JP2011143714A - Laminated film and vapor deposition film using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester-based laminated film and a vapor deposition film using the polyester-based laminated film excelling in gas barrier property and also excelling in flatness and interlayer adhesion force in spite of laminating different polyester. <P>SOLUTION: The laminated film includes at least a resin layer (A) containing polyglycolic acid having 70 mol% or more of a structure shown in formula 1, and a resin layer (B) mainly composed of polyester containing a dicarboxylic acid component and a glycol component. The amount of curl is to be 10 mm or less. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a laminated film excellent in gas barrier properties and excellent in flatness and interlayer adhesion even though different polyesters are laminated, and a vapor deposition film using the laminated film.

  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 a film material having excellent gas barrier properties used for this purpose, a composite film combining a film obtained by laminating an ethylene vinyl alcohol copolymer and a gas barrier film made of polyamide or the like has been developed. However, films such as ethylene vinyl alcohol copolymer and polyamide have a problem that the gas barrier property is dependent on humidity, and the gas barrier property is greatly deteriorated in a high humidity atmosphere.

  Polyglycolic acid (hereinafter abbreviated as PGA) is an example of a gas barrier polymer that is less dependent on humidity, and an oriented film made of polyglycolic acid (for example, Patent Document 1) has been proposed as a gas barrier film. 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 (for example, Patent Documents 2 and 3).

Japanese Patent No. 3731838 Japanese Patent No. 3913847 Japanese Patent No. 3978070

  However, in Patent Documents 2 and 3 described above, in order to ensure interlayer adhesion between the polyglycolic acid layer and the thermoplastic resin layer, a method of using an adhesive tie 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.

  In recent years, the required level of gas barrier properties has further increased, and the above-mentioned film does not necessarily have sufficient gas barrier properties.

  Therefore, the object of the present invention is to have excellent flatness and interlayer adhesion, and excellent gas barrier properties, workability and practicality despite the direct lamination of a polyglycolic acid layer and a different polyester layer. It is providing the laminated film which has these, and its vapor deposition film.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention as follows.
1) It has at least a resin layer (A) mainly composed of polyglycolic acid having a structure represented by Chemical Formula 1 of 70 mol% or more, and a resin layer (B) mainly composed of polyester composed of a dicarboxylic acid component and a glycol component. A laminated film,
The resin layer (A) and the resin layer (B) are directly laminated,
The resin layer (B) contains an interlayer adhesive,
A curled film having a curl amount of 10 mm or less after being stored at a temperature of 25 ° C. and a humidity of 60% for 24 hours.

2) At least one interlayer adhesive selected from the group consisting of polyglycolic acid, a polymer containing an ethylene component, a polymer containing an acrylic acid derivative component, and a polymer containing an ethylene component and an acrylic acid derivative component The resin film (B) contains the laminated film as described in 1) above.
3) The laminated film according to any one of 1) to 2) above, wherein the resin layer (B) has a glass transition temperature of 30 ° C. or higher and 65 ° C. or lower.
4) The polyester comprising the dicarboxylic acid component and the glycol component, which are the main components of the resin layer (B), contains any of the following (a) to (c): The laminated film according to any one of the above.
(A) Polyethylene terephthalate and polybutylene terephthalate (b) Copolymer of polyethylene terephthalate and polybutylene terephthalate (c) Copolymer of polyethylene terephthalate and polyethylene glycol 5) The dicarboxylic acid as the main component of the resin layer (B) The polyester comprising a component and a glycol component includes polyethylene terephthalate and polybutylene terephthalate,
The laminated film according to any one of 1) to 4), wherein the mass ratio is polyethylene terephthalate / polybutylene terephthalate = 70/30 to 30/70.
6) The polyester comprising the dicarboxylic acid component and the glycol component, which are the main components of the resin layer (B), includes a copolymer of polyethylene terephthalate and polyethylene glycol,
The molar ratio of the ethylene glycol unit of the polyethylene terephthalate part and the ethylene glycol unit of the polyethylene glycol part in the copolymer is such that the ethylene glycol unit of the polyethylene terephthalate part / the ethylene glycol unit of the polyethylene glycol part = 95/5 to 85/15. The laminated film according to any one of 1) to 4).
7) The resin layer (A) is at least one outermost layer,
The laminated film according to any one of 1) to 6) above, wherein the resin layer (A) has a center line surface roughness (Ra) of 5 nm to 50 nm.
8) 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 laminated | multilayer film in any one of said 1) -7).
9) The vapor-deposited film as described in 8) above, wherein the carbon dioxide gas permeability is 0.2 cc / (m ² · day · atm) or less.

  The laminated film of the present invention can be a film having excellent workability and practicality because it has excellent flatness even though layers having different polyester as a main constituent component are directly laminated, Since it has both high gas barrier properties and high interlayer adhesion due to the use of polyglycolic acid for one of these polyesters, it is a film particularly suitable for gas barrier applications. For this reason, it is easy to provide a vapor deposition layer in the 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.

  The laminated film of the present invention comprises a resin layer (A) mainly composed of polyglycolic acid having a structure represented by Chemical Formula 1 of 70 mol% or more, and a resin layer mainly composed of polyester composed of a dicarboxylic acid component and a glycol component (B ), The resin layer (A) and the resin layer (B) are directly laminated, the resin layer (B) contains an interlayer adhesive, and the curl amount is 10 mm or less.

  The content ratio of the repeating units represented by Chemical Formula 1 of the polyglycolic acid that is the main component of the resin layer (A) needs to be 70 mol% or more when the total monomer units of the polyglycolic acid are 100 mol%, Preferably it is 85 mol% or more, More preferably, it is 90 mol% or more, The upper limit is 100 mol%. When the content ratio of the repeating unit represented by Chemical Formula 1 of polyglycolic acid is less than 70 mol%, the gas barrier property and heat resistance of the laminated film are lowered. If the structure represented by Chemical Formula 1 in the polyglycolic acid that is the main component of the resin layer (A) is 70 mol% or more, a small amount of a copolymerization component (monomer) is introduced as the other component to obtain polyglycolic acid. The crystallinity can be controlled, the extrusion temperature can be lowered and the stretchability can be improved, and the roughening due to crystallization in the stretching step described later can be suppressed. In other words, as the polyglycolic acid, it is possible to use a polyglycolic acid copolymer resin into which a copolymerization component is introduced, and use any of the polyglycolic acid resins in which all monomer units have the structure shown in Chemical Formula 1. You can also.

  Polyglycolic acid can be synthesized by dehydration polycondensation of glycolic acid, dealcoholization polycondensation of glycolic acid alkyl ester, ring-opening polymerization of glycolide, and the like. Among these, glycolide is heated to a temperature of about 120 ° C. to about 250 ° C. in the presence of a small amount of a catalyst (for example, a cationic 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 resin layer (A) of the present invention is mainly composed of polyglycolic acid having 70 mol% or more of the structure represented by the above chemical formula 1, and the term “main body” as used here means that 100 mass of all components of the resin layer (A). % Means 50 mass% or more and 100 mass% or less. That is, the polyglycolic acid contained in the resin layer (A) is important to be 50% by mass or more, preferably 70% by mass when all the components of the resin layer (A) are 100% by mass. It is above, More preferably, it is 80 mass% or more, The upper limit is 100 mass%.

  In the range not impairing the object of the present invention, the resin layer (A) can contain polyglycolic acid, inorganic filler, other thermoplastic resin, plasticizer and the like. In addition, polyglycolic acid includes heat stabilizers, light stabilizers, moisture proofing agents, waterproofing agents, water repellents, lubricants, mold release agents, coupling agents, oxygen absorbers, pigments, dyes and the like as necessary. Various additives can be contained. These contents are within a range that does not impair the object of the present invention as described above. Specifically, when all the components of the resin layer (A) are 100% by mass, the polyglycolic acid is 50% by mass. Since it is contained in an amount of 100% by mass or less, the content of the inorganic filler, other thermoplastic resin, plasticizer, various additives, etc. is preferably in a smaller range, and all the components of the resin layer (A) are contained. When it is 100% by weight, it is preferably 30% by weight or less.

  From the viewpoint of improving the melt stability of polyglycolic acid, examples of heat stabilizers include phosphate esters having a pentaerythritol skeleton structure, phosphorus compounds having at least one hydroxyl group and at least one long-chain alkyl ester group, It is preferable to contain an activator, a metal carbonate, etc. in the resin layer (A). These heat stabilizers can be used alone or in combination of two or more.

