JP7069965B2 - Laminated film for packaging - Google Patents

Description

The present invention relates to a laminated film for packaging having a gas barrier property.

Packaging materials such as various plastic films, metal foils, and papers are used for packaging foods and pharmaceuticals. In particular, as a packaging form that can be stored for a long period of time in food / pharmaceutical applications, a suitable laminating structure is designed by laminating various films in order to prevent deterioration of the contents due to moisture and oxygen.

For example, properties required for packaging materials for retort and boiling include various gas barrier properties, heat and water resistance, aroma retention, impact resistance, pressure resistance, piercing resistance, and bending resistance. Polyethylene terephthalate (PET) film for heat resistance, barrier property, (aluminum) AL foil for fragrance retention, nylon (Ny) film for pressure resistance, piercing resistance, bending resistance, unstretched olefin film for sealing property A film having each characteristic such as an unstretched polypropylene (CPP) film is laminated and used as a packaging material in a composition such as PET / AL foil / Ny / CPP.

On the other hand, due to various environmental problems in recent years, various plastic disposal laws have been enacted, and the need for recycling of packaging materials is increasing. Material recycling has the smallest recycling load because it is melted and reused at a high temperature without decomposing the plastic resin, but it is difficult to remove it if it contains impurities, so the edges that are cut off during film formation , It is difficult to recycle materials other than recycling waste during manufacturing such as runners during injection molding.

Chemical recycling can be generally classified into four types: (1) raw material, (2) reducing agent, (3) gas / oil, and (4) thermal recycling. Among these, raw material conversion is a method of extracting the raw material monomer from the plastic material before recycling, and since the plastic is used again for the polycondensation reaction using this monomer, there is little deterioration in quality due to the recovery process, and it is a closed loop. Suitable as a recycling method.

As a method for using polyethylene terephthalate (PET) as a raw material for chemical recycling, a method of depolymerizing with ethylene glycol and transesterifying with methanol to obtain dimethyl terephthalate is widely known and industrially practiced. There is. (Patent Document 1)

However, in the laminated laminated film used as a packaging material, it is difficult to use it as a raw material for chemical recycling because different films of various materials are bonded together.
For example, in the case of PET / AL foil / Ny / CPP, which is a general laminated structure used for the above-mentioned packaging material for boil and retort, when a nylon polymer or the like is contained in the reaction for converting the PET material into a raw material, N-containing compounds are mixed with the raw material of PET, which causes a big problem in quality. Even in other films, the process of separating nylon film, AL foil, and olefin film has not been established, so the packaging material consisting of a laminated structure is currently either thermal recycled or buried without being recycled. Is.

Japanese Patent Application Laid-Open No. 2003-119316

In view of the above problems, in the present invention, the packaging material satisfying the required characteristics such as gas barrier property, heat resistance, water retention, fragrance retention, impact resistance, pressure resistance, piercing resistance, and bending resistance is mainly made of polyester material. It is an object of the present invention to provide a laminated film for packaging, which is easy to recycle by providing the laminated film, and in particular, can easily carry out chemical recycling of polyester.

In order to solve the above problems, the first invention of the present invention is
A gas barrier layer and a polyester film layer having a heat-sealing property are formed on a film base material containing a polyester resin having a butylene terephthalate unit as a main constituent unit.
It is a laminated film for packaging that is laminated in this order.

The second invention is
The gas barrier layer includes an inorganic compound vapor deposition layer made of an inorganic compound, a composite coating layer made of a composition containing at least one of a hydroxyl group-containing polymer compound, a metal alkoxide, a silane coupling agent, or a hydrolyzate thereof. The laminated film for packaging according to claim 1, wherein is sequentially laminated.

Moreover, the third invention is
The gas barrier layer is selected from the group consisting of a polycarboxylic acid-based polymer (A1), a silane coupling agent represented by the general formula ^R1 Si (OR ² ) ₃ , a hydrolyzate thereof, and a condensate thereof. The mass ratio (A1: A2) of at least one silicon-containing compound (A2) is 99.5: 0.5 to 80.0: 20.0 (however, the mass of the silicon-containing compound is the silane coupling. The laminated film for packaging according to claim 1, further comprising a first coating layer contained in terms of agent-equivalent mass) and a second coating layer containing a polyvalent metal compound.

