JP5640973B2 - Polyester-based laminated film, vapor-deposited film using the same, laminate, and package - Google Patents

Description

  The present invention relates to a polyester-based laminated film that is excellent in gas barrier properties and excellent in interlayer adhesion even when different polyesters are laminated, and a vapor-deposited film, a laminate, and a package using the same.

  2. Description of the Related Art Conventionally, a packaging material having an effect of blocking the invasion of gas from the outside is required in order to prevent the deterioration of contents such as food and medicine, and recently electronic parts. As film materials having excellent gas barrier properties used for this purpose, composite films in which a film in which an ethylene / vinyl alcohol copolymer is laminated or a gas barrier film made of polyamide or the like are combined have been developed. However, films of ethylene / vinyl alcohol copolymer, polyamide, and the like have a problem that the gas barrier property is dependent on humidity, and the gas barrier property is greatly deteriorated under high humidity.

  Polyglycolic acid (hereinafter abbreviated as PGA) is an example of a gas barrier polymer that is less dependent on humidity. In general, since such a polymer having excellent gas barrier properties is expensive, it is often laminated as a thin layer on another inexpensive resin layer (see, for example, Patent Documents 1 to 3).

  However, in the above-mentioned Patent Documents 1 and 2, in order to ensure interlayer adhesion between the polyglycolic acid layer and the thermoplastic resin layer, a method of using an adhesive layer between these layers is specifically disclosed. However, no clear guidance principle is disclosed regarding the method for improving the interlaminar adhesion when they are directly laminated. Patent Document 3 discloses a method of directly laminating a polyglycolic acid layer and a polylactic acid layer and heating the stretching point with an infrared heater or the like in order to improve interlayer adhesion. The effect of improving the property was hardly recognized.

  In recent years, the required level of gas barrier properties has further increased, and the above-mentioned film has become insufficient in gas barrier properties. Furthermore, with the recent increase in environmental awareness, there has been a growing demand for biodegradable gas barrier films.

Japanese Patent No. 3978070 Japanese Patent No. 3913847 JP 2006-130847 A

  Accordingly, an object of the present invention is to provide a laminate having excellent gas barrier properties, workability, and practicality with excellent interlayer adhesion, although a polyglycolic acid layer and a different polyester layer are directly laminated. It is providing a film and its vapor deposition film, a laminated body, and a package.

  As a result of intensive studies to solve the above problems, the present inventors have polyglycolic acid as the main constituent component on at least one side of the layer (A layer) containing “polyester other than polyglycolic acid” as the main constituent component. It has been found that a polyester-based laminated film having both excellent gas barrier properties, workability, and practicality can be provided by increasing the interlayer adhesion between the resin layers, including a configuration in which the layer (B layer) is directly laminated. Completed the invention. That is, the gist of the present invention is as follows.

  That is, the polyester-based laminated film of the present invention has a layer (B layer) containing polyglycolic acid as a main component on at least one side of a layer (A layer) containing “polyester other than polyglycolic acid” as a main component. Including a directly laminated structure, the A layer contains an interlayer adhesion improver.

  As another configuration, the polyester-based laminated film of the present invention is a layer containing polyglycolic acid as a main constituent component on at least one side of a layer (A layer) containing “polyester other than polyglycolic acid” as a main constituent component. Including a structure in which (B layer) is directly laminated, the interlayer adhesive force between the A layer and the B layer is 25 g / 15 mm or more. Furthermore, as a preferable aspect of the polyester-based laminated film of this embodiment, the A layer contains an interlayer adhesion improving agent.

  As a more preferred embodiment, the interlayer adhesion improving agent is a polymer containing at least one component selected from the group consisting of an ethylene component, an acrylic acid derivative component, and a glycidyl group-containing component as a comonomer component, The B layer contains an interlayer adhesion improver, and the content of the interlayer adhesion improver in the A layer and / or the B layer is 0.1 to 30% by mass with respect to 100% by mass of all components of each layer. The aspect ratio of each region dispersed in the layer A and / or the layer B of the interlayer adhesion improver is 5 or more and 30 or less, the polyester of the layer A is an aliphatic polyester, the layer B The polyglycolic acid is a copolymer containing a hydroxycarboxylic acid unit other than the glycolic acid unit as a comonomer unit, The unit is 1 to 30 mol% with respect to 100 mol% of all the monomer units of polyglycolic acid, the hydroxycarboxylic acid unit is a lactic acid unit, and layer B is at least one surface layer of the film. It is characterized by that.

  Moreover, as a preferable aspect using the said polyester-type laminated | multilayer film, the vapor deposition film which has the vapor deposition layer which consists of a metal or an inorganic oxide on the at least single side | surface of the said polyester-type laminated film, the said polyester-type multilayer film, and the said vapor deposition film are included. And a package comprising the polyester-based laminated film and the vapor-deposited film.

  The polyester-based laminated film of the present invention is excellent in workability and practicality because it has excellent interlayer adhesion even though layers mainly comprising different polyesters are directly laminated. Furthermore, since polyglycolic acid is used for one of the aforementioned polyesters, a film excellent in gas barrier properties such as oxygen and water vapor can be obtained. Therefore, it is easy to provide a vapor-deposited layer on the polyester-based laminated film of the present invention or to process it into a laminate or a package, and it can be suitably used as a packaging material or a general industrial film.

  Hereinafter, the present invention will be described in detail together with preferred embodiments.

As for the form of the polyester-based laminated film of the present invention, a layer (B layer) containing polyglycolic acid as a main constituent component is formed on at least one surface of a layer (A layer) containing “polyester other than polyglycolic acid” as a main constituent component. The polyester-based laminated film of the present invention (hereinafter sometimes simply referred to as the film of the present invention) is a film comprising a directly laminated structure, wherein the A layer contains an interlayer adhesion improver. The layer (B layer) which has polyglycolic acid as the main component is directly laminated on at least one side of the layer (A layer) whose main component is “polyester other than polyglycolic acid”. By setting it as such a laminated structure, it can be set as the film excellent in cost merit while showing the outstanding barrier property. Moreover, since the polyester-type laminated | multilayer film of this invention can provide the outstanding interlayer adhesive force as follows even if it is the structure laminated | stacked directly like this, it is excellent in workability and the practicality after a process. Further, in order to impart an interlayer adhesive force, it is common to use another layer for bonding (hereinafter referred to as an adhesive layer) between the A layer and the B layer. However, in this method, an extruder and a coextrusion device are required for the adhesive layer in addition to the A layer and the B layer, and in order to obtain a film having no lamination unevenness such as a flow mark (particularly coextrusion lamination). As a method, when the feed block method is used from the following methods, it is necessary to accurately control the melt viscosity of these at least three layers. In contrast, in the polyester-based laminated film of the present invention, since the A layer and the B layer are directly laminated, there is no need to additionally introduce an extruder or a co-extrusion device, and the lamination of the adhesive layer as described above There is no need to worry about unevenness. Therefore, the film of the present invention is economically excellent and has excellent handling properties during coextrusion.

  The A layer of the film of the present invention contains an interlayer adhesion improver. An interlayer adhesion improver is defined as a substance that improves the adhesion between each layer laminated in the film forming process. By including the interlayer adhesion improving agent, in the processing steps such as printing, laminating, coating, bag making and vapor deposition, separation between the A layer and the B layer hardly occurs, and the final product can be processed without any problem. For this reason, the film of this invention is excellent in workability. Moreover, even if the final product using the polyester-based laminated film is processed into a bag filled with the contents by, for example, bag making, the bag is difficult to delaminate between the A layer and the B layer. Excellent openability. For this reason, the film of this invention is excellent also in the utility after a process.

  The interlayer adhesion improver is preferably a polymer, and the monomer component of the polymer preferably contains at least one component selected from an ethylene component, an acrylic acid derivative component, and a glycidyl group-containing component.

  Further, the interlayer adhesion improver preferably contains an acrylic acid derivative component, and more preferably contains an acrylic acid derivative component and a glycidyl group-containing component.

  The interlayer adhesion improver is more preferably a copolymer obtained by copolymerizing other components in addition to the acrylic acid derivative component containing a glycidyl group, and the copolymer component is preferably an ethylene component. As a method for introducing a glycidyl group into the interlayer adhesion improver, it is preferable to introduce it as an acrylic acid derivative component shown below.

CH ₂ = CR ₁ COOR ₂
Here, R ₁ and R ₂ are preferably hydrogen or an alkyl group having 1 to 8 carbon atoms, an epoxy group, or a glycidyl group. More preferably, R ₂ is preferably a methyl group, an ethyl group, a t-butyl group, an n-butyl group, or a glycidyl group from the viewpoint of handleability during melt molding (for example, prevention of corrosion of an extruder) Of these, a glycidyl group is most preferred. It is also preferably exemplified that both R ₁ and R ₂ are glycidyl groups.

  Furthermore, when used in food packaging applications, from the viewpoint of melt moldability and the Food Sanitation Act provided by US FDA and other organizations, the interlayer adhesion improver is not only an acrylic acid derivative component as a monomer component. It is preferable that an olefin component, particularly an ethylene component is copolymerized. Furthermore, in addition to the ethylene component and acrylic acid derivative component, an acid anhydride derivative component typified by a glycidyl group-containing component or maleic anhydride may also be included as a copolymer component, which can further improve the interlayer adhesion. Is preferable.

  Examples of the interlaminar adhesion improver include glycidyl group-containing acrylic acid derivative components and ethylene component copolymers, which are the most preferred forms, such as “Elvalloy” and “Elvalloy AC” manufactured by Mitsui DuPont Polychemical Co., Ltd. , “High Milan”, “Nuclerel”, “HPR”; “Lotader MAH”, “Lotader GMA”, “BONDINE” manufactured by Arkema; “BONDFAST” manufactured by Sumitomo Chemical Co., Ltd .; “REXPEARL ET” manufactured by Nippon Polyethylene Co., Ltd. Examples include “Biomax strong” manufactured by EI du Pont de Nemours and Company. Among these, “Biomax strong 120” is most preferable because it conforms to FDA (CFR 175. 105), has a high effect of improving interlayer adhesion, and simultaneously improves stretch processability.

  The interlayer adhesion between the A layer and the B layer of the film of the present invention is preferably 25 g / 15 mm or more. Here, as described later, the interlayer adhesion is dry-laminated on one side of the laminated film of the present invention with an unstretched polypropylene film using a polyurethane-based adhesive, and a peel test is performed using a known tensile tester. It is the average value of the maximum value and the minimum value of the load value obtained at the time. In the polyester-based laminated film of the present invention, the interlaminar adhesion force is set to the above-described aspect, so that peeling is unlikely to occur between the A layer and the B layer in processing steps such as printing, laminating, coating, bag making, and vapor deposition. Can be processed into final products without problems. For this reason, the film of this invention is excellent in workability. Moreover, even if the final product using the polyester-based laminated film is processed into a bag filled with the contents by, for example, bag making, the bag is difficult to delaminate between the A layer and the B layer. Excellent openability. For this reason, the film of this invention is excellent also in the utility after a process. In addition, according to the measurement method, delamination often occurs at the interface between the A layer and the B layer, which are different polyesters having the lowest interlayer adhesion, but delamination occurs in the A film in the film of the present invention. It may be considered that it occurs at a place other than the interface between the layer and the B layer, or that cohesive failure occurs. In such a case, what is necessary is just to conclude that the interlayer adhesive force between A layer and B layer is more than the measured load value. Moreover, the interlayer adhesive force between the A layer and the B layer of the present invention is preferably as high as possible, more preferably 40 g / 15 mm or more, and still more preferably 80 g / 15 mm or more. The upper limit of the interlaminar adhesion force between the A layer and the B layer is not particularly limited, but it is estimated that about 1000 g / 15 mm is the upper limit.

  Moreover, the B layer of the film of the present invention may contain an interlayer adhesion improving agent. When layer B contains an interlayer adhesion improver, interlayer adhesion may be improved. However, when the polyester which is the main component of the A layer is polylactic acid, the interlayer adhesion tends to be higher when the interlayer adhesion improver is contained only in the A layer. As the interlayer adhesion improving agent, those having the same structure as the A layer are preferable.

  In the film of the present invention, the content of the interlayer adhesion improving agent in the A layer is preferably 0.1 to 30% by mass with respect to 100% by mass of all components in each layer. Moreover, it is preferable that the content of the interlayer adhesion improving agent of the B layer is 0.1 to 30% by mass with respect to 100% by mass of all components of each layer. If the content of the interlayer adhesion improving agent is less than 0.1% by mass, sufficient interlayer adhesion may not be exhibited. On the other hand, when the content of the interlayer adhesion improver exceeds 30% by mass, the effect of improving the interlayer adhesion tends to be saturated, the surface roughness of the resulting film increases, and the barrier property may deteriorate. The content of the interlayer adhesion improving agent is more preferably 0.5 to 20% by mass, still more preferably 1 to 15% by mass, and most preferably 2 to 10% by mass with respect to 100% by mass of all components in each layer. . However, when forming a vapor deposition layer directly on B layer, it is preferable to make content of an interlayer adhesion improving agent into the minimum, More preferably, it is 0.5-5 mass%, More preferably, it is 0.5-3 mass %.