The melt viscosity of the polyglycolic acid as the main component of the resin layer (A) is preferably 1000 to 10000 poise at 270 ° C. and 100 sec ⁻¹ , more preferably 2000 to 6000 poise, and further preferably 2500 to 5500 poise. When the melt viscosity of polyglycolic acid at 270 ° C. and 100 sec ⁻¹ is lower than 1000 poise, the molecular weight is low, and there is a possibility that it is likely to be decomposed. Further, when the polyglycolic acid has a melt viscosity exceeding 10,000 poise, there is a problem that the load on the extruder and the filtration pressure increase in the polymer extrusion process, or the lamination with the resin layer (B) described later becomes difficult. There is a fear.

  Although there is no restriction | limiting in particular in the thickness of the laminated | multilayer film of this invention, It is preferable that it is 5 micrometers-200 micrometers from a viewpoint of vapor deposition processing suitability, More preferably, it is 8-100 micrometers, More preferably, it is 10-50 micrometers.

  The laminated film of the present invention is a film having a structure in which the resin layer (B) is directly laminated on the resin layer (A), and in particular, the resin layer (A) and the resin layer (B) are directly laminated 2 A layer structure is a preferred embodiment. Originally, an adhesive tie layer is generally used between the resin layer (A) and the resin layer (B) in order to impart interlayer adhesion. However, in the method using the adhesive tie layer, an extruder and a co-extrusion device are required for the tie layer in addition to the resin layer (A) and the resin layer (B), and a film without uneven lamination such as a flow mark is used. In order to do so, it was necessary to control the melt viscosity of these at least three layers with high precision (especially when the feed block method is used among the methods shown below as the coextrusion lamination method). On the other hand, in the laminated film of the present invention, since the resin layer (A) and the resin layer (B) are directly laminated, there is no need to additionally introduce an extruder or a co-extrusion device, as described above. There is no need to worry about uneven lamination of the adhesive tie layer. Therefore, the film of the present invention is economically excellent and has excellent handling properties during coextrusion.

  In addition, the laminated film of the present invention has a resin layer (A) directly laminated with the resin layer (B), thereby reducing the amount of expensive polyglycolic acid used and making it a cost-effective film. be able to. In the laminated film of the present invention, the thickness of the resin layer (B) occupying the entire laminated film ((the thickness of the resin layer (B) here is a plurality of layers in the case of a laminated film having a plurality of resin layers (B)). The ratio is the total thickness of the resin layer (B).) When the total thickness of the laminated film is 1, the ratio is preferably 0.98 to 0.1, more preferably 0.95 to 0.3. More preferably, it is 0.95-0.6.

  In addition, when forming a vapor deposition layer in the laminated | multilayer film of this invention and making it a vapor deposition film, although a vapor deposition layer can be formed in any surface, a vapor deposition layer is formed on a resin layer (A). It is preferable that the resin layer (B), the resin layer (A), and the vapor deposition layer be laminated in this order.

  The melt viscosity of the resin layer (B) of the present invention is preferably equal to or slightly larger than the melt viscosity of the resin layer (A) at the extrusion temperature. When the melt viscosity of the resin layer (B) is extremely small, uniform lamination may be difficult. When the difference in melt viscosity between the resin layer (A) and the resin layer (B) is large, a method of providing an extrusion temperature difference and laminating with a die, a thickener, a crosslinking agent, a chain extender, etc. on the resin layer (B) It is preferable to correct by a method of increasing the viscosity by adding.

  As a resin preferably used for a polyester comprising a dicarboxylic acid component and a glycol component, which are the main components of the resin layer (B), aromatic polyester, aliphatic polyester, and their co-polymers from the viewpoints of extrusion characteristics, cost, and handleability Coalescence is mentioned. The resin layer (A) described above and the resin layer (B) mainly composed of these polyesters can be combined with heat resistance by using an aromatic polyester as the polyester mainly composed of the resin layer (B). In addition, stability over time can be improved and high barrier properties can be expressed.

  The resin layer (B) of the present invention is mainly composed of a polyester composed of the above-mentioned dicarboxylic acid component and glycol component. The main component of the resin layer (B) here is the entire resin layer (B). When the component is 100% by mass, the polyester is 70% by mass or more and 100% by mass or less. The polyester composed of the aforementioned dicarboxylic acid component and glycol component in the resin layer (B) is more preferably 80% by mass or more when the total component constituting the resin layer (B) is 100% by mass, More preferably, it is 90 mass%, and the upper limit is 100 mass%.

  The glass transition temperature of the resin layer (B) constituting the laminated film of the present invention is preferably 65 ° C. or lower so that the laminated film can be stretched at a temperature of 70 ° C. or lower. Stretching the laminated film at a temperature of 70 ° C. or less can adjust the crystallinity and orientation of the resin layer (A), and as a result, the surface of the resin layer (A) can be smoothed. The barrier property when a vapor deposition layer is provided on the layer (A) is further improved. The lower limit of the glass transition temperature of the resin layer (B) is preferably 30 ° C. or higher because the heat resistance of the laminated film is improved. The glass transition temperature here is a value obtained by DSC (differential scanning calorimetry) measured by the method described in JIS-K7121 (1987), and is an intermediate glass when the temperature is raised at 20 ° C./min. Transition temperature.

  A case where an aromatic polyester is used as the polyester composed of the above-described dicarboxylic acid component and glycol component, which is the main component of the resin layer (B), will be described. As such an aromatic polyester, various polyesters in which a dicarboxylic acid component and a glycol component are ester-bonded can be used. Examples of dicarboxylic acid components in this case include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and naphthalenedicarboxylic acid, and aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, and dimer acid. , Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, oxycarboxylic acids such as p-oxybenzoic acid, polyfunctional acids such as trimellitic acid and pyromellitic acid, and the like can be used. 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 glycols. Etc. can be used. Furthermore, polyethers such as polyethylene glycol and polytetramethylene glycol may be copolymerized. These dicarboxylic acid components and glycol components may be used in combination of two or more, or may be used by blending two or more types of polyester. In particular, polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, and polyesters copolymerized with isophthalic acid, sebacic acid and dimer acid, or a blend of two or more of them are preferably used.

Among the above, from the viewpoints of heat resistance, stability over time, and gas barrier properties, the polyester that is the main component of the resin layer (B) preferably includes any of the following (a) to (c).
(A) Polyethylene terephthalate and polybutylene terephthalate (b) Copolymer of polyethylene terephthalate and polybutylene terephthalate (c) Copolymer of polyethylene terephthalate and polyethylene glycol Further, as described above, a laminated film at a temperature of 70 ° C. or less In order to enable stretching of the polyester, the polyester as the main component of the resin layer (B) contains polyethylene terephthalate and polybutylene terephthalate, and the mass ratio thereof is polyethylene terephthalate / polybutylene terephthalate = 70/30 to 30 /. 70 is preferable. The polyester that is the main component of the resin layer (B) contains polyethylene terephthalate and polybutylene terephthalate, and the mass ratio of polyethylene terephthalate / polybutylene terephthalate is 70/30 to 30/70, so that the resin layer (B) Since the glass transition temperature of the film can be 30 ° C. or higher and 65 ° C. or lower, the laminated film can be stretched at a temperature of 70 ° C. or lower. As a result, the surface of the resin layer (A) of the laminated film is smoothed. It is preferable because it can be formed. The mass ratio of polyethylene terephthalate and polybutylene terephthalate is more preferably polyethylene terephthalate / polybutylene terephthalate = 60/40 to 30/70, and still more preferably 50/50 to 40/60.

  When the polyester as the main component of the resin layer (B) contains polyethylene terephthalate and polybutylene terephthalate and the mass ratio thereof is polyethylene terephthalate / polybutylene terephthalate = 70/30 to 30/70, the resin layer (B ) The total content of polyethylene terephthalate and polybutylene terephthalate in the polyester as the main component is not particularly limited, but all (100% by mass) of the polyester as the main component in the resin layer (B) is polyethylene terephthalate and polybutylene terephthalate. It is a particularly preferable embodiment.

  As described above, the polyester that is the main component of the resin layer (B) means that the polyester is 70% by mass or more and 100% by mass or less when the total component of the resin layer (B) is 100% by mass. Therefore, when the polyester which is the main component of the resin layer (B) contains polyethylene terephthalate and polybutylene terephthalate, the total amount of polyethylene terephthalate and polybutylene terephthalate in the resin layer (B) is the same as that of the resin layer (B). The total amount of polyethylene terephthalate and polybutylene terephthalate in the resin layer (B) is more preferably 70% by mass or more and 100% by mass or less at 100% by mass of all components. It is 80 mass% or more and 100 mass% or less in 100 mass% of a component, More preferably, it is resin layer (B). Is 100 wt% or less than 90 wt% in the component 100 wt%.