Moreover, the fourth invention is
The gas barrier layer is an inorganic compound vapor-deposited layer made of an inorganic compound, a polycarboxylic acid-based polymer (A1), a silane coupling agent represented by the general formula ^R1 Si (OR ² ) ₃ , a hydrolyzate thereof, and a hydrolyzate thereof. At least one silicon-containing compound (A2) selected from the group consisting of these condensates has a mass ratio of (A1: A2) = 99.5: 0.5 to 80.0: 20.0 (provided that it is used). 1. The mass of the silicon-containing compound is composed of a first coating layer contained in terms of the silane coupling agent equivalent) and a second coating layer containing a polyvalent metal compound. The laminated film for packaging described.

Moreover, the fifth invention is
The laminated film for packaging according to any one of claims 1 to 4, wherein a printing layer is provided between the gas barrier layer and the polyester film layer.

By providing a packaging material made of a laminated film containing only a polyester material as a main material, it is easy to recycle a single material, and in particular, it is possible to easily carry out chemical recycling of polyester. Furthermore, by using a film base material containing a polyester resin having a butylene terephthalate unit as a main constituent unit, the heat resistance, impact resistance, pressure resistance, piercing resistance, and bending resistance required for packaging materials are imparted. can do. Further, by laminating a gas barrier layer as a barrier property and laminating a polyester film having a heat sealing property as a sealing property, a packaging material satisfying the characteristics required for the packaging material can be provided mainly with the polyester material as a main component. Can be done.

It is a schematic diagram which showed the uniform state of the film which laminated the gas barrier layer on the base material which concerns on this invention. It is a schematic diagram which showed the other uniform state of the film which laminated the gas barrier layer on the base material which concerns on this invention. It is a schematic diagram which showed the other uniform state of the film which laminated the gas barrier layer on the base material which concerns on this invention. It is a schematic diagram which showed the uniform state of the laminated film for packaging which concerns on this invention. It is a schematic diagram which showed the other uniformity of the laminated film for packaging which concerns on this invention.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.

(Gas barrier film 11)
FIG. 1 is a schematic cross-sectional view of a gas barrier film according to this embodiment.
In the gas barrier film 11 of FIG. 1, the adhesion layer 2, the inorganic compound vapor deposition layer 3, and the composite coating layer 4 are sequentially laminated on the film base material 1, and the inorganic compound vapor deposition layer 3 and the composite coating layer 4 are formed together. The gas barrier layer 10a is formed. Each of these layers will be described below in sequence.

The film base material 1 is a film containing a polyester resin having a polybutylene terephthalate (PBT) unit as a main constituent unit.

As the film base material 1 used in the present invention, a stretched film is used instead of an unstretched film produced by a casting method. The unstretched PBT film has problems in strength and dimensional stability, so its use is limited, and it is not suitable as a film for laminating a barrier film in the next process. As the stretching method, any method may be used as long as a film having stable dimensions such as a stretched film by inflation or a uniaxially stretched or biaxially stretched PBT film can be supplied.

Stretched PBT film has properties such as gas barrier property, heat resistance, heat resistance water resistance, and fragrance retention, and has higher impact resistance, pressure resistance, piercing resistance, and bending resistance than stretched PET film, and is required for nylon film. Since it also has physical characteristics, it can be used as a packaging material for a wider range of purposes than PET base materials. In particular, in order to combine with a polyester film having heat-sealing properties, which will be described later, the polyester film has lower impact resistance, pressure resistance, piercing resistance, and bending resistance than the olefin-based film generally used as a sealant film. It is important that the base material 1 has these characteristics to develop the characteristics as a packaging material.

The thickness of the film base material 1 is not particularly limited. Depending on the application, those having a diameter of about 6 μm to 200 μm can be used.

Further, the film substrate 1 may be provided with various pretreatments such as corona treatment, plasma treatment, frame treatment, and a coat layer such as an easy-adhesion layer on the laminated surface as long as the barrier performance is not impaired.

The adhesion layer 2 is provided on the film substrate 1, and by improving the adhesion performance between the film substrate 1 and the inorganic vapor deposition layer 3 and smoothing the flat surface, the vapor deposition layer in the next step is uniformly formed without defects. It is a layer for the purpose of obtaining two effects of exhibiting a high barrier property, and is a layer containing an anchor coating agent. Although the adhesion layer 2 is not essential in the present invention, it is appropriately laminated depending on the intended use of the packaging material.