  In the film of the present invention, the aspect ratio of each region dispersed in the A layer and / or B layer of the interlayer adhesion improver is preferably 5 or more and 30 or less. When the aspect ratio is within this range, the interlayer adhesion improver forms a layered alloy structure and stabilizes the interface. In particular, when the interlayer adhesion improving agent has a reactive functional group such as a group, when heated during film formation, the resins forming the A layer and the B layer react with each other starting from the reactive functional group to form a graft copolymer. It is estimated that When the aspect ratio is less than 5, the ratio of the functional units involved in the adhesion between the layers decreases, and sufficient adhesive strength cannot be obtained. When the aspect ratio exceeds 30, it is a case where stretching at a high magnification is performed, and properties such as elongation are deteriorated. The aspect ratio is more preferably 10 or more and 20 or less because the balance between the adhesive force between the A layer and the B layer and other film properties is improved. The aspect ratio can be controlled by the extrusion temperature, stretching ratio, stretching temperature, and heat setting temperature. The aspect ratio can be produced by analyzing a cross-sectional photograph of the film using image conversion software or the like.

  The polyester that is the main constituent of the A layer of the film of the present invention (hereinafter, may be simply referred to as “A layer polyester”) is not particularly limited as long as it is a “polyester other than polyglycolic acid”, and is aromatic. Polyesters, aliphatic polyesters and blends or copolymers thereof are mentioned and are distinguished from the polyglycolic acid defined below in the present invention. When the polyester of the A layer is an aromatic polyester, high barrier properties can be exhibited by improving the heat resistance and stability over time of the resulting film. Moreover, when the polyester of A layer is aliphatic polyesters, such as polylactic acid, since it can be set as the gas barrier film which has biodegradability, it is preferable.

  In addition, in this invention, the layer (A layer) which has "the polyester other than polyglycolic acid" here as a main structural component is 70 mass% of the component with respect to 100 mass% of the polymer constituting the A layer. It is defined as above. That is, the fact that the polyester which is the main component of the A layer is an aliphatic polyester means that the aliphatic polyester is 70% by mass or more with respect to 100% by mass of the total polymer component of the A layer. Being a blend of an aliphatic polyester and an aliphatic polyester means that the total amount of the aromatic polyester and the aliphatic polyester is 70% by mass or more with respect to 100% by mass of the total polymer component of the A layer. In addition, regarding the upper limit of “polyester other than polyglycolic acid”, which is the main component in the A layer, in the film of the present invention, it is 99.9% by mass or less with respect to 100% by mass of the polymer constituting the A layer.

  In the film of the present invention, as the aromatic polyester or aliphatic polyester which is the “polyester other than polyglycolic acid” in the A layer, various polyesters obtained by ester-linking an acid component and a glycol component can be used. Examples of the acid component include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and naphthalenedicarboxylic acid; aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, and dimer acid; cyclohexanedicarboxylic acid Alicyclic dicarboxylic acids such as acids; hydroxycarboxylic acids such as lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid; polyfunctional acids such as trimellitic acid and pyromellitic acid be able to. On the other hand, examples of the glycol component include aliphatic diols such as ethylene glycol, diethylene glycol, butanediol and hexanediol; alicyclic diols such as cyclohexanedimethanol; aromatic glycols such as bisphenol A and bisphenol S; diethylene glycol and polyalkylene Glycol or the like can be used. Furthermore, polyethers such as polyethylene glycol and polytetramethylene glycol may be copolymerized. In addition, these dicarboxylic acid component and glycol component may use 2 or more types together, and may blend and use 2 or more types of polyester.

  As the aromatic polyester, for example, polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, and polyesters copolymerized with isophthalic acid, sebacic acid and dimer acid, or a blend of two or more kinds thereof are preferably used. . Examples of the aliphatic polyester having excellent biodegradability include polylactic acid, poly-3-hydroxybutyrate, poly-3-hydroxybutyrate-3-hydroxyvalerate, polycaprolactone, ethylene glycol, and 1,4-butane. Examples thereof include aliphatic polyesters composed of aliphatic diols such as diols and aliphatic dicarboxylic acids such as succinic acid and adipic acid. In addition, a copolymer of an aliphatic polyester and an aromatic polyester such as poly-butylene succinate-terephthalate and poly-butylene adipate-terephthalate can also be suitably used.

  In the film of the present invention, the mass average molecular weight of “polyester other than polyglycolic acid”, which is the main component of the A layer, is 50,000 in order to satisfy stable film-forming properties, good stretchability, and practical mechanical properties. It is preferably ˜500,000 g / mol, more preferably 100,000 to 250,000 g / mol. The mass average molecular weight as used herein refers to a molecular weight calculated by a polymethyl methacrylate conversion method after measurement with a chloroform solvent by gel permeation chromatography (GPC).

  In addition, from the viewpoints of heat resistance, resin supply stability, and plantiness, aliphatic polyesters that are particularly preferably used as “polyesters other than polyglycolic acid” that are the main constituents of layer A include L-lactic acid and / or It is a polylactic acid mainly composed of D-lactic acid. Here, the polylactic acid may contain a comonomer component other than lactic acid. Examples of the comonomer include ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopentylglycol, glycerin, and pentane. Glycol compounds such as erythritol, bisphenol A, polyethylene glycol, polypropylene glycol and polytetramethylene glycol, oxalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, glutaric acid, cyclohexanedicarboxylic acid, terephthalic acid , Isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4′-diphenyl ether di Dicarboxylic acids such as rubonic acid, 5-sodium sulfoisophthalic acid and 5-tetrabutylphosphonium isophthalic acid, glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid and other hydroxycarboxylic acids, caprolactone And lactones such as valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one.

  As the polylactic acid preferably used as the polyester for the A layer, L-lactic acid rich polylactic acid (poly L-lactic acid) is preferably used from the viewpoint of the solubility of the resin. As poly L-lactic acid, the content of L-lactic acid units in 100 mol% of total lactic acid units of poly L-lactic acid (the content of L-lactic acid units in 100 mol% of total lactic acid units of poly L-lactic acid is hereinafter referred to as A substance having an L content of 50 to 100 mol% is used. From the viewpoint of crystallinity and resin solubility, the L-form amount of poly-L-lactic acid is more preferably 80 to 100 mol%, still more preferably 95 to 100 mol%, and most preferably 97 to 100 mol%. On the other hand, when polylactic acid rich in D-lactic acid (poly-D-lactic acid) is used, the content of D-lactic acid units in 100 mol% of total lactic acid units in the poly-D-lactic acid (100 mols of total lactic acid units in poly-D-lactic acid) % D-lactic acid unit content is hereinafter referred to as D-form amount) of 50 to 100 mol%. From the viewpoint of crystallinity, the D-form amount of poly-D-lactic acid is more preferably 80 to 100 mol%, further preferably 95 to 100 mol%, and most preferably 97 to 100 mol%.

  The crystallinity of polylactic acid varies depending on the content ratio of L-lactic acid units or D-lactic acid units. That is, the higher the D-form amount in poly L-lactic acid, the lower the crystallinity of poly L-lactic acid and the closer it is to amorphous. On the other hand, the lower the D-form amount in poly L-lactic acid, the higher the crystallinity of poly L-lactic acid. Similarly, the crystallinity of poly D-lactic acid changes according to the L-form amount. That is, the higher the L-form amount in the poly-D-lactic acid, the lower the crystallinity of the poly-D-lactic acid becomes closer to amorphous, and conversely, the lower the L-form amount in the poly-D-lactic acid, The crystallinity of lactic acid is increased. In addition, when polylactic acid with low crystallinity is blended with polylactic acid with high crystallinity, it is preferable from the viewpoint of stretchability.

  In the film of the present invention, when polylactic acid is used as the “polyester other than polyglycolic acid”, which is the main component of the A layer, as the polylactic acid, 4032D (D-body weight = 1.4%) manufactured by Nature Works ), 4042D (D-form amount = 4.25%), 4050D (D-form amount = 5.5%), and the like. Among these, 4032D having high crystallinity is preferably used. In addition, in order to improve the stretchability of the A layer, 4032D and Nature Works 4060D (D amount = 12%) may be appropriately blended.

  For the resin used for the A layer of the film of the present invention, from the viewpoint of economy and the like, the waste film produced when the film of the present invention is produced and other films are produced within a range not impairing the effects of the present invention. It is also possible to blend and use the waste film produced during the process.

  Moreover, you may add a small amount of polyglycolic acid defined below to A layer of the film of this invention. That is, polyglycolic acid can be used as a component other than the main constituent components in the A layer. By including a small amount of polyglycolic acid in the A layer, the interlayer adhesion between the A layer and the B layer may be improved. The amount of polyglycolic acid contained in the A layer is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, and still more preferably 1 in 100% by mass of the polymer constituting the A layer. ˜5 mass%. The method for containing a small amount of polyglycolic acid in the A layer is not particularly limited as long as the effects of the present invention are not impaired, but the waste film produced when the film of the present invention is produced as described above is used for the A layer. It can be used by blending with a resin composition.

  Further, as described in detail below, when producing the film of the present invention, it is important to stretch at least 70 ° C. in at least one direction. In order to make the film stretchable at 70 ° C. or lower, the glass transition temperature (Tg) of the A layer is preferably 65 ° C. or lower. The glass transition temperature here is a value measured by a differential scanning calorimeter (DSC) according to the method described in JIS K7121 (1999), and is the midpoint glass when the temperature is raised at 20 ° C./min. Transition temperature. When the Tg of the A layer exceeds 65 ° C., the film-forming stability may be deteriorated when stretched at 70 ° C. or less in at least one direction. Further, when the stretching temperature is increased in order to maintain the film formation stability, the orientation crystallization of the B layer proceeds remarkably, especially when the B layer is used as the outermost layer of the film of the present invention, the B layer becomes rough, The barrier property of the obtained film may deteriorate. In order to enable stable film formation at 70 ° C. or lower, prevent blocking of the resulting film, and sufficiently increase the mechanical properties of the film, the Tg of the A layer is more preferably 0 to 65 ° C., and further preferably It is 30-65 degreeC, Most preferably, it is 40-60 degreeC. When polylactic acid is used as the polyester of the A layer, in order to maintain the film forming stability at 70 ° C. or less, the component (resin composition) of the A layer is a plastic that serves to lower the Tg of polylactic acid. Ingredients such as an agent and amorphous polylactic acid can be contained.

  The B layer of the film of the present invention contains polyglycolic acid as a main constituent. Here, in the present invention, the layer (B layer) containing polyglycolic acid as the main component is that whose component is 70% by mass or more and 100% by mass or less with respect to 100% by mass of the polymer constituting the B layer. Is defined. That is, the B layer needs to contain 70% by mass to 100% by mass of polyglycolic acid defined below. When the B layer is mainly composed of polyglycolic acid, a layer having a high gas barrier property is formed due to the high crystallinity of polyglycolic acid, and the gas barrier property is remarkably improved as a whole film. Moreover, when using aliphatic polyester, such as polylactic acid, as polyester of A layer, the biodegradability of the whole film can be improved. From the viewpoint of gas barrier properties, the content of polyglycolic acid in the B layer is preferably 80% by mass or more, more preferably 90% by mass or more, with respect to 100% by mass of the polymer constituting the B layer.

  In the film of the present invention, the polyglycolic acid that is the main constituent of the B layer (hereinafter, the polyglycolic acid that is the main constituent of the B layer may be simply referred to as polyglycolic acid of the B layer) In invention, when all the monomer units contained in the polyglycolic acid of B layer are 100 mol%, it means containing 70 mol% or more and 100 mol% or less of glycolic acid units as monomer units. By controlling the molecular structure of the polyglycolic acid in the B layer in this way, excellent gas barrier properties and heat resistance can be imparted. The content of glycolic acid units in the polyglycolic acid in the B layer is preferably 80 mol% or more, more preferably 90 mol% or more when the total monomer units contained in the polyglycolic acid in the B layer are 100 mol%.

  On the other hand, when a small amount of a copolymer component other than the glycolic acid unit is introduced as the polyglycolic acid in the B layer, the gas barrier property is slightly lowered, but the crystallinity of the polyglycolic acid can be suppressed, and the roughening in the stretching process is reduced. it can. This is preferable because the extrusion temperature during the molding process can be lowered and the stretchability can be improved. Examples of comonomer units that can be copolymerized with the polyglycolic acid in layer B include ethylene oxalate, lactide, and lactones (for example, β-propiolactone, β-butyrolactone, pivalolactone, γ-butyrolactone, δ-valerolactone, cyclic monomers such as β-methyl-δ-valerolactone, ε-caprolactone, trimethylene carbonate, and 1,3-dioxane; lactic acid, 3-hydroxypropanoic acid, 3-hydroxybutanoic acid, 4-hydroxybutanoic acid, 6 A hydroxycarboxylic acid such as hydroxycaproic acid or an alkyl ester thereof; an aliphatic diol such as ethylene glycol or 1,4-butanediol; and an aliphatic dicarboxylic acid such as succinic acid or adipic acid or an alkyl ester thereof. List equimolar mixtures Can. Among these, cyclic compounds such as lactide, caprolactone and trimethylene carbonate; hydroxycarboxylic acids such as lactic acid, and the like are preferably used because they are easy to copolymerize and are easy to obtain a copolymer having excellent physical properties. In particular, when polylactic acid is used as the main constituent polyester in the A layer, polyglycolic acid copolymerized with lactic acid units among hydroxycarboxylic acids is used as the polyglycolic acid in the B layer. Since melting | fusing point falls, extrusion temperature can be brought close to the extrusion temperature of polylactic acid, and since the interlayer adhesive force with A layer may be improved, it is preferable.

  Moreover, the copolymerization amount (amount of comonomer units) of the comonomer units in the polyglycolic acid is preferably 1 to 30 mol% when all the monomer units contained in the polyglycolic acid in the B layer are 100 mol%. If the copolymerization amount is less than 1 mol%, the above-described effects may not be obtained. When the copolymerization amount exceeds 30 mol%, the excellent gas barrier property of polyglycolic acid may be impaired. The amount of copolymerization is more preferably 3 to 20 mol%, still more preferably 5 to 15 mol%.