  When the polyester that is the main component of the resin layer (B) includes a copolymer composed of polyethylene terephthalate and polybutylene terephthalate, the polyethylene terephthalate portion in the copolymer and the polybutylene in the copolymer The mass ratio of the terephthalate portion is more preferably polyethylene terephthalate / polybutylene terephthalate = 60/40 to 20/80, and further preferably 35/65 to 45/55. When the polyester that is the main component of the resin layer (B) contains a copolymer composed of polyethylene terephthalate and polybutylene terephthalate, the content of the copolymer in the polyester that is the main component of the resin layer (B) is Although not particularly limited, it is a particularly preferable embodiment that all (100% by mass) of the polyester as the main component of the resin layer (B) is the copolymer.

  In addition, it is preferable that the polyester as the main component of the resin layer (B) includes a copolymer of polyethylene terephthalate and polyethylene glycol because extrusion characteristics are improved. When the polyester as the main component of the resin layer (B) is a copolymer of polyethylene terephthalate and polyethylene glycol, the ethylene glycol unit of the polyethylene terephthalate part and the ethylene glycol unit of the polyethylene glycol part in the copolymer By making the molar ratio ethylene glycol unit of polyethylene terephthalate part / ethylene glycol unit of polyethylene glycol part = 95/5 to 85/15, the glass transition temperature of the resin layer (B) is 30 ° C. or more and 65 ° C. or less. Therefore, the laminated film can be stretched at a temperature of 70 ° C. or lower, and as a result, the surface of the resin layer (A) of the laminated film can be smoothed, which is preferable.

  The polyester that is the main component of the resin layer (B) contains a copolymer of polyethylene terephthalate and polyethylene glycol, and the molar ratio of the ethylene glycol unit of the polyethylene terephthalate part to the ethylene glycol unit of the polyethylene glycol part in the copolymer is When the ethylene glycol unit of the polyethylene terephthalate part / the ethylene glycol unit of the polyethylene glycol part = 95/5 to 85/15, the content of the copolymer in the polyester that is the main component of the resin layer (B) is Although not particularly limited, it is a particularly preferable embodiment that all (100% by mass) of the polyester as the main component of the resin layer (B) is the copolymer.

  The laminated film of the present invention needs to have a curl amount of 10 mm or less after being stored at a temperature of 25 ° C. and a humidity of 60% for 24 hours. When the curl amount exceeds 10 mm, the slit property may be deteriorated, or when a vapor deposition layer is provided, vapor deposition spots or image sticking may occur. The curl amount is important to be 10 mm or less, preferably 8 mm, and most preferably 0 mm (horizontal). In the laminated film of the present invention, layers having different polymers as main constituent components are directly laminated. Therefore, when heat is applied in the film forming process, the flatness deteriorates due to the difference in thermal expansion coefficient of each layer. Often occurs. In order to reduce the curl amount after storage for 24 hours or more at a temperature of 25 ° C. and a humidity of 60% to 10 mm or less, a special relaxation method described later, or polyglycolic acid as an interlayer adhesive is added to the resin layer (B). The method of making it contain etc. can be mentioned, It is preferable to use these together especially.

  It is important that the laminated film of the present invention contains an interlayer adhesive in the resin layer (B). Although the curling is eliminated by a relaxation process described later, the interlayer adhesion and gas barrier properties may deteriorate in that case. When the resin layer (B) contains an interlayer adhesive, it is possible to suppress a decrease in interlayer adhesive force during the relaxation process. Further, since the resin layer (B) contains an interlayer adhesive, peeling occurs between the resin layer (A) and the resin layer (B) in processing steps such as printing, laminating, coating, bag making, and vapor deposition. It is difficult to improve processability. For this reason, even if the final product using the laminated film of the present invention in which the resin layer (B) contains an interlayer adhesive is processed into a bag filled with contents by bag making, for example, the bag Is difficult to delaminate between the resin layer (A) and the resin layer (B), and is excellent in opening of the bag.

  The interlayer adhesive is not particularly limited as long as it has a high molecular weight or low molecular weight as long as the interlayer adhesion can be increased as compared with the case where it is not added. In order to prevent bleed out with time on the film surface of the molecular weight, it is preferably a polymer type.

  As a method for increasing the interlayer adhesive force using an interlayer adhesive, the interlayer adhesion is achieved by using an interlayer adhesive having a molecular structure similar to the resin composition constituting the resin layer (A) or a molecular structure having a high affinity. A resin layer (B) containing an agent to improve wettability between the resin layer (A) and the resin layer (B), a method of forming entanglement between molecules, and a resin layer (A) A method of forming a chemical bond between the resin layer (A) and the resin layer (B) by using the interlayer adhesive having reactivity with the resin composition to be added and containing the interlayer adhesive in the resin layer (B) Etc.

  As the interlayer adhesive to be contained in the resin layer (B), it is particularly preferable to use the same polyglycolic acid as that of the resin layer (A). That is, the interlayer adhesive force between the resin layer (A) and the resin layer (B) is improved by containing polyglycolic acid as an interlayer adhesive in the resin layer (B). Moreover, since polyglycolic acid has a high barrier effect, the gas barrier property of the laminated film of the present invention is also improved by including polyglycolic acid in the resin layer (B). Furthermore, since the thermal expansion coefficient between the resin layer (A) and the resin layer (B) becomes closer and the curl amount generated in the film forming process can be reduced, the rate of relaxation can be reduced, and the resin layer ( Deterioration of the interlayer adhesive force and gas barrier property between A) and the resin layer (B) can be further reduced. The amount of polyglycolic acid contained in the resin layer (B) is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, and still more preferably 100% by mass of all components of the resin layer (B). 3 to 10% by mass. The method for incorporating the polyglycolic acid into the resin layer (B) is not particularly limited as long as the effects of the present invention are not impaired, but when the laminated film of the present invention is produced, the raw material of the resin layer (B) and poly Glycolic acid may be melt-kneaded and contained in an extruder, and melt-kneaded in advance with a twin-screw extruder or the like to produce a master raw material containing polyglycolic acid in a high concentration in the raw material of the resin layer (B). It can be used by diluting during film production. Moreover, the waste film produced when manufacturing the laminated | multilayer film of this invention can be blended and used for the resin composition of a resin layer (B).

  Moreover, the polymer containing an ethylene component and / or an acrylic-acid-type derivative component can be used as an interlayer adhesive contained in a resin layer (B). When a polymer containing an acrylic acid derivative component is used as an interlayer adhesive, a copolymer containing an acrylic acid derivative component shown below as a comonomer component is preferable.

CH ₂ = CR ₁ COOR ₂
Here, R ₁ is hydrogen or an alkyl group having 1 to 8 carbon atoms; R ₂ is hydrogen or an alkyl group having 1 to 8 carbon atoms. More preferably, R ₂ is not hydrogen, that is, an alkyl group having 1 to 8 carbon atoms, from the viewpoint of handling properties during melt molding (for example, prevention of corrosion of an extruder). Examples of preferable acrylic acid derivative components include derivative components such as acrylic acid (when R ₁ and R ₂ are hydrogen) and methacrylic acid (when R ₁ is a methyl group and R ₂ is hydrogen). . The derivative is preferably an esterified product in which R ₂ is a methyl group, an ethyl group, a t-butyl group, an n-butyl group, a glycidyl group, or the like, from the viewpoint of handleability during melt extrusion. In addition, from the viewpoint of melt moldability and the food hygiene law provided by the US FDA and other organizations, when the interlayer adhesive is a copolymer, not only an acrylic acid derivative component as a comonomer component but also an olefin as a comonomer component It is preferable that a component, particularly an ethylene component, is copolymerized. Furthermore, in addition to the ethylene component and the acrylic acid derivative component, other glycidyl group-containing components and / or acid anhydride derivative components represented by maleic anhydride are used as a copolymer component to form a polymer indirectly. This is preferable because the adhesion can be further improved. In particular, a polymer containing an ethylene component and / or an acrylic acid derivative component contains a component having reactivity with the terminal hydroxyl group or carboxyl group of the polyglycolic acid constituting the resin layer (A). It is preferable in terms of forming a chemical bond and increasing the adhesive force. In addition to an epoxy group (glycidyl group) -containing component and an acid anhydride derivative component, the same applies to polyfunctional components having a functional group such as a carbodiimide group, an isocyanate group, and an oxazoline group. Can be used.