Examples of such an adhesion layer 2 include a polyester-based polyurethane resin and a polyether-based polyurethane resin. Among these anchor coating agents, polyester polyurethane resin is preferable from the viewpoint of heat resistance and interlayer adhesion strength.

Of the gas barrier layer 10a according to the present invention, the inorganic compound vapor deposition layer 3 preferably contains at least one of Al and Si. More specifically, a metal oxide represented by SiOx or AlOx, or a mixture thereof can be used, but it may contain a simple substance atom of nitrogen or aluminum.

The film thickness of the inorganic compound vapor deposition layer 3 is preferably 5 nm or more and 100 nm or less. If the film thickness is less than 5 nm, sufficient water vapor barrier properties cannot be obtained. If it is larger than 100 nm, cracks are generated due to deformation of the thin film due to internal stress, and the water vapor barrier property is lowered. Further, the cost increases due to an increase in the amount of material used, a long film forming time, and the like, which is not preferable from an economical point of view.

The inorganic compound vapor deposition layer 3 may be a single-layer film or a multilayer film, but at least one layer needs to be formed by vacuum film formation. In the vacuum film formation, a physical vapor deposition method or a chemical vapor deposition method can be used. Examples of the physical vapor deposition method include, but are not limited to, a vacuum vapor deposition method, a sputtering method, and an ion plating method. Examples of the chemical vapor deposition method include, but are not limited to, a thermal CVD method, a plasma CVD method, and an optical CVD method.

In the vacuum film formation, resistance heating type vacuum deposition method, EB (Electron Beam) heating type vacuum deposition method, induction heating type vacuum deposition method, sputtering method, reactive sputtering method, dual magnetron sputtering method, plasma chemical vapor deposition method (PECVD method) and the like are particularly preferably used.

Although plasma is used in the methods after the above sputtering method, plasma generation such as DC (Direct Current) method, RF (Radio Frequency) method, MF (Middle Frequency) method, DC pulse method, RF pulse method, DC + RF superimposition method and the like is used. The law can be applied.

Next, the composite coating layer 4 will be described. As shown in FIG. 1, the composite coating layer 4 is laminated on the inorganic compound vapor deposition layer 3. Since the composite coating layer 4 has a gas barrier property, it is preferably formed from a composition containing at least one selected from the group consisting of a metal alkoxide represented by the following formula (1) and a hydrolyzate thereof.
M (OR ¹ ) m (R ² ) _nm ... (1)
In the above formula (1), R ¹ and R ² are independently monovalent organic groups having 1 to 8 carbon atoms, and are preferably alkyl groups such as a methyl group and an ethyl group. M represents an n-valent metal atom such as Si, Ti, Al, Zr and the like. m is an integer from 1 to n.

Examples of the metal alkoxide include tetraethoxysilane [Si (OC ₂ H ₅ ) ₄ ] and triisopropoxyaluminum [Al (O-iso-C ₃ H ₇ ) ₃ ].
The metal alkoxide is preferably tetraethoxysilane or triisopropoxyaluminum because it is relatively stable in an aqueous solvent after hydrolysis.

Examples of the hydrolyzate of the metal alkoxide include silicic acid (Si (OH) ₄ ), which is a hydrolyzate of tetraethoxysilane, and aluminum hydroxide (Al (OH) ₃ ), which is a hydrolyzate of tripropoxyaluminum. ) Etc. can be mentioned. These are not limited to one type, but can be used in combination of a plurality of types. The content of the metal alkoxide and its hydrolyzate in the above composition is, for example, 10 to 90% by mass.

The composition may further contain a hydroxyl group-containing polymer compound. Examples of the hydroxyl group-containing polymer compound include water-soluble polymers such as polyvinyl alcohol, polyvinylpyrrolidone and starch. The hydroxyl group-containing polymer compound is preferably polyvinyl alcohol from the viewpoint of barrier properties. These are not limited to one type, but can be used in combination of a plurality of types. The content of the hydroxyl group-containing polymer compound in the above composition is, for example, 10 to 90% by mass.

