the inorganic thin film layer is preferably 5.0 or less, more preferably 4.0 or less. If the water vapor permeability of the laminated film exceeds 5.0, sufficient gas barrier properties cannot be obtained.
  • the oxygen permeability (ml / m 2 ⁇ day ⁇ MPa) of the laminated film provided with the inorganic thin film layer is preferably 40.0 or less, more preferably 30.0 or less. If the oxygen permeability of the laminated film exceeds 40, sufficient gas barrier properties cannot be obtained.
  • the method for forming the inorganic thin film layer is not particularly limited.
  • a known vapor deposition method such as a vacuum vapor deposition method, a sputtering method, a physical vapor deposition method such as an ion plating method (PVD method), or a chemical vapor deposition method (CVD method).
  • PVD method physical vapor deposition method
  • CVD method chemical vapor deposition method
  • a typical method for forming the inorganic thin film layer will be described by taking a silicon oxide / aluminum oxide thin film as an example.
  • a mixture of SiO 2 and Al 2 O 3 or a mixture of SiO 2 and Al is preferably used as a deposition material.
  • particles are used as these vapor deposition materials.
  • the size of each particle is desirably such that the pressure during vapor deposition does not change, and the preferred particle diameter is 1 mm to 5 mm.
  • heating methods such as resistance heating, high frequency induction heating, electron beam heating, and laser heating can be employed.
  • reactive vapor deposition using oxygen, nitrogen, hydrogen, argon, carbon dioxide gas, water vapor or the like as a reactive gas, or using means such as ozone addition or ion assist.
  • the film forming conditions can be arbitrarily changed, for example, by applying a bias to the deposition target (laminated film to be deposited) or heating or cooling the deposition target.
  • a bias to the deposition target (laminated film to be deposited) or heating or cooling the deposition target.
  • Such a vapor deposition material, reaction gas, bias of the deposition target, heating / cooling, and the like can be similarly changed when a sputtering method or a CVD method is employed.
  • the laminated film of the present invention as described above becomes a gas barrier laminated film (laminate) having excellent oxygen barrier properties and water vapor barrier properties by having an inorganic thin film layer.
  • the gas barrier laminated film provided with the inorganic thin film layer using the laminated film of the present invention includes various known gas barrier laminated films as necessary. Can be provided.
  • a gas barrier laminate film having an inorganic thin film layer is used as a packaging material, it is preferable to form a heat sealable resin layer called a sealant.
  • the heat-sealable resin layer is usually provided on the inorganic thin film layer, but may be provided on the outer side of the base film (the surface opposite to the surface having the inorganic thin film layer).
  • the heat-sealable resin layer is usually formed by an extrusion lamination method or a dry lamination method.
  • thermoplastic polymer for forming the heat-sealable resin layer is not particularly limited as long as the sealant adhesiveness can be sufficiently exhibited, such as polyethylene resins such as HDPE, LDPE, LLDPE, polypropylene resin, and ethylene-vinyl acetate copolymer. , Ethylene- ⁇ -olefin random copolymers, ionomer resins, and the like can be used.
  • the gas barrier laminate film having an inorganic thin film layer includes a printed layer, other plastic substrate and / or paper substrate between or outside the inorganic thin film layer or substrate film and the heat-sealable resin layer. At least one layer may be laminated.
  • aqueous and solvent-based resin-containing printing inks can be preferably used as the printing ink for forming the printing layer.
  • the resin used in the printing ink include acrylic resins, urethane resins, polyester resins, vinyl chloride resins, vinyl acetate copolymer resins, and mixtures thereof.
  • the printing method for providing the printing layer is not particularly limited, and a known printing method such as an offset printing method, a gravure printing method, or a screen printing method can be used.
  • a known printing method such as an offset printing method, a gravure printing method, or a screen printing method
  • known drying methods such as hot air drying, hot roll drying, and infrared drying can be used.
  • plastic base materials and paper base materials paper, polyester resin, polyamide resin, biodegradable resin and the like are preferably used from the viewpoint of obtaining sufficient rigidity and strength of the laminate.
  • stretched films such as a biaxially stretched polyester film and a biaxially stretched nylon film, are preferable.
  • nylon film when using a gas barrier laminated film with an inorganic thin film layer as a packaging material, between the inorganic thin film layer and the heat-sealable resin layer, to improve mechanical properties such as pinhole property and piercing strength, It is preferable to laminate a nylon film.
  • nylon 6, nylon 66, metaxylene adipamide and the like are usually used as the type of nylon.