  Examples of the interlayer adhesive include “Elvalloy”, “Elvalloy AC”, “High Milan”, “Nucleel”, “HPR” manufactured by Mitsui DuPont Polychemical Co., Ltd .; “Lotader MAH”, “Lotader GMA” manufactured by Arkema, “BONDINE”; “BONDFAST” manufactured by Sumitomo Chemical Co., Ltd .; “REXPEARL ET” manufactured by Nippon Polyethylene Co., Ltd., “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.

  In the film of the present invention, when a polymer containing an ethylene component and / or an acrylic derivative component is used as an interlayer adhesive, the content in the resin layer (B) is 100% by mass of all components of the resin layer (B). It is preferable that it is 0.1-20 mass% with respect to. If the content of the polymer containing an ethylene component and / or an acrylic acid derivative component is less than 0.1% by mass, sufficient interlayer adhesion may not be exhibited. On the other hand, when the content exceeds 20% by mass, a difference in density and thermal expansion coefficient from the resin layer (A) tends to appear and the effect of improving the interlayer adhesion tends to be saturated, and the curl may be deteriorated. More preferably, it is 0.5-15 mass%, More preferably, it is 1-10 mass%.

  The method for adding a polymer containing an ethylene component and / or an acrylic acid derivative component as an interlayer adhesive to the resin layer (B) is not particularly limited as long as the effect of the present invention is not impaired. When the laminated film is produced, the raw material of the resin layer (B) (the raw material here means a raw material excluding the interlayer adhesive) and the interlayer adhesive may be melt-kneaded with an extruder and contained. In addition, an interlayer adhesive is contained in a high concentration in the raw material of the resin layer (B) (herein, the raw material means a raw material excluding the interlayer adhesive) that is melt-kneaded with a twin screw extruder or the like in advance. A master raw material can be produced and used by diluting during film production. In particular, the method of preparing and diluting a high-concentration master material in advance using a twin-screw extruder improves the dispersion state of the interlayer adhesive in the resin layer (B), and more uniformly expresses the interlayer adhesive force. Can be preferably used.

  In the film of the present invention, the interlayer adhesive is selected from the group consisting of polyglycolic acid, a polymer containing an ethylene component, a polymer containing an acrylic acid derivative component, and a polymer containing an ethylene component and an acrylic acid derivative component. Two or more selected may be used in combination. When using 2 or more types together, it is more preferable that at least one of the interlayer adhesives is polyglycolic acid from the viewpoint of the barrier property and curling suppressing effect. When two or more kinds of interlayer adhesives are used in combination, the content in the resin layer (B) is such that the total amount of each interlayer adhesive is 0.1 to 20 masses with respect to 100 mass% of all components of the resin layer (B). % Is preferred.

  In the laminated film of the present invention, it is preferable that the resin layer (A) is at least one outermost layer, and the centerline surface roughness (Ra) of the resin layer (A) is 5 to 50 nm. More preferably, it is 10-50 nm, More preferably, it is 15-30 nm. When the center line average roughness of the surface on the vapor deposition layer side of the resin layer (A) is 5 to 50 nm, the occurrence of pinholes during vapor deposition is suppressed, and good barrier properties are obtained, and also during film formation and vapor deposition processing. It is excellent in processing suitability. When the center line average roughness is smaller than 5 nm, the film slips poorly, and it becomes easy to induce blocking or electrostatic charging during winding or vapor deposition at the time of film formation, which may cause deterioration of the vapor deposition barrier property. On the other hand, if the center line average roughness exceeds 50 nm, a uniform vapor deposition layer cannot be formed, resulting in a significant deterioration in barrier properties. The method of keeping the center line average roughness of the resin layer (A) within 5 to 50 nm is not particularly limited, but polyglycolic acid has a high crystallization rate, and therefore the crystallization rate of the resin layer (A) is reduced, stretched, and heated. A method of controlling the orientation according to the conditions in the fixing step is preferably used. As an example of sequential biaxial stretching of a laminated film, it can be achieved by performing biaxial stretching at a stretching temperature of 70 ° C. or less and an area magnification of 4.0 times or more, and heat-treating. In addition, polyglycolic acid has low thermal stability, and it is easy for foreign substances such as gels to form in the molten polymer.Since these foreign substances become coarse protrusions and often rough the surface, stainless steel fibers are used to remove them. It is desirable to filter the molten polymer extruded from the extruder using a sintered and compressed filter or a filter obtained by sintering stainless steel powder. Details of the film forming method will be described later. In addition, in the case of the vapor deposition film of this invention which formed the vapor deposition layer in the laminated | multilayer film of this invention, the center of the surface (to-be-deposited surface) of the vapor deposition layer side of a resin layer (A) by removing a vapor deposition layer with an acid The line average roughness can be confirmed.

  The laminated film of the present invention preferably has a heat shrinkage in the longitudinal direction of 8% or less and a heat shrinkage in the width direction of 8% or less after heat treatment at 150 ° C. for 30 minutes. More preferably, the thermal contraction rate in the longitudinal direction is −1 to 6%, the thermal contraction rate in the width direction is −2 to 6%, and more preferably, the shrinkage rate in the longitudinal direction is 0 to 4%, and the thermal contraction rate in the width direction. The rate is -1 to 5%. If the thermal contraction rate in the longitudinal direction and the width direction after heat treatment at 150 ° C. for 30 minutes is 8% or less, it is excellent in heat-resistant dimensional stability, and the gas barrier property due to the structural change of the film due to heat during vapor deposition There is no deterioration, and it is also preferable from the viewpoints of processability such as printing and bag making, and printing accuracy. There is no particular limitation on the method for reducing the heat shrinkage rate in the longitudinal direction and the width direction after the heat treatment of the deposited film at 150 ° C. for 30 minutes to 8% or less, but at least in the heat setting step in the formation of the laminated film, the temperature and heat treatment A method for controlling time is preferably used.

  When the vapor deposition layer is formed on the resin layer (A), the resin layer (A) that becomes the vapor deposition surface is stretched by the tension during vapor deposition, the film surface is prevented from moving by heat, and cracks are generated due to the tension after vapor deposition. In order to suppress this, the tensile elastic modulus in the longitudinal direction and the width direction of the resin layer (A) of the present invention is preferably 3.0 GPa or more, more preferably 4.0 to 8.0 GPa, more preferably Preferably it is 5.0G-8.0GPa. If the elastic modulus is less than 3.0 GPa, the gas barrier property may be deteriorated due to the structural change of the film caused by the heat during vapor deposition. Although the upper limit is not particularly specified, it is usually 8.0 GPa. As a method for setting the tensile elastic modulus of the resin layer (A) to 3.0 GPa or more, a method of controlling the orientation by the stretching temperature and magnification in the stretching process of the laminated film and the heat treatment temperature in the heat setting process is preferably used.

  The resin layer (A) has a surface orientation obtained by measuring (Nx + Ny) / 2−Nz by measuring the longitudinal refractive index (Nx), the width direction refractive index (Ny), and the thickness direction refractive index (Nz) of the surface. The coefficient (hereinafter referred to as fn) is preferably 0.01 to 0.1. More preferably, it is 0.02-0.08, More preferably, it is 0.03-0.07. When fn is less than 0.01, the orientation is low, so there is a concern that the gas barrier property is deteriorated, and when it exceeds 0.1, there is a fear of cleavage. As a method of setting the fn of the resin layer (A) in the range of 0.01 to 0.1, depending on at least the stretching temperature in the stretching process of the film having the resin layer (A), the stretching ratio, and the heat treatment temperature in the heat setting process. A method for controlling the orientation is preferably used. Moreover, when it has a vapor deposition layer, a vapor deposition layer can be removed with an acid and a plane orientation coefficient can be confirmed. Even in the case of a laminated film in which the resin layer (B) is laminated on the resin layer (A), the plane orientation coefficient of the resin layer (A) can be confirmed by measuring the refractive index of the surface of the resin layer (A). .

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

  After the raw materials such as the polymer forming the resin layer (A) and the resin layer (B) are supplied to different extruders, foreign substances are removed by a filter and flow rate is optimized by a gear pump in different flow paths, and then a multilayer laminated die Alternatively, after merging and stacking in a feed block installed at the top of the base, or in a base having a plurality of manifolds inside, the sheet is discharged from the base into a sheet shape and brought into close contact with the casting drum by a method such as air knife or electrostatic application. Then, it is cooled and solidified to obtain an unstretched film.

  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 stainless steel fibers, 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.