The thickness of the composite coating layer 4 is preferably 50 to 1000 nm, preferably 100 to 500 nm. When the thickness of the composite coating layer 4 is 50 nm or more, more sufficient gas barrier properties tend to be obtained, and when the thickness is 1000 nm or less, sufficient flexibility tends to be maintained.

(Gas barrier film 12)
FIG. 2 is a schematic cross-sectional view of the gas barrier film according to the present embodiment.
In the gas barrier film 12 of FIG. 2, the adhesion layer 2 is laminated on the film substrate 1, the polycarboxylic acid-based polymer (A1) and the silane represented by the general formula ^R1Si _{(OR2) 3} ^are further laminated. A mass ratio (A1: A2) of at least one silicon-containing compound (A2) selected from the group consisting of a coupling agent, a hydrolyzate thereof, and a condensate thereof has a mass ratio (A1: A2) of 99.5: 0.5 to 80. .0: 20.0 (where the mass of the silicon-containing compound is the mass in terms of the silane coupling agent), the first coating layer (A) 5 and the second coating containing the polyvalent metal compound. The layer (B) 6 is sequentially laminated. The first coating layer (A) 5 and the second coating layer (B) 6 form a gas barrier layer 10b.

The first coating layer (A) and the second coating layer (B) containing the polyvalent metal compound will be described below.

[First coating layer (A)]
A polycarboxylic acid-based polymer (hereinafter referred to as "polycarboxylic acid-based polymer (A1) component"), a silane coupling agent represented by the general formula ^R1 Si (OR ² ) ₃ , a hydrolyzate thereof, and a hydrolyzate thereof. At least one kind of silicon-containing compound (hereinafter referred to as "silicon-containing compound A2" component) selected from the group consisting of these condensates has a mass ratio (A1: A2) of 99.5: 0.5 to 80. It is contained at 0.0: 20.0.
However, R ¹ is an organic group containing a glycidyloxy group or an amino group, R ² is an alkyl group, and the three R ^2s may be the same or different.
The mass of the silicon-containing compound component (A2) is the mass in terms of the silane coupling agent.

The polycarboxylic acid-based polymer is a polymer having two or more carboxy groups in the molecule.
The components of the polysaccharide-based polymer (A1) include, for example, a (co) polymer of ethylenically unsaturated carboxylic acid; a copolymer of ethylenically unsaturated carboxylic acid and another ethylenically unsaturated monomer; alginic acid. , Carboxymethyl cellulose, pectin and the like, and examples thereof include acidic polysaccharides having a carboxyl group in the molecule.
Examples of the ethylenically unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid.
Examples of the ethylenically unsaturated monomer copolymerizable with the ethylenically unsaturated carboxylic acid include saturated carboxylic acid vinyl esters such as ethylene, propylene and vinyl acetate, vinyl chloride, vinylidene chloride, styrene, acrylamide and acrylonitrile. Can be mentioned.
These polycarboxylic acid-based polymers may be used alone or in combination of two or more.

Among the above, the polycarboxylic acid-based polymer (A1) component is at least selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid from the viewpoint of the obtained gas barrier property. A polymer containing a structural unit derived from one type of polymerizable monomer is preferable, and among them, from at least one kind of polymerizable monomer selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, and maleic acid. Polymers containing the derived building blocks are particularly preferred.

The number average molecular weight of the polycarboxylic acid-based polymer (A1) component is preferably in the range of 2,000 to 10,000,000, more preferably 5,000 to 1,000,000. If the number average molecular weight is less than 2,000, the obtained gas barrier layer cannot achieve sufficient water resistance, and moisture may deteriorate the gas barrier property and transparency, or whitening may occur. On the other hand, if the number average molecular weight exceeds 10,000,000, the viscosity may increase and the coatability may be impaired before the first coating layer (A) is formed by coating.

In the polycarboxylic acid-based polymer (A1) component, a part of the carboxy group may be neutralized with a basic compound in advance. By neutralizing a part of the carboxy group of the polycarboxylic acid polymer (A1) component in advance, water resistance and heat resistance can be further improved.
As the basic compound, at least one basic compound selected from the group consisting of a polyvalent metal compound, a monovalent metal compound and ammonia is preferable. Examples of the polyvalent metal compound include those similar to the polyvalent metal compound described in the second gas barrier layer (B), and examples of the basic compound as the polyvalent metal compound include zinc oxide and calcium carbonate. Examples include sodium carbonate. Examples of the basic compound which is a monovalent metal compound include sodium hydroxide and potassium hydroxide.