  The polyglycolic acid of the B layer can be synthesized by dehydration polycondensation of glycolic acid, dealcohol polycondensation of glycolic acid alkyl ester, ring-opening polymerization of glycolide, or the like. Among these, glycolide is heated to a temperature of about 120 ° C. to 250 ° C. in the presence of a small amount of catalyst (for example, a cation catalyst such as tin organic carboxylate, tin halide, antimony halide, etc.) to open a ring. A method of synthesizing polyglycolic acid by a polymerization method is preferred. The ring-opening polymerization is preferably performed by a bulk polymerization method or a solution polymerization method.

The melt viscosity of all components constituting the B layer is preferably 1000 poise to 10,000 poise at 270 ° C. and 100 sec ⁻¹ , more preferably 2000 poise to 6000 poise, and further preferably 2500 poise to 5500 poise. When the melt viscosity of all the components constituting the B layer at 270 ° C. and 100 sec ⁻¹ is less than 1000 poise, the molecular weight of polyglycolic acid, which is the main constituent of the B layer, is low and may be easily decomposed. Moreover, when the melt viscosity of all the components constituting the B layer exceeds 10,000 poise, the load on the extruder and the filtration pressure in the extrusion process become high, and coextrusion lamination with the A layer may be difficult.

  The A layer and the B layer of the film of the present invention are, for example, a flame retardant, a heat stabilizer, a light stabilizer, an antioxidant, a moisture proof agent, a water repellent, as long as the effects of the present invention are not impaired. Waterproofing agent, mold release agent, coupling agent, chain extender, terminal blocker, oxygen absorber, anti-coloring agent, UV absorber, antistatic agent, plasticizer, crystal nucleating agent, tackifier, low fatty acid ester Organic lubricants such as molecular weight bodies and waxes, antifoaming agents such as polysiloxane, and colorants such as pigments and dyes may be contained. The additive can be contained in the A layer and / or B layer of the film of the present invention in an amount of 0 to 30% by mass with respect to 100% by mass of the total components of the respective layers.

  For example, in the B layer, in order to improve the melt stability of the polyglycolic acid in the B layer, as a heat stabilizer, a phosphate ester having a pentaerythritol skeleton structure, at least one hydroxyl group and at least one long-chain alkyl ester group A phosphorus compound having a heavy metal, a heavy metal deactivator, a metal carbonate, and the like can be contained. These heat stabilizers can be used alone or in combination of two or more.

  The layer structure of the film of the present invention is not particularly limited as long as it includes a structure in which the B layer is directly laminated on at least one surface of the A layer and a structure of A layer / B layer (“/” indicates a laminated interface). For example, what is necessary is just to select suitably in the range which does not impair the effect of this invention from structures, such as A layer / B layer, A layer / B layer / A layer, B layer / A layer / B layer. Furthermore, additive scattering / bleed-out suppression, coating film / deposition film easy adhesion, easy printability, heat sealability, print lamination, gloss, slipperiness, mold release, easy peel, Depending on various purposes, such as surface hardness improvement, smoothness imparting, surface roughness enhancement, hand cutting property imparting, surface hydrophilicity imparting, optical property control, surface heat resistance imparting, concealing property improving etc. One or more layers may be stacked. For example, it can also be set as a film layer structure asymmetrical in the thickness direction, such as B layer / A layer / C layer, A layer / B layer / C layer. Further, when the interlayer adhesive force between the C layer and the B layer or the A layer is insufficient, an adhesive layer D layer can be used between the C layer and the A layer or B layer. In this case, it can be set as film layer structure, such as B layer / A layer / D layer / C layer, A layer / B layer / D layer / C layer, for example. Here, the C layer is preferably used as a heat seal layer. As will be described later, so-called amorphous polylactic acid such as poly L-lactic acid having a high D-form amount and poly D-lactic acid having a high L-form quantity. Is preferably exemplified. Here, the D layer is preferably a biodegradable polymer having a low melting point relative to polylactic acid. For example, polybutylene adipate, polybutylene terephthalate, polybutylene adipate, polytetramethylene terephthalate, polytetramethylene adipate. And so on.

  Here, the directly laminated structure means an aspect in which an intermediate layer such as an adhesive layer is not provided between the A layer and the B layer and is in a directly laminated form. Specifically, for example, A layer / B layer, A layer / B layer / A layer, B layer / A layer, and the like are exemplified. The directly laminated structure is more preferably a structure in which the A layer and the B layer are laminated by a coextrusion method as described in detail below.

  As the other resin layers, known thermoplastic resins can be used, and are not particularly limited. When an aliphatic polyester is used as the “polyester other than polyglycolic acid” which is the main component of the A layer, the aliphatic polyester defined above or a copolymer thereof is added to other polyesters from the viewpoint of waste film recoverability. It is preferable to use it as the main component of the resin layer.

  In the film of the present invention, the B layer is preferably at least one surface layer. Among the above examples, A layer / B layer, B layer / A layer / B layer, B layer / A layer / C layer, and B layer / A layer / D layer / C layer correspond to this. By making the B layer the outermost layer, as described in detail below, it becomes possible to deposit on the B layer, while suppressing the decomposition of the B layer, forming a high-quality deposited film, and excellent in gas barrier properties It can be set as a deposited film.

  For example, when polylactic acid is used as the “polyester other than polyglycolic acid”, which is the main component of the A layer, the poly L-lactic acid having a high D-form amount in the C layer as the B layer / A layer / C layer film configuration It is preferable to use so-called amorphous polylactic acid such as poly-D-lactic acid having a high L-form amount. When laminating the C layer to impart heat sealability, the D-form amount of the poly L-lactic acid used in the C layer is preferably 8 to 20 mol%, and the L-form amount of the poly D-lactic acid is preferably 8 to 20 mol%. . An example of poly L-lactic acid having a high D-form amount and preferably used for imparting heat-sealability to the film of the present invention is Nature Works 4060D (D-form quantity = 12%).

  The thickness of the film of the present invention is not particularly limited, but is preferably 5 to 100 μm, more preferably 8 to 50 μm, and still more preferably from the viewpoints of handling properties and suitability for vapor deposition processing when processed into a packaging material. 10-25 μm. In the film of the present invention, the ratio of the B layer to the film thickness is preferably 0.01 to 0.3 when the total film thickness is 1. When the ratio of the thickness of the B layer (the thickness of the B layer referred to here means the total thickness of the B layer when a plurality of B layers are present) is less than 0.01, the gas barrier property of the film is It may be bad, and if it exceeds 0.3, the stretchability of the film may deteriorate. The ratio of the thickness of the B layer is more preferably 0.02 to 0.25, and still more preferably 0.025 to 0.2.

  The film of the present invention is preferably biaxially oriented. When the film is biaxially oriented, good gas barrier properties can be exhibited. In order to biaxially orient the film of the present invention, it is preferable to use a known biaxial stretching method which will be described in detail below.

  The film of the present invention measures the longitudinal refractive index (Nx), lateral refractive index (Ny), and thickness direction refractive index (Nz) of the surface, and the plane orientation coefficient (fn) determined by (Nx + Ny) / 2−Nz. Hereinafter may be abbreviated as fn of the film) is preferably 0.01 to 0.1. More preferably, it is 0.02-0.08, More preferably, it is 0.03-0.07. If fn is less than 0.01, the gas barrier property may be deteriorated because the plane orientation is low. If fn exceeds 0.1, the film may be easily cleaved. In order to make fn of the film of the present invention in the range of 0.01 to 0.1, when producing the film by biaxial stretching, the stretching temperature in the stretching step, the stretching ratio, and the heat treatment in the heat setting step A method of controlling the orientation by temperature or the like is preferably used. Moreover, when a vapor deposition layer is provided on at least one surface of the film of the present invention as described below to form a vapor deposition film, the vapor deposition layer can be removed with an acid and the plane orientation coefficient can be confirmed even after vapor deposition.

  When the B layer of the film of the present invention is a surface layer and a vapor deposition layer is provided on the B layer, it is important that the center line average roughness (Ra) of the B layer is 3 nm to 50 nm. When the Ra of the B layer is less than 3 nm, the slipperiness of the film is inferior, and in the winding process during film formation, in the processing process such as printing, laminating, coating, bag making, vapor deposition, blocking or unwinding may occur. Charges due to static electricity are likely to be induced, resulting in inferior handling properties and significant deterioration in gas barrier properties. On the other hand, when Ra of the B layer exceeds 50 nm, a uniform vapor deposition layer is not formed on the B layer, or pinholes are generated in the vapor deposition film, so that the gas barrier property is often greatly deteriorated. Ra of B layer becomes like this. More preferably, it is 5-50 nm, More preferably, it is 15-40 nm. Ra of layer B controls the crystallization of polyglycolic acid in layer B according to the stretching temperature, stretching ratio, heat setting temperature in the heat setting step, etc., when the film of the present invention is biaxially stretched. Can be adjusted. For example, sequential biaxial stretching can be achieved by performing biaxial stretching at a stretching temperature of 70 ° C. or lower and an area magnification of 4.0 times or higher, followed by heat treatment. In addition, polyglycolic acid has low thermal stability, and foreign substances such as gel are likely to be generated in the molten polymer, but these foreign substances become coarse protrusions and often rough the surface. It is preferable to filter the molten polymer extruded from the extruder using a filter obtained by sintering and compressing and a filter obtained by sintering stainless steel powder. Details of the film forming method will be described later.

  The Young's modulus in the longitudinal direction and the transverse direction of the film of the present invention is preferably 2.5 GPa or more, respectively. When the Young's modulus is less than 2.5 GPa, for example, when the film of the present invention is vapor-deposited and processed into a vapor-deposited film, the film stretches due to tension, or the structural change of the film is induced by heat during vapor deposition, resulting in gas barrier properties. It may get worse. In addition, even after vapor deposition, the film stretches due to processing tension in subsequent processing steps and cracks are generated in the vapor deposition film, so that the gas barrier property may be deteriorated. The Young's modulus in the longitudinal direction and the transverse direction of the film of the present invention is more preferably 3 to 8 GPa, and still more preferably 4 to 8 GPa. In order to make the Young's modulus in the longitudinal direction and the transverse direction of the film of the present invention 2.5 GPa or more, the film of the present invention is produced by a biaxial stretching method, and the stretching temperature, magnification, and heat setting process of the stretching process are performed. A method of controlling the plane orientation by the heat setting temperature of the is preferably used.

  It is preferable that the shrinkage in the vertical and horizontal directions when the film of the present invention is heat-treated at 120 ° C. for 15 minutes is 10% or less, respectively. If the heat shrinkage rate exceeds 10%, the film may be greatly shrunk by heat applied during processing in printing, laminating, coating, bag making, vapor deposition and the like, and handling properties may be inferior. Further, the gas barrier property may be significantly deteriorated due to the structural change of the film due to shrinkage. The thermal contraction rate in the vertical direction and the horizontal direction is more preferably 8% or less, and further preferably 6% or less. In order to make the heat shrinkage rate 10% or less, for example, in the production of the film of the present invention, it is preferable to control the heat setting temperature and the heat setting time in the heat setting step. In addition, although the heat shrinkage rate of the film of this invention does not provide a minimum in particular, it is guessed that the range which can be manufactured stably is about -2% (it is also allowed to extend). Furthermore, it is most preferable that both the vertical direction and the horizontal direction are zero.

  As described above, the film of the present invention is preferably biaxially oriented. The biaxial orientation of the film of the present invention is not particularly limited, and a known biaxial stretching method such as a sequential biaxial stretching method and a simultaneous biaxial stretching method, or a combination of these methods can be used.

  Below, the manufacturing method of the film of this invention is described.

  From the extruder (a), the resin composition used for the A layer containing “polyester other than polyglycolic acid” as the main constituent is melt-extruded, foreign matter is removed by a filter, and flow rate is optimized by a gear pump. Supply to a multi-manifold base having a plurality of manifolds or a feed block installed on the top of the base. Further, from the extruder (b), the resin composition used for the B layer, which is mainly composed of polyglycolic acid, is melt-extruded, and a foreign substance is removed by a filter in a flow path different from the extruder (a), by a gear pump. After optimizing the flow rate, it is supplied to the multi-manifold base or feed block. When laminating other resin layers other than the A layer and the B layer, the resin composition according to the purpose is melt-extruded from another extruder (a plurality of extruders), and another flow path is similarly formed. To supply to the multi-manifold base or feed block. Note that the multi-manifold base or the feed block needs to be provided with channels for the required number of layers according to the required film layer configuration. The molten resin extruded from each extruder is merged by the multi-manifold die or the feed block as described above, and coextruded into a sheet form from the die. The multilayer sheet is brought into close contact with a casting drum by a method such as air knife or electrostatic application, and is cooled and solidified to form an unstretched sheet.

  Here, in order to prevent surface roughness due to foreign matters such as gels and thermally deteriorated products, it is preferable to use a filter obtained by sintering and compressing stainless steel fibers having an average opening of 5 to 40 μm as a filter during film formation. Further, after the filter obtained by sintering and compressing the stainless steel fiber, a filter obtained by sintering stainless steel powder having an average opening of 10 to 50 μm is continuously filtered in this order, or the above two types of filters are combined in one capsule. The use of a composite filter is preferable because it can efficiently remove gels and thermally deteriorated materials, and is desirable because of the cost merit that the film forming edge and the core portion can be reused.

  The stretching conditions of the film of the present invention adjust the crystallinity and orientation of the polyglycolic acid of the B layer, improve the film forming property, and smooth the surface (when the B layer is the outermost layer of the film of the present invention). Therefore, it is preferable to stretch in at least one direction, and more preferably in two directions.