  Next, in the case of the sequential biaxial stretching method, the unstretched sheet is preheated by passing it through a roll, and subsequently passed between rolls having a difference in peripheral speed, stretched in the longitudinal direction, immediately cooled to room temperature, and then the stretched film is It is guided to a tenter, stretched, and then heat-fixed and wound while being relaxed in the width direction. Or you may extend | stretch by the method of extending | stretching a longitudinal direction and a horizontal direction simultaneously, and may extend | stretch by the method etc. which perform extending | stretching of a longitudinal direction and the extending | stretching of the width direction in combination several times.

  Further, the tenter simultaneous biaxial stretching method is advantageous from the viewpoint of surface smoothness because the crystallinity of polyglycolic acid after uniaxial stretching is improved and the risk of roughening the resin layer (A) is reduced. Furthermore, since stretchability is improved as compared with sequential biaxial stretching, it is possible to stretch at a high magnification, which is preferable because there is a merit that a high elastic modulus and a high orientation can be achieved.

  The stretching condition of the laminated film is preferably stretched at 70 ° C. or less from the viewpoint of adjusting the crystallinity and orientation of the resin layer (A) and smoothing the surface, specifically, the stretching temperature in the longitudinal direction is 40. It is preferable to set it to -70 degreeC. More preferably, it is 40-65 degreeC, More preferably, it is 50-60 degreeC. 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 width direction is also preferably 70 ° C. or lower, and specifically 40 to 70 ° C. More preferably, it is 40-65 degreeC, More preferably, it is 45-55 degreeC. 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, when the stretching temperature exceeds 70 ° C., the crystallization of polyglycolic acid proceeds in the transverse stretching step, and the surface is likely to become rough after 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, the thermal crystallization of polyglycolic acid in the heat setting step tends to be roughened.

  After stretching, preferably 120 ° C. to (melting point of polyglycolic acid in resin layer (A)) ° C., more preferably 150 ° C. to (melting point of polyglycolic acid in resin layer (A) −10) ° C., more preferably 170 ° C. A relaxing treatment is carried out at a temperature of from 0 ° C. to (the melting point of the polyglycolic acid of the resin layer (A) −20) ° C., and then cooled. After proper stretching, the surface smoothness of the resin layer (A) is maintained by relaxing treatment within this range, and the surface that satisfies the range of low thermal shrinkage rate, high elastic modulus, and constant plane orientation coefficient and curl is suppressed. A film having good properties can be obtained. If the relaxation treatment temperature is higher than the melting point of the polyglycolic acid in the resin layer (A), the polyglycolic acid crystals may melt and become non-oriented, and the resin layer (A) may be roughened due to the temperature-falling crystallization. On the other hand, when the relaxation treatment temperature is less than 120 ° C., the heat resistance is greatly reduced, and troubles such as shrinkage during vapor deposition are likely to occur. The relaxation rate is preferably 1 to 8%, and more preferably 2 to 6%. When the relaxation ratio is less than 1%, curling is not sufficiently eliminated. When the relaxation ratio exceeds 8%, curling is eliminated, but interlayer adhesion and gas barrier properties deteriorate.

  The obtained stretched film is further improved in gas barrier properties by performing vapor deposition. Examples of the metal or metal oxide used for the vapor deposition layer include aluminum, aluminum oxide, silicon oxide, silicon oxynitride, cerium oxide, calcium oxide, diamond-like carbon film, and a mixture thereof. Aluminum, aluminum oxide Silicon oxide can be preferably used from the viewpoints of gas barrier properties and productivity. 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. The deposited film of the present invention has a deposited layer on at least one side of the laminated film of the present invention. When the laminated film is composed of the resin layer (A) and the resin layer (B), there is no particular limitation on the surface on which the vapor deposition layer is provided, but the resin layer (A) is used because the decomposition of the resin layer (A) can be suppressed. A layer structure covered with a vapor deposition layer is preferred. That is, a configuration such as resin layer (B) / resin layer (A) / deposition layer is preferable. In addition, when the laminated film has a laminated structure of resin layer (A) / resin layer (B) / resin layer (A), the vapor-deposited layer can be provided with vapor-deposited layers on both sides of the laminated film. Although preferable from the viewpoint, it is higher than single-sided vapor deposition in terms of cost.

  A vacuum process is used as a method for forming the vapor deposition layer of the vapor deposition film of the present invention. As the vacuum process, a vacuum deposition method, a sputtering method, an ion plating method, a chemical vapor deposition method, or the like is appropriately used, and any of them is not limited. For example, a reactive vapor deposition method can be used more preferably in terms of productivity and cost to provide a metal oxide vapor deposition layer.

In the vacuum process, it is preferable to subject the surface of the film before vapor deposition to plasma treatment or corona treatment in order to further improve the gas barrier property. Processing strength when subjected to corona treatment is preferably 5~50W · min / ^{m 2,} more preferably 10~45W · min / ^{m 2.} Moreover, before providing the vapor deposition layer which consists of a metal or a metal oxide, it is preferable from a viewpoint of the adhesive improvement of a vapor deposition layer to provide a metal deposition layer with a nucleus under plasma discharge. In this case, it is most preferable to use copper as the cored metal in an oxygen and / or nitrogen gas atmosphere.

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. The method is adopted. 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, Most preferably, it is 5-30 nm. If the thickness of the vapor deposition layer is less than 5 nm, vapor deposition layer defects are likely to occur, and the gas barrier properties deteriorate. If the thickness of the vapor deposition layer is greater than 100 nm, the cost during vapor deposition may increase, or the color of the vapor deposition layer may become remarkable and the appearance may be inferior.

  The vapor deposition film of the present invention can obtain higher gas barrier properties when used in combination with a coating technique. In other words, if the anchor coat agent is previously formed on the resin layer (A) in-line or off-line to form the anchor coat layer, the vapor deposition layer formed on the anchor coat layer becomes a highly adhesive layer, and the gas barrier (In this case, the deposited film of the present invention has at least the resin layer (A) / anchor coat layer / deposited layer in this order).

  Moreover, if an overcoat agent is formed on the vapor deposition layer to form an overcoat layer, defects in the vapor deposition layer are complemented and gas barrier properties are improved (in this case, the vapor deposition film of the present invention includes at least a resin layer) (A) / deposition layer / overcoat layer in this order).

  As an anchor coat agent and an overcoat agent (hereinafter, the anchor coat agent and the overcoat agent are referred to as a coat agent), polyvinylidene chloride, polyvinyl alcohol, polyethylene-vinyl alcohol, acrylic, polyacrylonitrile, polyester, polyurethane, and At least one resin selected from polyester-polyurethane resins is preferably used. Among them, a coating agent containing at least one resin selected from polyethylene-vinyl alcohol, polyacrylonitrile, and polyurethane-based resin is used as the resin layer (A). From the standpoint of inhibiting low molecular weight substances such as oligomers and complementing gas barrier properties.

  In the coating agent containing an ethylene-vinyl alcohol resin, the ethylene component amount in 100 mol% of all monomer units of the ethylene-vinyl alcohol resin is preferably 1-50 mol%, and is 2-40 mol%. More preferably. When the ethylene component amount is less than 1 mol%, the compatibility with the resin layer (A) described above is poor, the anchor coat layer becomes opaque, and when the ethylene component amount exceeds 50 mol%, the ethylene-vinyl alcohol-based resin Solubility in the solvent is poor and processability is reduced. The degree of saponification is preferably 95 mol% or more, more preferably 97 mol% or more.

  In the coating agent containing a polyacrylonitrile-based resin, the nitrile group is preferably included in an amount of 5 to 70% by mass, more preferably 10 to 50% by mass in 100% by mass of the polyacrylonitrile-based resin. The approximate range is preferable because it is easy to balance the effect of improving the gas barrier property, the uniformity of the coating film, and the handleability of the coating material. The glass transition temperature of the polyacrylonitrile resin is preferably 50 ° C. to 100 ° C. from the viewpoint of the uniformity of the coating film.

  Examples of the monomer copolymerized with acrylonitrile in the polyacrylonitrile resin include, for example, ethylenically unsaturated carboxylic acid esters such as various acrylic acid esters and various methacrylic acid esters; acrylamide, methacrylamide; ethylene such as acrylic acid and methacrylic acid Unsaturated carboxylic acids; vinyl esters such as vinyl acetate; styrene monomers such as styrene and methylstyrene; methacrylonitrile and the like.