  • the thickness of the nylon film is usually 10-30 ⁇ m, preferably 15-25 ⁇ m. If the nylon film is thinner than 10 ⁇ m, the strength may be insufficient. On the other hand, if the nylon film exceeds 30 ⁇ m, the waist is strong and may not be suitable for processing.
  • the nylon film is preferably a biaxially stretched film having a stretching ratio in each of the vertical and horizontal directions of usually 2 times or more, preferably about 2.5 to 4 times.
  • the laminated film of the present invention includes an embodiment having each of the above-described layers other than the inorganic thin film layer.
  • IV Intrinsic viscosity of the resin constituting the raw resin and film
  • Refractive index in the thickness direction of the substrate film was determined using an Abbe refractometer NAR-1T (manufactured by Atago Co., Ltd.) in accordance with JIS K7142.
  • the light source was a sodium D line, a test piece having a refractive index of 1.74 was used, and methylene iodide was used as an intermediate solution.
  • Laminate strength of base film Film base film and 40 ⁇ m thick polyethylene film (“L4102" manufactured by Toyobo Co., Ltd.) urethane adhesive (Toyo Morton, TM569, CAT10L, ethyl acetate 33.6: 4.0: 62.4 (weight ratio)) is laminated on the opposite side of the surface of the base film on which the inorganic thin film layer is laminated by dry laminating, and aged for 4 days at 40 ° C. A laminate for evaluation was obtained. The bonding conditions were such that the line speed was 20 m / min, the dryer temperature was 80 ° C., and the coating amount after drying was 3 g / m 2 .
  • the laminate was cut to a width of 15 mm and a length of 200 mm to form a test piece.
  • “Tensilon UMT-II-500 type” manufactured by Toyo Baldwin Co., Ltd. under the conditions of a temperature of 23 ° C. and a relative humidity of 65%.
  • the peel strength (N / 15 mm) at the joint surface of the material film opposite to the laminated surface of the inorganic thin film layer and the polyolefin resin layer was measured.
  • the tensile speed was 20 cm / min and the peeling angle was 180 degrees.
  • the film thickness of the inorganic thin film layer was determined by a fluorescent X-ray analysis method using a calibration curve prepared in advance using a film having a known film thickness.
  • Several types of inorganic thin films with different thicknesses and compositions were prepared and measured with a fluorescent X-ray apparatus to obtain a calibration curve for measuring the thickness.
  • the fluorescent X-ray analysis conditions were as follows: the tube voltage was 50 kV and the tube current was 40 mA as the excitation X-ray tube conditions.
  • composition of the inorganic thin film layer was determined by a wavelength dispersive fluorescent X-ray measurement method.
  • the tube voltage was set to 50 kV and the tube current was set to 40 mA as the conditions for the excitation X-ray tube, as in the above-described evaluation method of the film thickness.
  • the element concentration of each element was determined by a calibration curve method, and the composition of the inorganic thin film layer was calculated from the determined element concentration.
  • Example 1 Adjustment of polyester resin recycled from plastic bottles
  • the flakes obtained by crushing are melted with an extruder, and the filter is changed to a finer one with a mesh size, and the finer foreign matter is filtered twice. Separately, it was filtered with a filter having the smallest opening size of 50 ⁇ m the third time to obtain a recycled polyester material.
  • Polyester C is an amorphous silica having an average particle diameter of 1.5 ⁇ m.
  • the temperature from the extruder to the melt line, filter and T-die was set so that the resin temperature would be 280 ° C. However, the temperature of the resin was set to be 305 ° C. for 30 seconds from the start point of the compression portion of the screw of the extruder, and then again 280 ° C.
  • the melt extruded from the T-die was brought into close contact with the cooling roll to obtain an unstretched sheet, which was then stretched 1.41 times in the machine direction with a roll having a peripheral speed difference heated to 118 ° C. (MD1), Further, the film was stretched 2.92 times (MD2) in the machine direction with a roll heated at 128 ° C. and having a peripheral speed difference.
  • MD1 118 ° C.
  • MD2 2.92 times
  • the longitudinally stretched sheet was guided to a tenter, preheated at 121 ° C., and then stretched 4.3 times at 131 ° C. Subsequently, heat fixation was performed at 180 ° C. without relaxation (0%) for 2.5 seconds (TS1), followed by 231 ° C., relaxation at 5% for 3.0 seconds (TS2), then 222 ° C.
  • a composite inorganic oxide layer of silicon dioxide and aluminum oxide was formed as an inorganic thin film layer on one side of the obtained biaxially stretched polyester film by an electron beam evaporation method.