  When the film of the present invention is produced by a sequential biaxial stretching method, the unstretched sheet is preheated by passing it through a roll, and subsequently passed between rolls with a difference in peripheral speed, and stretched in the longitudinal direction, immediately after the glass transition of the resin. After cooling to a temperature below, the longitudinally uniaxially stretched film is guided to a tenter and stretched transversely, and then heat-fixed and wound while being relaxed in the transverse direction. Alternatively, it may be stretched by a method in which the machine direction and the transverse direction are simultaneously stretched, or may be stretched by a method in which the stretching in the longitudinal direction and the stretching in the transverse direction are combined a plurality of times, or the longitudinal direction after the longitudinal-lateral stretching. Re-stretching may be performed once or more in the direction and / or the transverse direction.

  When the sequential biaxial stretching method is used, the crystallinity of polyglycolic acid after uniaxial stretching is increased and the B layer may be roughened. Therefore, the film is formed at a stretching temperature and a stretching ratio within the ranges described below. It is preferable to create. On the other hand, when the film of the present invention is produced by the tenter simultaneous biaxial stretching method, the unstretched sheet can be stretched at once in the longitudinal and lateral directions, and therefore, it is difficult to roughen and is preferable from the viewpoint of surface smoothness. In addition, since the film can be stretched in the longitudinal and transverse directions at once, stretchability is improved, high-magnification stretching is possible, and high orientation and high Young's modulus may be possible.

  When manufacturing by a sequential biaxial stretching method, it is preferable that the extending | stretching temperature of a vertical direction shall be 40-70 degreeC. The stretching temperature in the machine direction is more preferably 40 to 65 ° C, and further preferably 50 to 60 ° C. The longitudinal draw ratio is preferably 2.0 to 5.0 times, more preferably 2.5 to 4.5 times, and still more preferably 3.0 to 4.5 times. The stretching temperature in the transverse direction is also preferably 70 ° C. or less, and specifically 40 to 70 ° C. is preferable. The stretching temperature in the transverse direction is more preferably 40 to 65 ° C, and further preferably 45 to 55 ° C. The transverse draw ratio is preferably 2.0 to 5.0 times, more preferably 2.5 to 4.5 times, and still more preferably 3.0 to 4.5 times. In the case of the sequential biaxial stretching method, if the stretching temperature in either the longitudinal stretching or the transverse stretching exceeds 70 ° C., the crystallization of polyglycolic acid is likely to proceed from the preheating stage in the transverse stretching process, and the B layer is formed of the film of the present invention. In the case of the outermost layer, the surface of the layer B tends to be rough after stretching and heat setting. Moreover, when the area magnification, which is the product of the longitudinal draw ratio and the transverse draw ratio, is 4.0 times or less, thermal crystallization of polyglycolic acid in the heat setting step tends to progress and roughen the surface. Furthermore, in order to make the aspect ratio of the interlayer adhesion improver within the range of the present invention, it is necessary to be 4 times or more and 15 times or less.

  When manufacturing by a simultaneous biaxial stretching method, it is preferable to make extending | stretching temperature 40-70 degreeC. The stretching temperature is more preferably 40 to 65 ° C, still more preferably 50 ° C to 60 ° C. The draw ratio needs to be 4 times or more and 15 times or less so that the aspect ratio of the interlayer adhesion improving agent is within the range of the present invention. Moreover, in order not to disturb the balance of the physical properties of the film in the vertical and horizontal directions, the ratio of the vertical draw ratio and the horizontal draw ratio is preferably 0.5 or more and 2 or less.

  After stretching, the temperature is preferably 120 ° C. or higher and the temperature below the lower melting point of the polyester in the A layer and the polyglycolic acid in the B layer, more preferably 130 ° C. or higher, the polyester in the A layer and the polyglycolic acid in the B layer. Relaxing heat treatment is performed at a temperature 5 ° C. or more lower than the lower melting point, more preferably 140 ° C. or more, and at a temperature 10 ° C. or more lower than the lower melting point of the polyester A and the polyglycolic acid B layer, and cooling. It is preferable to do. The heating time during the relaxation heat treatment is preferably 30 seconds or more and 5 minutes or less in order to allow the interlayer adhesion improver to sufficiently react. In addition, by performing relaxation heat treatment under such conditions after appropriate stretching, the surface smoothness of the B layer is maintained (when the B layer is the outermost layer of the film of the present invention), a low heat shrinkage rate, A film with good flatness that satisfies the range of the elastic modulus and the constant plane orientation coefficient and suppresses curling can be obtained. When the relaxation heat treatment temperature is set to a temperature higher than the lower melting point of the polyester of the A layer and the polyglycolic acid of the B layer, the layer having the melting point may be melted and non-oriented, and the film forming property may be significantly impaired. . Further, when the relaxation heat treatment temperature is set to be equal to or higher than the melting point of the polyglycolic acid of the B layer, the polyglycolic acid is melted and the B layer is recrystallized by the temperature-falling crystallization after the relaxation heat treatment. The B layer may become rough. On the other hand, when the relaxation heat treatment temperature is less than 120 ° C., the heat resistance of the resulting film is greatly reduced, or the film is heated by the heat applied during processing in printing, laminating, coating, bag making, vapor deposition and other processing steps. It shrinks greatly and may be inferior in handling property.

  It is preferable that at least one surface of the film of the present invention is provided as a vapor deposition film by providing a vapor deposition layer by vapor deposition. By providing a vapor deposition layer on at least one side of the film of the present invention, the gas barrier property can be remarkably improved. Moreover, the decomposition rate of the polyglycolic acid of B layer which is easily decomposable can be reduced.

  When the film of the present invention is used after being processed into a vapor deposition film, the B layer is preferably the outermost layer on at least one side of the film, and the vapor deposition layer is preferably formed on the B layer. Examples of such a configuration include vapor deposition layer / B layer / A layer. For example, the B layer and other resin layers can be laminated on the A layer side of the vapor deposition layer / B layer / A layer according to the purpose within a range not impairing the effects of the present invention. By forming a vapor deposition layer on the B layer, decomposition of the B layer can be remarkably suppressed. Moreover, a vapor deposition layer can also be formed in both surface layers of a film.

  The metal or inorganic oxide used for the vapor deposition layer is not particularly limited, and examples thereof include aluminum, aluminum oxide, silicon oxide, silicon oxynitride, cerium oxide, calcium oxide, diamond-like carbon film, and a mixture thereof. It is done. In order to improve gas barrier properties while maintaining or improving productivity, aluminum, aluminum oxide, and silicon oxide are more preferably used. A vapor deposition layer using aluminum is preferable because it is excellent in economy and gas barrier performance, and a vapor deposition layer using aluminum oxide or silicon oxide is preferable in terms of cost and transparency.

  When using the film of this invention as a vapor deposition film, a vacuum process is used as a formation method of a vapor deposition layer. Although it does not specifically limit as a vacuum process, For example, a vacuum evaporation method, sputtering method, an ion plating method, a chemical vapor deposition method etc. are used preferably. For example, in order to provide an inorganic oxide vapor deposition layer, a reactive vapor deposition method is more preferably used in terms of productivity and cost.

  In the vacuum process, it is preferable to subject the surface of the pre-deposition film to plasma treatment or corona treatment in order to further improve the gas barrier property. The treatment strength when performing the corona treatment is preferably 5 to 50 W · min / m 2, more preferably 10 to 45 W · min / m 2. In addition, it is preferable to provide a cored metal vapor deposition layer under plasma discharge before providing a vapor deposition layer made of a metal or an inorganic oxide from the viewpoint of improving the adhesion of the vapor deposition layer and, consequently, improving the gas barrier property. In this case, plasma discharge is preferably performed in an oxygen and / or nitrogen gas atmosphere, and copper is preferably used as the cored metal.

To deposit aluminum oxide by reactive vapor deposition, aluminum metal and alumina are evaporated by resistance heating boat method, crucible high frequency induction heating, electron beam heating method, and aluminum oxide is deposited on the film in an oxidizing atmosphere. A method is preferably employed. Oxygen is used as a reactive gas for forming an oxidizing atmosphere, but a gas mainly composed of oxygen and added with water vapor or a rare gas may be used. Further, ozone may be added or a method for promoting a reaction such as ion assist may be used in combination. In order to form a silicon oxide vapor deposition layer by a reactive vapor deposition method, a method of evaporating Si metal, SiO or SiO ₂ by an electron beam heating method and depositing silicon oxide on a film in an oxidizing atmosphere is employed. The method described above is used as a method of forming the oxidizing atmosphere.

  Moreover, although the thickness of a vapor deposition layer is not specifically limited, 5-100 nm is suitable from productivity, handling property, and external appearance, More preferably, it is 5-50 nm. If the thickness of the deposited layer is less than 5 nm, defects in the deposited layer are likely to occur, and the gas barrier property may be significantly deteriorated. When the thickness of the vapor deposition layer is greater than 100 nm, the cost during vapor deposition increases, the coloring of the vapor deposition layer becomes significant, and the appearance may be inferior.

When the film of the present invention is used after being processed into a vapor deposition film, the vapor permeability of the vapor deposition film is preferably 1.5 g / m ² / day or less. When the vapor permeability of the vapor deposition film exceeds 1.5 g / m ² / day, the vapor barrier property is inferior, and when the vapor deposition film is processed into a package using the vapor deposition film as a packaging material, the freshness retention of the contents is inferior There is. The vapor permeability of the vapor-deposited film is more preferably 1 g / m ² / day or less, more preferably 0.5 g / m ² / day or less, and most preferably for applications that require better water vapor barrier properties. It is 0.3 g / m ² / day or less. In addition, water vapor | steam barrier property is so preferable that it is preferable, and especially a minimum is not provided, but it is guessed that about 0.01 g / m < ² > / day is a minimum which can be implement | achieved. The water vapor permeability of the deposited film is the average surface roughness of the layer on which the deposited layer is formed (when the B layer is the outermost layer of the film of the present invention and the deposited layer is formed on the B layer). It can be controlled by the lamination thickness, the film fn, the type of metal or inorganic oxide of the vapor deposition layer, the thickness of the vapor deposition layer, the amount of defects (pinholes, scratches, etc.) of the vapor deposition layer, and the like.

When the film of the present invention is processed into a vapor deposition film and used, the oxygen permeability of the vapor deposition film is preferably ² cc / m ² / day / atm or less. When the oxygen permeability of the vapor-deposited film exceeds ² cc / m ² / day / atm, the oxygen barrier property is poor, and when the vapor-deposited film is processed into a packaging body using the vapor-deposited film as a packaging material, the freshness retention of the contents is inferior There is. Oxygen permeability of the deposited film is to use a more excellent oxygen barrier properties is desired, more preferably not more than ^{1cc / m 2 / day / atm} , more preferably 0.5cc ^/ m 2 ^/ day ^/ atm or less Most preferably, it is 0.2 cc / m ² / day / atm or less. In addition, although oxygen barrier property is so preferable that it is favorable, especially a minimum is not provided, About 0.01cc / m < ² > / day / atm is estimated as the minimum which can be implement | achieved. The oxygen permeability of the deposited film is the average surface roughness of the layer on which the deposited layer is formed (when the B layer is the outermost layer of the film of the present invention and the deposited layer is formed on the B layer). It can be controlled by the lamination thickness, the film fn, the type of metal or inorganic oxide of the vapor deposition layer, the thickness of the vapor deposition layer, the amount of defects (pinholes, scratches, etc.) of the vapor deposition layer, and the like.

  When the film of the present invention is used after being processed into a vapor deposition film, the vapor deposition layer adhesion of the vapor deposition film is preferably 25 g / 15 mm or more. When the adhesion of the deposited layer is less than 25 g / 15 mm, the adhesion between the deposited layer and the film of the present invention tends to be lower than the peeling between the A layer and the B layer of the film of the present invention. It may be inferior in workability and handling at the time of processing, or inferior in practicality of the package after processing. The adhesion strength of the deposited layer is more preferably 30 g / 15 mm or more, still more preferably 50 g / 15 mm or more, and most preferably 80 g / 15 mm or more. The higher the adhesion of the deposited layer, the better. The upper limit is not particularly set, but it is estimated that about 1000 g / 15 mm is an upper limit that can be realized. The deposited layer adhesion strength of the deposited film is the crystallinity of the layer on which the deposited layer is formed, the average surface roughness of the layer on which the deposited layer is formed, (B layer is the outermost layer of the film of the present invention, and B layer When forming a vapor deposition layer on top) It can control by the lamination | stacking thickness of B layer, fn of a film, the kind of metal or inorganic oxide of a vapor deposition layer, the thickness of a vapor deposition layer, etc.

  The film and vapor-deposited film of the present invention are preferably used as various packaging materials for packaging materials. The package is not particularly limited to these, but includes a vertical pillow package, a horizontal pillow package, a three-side seal package, a four-side seal package, a vacuum package, a stand pouch, an overwrap package, and the like. Can be mentioned.