  The polyurethane resin, which is the main component of the urethane coating, preferably has a high total concentration of urethane groups and urea groups from the viewpoint of gas barrier properties. However, if the total concentration of urethane groups and urea groups is too high, it will become an emulsion. Therefore, the total of urethane groups and urea groups is preferably 20 to 70% by mass and more preferably 25 to 60% by mass in 100% by mass of the polyurethane resin. The urethane group concentration is a value obtained by dividing the molecular weight of the urethane group by the molecular weight of the repeating structural unit structure, and the urea group concentration is a value obtained by dividing the molecular weight of the urea group by the molecular weight of the repeating structural unit structure.

  From the viewpoint of gas barrier properties, the polyurethane-based resin contained in the urethane-based coating is 1,3- or 1,4-xylylene diisocyanate, 1,3- or 1,4-tetramethylxylylene diisocyanate, and Hydrogenated xylylene diol is preferably used as 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane and 1,3- or 1,4-xylylene diol as the polyol, and combinations thereof are preferred.

  It is preferable that these coating agents contain a cross-linking agent, if necessary, to improve water resistance and gas barrier properties. Various coupling agents such as epoxy, amine, melamine, isocyanate, oxazoline-based crosslinking agents, titanium coupling agents, and silane coupling agents can be suitably used.

The coating amount of the coating agent is preferably in the range of 0.01 to ² g / m ² , more preferably in the range of 0.01 to 1 g / m ² . When the coating amount is less than 0.01 g / m ² , defects such as film breakage and repellency are likely to occur even in an in-line coating method capable of forming a relatively thin resin film, and it is difficult to form a uniform resin film. Even when an inorganic oxide layer is formed on the resin layer, there is a tendency that sufficient gas barrier properties are not exhibited. On the other hand, when the coating amount is larger than 2 g / m ² , it is necessary to increase the drying conditions at the time of coating in order to sufficiently evaporate the solvent and to increase the time, and the film is likely to be deformed such as curling. There is concern about residual solvent, and this is not preferable from the viewpoint of cost.

The vapor deposition film of the present invention preferably has a carbon dioxide gas permeability of 0.2 cc / (m ² · day · atm) or less. When the carbon dioxide gas permeability exceeds 0.2 cc / (m ² · day · atm), when the vapor-deposited film is used as a gas-filled packaging material such as a heat insulating material or food, the filling gas is diffused and the heat insulating performance is improved. May deteriorate over time. The carbon dioxide gas permeability of the deposited film is more preferably 0.05 c / (m ² · day · atm) or less, and further preferably 0.02 cc / (m ² · day · atm) or less. The better the carbon dioxide gas barrier property is, the lower limit is not particularly set. However, the lower limit is about 0.002 cc / (m ² · day · atm).

Moreover, it is preferable that the water vapor transmission rate of the vapor deposition film of this invention is 1.5 g / (m < ² > * day * atm) or less. When the water vapor permeability exceeds 1.5 g / (m ² · day · atm), the water vapor barrier property is inferior, and when the vapor-deposited film is used as a packaging material to be processed into a package, the freshness retention of the contents is inferior. There is a case. The water vapor permeability of the deposited film is more preferably 1 g / (m ² · day · atm) or less, and further preferably 0.5 g / (m ² · day · atm) 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 * atm) is a realizable lower limit.

The oxygen permeability of the vapor deposition film of the present invention is preferably ² cc / (m ² · day · atm) or less. When the oxygen permeability of the vapor deposition film exceeds ² cc / (m ² · day · atm), the oxygen barrier property is inferior, and when the vapor deposition film is processed as a packaging material into a package, the freshness of the contents is maintained. May be inferior. The oxygen permeability of the deposited film is more preferably 1 cc / (m ² · day · atm) or less, and further preferably 0.5 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, but about 0.01 cc / (m < ² > * day * atm) is estimated as the minimum which can be implement | achieved.

  The laminated 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 packages, heat sealability is required on at least one side of the laminated film of the present invention. For this purpose, it can be set as the film structure which formed the heat seal layer (C) in the film of this invention. (For example, resin layer (A) / resin layer (B) / heat seal layer (C). In order to further enhance the heat seal force, polypropylene alone, ethylene / propylene copolymer, ethylene / propylene / butene Polymer, low density polyethylene, polyethylene or polypropylene using metallocene catalyst, ethylene / propylene copolymer, ethylene / vinyl acetate copolymer, known amorphous polyester, heat sealable resin represented by acrylic resin, etc. 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.

  Furthermore, the laminated film of the present invention can be laminated with another film other than those described above as appropriate according to the purpose, and can be processed into a package using the laminate. In order to further improve the gas barrier performance of the laminated film of the present invention, an 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.

  As described above, it is possible to obtain a polyester-based laminated film excellent in gas barrier properties and having excellent flatness and interlayer adhesion even though different polyesters are laminated, and a vapor deposition film using the same. Moreover, it can use suitably as a film for general industries, a packaging material, etc. excellent in gas barrier property by using the laminated | multilayer film and vapor deposition film of this invention.

Next, an Example is given and this invention vapor deposition film is demonstrated concretely.
<Evaluation method of characteristics>
The characteristic evaluation method used in the present invention is as follows.
[Mass average molecular weight]
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 a known PMMA (polymethyl methacrylate) standard substance 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 created in advance, and mass average molecular weight is calculated from the elution time did.
[Melt viscosity]
Using a 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, and the load is changed to 5, 10, 15, 20 kg. Measured at 5 minutes. The relationship between the shear rate and the melt viscosity was measured, and the melt viscosity in the vicinity of 100 sec ⁻¹ was determined.
[Glass transition temperature (Tg)]
Based on JIS K7121 (1987), a differential scanning calorimeter “Robot DSC-RDC220” manufactured by Seiko Denshi Kogyo Co., Ltd. was used, and a disk session “SSC / 5200” was used for data analysis. A sample of the resin composition scraped from the resin layer (B) on the sample pan was weighed in an amount of 5 mg, and scanned at a rate of temperature increase 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 of the resin layer (B) was determined. The Tg of the resin layer (A) was determined in the same manner.
[Film thickness]
It measured using the dial gauge type thickness meter according to JIS-B7509 (1955).
[Thickness of each layer]
A sample was cut out from the center portion in the width direction, and an ultrathin section was collected at −100 ° C. using the freeze microtome method 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 of each layer at the center in the film width direction (μm) It was confirmed.
[Center line average surface roughness (Ra)]
According to JIS B0601 (1976), the deposition surface of the film (base film) was measured using a stylus type surface roughness meter (manufactured by Kosaka Laboratory Ltd., high-precision thin film level difference measuring instrument, type ET30HK). The conditions at this time were a stylus diameter cone type of 0.5 μmR, a load of 16 mg, and a cutoff of 0.08 mm. When the portion of the measurement length L is extracted from the roughness curve in the direction of the center line, the center line of the extracted portion is the X axis, the vertical direction is the Y axis, and the roughness curve is expressed by y = f (X) The value (μm) obtained by the following formula is defined as the center line average surface roughness Ra.
Ra = (1 / L) ∫ | f (X) | dx.
In addition, the same measurement was performed 5 times for the same sample arbitrarily at different locations, and an average value of the five values obtained was defined as Ra.
[Curl measurement]
A film is cut into a square with a side of 100 mm and adjusted for 24 hours in a room adjusted to a temperature of 25 ° C. and a humidity of 60%. The adjusted sample was placed on a flat table, and the floating height (mm) of the sample curled from the table was measured and evaluated according to the following criteria. Note that, regardless of whether the curl of the sample is concave or convex, the maximum value of the floating height of the sample is adopted and this is used as the curl amount.
○: 0 mm or more and less than 5 mm Δ: 5 mm or more and less than 10 mm x: 10 mm or more, or in the above rank in which the sample is rounded and cylindrical, ○ and Δ can be put to practical use.
[Interlayer adhesion]
A film was cut out in a strip shape of 100 mm in the longitudinal direction and 10 mm in the width direction, placed on a flat table, and bent 180 ° at 50 mm in the longitudinal direction. This operation was repeated up to 50 times, and the state between the resin layer (A) and the resin layer (B) was visually confirmed every 10 times and evaluated according to the following criteria.
○: No peeling up to 50 times Δ: Peeling 20 to 40 times ×: Peeling 10 times Among the above ranks, ○ and Δ can be put to practical use.
[Carbon dioxide permeability]
Based on the gas chromatographic method described in JIS K7126-1 Annex 2 (2006) using a mixed gas permeability measuring device GPM-250 manufactured by GL Sciences under the conditions of a temperature of 35 ° C. and a humidity of 0% RH. It was measured. Further, the measurement was carried out twice by applying a carbon dioxide gas flow from the vapor deposition layer side of the vapor deposition film and detecting on the opposite side, and the average value was defined as the carbon dioxide gas permeability in each example and comparative example.