  • the evaporation source particulate SiO 2 (purity 99.9%) and A1 2 O 3 (purity 99.9%) of about 3 mm to 5 mm were used.
  • the film thickness of the inorganic thin film layer (SiO 2 / A1 2 O 3 composite oxide layer) in the film thus obtained (inorganic thin film layer / biaxially stretched polyester film) was 13 nm.
  • a laminated film of the present invention having an inorganic thin film layer on a biaxially stretched polyester film was obtained.
  • oxygen permeability and water vapor permeability were evaluated.
  • Example 3 In the same manner as in Example 2, except that the resin temperature was set to 305 ° C. for 45 seconds from the start point of the compression part of the screw of the extruder, and finally the film was 12 ⁇ m thick. A laminated film having an inorganic thin film layer on a stretched polyester film was obtained.
  • Examples 4 and 5 Adjustment of polyester resin recycled from plastic bottles
  • the filter was changed to fine ones with an opening size of 2 times. Further, fine foreign matters were filtered off and filtered with a filter having the smallest opening size of 50 ⁇ m for the third time to obtain a recycled polyester material.
  • Example 6 A laminated film having an inorganic thin film layer on a biaxially stretched polyester film having a thickness of 18 ⁇ m was obtained in the same manner as in Example 1 except that an aluminum alloy was formed by electron beam evaporation as the inorganic thin film layer.
  • the formation of the inorganic thin film layer is as follows.
  • Example 7 Laminate having an inorganic thin film layer on a biaxially stretched polyester film having a thickness of 18 ⁇ m in the same manner as in Example 1 except that an aluminum alloy and silicon oxide, which is an inorganic oxide, were formed by electron beam evaporation as the inorganic thin film layer. A film was obtained.
  • the formation of the inorganic thin film layer is as follows.
  • a composite of an aluminum alloy and silicon dioxide was formed as an inorganic thin film layer on one side of the biaxially stretched polyester film obtained by producing the film of Example 1 by an electron beam evaporation method.
  • an aluminum alloy containing 2 mol% of magnesium and particulate SiO 2 (purity 99.9%) of about 3 mm to 5 mm were used.
  • the film thickness of the inorganic thin film layer (aluminum alloy / silicon dioxide composite layer) in the film thus obtained (inorganic thin film layer / biaxially stretched polyester film) was 13 nm.
  • a laminated film of the present invention having an inorganic thin film layer on a biaxially stretched polyester film was obtained.
  • oxygen permeability and water vapor permeability were evaluated.
  • Example 2 Biaxially stretched polyester having a thickness of 18 ⁇ m in the same manner as in Example 2 except that the temperature of the resin is set to 280 ° C. in all regions of the melt line, filter, and T-die from the extruder. A laminated film having an inorganic thin film layer on the film was obtained.
  • the longitudinally stretched sheet was guided to a tenter, preheated at 100 ° C., and then laterally stretched 3.9 times at 105 ° C. Thereafter, heat treatment was carried out as heat setting at 228 ° C. for 3.0 seconds without relaxation (TS2) and at 228 ° C. at 5.0% relaxation for 2.5 seconds, except that TS1 and the cooling step were not provided.
  • TS2 3.0 seconds without relaxation
  • TS1 and the cooling step were not provided.
  • a laminated film having an inorganic thin film layer on a biaxially stretched polyester film having a thickness of 18 ⁇ m was obtained.
  • MD1 Further, it was stretched 1.3 times in the machine direction with a roll having a circumferential speed difference heated to 126 ° C. (MD2), and further stretched 2.3 times in the machine direction in a roll with a circumferential speed difference heated to 118 ° C. MD3).
  • the longitudinally stretched sheet was guided to a tenter, preheated at 110 ° C, and then stretched 4.6 times at 120 ° C. Thereafter, heat treatment was performed at 205 ° C. for 5.0 seconds without relaxation (TS2), and TS1 and TS3 and a cooling step were not provided.
  • TS2 5.0 seconds without relaxation
  • the biaxially stretched PET films obtained in Examples 1 to 7 had good thickness unevenness, excellent laminate strength, and good appearance after lamination.
  • the laminated film obtained by providing the inorganic thin film layer on the biaxially stretched PET films obtained in Examples 1 to 7 had good water vapor permeability and oxygen permeability, and exhibited excellent gas barrier properties.
  • Comparative Example 1 since there was no TS1 and a cooling step, the thickness unevenness was large due to shrinkage due to a rapid temperature change, the thickness of the inorganic thin film layer was not uniform, and the gas barrier property was poor.