  In these packaging bodies, heat sealability is required on at least one side of the film of the present invention. For this purpose, a film structure in which a heat seal layer (C layer) is formed on the film of the present invention (for example, B layer / A layer / C layer), and an appropriate vapor deposition layer is formed thereon (for example, vapor deposition layer / B layer / A layer / C layer) and C layer can be used as the heat seal layer. In order to further enhance the heat sealing power, polypropylene alone, ethylene / propylene copolymer, ethylene / propylene / butene copolymer, low density polyethylene, polyethylene or polypropylene or ethylene / propylene copolymer using metallocene catalyst A heat-sealable resin typified by an ethylene / vinyl acetate copolymer, a known amorphous polyester, or an acrylic resin can be formed on at least one surface of the film of the present invention. The heat-sealable resin can be directly formed on the film of the present invention by an extrusion laminating method or a wet coating method (laminate structure example: film / heat-sealable resin layer of the present invention). In addition, the film made of the heat-sealable resin can be dry-laminated on the film of the present invention via an adhesive layer made of a known adhesive typified by a polyester-based, polyurethane-based, polyether-based adhesive, or the like. It is also possible to use a method of extrusion laminating (polysand laminating) to the film of the present invention through an adhesive layer made of a thermoplastic resin typified by a resin (laminate structure example: film / adhesive layer / heat of the present invention) Sealing resin layer).

  Furthermore, the film of the present invention can be laminated with a film other than the above as appropriate according to the purpose to form a laminate, which can be processed into a package. For example, a printing film in which at least one printing layer is formed on at least one surface can be laminated on the film of the present invention by the above-described laminating method using the above-mentioned adhesive layer (for example, printing film / Adhesive layer / film of the present invention / adhesive layer / heat seal resin layer). The printing surface may be selected as the outer surface or the inner surface according to the purpose. Further, in order to further enhance the gas barrier performance of the film of the present invention, aluminum foil is laminated, or a gas barrier resin typified by ethylene / vinyl alcohol copolymer (EVOH) is laminated by the laminating method exemplified above. You can also. Here, the laminate is obtained by laminating the above-described heat-sealable resin, aluminum foil, ethylene / vinyl alcohol copolymer, other laminate materials such as films on at least one layer of the film of the present invention. Means.

  Further, in order to further improve the gas barrier property of the film of the present invention before lamination, a coating agent may be applied to the film of the present invention in-line and / or off-line. The coating agent is not particularly limited. For example, at least one resin selected from polyvinylidene chloride, polyvinyl alcohol, EVOH, acrylic, polyacrylonitrile, polyester, polyurethane, polyester urethane, and the like is used as water, an organic solvent, or the like. Those dissolved or emulsified in a mixed solvent are preferably used. When the film of the present invention is processed into a vapor deposition film and used, the coating agent may be applied to the film surface as an anchor coating agent before vapor deposition, or may be applied to the vapor deposition layer as an overcoat agent after vapor deposition. However, both may be performed. In any case, the gas barrier property of the vapor deposition film of the present invention can be enhanced by using a resin having a high gas barrier property as a coating agent. Moreover, by forming the anchor coat layer, the gas barrier property may be improved by improving the adhesion between the anchor coat layer and the vapor deposition layer formed thereon. By forming the overcoat layer, gas barrier properties may be improved by complementing defects (pinholes, scratches, etc.) in the vapor deposition layer.

  When the A layer of the film of the present invention is an aliphatic polyester having biodegradability typified by polylactic acid, it can also be applied to laminate materials such as the above heat seal layer, adhesive layer, and other films typified by printed films. By using a biodegradable material, biodegradability can be imparted to the obtained laminate and package. Moreover, since the plant degree of a laminated body and a package body improves, the plant degree of these materials is preferable.

  The laminate obtained in this way is formed into a bag by a known processing machine such as a vertical or horizontal bag making and filling machine, a vacuum packaging machine, a square folding packaging machine, etc. Processed into a finished package. At this time, the contents to be filled include, for example, seafood such as snacks, candy, chocolate, cookies, cheese, delicacies, raw meat, fish fillets, and other confectionery such as fruits and vegetables, frozen confectionery, Japanese confectionery, Western confectionery; Foods such as hamburger and noodles; Seasonings such as flour, sugar, soy sauce, miso, mayonnaise, ketchup; bath products such as soap, sponge, shampoo, rinse, body soap; liquid detergent; coffee beans; , Agricultural chemicals, vinyl tape, various parts of metal or plastic, industrial products, books, etc., but not particularly limited.

  Since the film and vapor-deposited film of the present invention are excellent in gas barrier properties, laminates and packages using these can also exhibit extremely excellent gas barrier properties. In addition, the film or vapor-deposited film of the present invention is excellent in interlayer adhesive force despite being directly laminated with the A layer and B layer mainly composed of different polyesters. In the processing step of processing, peeling between the A layer and the B layer hardly occurs, and the processability is excellent. Furthermore, for example, when a film inferior in interlayer adhesion is formed into a bag shape in the same manner as described above and filled with the contents, peeling occurs at the interface between the layers inferior in interlayer adhesion when opening the bag, A part of the structure of the laminate may remain unopened. The package using the film of the present invention and the vapor-deposited film is excellent in interlayer adhesive force despite being directly laminated with the A layer and the B layer, so that the above-described poor openability hardly occurs. Excellent practicality. From the above, the film and vapor-deposited film of the present invention exhibit excellent gas barrier properties, and at the same time, exhibit a good interlayer adhesion that could not be achieved by the prior art, and have excellent workability and practicality. It can be set as a package. From the above, the film and vapor-deposited film of the present invention can be preferably used for packaging, industrial use and the like.

Next, an Example is given and the film of this invention is demonstrated concretely.
[Measurement and evaluation method]
The characteristic evaluation method used in the present invention is as follows.
1. Interlaminar Adhesive Strength The films of the present invention and an unstretched polypropylene film (hereinafter sometimes referred to as CPP) were aligned in the longitudinal direction and were dry laminated under the following conditions.
Corona treatment: A handy type corona treatment device (Densok Precision Industries Corp, Type: Pinhole Tester, No. F4366, trowel-type electrode (electrode treatment part dimensions: thickness = 1 mm, width = 70 mm) was used) . When the dial of the device is fully rotated in the “weak” direction, the rotation is zero, and the dial is rotated once in the “strong” direction. The electrode is rotated twice under the conditions of a speed of 45 mm / second and an electrode-film distance of 0.33 mm. By running, the laminate surface of the film of the present invention was subjected to corona discharge treatment in the atmosphere.
・ CPP: “Torayfan” NO # 60 ZK93KM manufactured by Toray Film Processing Co., Ltd.
-Adhesive: AD503 / cat10 manufactured by Toyo Morton Co., Ltd.
-Blending amount: AD503 / cat10 / ethyl acetate = 20 parts by weight / 1 part by weight / 20 parts by weight-Laminate surface: For the film of the present invention, when layer B is the outermost layer, it is on layer B and layer B Was not any outermost layer, it was made into both surfaces of a film as follows. For CPP, the corona-treated surface was the laminate surface.
Application: An adhesive was applied to the laminate surface (corona-treated surface) side of CPP using Metabar # 12.
Drying: 80 ° C., 45 seconds Lamination: After drying, the adhesive-coated surface on the CPP was laminated to the laminate surface of the film of the present invention.
Curing: A test piece having a width of 15 mm was cut out from a sample obtained at 40 ° C. for 48 hours, and a peel test was performed under the following conditions. In the peel force curve, the upper limit value and the lower limit value were read and used as interlayer adhesion strength.
・ Peel tester: Tensile Seiki Seisakusho tensile tester ・ Peel angle: 180 °
-Peeling speed: 200 mm / min-Chart speed: 20 mm / min-Peeling direction: Longitudinal direction Six test pieces were collected from the same sample, and the same measurement was performed. The average value of the obtained 6 pieces was taken as the interlayer adhesion (g / 15 mm). In addition, when the B layer is not any outermost layer of the film of the present invention, three times for a test piece laminated with CPP on one side of the film, three times for a test piece laminated with CPP on the other side of the film, A total of 6 measurements were made and the interlayer adhesion was measured in the same manner.

2. Mass average molecular weight (M _W )
Hexafluoroisopropanol was used as a solvent and passed through a column (HFIP-LG + HFIP-806M × 2: SHODEX) at 40 ° C. and 1 mL / min, and molecular weights 827,000, 101,000, 34,000, 1.0 A calibration curve obtained from the elution time by differential refractive index detection of PMMA (polymethyl methacrylate) standard substance having a known molecular weight of 10,000 and 20,000 was prepared in advance, and the mass average molecular weight was calculated from the elution time. However, polyglycolic acid is a column made at 40 ° C. and 0.6 mL / min using hexafluoroisopropanol in which 5 mM sodium trifluoroacetate is dissolved using “Shodex-104” manufactured by Showa Denko K.K. A calibration curve obtained from elution time by differential refractive index detection of PMMA standard substances of 7 different molecular weights through (HFIP-606M, 2 lines and precolumn) is prepared in advance, and mass average molecular weight is calculated from the elution time did.

3. Copolymerization component amount Using JNM-30AL400 manufactured by JEOL, the spectrum was measured by solution proton nuclear magnetic resonance ( ¹ H-NMR), and calculated in the form of mass% from the composition ratio determined from the integrated intensity of each peak. .

Measurement conditions were as follows: Desolved solvent in deuterated chloroform at room temperature, sample concentration 20 mg / mL, pulse width 11 μs / 45 °, pulse line repetition time 9 seconds, integration number 256 times, and measurement at 23 ° C. . However, the polyglycolic acid was measured in the form of mass% from the composition ratio obtained from the integrated intensity of each peak by measuring the spectrum by solution proton nuclear magnetic resonance ( ¹ H-NMR) using Bruker AVANCE400. . Measurement conditions were as follows: solvent was CDCl ₃ : HFIP = 1: 1 at room temperature, sample concentration was 20 mg / mL, pulse width was 4.4 μs / 45 °, uptake time was 9 seconds, integration number was 8 times, 27 Measured at ° C.

4). Glass transition temperature (Tg) of layer A
Based on JIS K7121 (1999), a differential scanning calorimeter “Robot DSC-RDC220” manufactured by Seiko Instruments Inc. was used, and a disk session “SSC / 5200” was used for data analysis. A sample of the resin composition scraped from the A layer on the sample pan was weighed in an amount of 5 mg, and scanned at a temperature rising rate of 20 ° C./min. In the stepwise change portion of the glass transition of the differential scanning calorimetry chart, from the point where the straight line equidistant from the extended straight line of each base line and the curve of the stepwise change portion of the glass transition intersect. Tg was determined. The measurement was performed three times for the same sample, and the average value of the obtained values was defined as Tg (° C.) of the sample.

5. Using a melt viscosity flow tester CFT-500 (manufactured by Shimadzu Corporation), the base length is changed to 10 mm, the base diameter is changed to 1.0 mm, the load is changed to 5, 10, 15, 20 kg, the measurement temperature is 270 ° C., the preheating time. Measured at 5 minutes. The relationship between the shear rate and the melt viscosity was measured, and the melt viscosity at 100 sec ⁻¹ was determined. The measurement was performed three times for the same sample, and the average value of the obtained values was taken as the melt viscosity of the sample.

6). Thickness of each layer A sample was cut from the center portion in the lateral direction of the film of the present invention. Using a freezing microtome method, an ultrathin section was collected at −100 ° C. so that the longitudinal direction-thickness direction cross section of the sample piece was the observation surface. A thin film slice of this film cross section was photographed with a transmission electron microscope at a magnification of 20,000 times (the magnification was changed as necessary), and the thickness (μm) of each layer at the center in the lateral direction of the film It was confirmed.

7). Using a film thickness dial gauge thickness gauge (JIS B7503 (1997), UPAIGHT DIAL GAUGE (0.001 × 2 mm), No. 25, measuring element 5 mmφ flat type manufactured by PEACOCK) in the vertical and horizontal directions of the film 10 cm Ten points were measured at intervals, and the average value thereof was defined as the film thickness of the sample (unit: μm).

8). Plane orientation coefficient (fn) of the film
Using a sodium D line (wavelength 589 nm) as a light source and using an Abbe refractometer, the longitudinal refractive index (Nx), lateral refractive index (Ny), and thickness direction refractive index (Nz) of the film of the present invention are measured. The plane orientation coefficient (fn) was calculated from the following formula. The mounting solution was methyl salicylate.
fn = (Nx + Ny) / 2−Nz
9. Center line average surface roughness (Ra) of layer B
According to JIS B0601 (2001), the surface on which the film is deposited is measured under the following conditions using a stylus type surface roughness meter (manufactured by Kosaka Laboratory Ltd., high-precision thin film level difference measuring instrument, model: ET30HK). went. The conditions at this time were as follows.
-Stylus scanning direction: Film lateral direction-Measurement mode: Stylus type (STYLUS)
・ Processing mode: 8 (ROUGHNESS)
・ Measurement length: 1mm
-Stylus diameter: Conical 0.5μmR
・ Load: 16mg
・ Cutoff: 250μm
・ Number of measurement lines: 30 ・ Scanning speed: 100 μm / second ・ Pitch: 4 μm in the X direction, 10 μm in the Y direction
・ SLOPE COMP: ON
・ GAIN: × 1
Measurement area: 0.2988 mm ²
Standard area: 0.1 mm ² .
The centerline average surface roughness is obtained by extracting a portion having a measurement length L from the roughness curve in the direction of the centerline, setting the centerline of the extracted portion as the X axis and the vertical direction as the Y axis, and expressing the roughness curve as y = When expressed by f (X), a value (μm) obtained by the following formula is defined as a center line average surface roughness Ra.
Ra = (1 / L) ∫ | f (X) | dx.
The same measurement was performed three times for each sample while changing the measurement location, and the average value of the obtained values was calculated and used as Ra (μm) of the layer on which the film was deposited.