The polymers used in Examples and Comparative Examples of the present invention are as follows.
[Polymerization of polyethylene terephthalate (PET)]
To 194 parts by mass of dimethyl terephthalate and 124 parts by mass of ethylene glycol, 0.1 part by mass of magnesium acetate tetrahydrate and 0.05 part by mass of antimony trioxide are added, and the ester exchange reaction is carried out while distilling methanol at 140 to 230 ° C. went. Next, the system was transferred to a polycondensation reaction can, and after adding 0.05 parts by mass of ethylene glycol solution of phosphoric acid and stirring for 5 minutes, the reaction system was gradually heated from 230 ° C. to 290 ° C. while stirring the low polymer at 30 rpm. And the pressure was reduced to 100 Pa. When the polymerization reaction is carried out for 3 hours and the predetermined stirring torque is reached, the polycondensation reaction is stopped, discharged into cold water in the form of a strand, immediately cut, then charged into a rotary reaction vessel, and subjected to 5 ° C. at 190 ° C. under a reduced pressure of 67 Pa. Solid phase polymerization was performed for a period of time to obtain polyethylene terephthalate pellets having an intrinsic viscosity of 0.79. The melt viscosity at 270 ° C. and 100 sec ⁻¹ was 4800 poise.
[Polybutylene terephthalate (PBT) polymerization]
A mixture of 100 parts by mass of terephthalic acid and 110 parts by mass of 1,4-butanediol was heated to 140 ° C. in a nitrogen atmosphere to obtain a uniform solution. Then, 0.067 parts by mass of tetra-n-butyl titanate and 0.067 parts by mass of monohydroxybutyltin oxide were added, the temperature was raised to 160 ° C. to 230 ° C., and the esterification reaction was carried out while distilling off the generated water and tetrahydrofuran. . The esterification reaction product was transferred to a polycondensation reaction can, 0.09 parts by mass of tetra-n-butyl titanate, 0.13 parts by mass of “Irganox 1010” manufactured by Nippon Ciba-Geigy Co., Ltd. and 0.026 parts by mass of phosphoric acid. Parts were added. Next, the reaction system was gradually heated from 230 ° C. to 250 ° C., and the pressure was reduced from normal pressure to 133 Pa or less. After 2 hours and 50 minutes, the polycondensation reaction was completed, discharged into cold water in the form of a strand, and immediately cut to obtain polybutylene terephthalate pellets having an intrinsic viscosity of 0.90. Thereafter, the reaction vessel was charged into a rotary reaction vessel and subjected to solid phase polymerization for 8 hours under reduced pressure of 190 ° C. and 67 Pa to obtain a polybutylene terephthalate resin. The obtained polybutylene terephthalate had an intrinsic viscosity of 1.20, a melting point of 230 ° C., 270 ° C. and 100 sec ⁻¹ , and a melt viscosity of 3000 poise.
[Polymerization of polyethylene terephthalate and polyethylene glycol (PET-PEG)]
A copolymer was obtained by transesterification using 90 parts by mass of PET and 10 parts by mass of polyethylene glycol having a mass average molecular weight of 4000 using calcium phosphate and antimony trioxide as catalysts.
[Polyglycolic acid (PGA)]
A homopolyglycolic acid resin having a mass average molecular weight of 180,000, melting point of 221 ° C., Tg of 42 ° C., 270 ° C. of 100 sec ⁻¹ and a melt viscosity of 3500 poise was prepared and used after drying at 150 ° C. for 4 hours in a rotary vacuum dryer.
Example 1
100 parts by mass of PGA as a resin layer (A) is supplied to the single screw extruder-1 and extruded at 265 ° C., and the polymer is filtered with a filter obtained by sintering and compressing stainless steel fibers having an average opening of 25 μm. PET: 40 parts by mass, PBT: 55 parts by mass, PGA: 5 parts by mass are supplied to the shaft extruder-2 as a resin layer (B), extruded at 270 ° C., and stainless steel fibers having an average opening of 12 μm are sintered and compressed. After filtering the polymer with the filter, it is laminated with a multi-layer die so as to have a two-layer structure of resin layer (A) / resin layer (B), wound around a drum at a temperature of 25 ° C., and cooled and solidified into a sheet shape did. The film was stretched 4.0 times in the longitudinal direction at 60 ° C. on a roll, immediately cooled to room temperature, led to a tenter, stretched 4.0 times in the width direction at a temperature of 50 ° C., and then 3 times in the width direction. Heat treatment was performed at a temperature of 190 ° C. while giving% relaxation, and a biaxially stretched film was obtained. The thickness of the obtained film was 15.0 μm, and the thickness ratio of the resin layer (A) / resin layer (B) was 1: 8.

The obtained film was wound by applying a corona discharge treatment at 30 W · min / m ² while maintaining the film temperature at 60 ° C. in an atmosphere of a mixed gas of nitrogen and carbon dioxide (carbon dioxide concentration ratio: 15 vol%). . It set in the vacuum evaporation apparatus which equipped the film travel apparatus, and after making it the high pressure reduction state of 1.00 * 10 ^<-2 > Pa, it was made to travel through a 20 degreeC cooling metal drum. At this time, the aluminum metal was evaporated by heating, and a vapor deposition layer was formed on the resin layer (A) side of the film while blowing oxygen gas. After vapor deposition, the inside of the vacuum vapor deposition apparatus was returned to normal pressure, and the wound film was rolled back and aged at a temperature of 40 ° C. for 2 days to obtain a vapor deposited film. The optical density of the deposited film was controlled in-line during the deposition and controlled to be 0.08.

Table 1 shows the composition of the obtained film, film forming conditions, and evaluation results. The obtained film exhibited good flatness and interlayer adhesion, and had sufficient barrier properties to be used as a packaging material.
(Example 2)
In Example 1, except that PET-PEG: 95 parts by mass and PGA: 5 parts by mass are used as the resin layer (B), the film is formed to have a film thickness of 15.0 μm in the same manner as in Example 1, and then vapor deposition is performed. To obtain a deposited film.

The flatness, interlayer adhesion and barrier properties were all excellent.
(Example 3)
In Example 1, except that the relaxation ratio was changed to 5%, a film was formed to have a film thickness of 15.0 μm in the same manner as in Example 1, and then vapor deposition was performed to obtain a vapor deposition film.

By increasing the rate of relaxation, the flatness and interlayer adhesion were excellent, but the barrier properties were slightly deteriorated within the practical range.
Example 4
In Example 1, it formed into film thickness so that it might become film thickness 15.0micrometer like Example 1 except using PET: 40 mass parts, PBT: 40 mass parts, and PGA: 20 weight part as a resin layer (B), Thereafter, a vapor deposition process was performed to obtain a vapor deposition film. However, since the stretchability was reduced by increasing the amount of PGA in the resin layer (B), the stretch ratio was 2.0 times in the longitudinal direction and 3.0 times in the width direction.

By reducing the draw ratio, the surface became rough and the barrier properties slightly deteriorated, but were within the practical range.
(Example 5)
In Example 1, it formed into film thickness so that it might become film thickness 15.0micrometer like Example 1 except using PET: 40 mass parts, PBT: 59 mass parts, and PGA: 1 mass part as a resin layer (B), Thereafter, a vapor deposition process was performed to obtain a vapor deposition film.

By reducing the amount of PGA added, the flatness, interlayer adhesion, and barrier properties all deteriorated slightly, but were within the practical range.
(Example 6)
In Example 1, except that the relaxation temperature was set to 130 ° C., a film was formed to have a film thickness of 15.0 μm in the same manner as in Example 1, and then vapor deposition was performed to obtain a vapor deposition film.

By reducing the relaxation temperature, the interlayer adhesion was excellent, but the flatness and barrier properties were slightly deteriorated within the practical range.
(Example 7)
In Example 1, except that PET: 75 parts by mass, PBT: 20 parts by mass, and PGA: 5 parts by mass were used as the resin layer (B), the film was formed to have a film thickness of 15.0 μm in the same manner as in Example 1, Thereafter, a vapor deposition process was performed to obtain a vapor deposition film. The stretching temperature was changed to 75 ° C. in the longitudinal direction and 70 ° C. in the width direction because the Tg of the resin layer (B) layer was increased.