As the degree of neutralization of the carboxy group, the first coating layer (A) is composed of the first coating liquid (a) containing the polycarboxylic acid-based polymer (A1) component and the silicon-containing compound (A2) component. When the coating film is formed by drying, it is preferably 30 mol% or less, preferably 25 mol% or less, from the viewpoint of the coatability and the coating liquid stability of the first coating liquid (a). More preferred. As the polycarboxylic acid-based polymer (A1) component, one type may be used alone, or two or more types may be mixed and used.

The silicon-containing compound (A2) component is a general formula R ¹ Si (OR ² ) ₃ (where R ¹ is an organic group containing a glycidyloxy group or an amino group, R ² is an alkyl group, and three. R ² is at least one silicon-containing compound selected from the group consisting of a silane coupling agent represented by (which may be the same or different), a hydrolyzate thereof, and a condensate thereof. The silicon-containing compound (A2) component improves the adhesion between the adhesion layer 2 and the first coating layer (A) even in a small amount, and improves heat resistance, water resistance, and the like.

In the above general formula, examples of the organic group in R ¹ include a glycidyloxyalkyl group and an aminoalkyl group. As the alkyl group of ^R2 , an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group or an ethyl group is particularly preferable. Specific examples of the silane coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane and the like. .. Among these, γ-glycidoxypropyltrimethoxysilane and γ-aminopropyltrimethoxysilane are preferable.

The silicon-containing compound (A2) component may be the silane coupling agent itself, a hydrolyzed product obtained by hydrolyzing the silane coupling agent, or a condensate thereof. Examples of the hydrolyzate include those in which at least one of the three OR ^2s in the general formula is OH. Examples of the condensate include those in which at least two molecules of the hydrolyzate Si—OH are condensed to form a Si—O—Si bond. In the following, the condensed product of the hydrolyzate of the silane coupling agent may be referred to as a hydrolyzed condensate.

As the silicon-containing compound (A2) component, a compound obtained by hydrolyzing and condensing the silane coupling agent (1) using the sol-gel method can be used. Usually, the silane coupling agent (1) easily hydrolyzes, and the condensation reaction easily occurs in the presence of an acid or an alkali. Therefore, only the silane coupling agent (1), its hydrolyzate only, or them. It is rarely present only in the condensate of. That is, the silicon-containing compound (A2) component usually contains a silane coupling agent (1), a hydrolyzate thereof, and a condensate thereof. Further, the hydrolyzate includes a partial hydrolyzate and a complete hydrolyzate.

The silicon-containing compound (A2) component preferably contains at least a hydrolyzed condensate. As a method for producing the hydrolyzed condensate, the silane coupling agent (1) may be directly mixed with the liquid containing the polycarboxylic acid polymer (A1) component and water, and the silane coupling agent may be used. By adding water, a hydrolysis and a subsequent condensation reaction may be carried out to obtain a hydrolyzed condensate before mixing with the polycarboxylic acid-based polymer.

The first coating layer (A) contains the polycarboxylic acid-based polymer (A1) component and the silicon-containing compound (A2) component in a mass ratio (A1: A2) of 99.5: 0.5 to 80. It is contained at 0: 20.0. However, the mass of the silicon-containing compound (A2) component is the mass in terms of the silane coupling agent (1).

That is, as described above, the silicon-containing compound (A2) component usually contains a silane coupling agent, a hydrolyzate thereof, and a condensate thereof, but the mass of the silicon-containing compound (A2) component is the silane. It is a value converted into a coupling agent, that is, the amount of the silane coupling agent charged. Within the above range, a gas barrier laminate having excellent abuse resistance can be obtained.