10. According to JIS K7127 (1999, specimen type 2) and JIS K7161 (1994), the Young's modulus of the film is 25 ° C. using a film strength measuring device (AMF / RTA-100) manufactured by Orientec Co., Ltd. Measured at 65% RH. A sample was cut into a size of 15 cm in the measurement direction and 1 cm in the orthogonal direction, stretched at an original length of 50 mm, and a tensile speed of 300 mm / min, and the Young's modulus in the vertical and horizontal directions was measured. The same measurement was performed five times in each direction of each sample, and the average value of the obtained values was calculated and used as the Young's modulus (GPa) in the vertical and horizontal directions of the sample.

11. Heat Shrinkage Ratio The film of the present invention was cut into a rectangle having a length of 200 mm and a width of 10 mm in the vertical direction and the horizontal direction, and used as a sample. Marks were drawn on the sample at intervals of 150 mm, a 3 g weight was suspended and placed in a hot air oven heated to 120 ° C. for 15 minutes and subjected to heat treatment. The distance between the marked lines was measured after the heat treatment, the thermal shrinkage rate was calculated from the change in the distance between the marked lines before and after heating, and used as an index of dimensional stability. The same measurement was performed 5 times in each direction of each sample, and the average value of the obtained values was calculated and used as the thermal shrinkage rate in the vertical and horizontal directions of the sample.

12 Using a water vapor transmission rate measuring device (model name, “Permatran” (registered trademark) W3 / 31) manufactured by MOCON, USA, under conditions of a water vapor transmission temperature of 38 ° C. and a humidity of 90% RH It measured based on B method (infrared sensor method) as described in JIS K7129 (2000). In addition, the measurement was performed twice by applying a water vapor flow from the vapor deposition layer side and detecting on the opposite side, and the average value of the two measurement values was taken as the water vapor transmission rate (g / m ² / day) of the sample. .

13. Oxygen permeability measuring device (model name, “Oxytran” (registered trademark) (“OXTRAN” 2/20)) manufactured by MOCON, USA, under conditions of an oxygen permeability temperature of 23 ° C. and a humidity of 0% RH It was measured based on the electrolytic sensor method described in JIS K7126-2 (2006). In addition, the measurement was performed twice by applying an oxygen stream from the vapor deposition layer side and detecting on the opposite side, and the average value of the two measured values was the oxygen permeability of the sample (cc / m ² / day / atm). It was.

14 Adhesive strength of the vapor deposition layer The vapor deposition film obtained by forming the vapor deposition layer on the film of the present invention was aligned in the longitudinal direction of the unstretched polypropylene film (CPP), and dry laminated under the following conditions.
・ CPP: “Torayfan” NO # 60 ZK93KM manufactured by Toray Film Processing Co., Ltd.
-Adhesive: AD503 / cat10 manufactured by Toyo Morton Co., Ltd.
-Blending amount: AD503 / cat10 / ethyl acetate = 20/1/20 parts by mass-Application: Metabar # 12 was used, and an adhesive was applied to the corona-treated surface side of CPP.
Drying: 80 ° C., 45 seconds Lamination: After drying, the coated surface on the CPP was laminated to the vapor deposition surface of the vapor deposition film of the present invention.
Curing: A test piece having a width of 15 mm was taken out from a sample obtained at 40 ° C. for 48 hours, and a peel test was performed under the following conditions. In the peel force curve, the upper limit value and the lower limit value were read and used as the adhesion strength of the deposited layer.
-Peel tester: Tensile Seiki Seisakusho tensile tester-Peel angle: 180 °
・ Peeling speed: 200 mm / min ・ Chart speed: 20 mm / min ・ Peeling direction: longitudinal direction ・ Sample width: 15 mm
Three test pieces were collected from the same sample, and the same measurement was performed three times. The average value of the obtained values was defined as the adhesion (g / 15 mm) of the deposited layer.

15. An unstretched sheet extruded from an effective stretch ratio slit-shaped base, wound around a metal drum and cooled and solidified into a sheet so that each side of the square of 1 cm in length is parallel to the longitudinal and lateral directions of the film After engraving with a stamp, the film was stretched and wound, and the length (cm) of the resulting film was measured, and this was taken as the effective stretching ratio in the machine direction and the transverse direction.

16. Deposition layer thickness A sample was cut out from the lateral center of the film of the present invention. Using a freezing microtome method, an ultrathin section was collected at −100 ° C. so that the longitudinal direction-thickness direction cross section of the sample piece was the observation surface. A thin film slice of this film cross section was photographed with a transmission electron microscope at a magnification of 20,000 times (the magnification was changed as necessary), and the thickness (μm) of each layer at the center in the lateral direction of the film It was confirmed.
An ultra-thin slice having a cross section in the transverse direction-thickness direction of the deposited film of the present invention was collected by an ultramicrotome by a resin embedding method using an epoxy resin. The collected ultrathin slice was observed under the following conditions using a transmission electron microscope (TEM), and the thickness of the deposited layer was measured. In addition, the same measurement was performed twice about the same sample, and the average value of the obtained value was made into the thickness (nm) of a vapor deposition layer.
Apparatus: Transmission electron microscope (TEM) H-7100FA manufactured by Hitachi, Ltd.
・ Acceleration voltage: 100 kV
-Observation magnification: 40000 times.

17. Evaluation of processability and practicality A biaxially stretched polylactic acid film (“Ecodia” manufactured by Toray Industries, Inc.) with a thickness of 20 μm is formed on the opposite side of the vapor deposition surface of the vapor deposition film of the present invention having a length of 1000 m and a thickness of 15 μm. 20 μm thick unstretched polypropylene film (CPP; “Torefan” NO # 20 9141 manufactured by Toray Film Processing Co., Ltd.), urethane adhesives (adhesives using 1 and 15 above, similar blending amounts and drying conditions) And then dried so as to have a coating thickness of 4 μm after drying, and the obtained roll was aged at 40 ° C. for 48 hours. The laminate was placed in the CPP side inside, and the film was inserted into a cylindrical shape using a vertical pillow packaging machine (FUJI FW-77) manufactured by Fujikikai Co., Ltd. to make a bag. At this time, no contents were filled. About the obtained bag, sensory evaluation was performed on the following reference | standard. The bag was opened with both hands holding the vicinity of the seal portion of the bag mouth with the index finger and thumb of the right hand and left hand, and spreading the bag outward to peel off the seal portion.
GOOD: Wrinkles and stretches do not enter the film, and the shape of the bag-making product is good. And the bag can be opened without problems.
ENOUGH: Wrinkles and stretches do not enter the film, and the shape of the bag-making product is good. And although a bag can be opened at the time of opening of a bag, some delamination arises in the film of this invention, and delamination is observed.
BAD: The film has large wrinkles, elongation, etc., and the shape of the bag-making product is poor. Alternatively, delamination occurs on the entire surface of the film of the present invention when the bag is opened, and a part of the film layer remains without being opened.

18. It calculated from the cross-sectional photograph of the film in the procedure below the aspect ratio of an interlayer adhesion improving agent.
1) Cross-sectional photography / equipment Transmission electron microscope (H-7100FA made by Hitachi)
・ Acceleration voltage 100kV
・ Sample preparation RuO ₄ stained ultra-thin film section method ・ Observation surface Horizontal direction: Longitudinal direction, Vertical direction: Surface of the film cut in the thickness direction
Horizontal direction: Horizontal direction, Vertical direction: Surface of film cut in the thickness direction, Observation magnification: 8000x, Imaging area: 14μm × 14μm
2) Calculation of aspect ratio Two photographs for each cross section observed in 1) were digitized using the software "ImageJ" made by the National Institutes of Health (NIH) under the following conditions. The average value of a total of 4 sheets was calculated.
・ Gifify the data TEM photograph of each area of the interlayer adhesion improver dispersed in layer A and read it with the above software. The concentration was divided into 255 levels, and the region from the darkest to the 90th was made the region composed of the interlayer adhesion improver.
・ Automatic calculation of number count and aspect ratio To avoid picking up the roughness of the image, we limited it to 50 pixels or more and performed the automatic calculation with the “Shape descriptors” function to obtain the average value of each photo. Aspect ratio = length in the horizontal direction / length in the vertical direction.

(Example)
The raw materials used in Examples and Comparative Examples of the present invention are as follows.
[PGA]
A polymerization raw material consisting of 90 parts by mass of glycolide (GL), 10 parts by mass of L-lactide (LLA) and 0.003 parts by mass of tin dichloride dihydrate as a catalyst was charged and heated at 170 ° C. for 24 hours to perform bulk polymerization. After cooling, the polymer was taken out by cooling over 2 hours. The obtained copolymer was pulverized to an average particle size of 5 mm or less, and then treated at 120 ° C. under reduced pressure in a vacuum dryer for 2 hours to remove low molecular weight volatile components. On the other hand, 0.03 parts by mass of a phosphite-based antioxidant (“AdekaStap PEP8” manufactured by Asahi Denka Kogyo Co., Ltd.) is added and 220 to 240 ° C. (C1 = 220 ° C., C2 = 230 ° C., C3 in order from the supply unit). Melting extrusion with a residence time of about 5 minutes in a twin-screw kneading extruder set to 240 ° C and die = 230 ° C (5mmφ strand die attached to “Lab Plast Mill 2D25S” manufactured by Toyo Seiki Seisakusho Co., Ltd.) The pellets having a diameter of about 5 mm and a length of about 10 mm were obtained while air cooling the extruded strand. The pellet was prepared by preparing a homopolyglycolic acid resin having a molecular weight of 180,000, a melting point of 221 ° C., a Tg of 42 ° C., 270 ° C. and a melt viscosity of 3500 poise at 100 sec ⁻¹ and drying at 120 ° C. for 8 hours in a rotary vacuum dryer. Using.

[PGLLA1]
In the above PGA production method, pellets were prepared in the same manner except that GL 100 parts by mass was changed to GL 90 parts by mass and L-lactide (LLA) 10 parts by mass. Pellets, molecular weight 170,000, was L- lactic acid 10 mol% random copolymer polyglycolic acid melt viscosity 3000poise of melting point 205 ° C. Tg: 40 ° C. 270 ° C. and 100 sec ^-1.

[PGLLA2]
Pellets were produced by the same method except that the GL100 mass part was changed to GL90 mass part and LLA20 mass part in the production method of the PGA. Pellets, molecular weight 170,000, was L- lactic acid 30 mol% random copolymer polyglycolic acid melt viscosity 3000poise of melting point 205 ° C. Tg: 40 ° C. 270 ° C. and 100 sec ^-1.

[PGLLA3]
Pellets were prepared by the same method except that the GL100 mass part was changed to GL90 mass part and LLA30 mass part in the production method of the PGA. The pellets were 35 mol% L-lactic acid random copolymer polyglycolic acid with a molecular weight of 170,000, a melting point of 205 ° C., a Tg of 40 ° C., 270 ° C., and a melt viscosity of 3000 poise at 100 sec ⁻¹ .

[CPLA]
Crystalline poly-L-lactic acid (“Ingeo” 4032D manufactured by Nature Works; D-form amount = 1.4 mol%, melting point = 168 ° C., Tg = 58 ° C.) dried at 100 ° C. for 4 hours in a rotary vacuum dryer.

[APLA]
Amorphous poly L-lactic acid (“Ingeo” 4060D manufactured by Nature Works; D-form amount = 12 mol%, Tg = 58 ° C.) dried for 8 hours at 50 ° C. in a rotary vacuum dryer.

[EA1]
Glycidyl group-containing ethylene acrylate copolymer ("Biomax" strong 120, manufactured by EI du Pont de Nemours and Company) dried at 50 ° C for 8 hours in a stationary vacuum dryer.

[EA2]
Glycidyl group-containing ethylene acrylate copolymer (lotaderAX8900 manufactured by Arkema) dried for 8 hours at 50 ° C. in a stationary vacuum dryer.

[PLA-PEG]
62 parts by mass of polyethylene glycol having a number average molecular weight of 8,000, 38 parts by mass of L-lactide and 0.05 parts by mass of tin octylate are mixed and polymerized in a reaction vessel equipped with a stirrer at 160 ° C. for 3 hours in a nitrogen atmosphere. Thus, a block copolymer plasticizer having a polylactic acid segment having a number average molecular weight of 2,500 at both ends of polyethylene glycol having a number average molecular weight of 8,000 was prepared and used as an interlayer adhesion improver.

[CaPLA]
After blending 85% by mass of the above-mentioned cPLA and 15% by mass of aPLA, the mixture was supplied to a twin screw extruder having a cylinder temperature of 200 ° C., homogenized by melt kneading, and then pelletized into chips. The obtained chip was dried at 100 ° C. for 4 hours in a rotary vacuum dryer.

  The present invention will be described based on examples and comparative examples. In addition, in order to obtain a film having a desired thickness configuration, the polymer extrusion amount of each extruder was adjusted to a predetermined value unless otherwise specified. Moreover, when films other than the comparative example 1 confirmed the peeling surface after the interlayer adhesion test, it confirmed that it was an interface of A layer / B layer. Furthermore, when it was set as a vapor deposition film, unless there was particular notice, it vapor-deposited on B layer. Only Comparative Example 1 was deposited on the A layer. Moreover, the surface roughness was measured with respect to the surface which deposits a film.

Example 1
A single-axis extruder (a) is supplied with a blend raw material in which 95 parts by mass of cPLA and 5 parts by mass of EA1 are mixed in advance as a resin composition of the A layer, extruded at 220 ° C., and a stainless steel fiber having an average opening of 25 μm. The polymer was filtered with a filter obtained by sintering and compression, and supplied to a two-layer type die. Further, 100 parts by mass of PGA is supplied to the single-screw extruder (b) as the resin of the B layer, extruded at 250 ° C., and stainless steel having an average opening of 25 μm in a flow path different from the extruder (a). The polymer was filtered with a filter in which the fibers were sintered and compressed, and then supplied to the die. At this time, 235 ° C. was used as the set temperature of the flow path (polymer tube).