  • Comparative Example 2 since the temperature of the compression portion of the screw was low, sufficient melting could not be performed, the thickness unevenness was large, the thickness of the inorganic thin film layer was not uniform, and the gas barrier property was poor.
  • Comparative Example 3 since the content of the isophthalic acid component is high and the crystallinity is low, the resin is soft, sufficient force is not applied by stretching, the thickness unevenness is large, the thickness of the inorganic thin film layer is not uniform, and the gas barrier The nature was bad.
  • Comparative Example 4 since the TS3 temperature was low, the refractive index in the thickness direction was low, and the laminate strength was insufficient.
  • Comparative Example 5 since the TD stretching temperature was low and there was no cooling step after heat setting, the thickness unevenness was large due to rapid cooling, the thickness of the inorganic thin film layer was not uniform, and the gas barrier property was poor.
  • Comparative Example 6 MD stretching is carried out in three stages, but the extrusion temperature is as high as 310 ° C., the intrinsic viscosity of the film is low, the heat shrinkage is insufficient, the heat shrinkage rate is high, and the inorganic thin film The layer thickness was not uniform and the gas barrier property was poor.
  • Comparative Example 7 since there was no cooling step after heat setting, the thickness unevenness was poor due to rapid cooling, the thickness of the inorganic thin film layer was not uniform, and the gas barrier property was poor. Since Comparative Example 8 does not use recycled raw materials consisting of PET bottles, it was gradually cooled by lowering the TS3 temperature, and the thickness unevenness was small, but the refractive index in the thickness direction was low due to insufficient temperature of TS3, and the laminate strength was low. It was insufficient.
  • the present invention it becomes possible to provide a laminated film using a polyester film containing a polyester resin recycled from a high-quality PET bottle, and more specifically, including a polyester resin recycled from a PET bottle. It has become possible to provide a laminated film having an excellent gas barrier property having an inorganic thin film layer using a polyester film having a small lamination strength and uneven thickness.

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Abstract

La présente invention concerne un film stratifié présentant une résistance élevée de stratifié et qui comporte une couche de film mince inorganique, et dans lequel on utilise une résine de polyester présentant une irrégularité d'épaisseur minimale, cette résine étant recyclée à partir de bouteilles en PET. Ce film stratifié est un film de polyester contenant 50 à 95 % en poids de résine de polyester recyclée à partir de bouteilles en PET ; le rapport entre le composant d'acide isophtalique et le composant d'acide dicarboxylique total de la quantité totale de résine de polyester du film de polyester est de 0,5 à 5,0 % molaire, ce film stratifié comportant une couche de film mince inorganique, dans laquelle on utilise un film de polyester présentant des caractéristiques spécifiées de viscosité intrinsèque, de retrait thermique, de résistance de stratifié et d'irrégularité d'épaisseur.
PCT/JP2015/056050 2014-03-26 2015-03-02 Film stratifie WO2015146496A1 (fr)

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JP2020066228A (ja) * 2018-10-19 2020-04-30 大日本印刷株式会社 包装材料
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JP2022168190A (ja) * 2017-07-27 2022-11-04 大日本印刷株式会社 積層体
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JP7333011B2 (ja) 2018-10-19 2023-08-24 大日本印刷株式会社 包装材料
JP2020066228A (ja) * 2018-10-19 2020-04-30 大日本印刷株式会社 包装材料
JP2020066230A (ja) * 2018-10-19 2020-04-30 大日本印刷株式会社 包装材料
JP7333012B2 (ja) 2018-10-19 2023-08-24 大日本印刷株式会社 包装材料
JP2021024112A (ja) * 2019-07-31 2021-02-22 大日本印刷株式会社 積層体および包装体
WO2021111941A1 (fr) * 2019-12-05 2021-06-10 東洋紡株式会社 Corps en couches stratifié
EP4137310A4 (fr) * 2020-04-13 2024-04-17 Toyobo Co., Ltd. Corps en couches stratifié
WO2022118710A1 (fr) 2020-12-02 2022-06-09 東洋紡株式会社 Film transparent barrière au gaz
KR20230109137A (ko) 2020-12-02 2023-07-19 도요보 가부시키가이샤 투명 가스 배리어 필름

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JP2017210002A (ja) 2017-11-30
JPWO2015146496A1 (ja) 2017-04-13
TWI652169B (zh) 2019-03-01
JP2017222180A (ja) 2017-12-21

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