Further, the presence of the silicon-containing compound (A2) component makes the gas barrier layer of the present invention resistant to acid. When R ¹ is an organic group containing a glycidyloxy group (γ-glycidoxypropyltrimethoxysilane or γ-glycidoxypropyltriethoxysilane) as the silane coupling agent, a polycarboxylic acid is used. The mass ratio (A1: A2) of the system polymer (A1) component to the silicon-containing compound (A2) component is preferably 99.5: 0.5 to 90.0: 10.0, preferably 99. It is particularly preferable that it is 0: 1.0 to 95.0: 5.0.
When a polycarboxylic acid-based polymer (γ-aminopropyltrimethoxysilane or γ-aminopropyltriethoxysilane) in which R ¹ is an organic group containing an amino group is used as the silane coupling agent, a polycarboxylic acid-based polymer ( The mass ratio (A1: A2) of the A1) component to the silicon-containing compound (A2) component is preferably 99.0: 1.0 to 80.0: 20.0, preferably 95.0: 5. It is particularly preferable that it is 0 to 80.0: 20.0.

The first coating layer (A) may contain various additives. Examples of the additive include plasticizers, resins, dispersants, surfactants, softeners, stabilizers, antiblocking agents, film forming agents, pressure-sensitive adhesives, oxygen absorbers and the like. For example, as the plasticizer, it is possible to appropriately select and use from known plasticizers.
Specific examples of the plasticizer include ethylene glycol, trimethylene glycol, propylene glycol, tetramethylene glycol, 1,3-butanediol, 2,3-butanediol, pentamethylene glycol, hexamethylene glycol, and diethylene glycol. Examples thereof include triethylene glycol, polyethylene glycol, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyethylene oxide, sorbitol, mannitol, zulcitol, erythritol, glycerin, lactic acid, fatty acid, starch, and phthalic acid ester. These may be used as a mixture if necessary.

Among these, polyethylene glycol, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, glycerin, and starch are preferable from the viewpoint of stretchability and gas barrier property. When such a plasticizer is contained, the abuse resistance can be further improved. When the additive contains a compound having two or more hydroxyl groups such as polyvinyl alcohol, the hydroxyl group of the compound and a part of the carboxy group of the polycarboxylic acid polymer (A1) component form an ester bond. May be good. When the first coating layer (A) contains an additive, the mass ratio of the polycarboxylic acid-based polymer (A1) component to the additive (polycarboxylic acid-based polymer (A1) component: addition The agent) is usually in the range of 70:30 to 99.9: 0.1, preferably 80:20 to 98: 2.

The thickness of the first coating layer (A) is preferably in the range of 0.01 to 5 μm, more preferably in the range of 0.02 to 3 μm, and further preferably in the range of 0.04 from the viewpoint of gas barrier properties. The range is ~ 1.2 μm. Even when the coating layer contains a plurality of the first coating layers (A), the total preferable thickness of the first coating layers (A) in the coating layer is the same as described above.

(Method for forming the first coating layer (A))
The first coating layer (A) can usually be formed by a coating method. Specifically, it can be formed by drying a coating film composed of the first coating liquid (a) containing the polycarboxylic acid-based polymer (A1) component and the silicon-containing compound (A2) component. As the polycarboxylic acid-based polymer (A1) component and the silicon-containing compound (A2) component contained in the first coating liquid (a), the same components as described above can be used.

The first coating liquid (a) contains the polycarboxylic acid-based polymer (A1) component and the silicon-containing compound (A2) component in a mass ratio of 99.5: 0.5 to 80.0: 20.0. Ratio (However, the mass of the silicon-containing compound (A2) component is the mass in terms of the silane coupling agent). The preferred reason is the same as described above.

When R ¹ is an organic group containing a glycidyloxy group (γ-glycidoxypropyltrimethoxysilane or γ-glycidoxypropyltriethoxysilane) as the silane coupling agent, a polycarboxylic acid is used. The mass ratio of the system polymer (A1) component to the silicon-containing compound (A2) component is preferably 99.5: 0.5 to 90.0: 10.0, and 99.0: 1.0 to 10. 95.0: 5.0 is particularly preferable.

When a silane coupling agent in which R ¹ is an organic group containing an amino group (γ-aminopropyltrimethoxysilane or γ-aminopropyltriethoxysilane) is used, a polycarboxylic acid-based polymer (A1) is used. The mass ratio of the component) to the silicon-containing compound (A2) component is preferably 99.0: 1.0 to 80.0: 20.0, and 95.0: 5.0 to 80.0: 20. It is particularly preferable that it is 0.0.
The mass ratio of the polycarboxylic acid-based polymer (A1) component and the silicon-containing compound (A2) component normally contained in the first coating liquid (a) and the first coating liquid (a). The mass ratio of the polycarboxylic acid-based polymer (A1) component and the silicon-containing compound (A2) component in the first gas barrier layer (A) formed using the above is the same, but for example, the polycarboxylic acid-based weight. It may be different when the combined (A1) component reacts with the additive, or when the polycarboxylic acid-based polymer (A1) component reacts with the silicon-containing compound (A2) component.