  Next, the molten polymer from each extruder was merged in the die so as to be laminated in the order of extruder (b) / extruder (a), and coextruded into a sheet form from the die. At this time, the extruded sheet was cast on a mirror metal drum having a temperature of 30 ° C. and cooled and solidified into a sheet. Moreover, it casted so that the B layer supplied from the extruder (b) might contact a metal drum.

  The obtained unstretched sheet was stretched 3 times in the longitudinal direction at 70 ° C. with a roll stretching machine, and immediately cooled to room temperature. Next, the obtained uniaxially stretched film was introduced into a tenter and stretched 3.5 times in the transverse direction at 60 ° C. while holding both edges with clips, and then 150 ° C. while giving 3% relaxation in the transverse direction. After heat treatment, it was cooled and wound up. The thickness configuration of the obtained biaxially oriented film was B layer / A layer = 2/18 μm.

After aging for 24 hours in a roll state under an atmosphere of 23 ° C. and 65%, the obtained biaxially oriented film was set in a vacuum deposition apparatus equipped with a film running apparatus. After making it the high pressure reduction state of 1.00 * 10 ^<-2 > Pa, it was made to drive | work on the 0 degreeC cooling metal drum. At this time, the aluminum metal was evaporated by heating to form a vapor deposition layer on the B layer. The vapor deposition film thus obtained was aged for 48 hours to obtain the vapor deposition film of the present invention. In addition, the optical density of the vapor deposition film was confirmed online during vapor deposition, and the vapor deposition thickness was controlled to be 2.5.

  The film forming conditions of the obtained film are shown in Table 1, and the evaluation results of the film and the deposited film are shown in Tables 2 and 3. The obtained film contains a specific interlayer adhesion improver in the A layer and has a high aspect ratio of 18.4. Therefore, the film exhibits high interlayer adhesion and sufficient mechanical properties and dimensions for use as a packaging material. It had stability. Moreover, the adhesive force with the vapor deposition layer of a vapor deposition film was high, and it was excellent in water vapor | steam barrier property and oxygen barrier property. Furthermore, in the bag produced using the vapor deposition film, defects such as wrinkles were not observed, and delamination was confirmed in a part of the film at the time of opening, but it was at a level that does not hinder practicality.

(Example 2)
A biaxially oriented film and a vapor-deposited film produced in the same manner as in Example 1 except that the resin supplied to the extruder (a) was changed as shown in Table 1 were taken as Example 2. The thickness of the film was B layer / A layer = 2/18 μm. The obtained film contains a specific interlayer adhesion improver in the A layer and has a high aspect ratio of 15.8. Therefore, the film exhibits high interlayer adhesion and sufficient mechanical properties and dimensions for use as a packaging material. It had stability. Moreover, the adhesive force with the vapor deposition layer of a vapor deposition film was high, and it was excellent in water vapor | steam barrier property and oxygen barrier property. Furthermore, the bag produced using the said vapor deposition film did not observe defects, such as wrinkles, and was excellent in openability.

Example 3
A single-axis extruder (a) is supplied with a blend raw material in which 95 parts by mass of cPLA and 5 parts by mass of EA1 are mixed in advance as a resin composition of the A layer, extruded at 220 ° C., and a stainless steel fiber having an average opening of 25 μm. The polymer was filtered through a filter obtained by sintering and compressing and supplied to a three-layer type multi-manifold die. Further, 100 parts by mass of PGA is supplied to the single-screw extruder (b) as the resin of the B layer, extruded at 250 ° C., and stainless steel having an average opening of 25 μm in a flow path different from the extruder (a). The polymer was filtered through a filter in which the fibers were sintered and compressed, and then supplied to the multi-manifold die. At this time, 235 ° C. was used as the set temperature of the flow path (polymer tube). Furthermore, 100 parts by mass of aPLA was supplied to the single screw extruder (c), extruded at 220 ° C., and the polymer was filtered through a filter obtained by sintering and compressing stainless steel fibers having an average opening of 25 μm. Supplied.

Next, the molten polymer from each extruder is merged in a multi-manifold die so as to be laminated in the order of extruder (b) / extruder (a) / extruder (c), and co-extruded into a sheet form from the die. did. At this time, the extruded sheet was cast on a mirror metal drum having a temperature of 30 ° C. and cooled and solidified into a sheet. Moreover, it casted so that the B layer supplied from the extruder (b) might contact a metal drum.
The obtained unstretched sheet was stretched 3 times in the longitudinal direction at 70 ° C. with a roll stretching machine, and immediately cooled to room temperature. Next, the obtained uniaxially stretched film was introduced into a tenter and stretched 3.5 times in the transverse direction at 60 ° C. while holding both edges with clips, and then 145 ° C. while giving 3% relaxation in the transverse direction. After heat treatment, it was cooled and wound up. The thickness configuration of the obtained biaxially oriented film was B layer / A layer / C layer = 2/16/2 μm.

After aging for 24 hours in a roll state under an atmosphere of 23 ° C. and 65%, the obtained biaxially oriented film was set in a vacuum deposition apparatus equipped with a film running apparatus. After making it the high pressure reduction state of 1.00 * 10 ^<-2 > Pa, it was made to drive | work on the 0 degreeC cooling metal drum. At this time, the aluminum metal was evaporated by heating to form a vapor deposition layer on the B layer. The vapor deposition film thus obtained was aged for 48 hours to obtain the vapor deposition film of the present invention. In addition, the optical density of the vapor deposition film was confirmed online during vapor deposition, and the vapor deposition thickness was controlled to be 2.5.

The film forming conditions of the obtained film are shown in Table 1, and the evaluation results of the film and the deposited film are shown in Tables 2 and 3.
The obtained film contains a specific interlayer adhesion improver in the A layer and has a high aspect ratio of 18.5. Therefore, the film exhibits high interlayer adhesion and sufficient mechanical properties and dimensions for use as a packaging material. It had stability. Moreover, the adhesive force with the vapor deposition layer of a vapor deposition film was high, and it was excellent in water vapor | steam barrier property and oxygen barrier property. Furthermore, the bag produced using the said vapor deposition film did not observe defects, such as wrinkles, and was excellent in openability.

Example 4
In Example 3, a biaxially oriented film and a vapor deposition film produced in the same manner except that the thicknesses of the B layer and the A layer were 1 μm and 17 μm, respectively, were used as Example 4. In addition, the thickness structure of the film was B layer / A layer / C layer = 1/17/2 μm. The obtained film contains a specific interlayer adhesion improver in the A layer and has an aspect ratio as high as 18.6. Therefore, the film exhibits high interlayer adhesion and sufficient mechanical properties and dimensions for use as a packaging material. It had stability. Moreover, the adhesive force with the vapor deposition layer of a vapor deposition film was high, and it was excellent in water vapor | steam barrier property and oxygen barrier property. Furthermore, the bag produced using the said vapor deposition film did not observe defects, such as wrinkles, and was excellent in openability.

(Example 5)
A biaxially oriented film and a vapor-deposited film produced in the same manner as in Example 3 except that the resin supplied to the extruder (a) and the extruder (b) were changed as shown in Table 1 were used as Example 5. In addition, the thickness structure of the film was B layer / A layer / C layer = 2/16/2 μm. The obtained film contains a specific interlayer adhesion improver in the A layer and the B layer, and has high aspect ratios of 18.2 and 17.8, respectively. Therefore, the film exhibits high interlayer adhesion and is used as a packaging material. It had sufficient mechanical properties and dimensional stability. Moreover, the adhesive force with the vapor deposition layer of a vapor deposition film was high, and it was excellent in water vapor | steam barrier property and oxygen barrier property. Furthermore, in the bag produced using the vapor deposition film, defects such as wrinkles were not observed, and delamination was confirmed in a part of the film at the time of opening, but it was at a level that does not hinder practicality.

(Example 6)
A biaxially oriented film and a vapor-deposited film produced in the same manner as in Example 5 except that the resin supplied to the extruder (b) was changed as shown in Table 1 were taken as Example 6. In addition, the thickness structure of the film was B layer / A layer / C layer = 2/16/2 μm. The obtained film contains a specific interlayer adhesion improver in the A layer and has an aspect ratio as high as 18.8. Therefore, the film exhibits extremely high interlayer adhesion and sufficient mechanical properties to be used as a packaging material. It had dimensional stability. Moreover, the adhesive force with the vapor deposition layer of a vapor deposition film was high, and it was excellent in water vapor | steam barrier property and oxygen barrier property. Furthermore, the bag produced using the said vapor deposition film did not observe defects, such as wrinkles, and was excellent in openability.

(Example 7)
A biaxially oriented film and a vapor-deposited film produced in the same manner as in Example 5 except that the resin supplied to the extruder (b) was changed as shown in Table 1 were taken as Example 7. In addition, the thickness structure of the film was B layer / A layer / C layer = 2/16/2 μm. The obtained film contains specific interlayer adhesion improvers in the A layer and the B layer, and has an aspect ratio as high as 17.9 and 18.3, respectively. It had sufficient mechanical properties and dimensional stability to be used. Moreover, the adhesive force with the vapor deposition layer of a vapor deposition film was high, and it was excellent in water vapor | steam barrier property and oxygen barrier property. Furthermore, the bag produced using the said vapor deposition film did not observe defects, such as wrinkles, and was excellent in openability.

(Example 8)
In Example 7, a biaxially oriented film and a vapor deposition film produced in the same manner except that the resins supplied to the extruders (a) and (b) were changed as shown in Table 1 were used as Example 7. In addition, the thickness structure of the film was B layer / A layer / C layer = 2/16/2 μm. The obtained film contains a specific interlayer adhesion improver in the A layer and the B layer, and has a high aspect ratio of 22.2 and 21.3, respectively. Therefore, the film exhibits high interlayer adhesion and is used as a packaging material. It had sufficient mechanical properties and dimensional stability. Moreover, the adhesive force with the vapor deposition layer of a vapor deposition film was high, and it was excellent in water vapor | steam barrier property and oxygen barrier property. Furthermore, the bag produced using the said vapor deposition film did not observe defects, such as wrinkles, and was excellent in openability.

Example 9
A biaxially oriented film and a vapor-deposited film produced in the same manner as in Example 1 except that the resin supplied to the extruder (a) was changed as shown in Table 1 were taken as Example 9. The thickness of the film was B layer / A layer = 2/18 μm. The resulting film had a large aspect ratio of 28.2 due to a decrease in the interlayer adhesion improver for the A layer, but the interlayer adhesion decreased within the practical range. It had sufficient mechanical properties and dimensional stability for use as a packaging material. Moreover, the adhesive force with the vapor deposition layer of a vapor deposition film was high, and it was excellent in water vapor | steam barrier property and oxygen barrier property. Furthermore, the bag produced using the vapor deposition film satisfied practical characteristics.

(Example 10)
A biaxially oriented film and a vapor-deposited film produced in the same manner as in Example 1 except that the resin supplied to the extruder (a) was changed as shown in Table 1 were taken as Example 10. The thickness of the film was B layer / A layer = 2/18 μm. The resulting film has an aspect ratio as small as 7.1 due to an increase in the interlayer adhesion improver for layer A, but the interlayer adhesion is further improved and the mechanical properties and dimensional stability are reduced. As a practical range. Moreover, the adhesive force with the vapor deposition layer of a vapor deposition film was high, and it was excellent in water vapor | steam barrier property and oxygen barrier property. Furthermore, the bag produced using the vapor deposition film satisfied practical characteristics.

(Example 11)
A biaxially oriented film and a vapor-deposited film produced in the same manner as in Example 1 except that the resin supplied to the extruder (a) was changed as shown in Table 1 were taken as Example 11. The thickness of the film was B layer / A layer = 2/18 μm. The resulting film had a smaller aspect ratio of 5.2 due to a further increase in the interlayer adhesion improver for layer A, but the interlayer adhesion was further improved. Although mechanical properties and dimensional stability were lowered, they were within the practical range as packaging materials. Moreover, although the adhesive force with the vapor deposition layer of a vapor deposition film was high, since the surface became rough, water vapor | steam barrier property and oxygen barrier property deteriorated a little, but were in a practical range. Furthermore, the bag produced using the vapor deposition film satisfied practical characteristics.

(Example 12)
A biaxially oriented film and a vapor-deposited film produced in the same manner as in Example 1 except that the resin supplied to the extruder (a) was changed as shown in Table 1 were taken as Example 12. The thickness of the film was B layer / A layer = 2/18 μm. The obtained film is obtained by adding an interlayer adhesion improver to the A layer and having an aspect ratio as high as 18.3. Therefore, the interlayer adhesion is further improved and sufficient mechanical properties and dimensional stability to be used as a packaging material. Had. Moreover, although the adhesive force with the vapor deposition layer of a vapor deposition film was high and the water vapor | steam barrier property fell, it was in the practical range and the oxygen barrier property was excellent. Furthermore, the bag produced using the vapor deposition film satisfied practical characteristics.

(Example 13)
A biaxially oriented film and a vapor deposition film produced in the same manner as in Example 1 except that the extrusion amount was 1 / 2.6 and the draw ratio was changed as shown in Table 1 were taken as Example 13. The thickness of the film was B layer / A layer = 2/18 μm. The obtained film had an aspect ratio of the interlayer adhesion improving agent for the A layer as small as 3.5 and the interlayer adhesive strength was reduced, but was within the practical range. It had sufficient mechanical properties and dimensional stability for use as a packaging material. Moreover, the adhesive force with the vapor deposition layer of a vapor deposition film was high, and it was excellent in water vapor | steam barrier property and oxygen barrier property. Furthermore, the bag produced using the vapor deposition film satisfied practical characteristics.