By increasing the addition amount of PET, the film surface on the resin layer (A) side became clear and the barrier property was slightly deteriorated, but it was within the practical range.
(Example 8)
In Example 1, except that PET: 40 parts by mass, PBT: 55 parts by mass, ethylene acrylate copolymer (“Biomax” strong 120 manufactured by EI du Pont de Nemours and Company): 5 parts by weight are used as the resin layer (B). In the same manner as in Example 1, a film was formed so as to have a film thickness of 15.0 μm, and then vapor deposition was performed to obtain a vapor deposition film.

By using an ethylene acrylate copolymer in place of PGA in the resin layer (B), the planarity and interlayer adhesion were excellent, but the barrier properties were slightly deteriorated within the practical range.
(Comparative Example 1)
In Example 1, the film thickness was 15.0 μm as in Example 1 except that PET: 40 parts by mass and PBT: 60 parts by mass were used as the resin layer (B) and heat treatment was performed at a constant length without relaxing. Film formation was performed, and then vapor deposition processing was performed to obtain a vapor deposition film.

By not relaxing, the flatness was greatly deteriorated.
(Comparative Example 2)
In Example 1, except that PET: 40 parts by mass and PBT: 60 parts by mass were used as the resin layer (B), the film was formed to have a film thickness of 15.0 μm in the same manner as in Example 1, and then vapor deposition was performed. A vapor deposited film was obtained.

By not adding PGA in the resin layer (B), interlaminar adhesion and barrier properties were greatly deteriorated, and were outside the practical range.
(Comparative Example 3)
In Example 1, except that PET: 40 parts by mass and PBT: 60 parts by mass were used as the resin layer (B), and the ratio of relaxation was changed to 5% so that the film thickness was 15.0 μm as in Example 1. The film was formed and then subjected to vapor deposition to obtain a vapor deposition film.

Compared to Comparative Example 1, the flatness was improved by increasing the relaxation rate, but the interlayer adhesion and barrier properties were further deteriorated.
(Comparative Example 4)
In Example 1, a film was formed to have a film thickness of 15.0 μm in the same manner as in Example 1 except that the film was heat treated at a constant length without relaxing. A vapor deposition process was then performed to obtain a vapor deposition film.

By not relaxing, the flatness was greatly deteriorated.
Example 9
The film obtained in the same manner as in Example 1 was set in a vacuum vapor deposition apparatus equipped with a film traveling apparatus, and after being brought to a high vacuum state of 1.00 × 10 ⁻² Pa, it was passed through a cooling metal drum at 0 ° C. And let it run. At this time, the aluminum metal was evaporated by heating to form a vapor deposition layer on the resin layer (A).

  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.

Table 3 shows the film forming conditions of the obtained film and the evaluation results of the film. The obtained film exhibited good flatness and interlayer adhesion, and had sufficient barrier properties to be used as a packaging material.
(Examples 10 to 12)
About the film obtained in Example 2, 3 and 8, the aluminum metal was heated and evaporated by the method similar to Example 9, respectively, and the vapor deposition layer was formed. Table 3 shows the film forming conditions of the obtained film and the evaluation results of the film. The obtained film exhibited good flatness and interlayer adhesion, and had sufficient barrier properties to be used as a packaging material.
(Example 13)
90 parts by weight of PBT and 10 parts by weight of an ethylene acrylate copolymer (“Lotader GMA” AX8900 made by Arkema) are fed to a twin screw extruder, kneaded at 250 ° C., discharged into cold water as a strand, immediately cut, and then rotationally dried. A machine was dried at 120 ° C. for 4 hours to prepare a chip-like master material.

  Example 1 was prepared by using a master raw material as the resin layer (B) and supplying PET: 40 parts by mass, PBT: 55 parts by mass, ethylene acrylate copolymer (“Lotader GMA” AX8900 manufactured by Arkema): 5 parts by mass. Similarly, a film was formed so as to have a film thickness of 15.0 μm, and then vapor deposition was performed in the same manner as in Example 9 to obtain a vapor deposited film.

By using an ethylene acrylate copolymer in place of PGA in the resin layer (B), the interlayer adhesion was excellent, but the barrier property was slightly deteriorated within the practical range.
(Example 14)
Ethylene acrylate copolymer (“BONDINE” TX8030 manufactured by Arkema): A vapor-deposited film was obtained in the same manner as in Example 13 except that 5 parts by mass was used.

By using an ethylene acrylate copolymer in place of PGA in the resin layer (B), the interlayer adhesion was excellent, but the barrier property was slightly deteriorated within the practical range.
(Example 15)
90 parts by weight of PBT and 10 parts by weight of an ethylene acrylate copolymer (“Biomax” strong 120 manufactured by EI du Pont de Nemours and Company) are fed to a twin screw extruder, kneaded at 250 ° C., discharged into cold water as a strand, and immediately cut. After that, it was dried at 120 ° C. for 4 hours with a rotary dryer to prepare a chip-like master material.

  Using the master raw material as the resin layer (B), PET: 38 parts by mass, PBT: 54 parts by mass, PGA: 5 parts by mass, ethylene acrylate copolymer (“Biomax” strong 120 manufactured by EI du Pont de Nemours and Company) 3 parts by mass The film was formed to have a film thickness of 15.0 μm in the same manner as in Example 1 except that the heat treatment temperature was changed except that the heat treatment temperature was changed. Got.

  The obtained film exhibited good flatness and interlayer adhesion, and had sufficient barrier properties to be used as a packaging material.

However, the description in the table is as follows.
PBT: Polybutylene terephthalate PET: Polyethylene terephthalate PET-PEG: Polyethylene terephthalate-polyethylene glycol copolymer PGA: Polyglycolic acid ethylene acrylate 1: Ethylene acrylate-glycidyl methacrylate copolymer ("Biomax" manufactured by EI du Pont de Nemours and Company strong 120)
Ethylene acrylate 2: ethylene-acrylic ester-glycidyl methacrylate copolymer (Arkema “Lotader GMA” AX8900)
Ethylene acrylate 3: ethylene-acrylic acid ester-maleic anhydride copolymer (“BONDINE” TX8030 from Arkema)
Aluminum: Aluminum Alumina: Aluminum oxide

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

Claims (9)

A laminated film having at least a resin layer (A) mainly composed of polyglycolic acid having a structure represented by chemical formula 1 and having 70 mol% or more, and a resin layer (B) mainly composed of polyester composed of a dicarboxylic acid component and a glycol component. Because
The resin layer (A) and the resin layer (B) are directly laminated,
The resin layer (B) contains an interlayer adhesive,
A curled film having a curl amount of 10 mm or less after being stored at a temperature of 25 ° C. and a humidity of 60% for 24 hours.

  At least one interlayer adhesive selected from the group consisting of polyglycolic acid, a polymer containing an ethylene component, a polymer containing an acrylic acid derivative component, and a polymer containing an ethylene component and an acrylic acid derivative component, The laminated film according to claim 1, wherein the resin layer (B) is contained.   The laminated film according to claim 1, wherein the resin layer (B) has a glass transition temperature of 30 ° C. or more and 65 ° C. or less. The polyester comprising the dicarboxylic acid component and the glycol component, which are the main components of the resin layer (B), includes any of the following (a) to (c). The laminated film as described.
(A) Polyethylene terephthalate and polybutylene terephthalate (b) Copolymer of polyethylene terephthalate and polybutylene terephthalate (c) Copolymer of polyethylene terephthalate and polyethylene glycol The polyester comprising the dicarboxylic acid component and the glycol component, which are the main components of the resin layer (B), includes polyethylene terephthalate and polybutylene terephthalate,
The laminated film according to any one of claims 1 to 4, wherein the mass ratio is polyethylene terephthalate / polybutylene terephthalate = 70/30 to 30/70. The polyester comprising the dicarboxylic acid component and the glycol component, which are the main components of the resin layer (B), includes a copolymer of polyethylene terephthalate and polyethylene glycol,
The molar ratio of the ethylene glycol unit of the polyethylene terephthalate part and the ethylene glycol unit of the polyethylene glycol part in the copolymer is such that the ethylene glycol unit of the polyethylene terephthalate part / the ethylene glycol unit of the polyethylene glycol part = 95/5 to 85/15. The laminated film according to any one of claims 1 to 4, wherein: The resin layer (A) is at least one outermost layer,
The laminated film according to any one of claims 1 to 6, wherein the resin layer (A) has a center line surface roughness (Ra) of 5 nm to 50 nm.   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 laminated | multilayer film in any one of Claims 1-7. The vapor deposition film of Claim 8 whose carbon dioxide gas permeability is 0.2 cc / (m < ² > * day * atm) or less.