(Example 14)
A biaxially oriented film and a vapor deposition film produced in the same manner as in Example 1 except that the extrusion amount was 1.5 times and the stretch ratio was changed as shown in Table 1 were made as Example 14. The thickness of the film was B layer / A layer = 2/18 μm. In the obtained film, the aspect ratio of the interlayer adhesion improving agent for the A layer was as large as 34.5, and the interlayer adhesion was improved. Although mechanical properties and dimensional stability were lowered, they were within the practical range as packaging materials. Moreover, the adhesive force with the vapor deposition layer of a vapor deposition film was high, and it was excellent in water vapor | steam barrier property and oxygen barrier property. Furthermore, the bag produced using the vapor deposition film satisfied practical characteristics.

(Example 15)
A biaxially oriented film and a vapor-deposited film produced in the same manner as in Example 6 except that the resin supplied to the extruder (b) was changed as shown in Table 1 were taken as Example 15. In addition, the thickness structure of the film was B layer / A layer / C layer = 2/16/2 μm. The resulting film was obtained by adding an interlayer adhesion improver to the A layer, having a high aspect ratio of 18.5, and further increasing the amount of copolymerization of the polylactic acid units of the B layer. became. It had sufficient mechanical properties and dimensional stability for use as a packaging material. Moreover, the adhesive force with the vapor deposition layer of a vapor deposition film was high, and it was excellent in water vapor | steam barrier property and oxygen barrier property. Furthermore, the bag produced using the said vapor deposition film did not observe defects, such as wrinkles, and was excellent in openability.

(Example 16)
In Example 6, a biaxially oriented film and a vapor deposition film produced in the same manner except that the resin supplied to the extruder (b) was changed as shown in Table 1 were used as Example 16. In addition, the thickness structure of the film was B layer / A layer / C layer = 2/16/2 μm. The resulting film was obtained by adding an interlayer adhesion improver to layer A, having a high aspect ratio of 19.1, and further increasing the amount of copolymerization of the polylactic acid units of layer B, resulting in higher interlayer adhesion. became. It had sufficient mechanical properties and dimensional stability for use as a packaging material. Moreover, the adhesive force with the vapor deposition layer of a vapor deposition film was high. Since there were too many polylactic acid units, water vapor | steam barrier property and oxygen barrier property fell, but it was in the practical range. Furthermore, the bag produced using the said vapor deposition film did not observe defects, such as wrinkles, and was excellent in openability.

(Example 17)
A biaxially oriented film and a vapor-deposited film produced in the same manner as in Example 1 except that the resin supplied to the extruder (a) was changed as shown in Table 1 were taken as Example 17. The thickness of the film was B layer / A layer = 2/18 μm. The obtained film was sufficient although the interlayer adhesion was slightly reduced because the interlayer adhesion improver of the A layer was changed and the aspect ratio was as small as 8.3. It had sufficient mechanical properties and dimensional stability for use as a packaging material. Moreover, the adhesive force with the vapor deposition layer of a vapor deposition film was high, and it was excellent in water vapor | steam barrier property and oxygen barrier property. Furthermore, defects such as wrinkles were not observed in the bag produced using the vapor-deposited film, and the openability was within the practical range.

(Comparative Example 1)
100 parts by mass of caPLA is supplied to the single screw extruder (a), extruded at 220 ° C., and the polymer is filtered through a filter obtained by sintering and compressing stainless steel fibers having an average opening of 25 μm. Supplied to. In addition, 100 parts by mass of caPLA was supplied to the single-screw extruder (b), extruded at 220 ° C., and stainless steel fibers having an average opening of 25 μm were sintered and compressed in a flow path different from the extruder (a). The polymer was filtered with a filter and then supplied to the multi-manifold die. Next, the molten polymer from each extruder was merged in the multi-manifold die so as to be laminated in the order of extruder (b) / extruder (a), and cooled and solidified into a sheet form from the die. Moreover, the resin layer supplied from the extruder (b) was coextruded so as to contact the metal drum. At this time, the extruded sheet was cast into a mirror metal drum having a temperature of 30 ° C. and cast into a sheet.

  The obtained unstretched sheet was stretched 2.8 times in the longitudinal direction at 80 ° C. with a roll stretching machine, and immediately cooled to room temperature. Next, the obtained uniaxially stretched film was introduced into a tenter and stretched 3.5 times in the transverse direction at 75 ° C. while holding both edges with clips, and subsequently 140 ° C. while giving 5% relaxation in the transverse direction. After heat treatment, it was cooled and wound up. The thickness structure of the obtained biaxially oriented film was A layer / B layer = 18/2 μm.

  After aging for 24 hours in a roll state under an atmosphere of 23 ° C. and 65%, the obtained biaxially oriented film was subjected to the same procedure as in Example 1 except that the deposited layer was formed on the A layer (from the extruder (b)). On the surface of the supplied resin layer).

  The film forming conditions of the obtained film are shown in Table 1, and the evaluation results of the film and the deposited film are shown in Tables 2 and 3. The obtained film was excellent in interlayer adhesive strength (not peeled off between any layers, peeled off between CPP-films), and was excellent in opening the bag, but it did not contain the B layer. It was inferior to.

(Comparative Example 2)
In Example 3, a biaxially oriented film and a vapor-deposited film produced in the same manner except that EA1, which is an interlayer adhesion improving agent, was removed from the resin supplied to the extruder (a) and 100 parts by mass of caPLA were supplied. It was. In addition, the thickness structure of the film was A layer / B layer / C layer = 2/16/2 μm. The obtained film had good gas barrier properties after vapor deposition, but was inferior in interlayer adhesive strength because it did not contain an interlayer adhesion improver in the A layer and the B layer. For this reason, the bag produced using the said vapor deposition film produced the delamination of the whole surface at the time of opening, and was remarkably inferior to openability.

(Comparative Example 3)
In Example 6, from the resin supplied to the extruder (a), the biaxially oriented film and the vapor-deposited film produced in the same manner except that EA1 which is an interlayer adhesion improver and 100 parts by mass of caPLA were supplied were used as Comparative Example 3. It was. In addition, the thickness structure of the film was A layer / B layer / C layer = 2/16/2 μm. The obtained film had good gas barrier properties after vapor deposition, but was inferior in interlayer adhesive strength because it did not contain an interlayer adhesion improver in the A layer and the B layer. For this reason, the bag produced using the said vapor deposition film produced the delamination of the whole surface at the time of opening, and was remarkably inferior to openability.

(Comparative Example 4)
In order to obtain the improvement effect of the interlayer adhesive force based on the method of heating the stretching point disclosed in Example 1 of Patent Document 3 (Japanese Patent Application Laid-Open No. 2006-130847), studies were conducted.

  In the extruder (b) and the extruder (c), 100 parts by mass of cPLA was supplied as a resin composition of the A layer, extruded at 220 ° C., and a stainless steel fiber having an average opening of 25 μm was sintered and compressed. The polymer was filtered and fed to a three-layer type multi-manifold die. The short-axis extruder (a) is supplied with 100 parts by mass of PGA as a resin composition of the B layer, extruded at 250 ° C., and polymerized by a filter obtained by sintering and compressing stainless steel fibers having an average opening of 25 microns. Was filtered and supplied to the multi-manifold die. Next, the molten polymer from each extruder is merged in a multi-manifold die so as to be laminated in the order of extruder (b) / extruder (a) / extruder (c), and co-extruded into a sheet form from the die. did. At this time, the extruded sheet was cast on a mirror metal drum having a temperature of 30 ° C. and cooled and solidified into a sheet. Moreover, it casted so that the A layer supplied from the extruder (b) might contact a metal drum.

  The obtained unstretched sheet was stretched 3 times in the longitudinal direction at 60 ° C. with a roll stretching machine, and immediately cooled to room temperature. Under the present circumstances, the extending | stretching point of the lamination sheet was heated using the infrared heater installed between the low speed roll and the high speed roll. Next, the obtained uniaxially stretched film is introduced into a tenter, stretched 3.5 times in the transverse direction at 80 ° C. while holding both edges with clips, subsequently heat treated at 160 ° C., cooled, and wound up It was. At this time, the line speed was adjusted so that the heat treatment time was 3 seconds. The thickness structure of the obtained biaxially oriented film was A layer / B layer / A layer = 6/6/6 μm.

  After aging for 24 hours in a roll state under an atmosphere of 23 ° C. and 65%, the obtained biaxially oriented film was subjected to the same procedure as in Example 1 except that the deposited layer was formed on the A layer (from the extruder (b)). On the surface of the supplied resin layer).

  The film forming conditions of the obtained film are shown in Table 1, and the evaluation results of the film and the deposited film are shown in Tables 2 and 3. The resulting film had good gas barrier properties after vapor deposition, but was inferior in interlayer adhesion. For this reason, the bag produced using the said vapor deposition film produced the delamination on the whole at the time of opening, and was inferior to openability.

(Comparative Example 5)
In Comparative Example 2, a biaxially oriented film and a vapor deposition film produced in the same manner except that the stretching point between the low-speed roll and the high-speed roll in the longitudinal stretching process was heated using an infrared heater in the same manner as in Comparative Example 4. It was set as Comparative Example 5. In addition, the thickness structure of the film was A layer / B layer / C layer = 2/16/2 μm. Although the obtained film had good gas barrier properties after vapor deposition, it did not contain an interlayer adhesion improver in the A layer and the B layer, so the interlayer adhesion was inferior, and the effect of heating at the stretching point was almost completely confirmed. Was not. For this reason, the bag produced using the said vapor deposition film produced the delamination of the whole surface at the time of opening, and was remarkably inferior to openability.

However, the description in the table is as follows.
MD: The vertical direction of the film.
TD: The lateral direction of the film.
PGA: Polyglycolic acid.
PGLLA: L-lactic acid 10 mol% random copolymerized polyglycolic acid.
cPLA: “Ingeo” 4032D from Nature Works.
aPLA: “Ingeo” 4060D from Nature Works.
caPLA: A melt blend of 85% by mass of cPLA and 15% by mass of aPLA.
EA1: “Biomax” strong 120 from EI du Pont de Nemours and Company.
EA2: Arkema lotaderAX8900.

  As shown in Tables 1 to 3, the film of the present invention was excellent in interlayer adhesive force even though different polyesters were laminated. The vapor deposition film using the said film showed the high vapor deposition layer adhesive force and the outstanding gas barrier property. Moreover, since the package using the said vapor deposition film was excellent in bag-making processability and excellent in opening property, it was excellent in workability and practicality. Furthermore, the film of the present invention had no trouble in the film forming process and the vapor deposition process, and was excellent in film forming stability and vapor deposition processability. On the other hand, the film of the comparative example which does not contain an interlayer adhesion improving agent in both the B layer and the A layer has poor workability and practicality because of low interlayer adhesion.

  From the above, since the film of the present invention contains an interlayer adhesion improver in the B layer and the A layer, even if the B layer and the A layer are directly laminated without using the adhesive layer, the film has excellent interlayer adhesion force. In addition, it showed excellent gas barrier properties, workability, and practicality. These excellent characteristic values could be controlled by, for example, the film thickness configuration, the content of the interlayer adhesion improver, the molecular structure of the polyglycolic acid in the B layer, and the like.

  The present invention relates to a polyester-based laminated film having excellent gas barrier properties and excellent interlayer adhesion even when different polyesters are laminated, and a vapor-deposited film, a laminate, and a package using the same.

Claims (13)

A layer (B layer) comprising polyglycolic acid as a main constituent component is directly laminated on at least one side of a layer (A layer) comprising a polyester other than polyglycolic acid as a main constituent component; polyester laminate film containing adhesion promoter, the interlayer adhesion promoter is characterized glycidyl group-containing ethylene acrylate copolymer der Rukoto. The polyester-based laminated film according to claim 1 , wherein the B layer contains an interlayer adhesion improver. The polyester-based laminated film according to claim 1 or 2 , wherein the content of the interlayer adhesion improving agent of the A layer and / or the B layer is 0.1 to 30% by mass with respect to 100% by mass of all components of each layer. The polyester-based laminated film according to any one of claims 1 to 3 , wherein an interlayer adhesive force between the A layer and the B layer is 25 g / 15 mm or more. The polyester-based laminated film according to any one of claims 1 to 4 , wherein an aspect ratio of each region dispersed in the A layer and / or the B layer of the interlayer adhesion improving agent is 5 or more and 30 or less. The polyester-based laminated film according to any one of claims 1 to 5 , wherein the polyester of the A layer is an aliphatic polyester. The polyester-based laminated film according to any one of claims 1 to 6 , wherein the polyglycolic acid of the B layer is a copolymer containing a hydroxycarboxylic acid unit other than a glycolic acid unit as a comonomer unit. The polyester-based laminated film according to claim 7 , wherein the hydroxycarboxylic acid unit is 1 to 30 mol% with respect to 100 mol% of all monomer units of polyglycolic acid. The polyester-based laminated film according to claim 7 or 8 , wherein the hydroxycarboxylic acid unit is a lactic acid unit. Polyester laminate film according to any one of claims 1 to 9, wherein the B layer is at least one surface layer of the film. The vapor deposition film which has a vapor deposition layer which consists of a metal or an inorganic oxide in the at least single side | surface of the polyester-type laminated | multilayer film in any one of Claims 1-10 . Polyester laminate film, or laminate comprising a vapor deposition film according to claim 11 according to any of claims 1-10. The package which comprises the polyester-type laminated | multilayer film in any one of Claims 1-10 , or the vapor deposition film of Claim 11 .