The first coating liquid (a) can be adjusted by mixing a polycarboxylic acid-based polymer (A1) component, a silicon-containing compound (A2) component, and an additive contained as necessary with a solvent.

The solvent used for the first coating liquid (a) is not particularly limited as long as it can dissolve the polycarboxylic acid-based polymer (A1) component and the silicon-containing compound (A2) component, but is usually a silane cup. Since water is required for the hydrolysis reaction of the ring agent, water, a mixed solvent of water and an organic solvent, and the like are preferable. Water is most preferable in terms of solubility and cost of the polycarboxylic acid polymer (A1) component.

An organic solvent such as alcohol is preferable in terms of improving the solubility of the silane coupling agent and the coatability of the first coating liquid (a). As the organic solvent, it is preferable to use at least one organic solvent selected from the group consisting of alcohols having 1 to 5 carbon atoms and ketones having 3 to 5 carbon atoms. Specific examples of such an organic solvent include methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, acetone, methyl ethyl ketone and the like.
As the mixed solvent of the organic solvent with water, the above-mentioned mixed solvent of water and the organic solvent is preferable, and the mixed solvent of water and alcohol having 1 to 5 carbon atoms is more preferable. As the mixed solvent, water is present in an amount of 20 to 95% by mass, and an organic solvent is present in an amount of 80 to 5% by mass (however, the total of water and the organic solvent is 100% by mass). preferable.

In the first coating liquid (a), from the viewpoint of gas barrier property and coatability, the polycarboxylic acid-based polymer (A1) component and the silicon-containing compound (A2) component in the first coating liquid (a). The total content (solid content) of the compound and the additives contained as necessary is preferably 0.5 to 50% by mass, preferably 0.8 to 50% by mass, based on the total weight of the first coating liquid (a). 30% by mass is more preferable, and 1.0 to 20% by mass is particularly preferable.

The first coating liquid (a) is applied onto the surface to be laminated as the first gas barrier layer (A), that is, on the adhesion layer 2, to form a coating film, and the coating film is dried to obtain the first coating film. One coating layer (A) can be formed.

The coating method of the first coating liquid (a) is not particularly limited and can be appropriately selected from known coating methods. For example, a casting method, a dipping method, a roll coating method, a gravure coating method, a screen printing method, and a reverse method can be selected. Examples include a coating method, a spray coating method, a kit coating method, a die coating method, a metering bar coating method, a chamber doctor combined coating method, and a curtain coating method. The amount of the first coating liquid (a) applied is set according to the thickness of the first coating layer (A) to be formed.

After applying the first coating liquid (a), the first coating layer (A) is formed by removing the solvent of the first coating liquid (a) contained in the coating liquid by drying. ..

The drying method is not particularly limited, and examples thereof include a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method. Any of these methods may be used alone or in combination of two or more.
The first gas barrier layer (A) thus formed contains a polycarboxylic acid-based polymer (A1) component and a silicon-containing compound (A2) component, and further, a first coating liquid (a). ) Contains other components such as additives, the other components are included. When a compound having two or more hydroxyl groups such as polyvinyl alcohol is used as an additive for the first coating liquid (a), the hydroxyl groups of the compound and the polycarboxylic acid system are used during the drying, aging treatment, heat treatment and the like. A part of the carboxy group of the polymer (A1) component may react with each other to form an ester bond.

[Second coating layer (B)]
The second coating layer (B) contains a polyvalent metal compound. The polyvalent metal compound is a compound of a polyvalent metal having a metal ion valence of 2 or more.
Examples of polyvalent metals include alkaline earth metals such as beryllium, magnesium and calcium; transition metals such as titanium, zirconium, chromium, manganese, iron, cobalt, nickel, copper and zinc; aluminum and silicon. As the multivalent metal, calcium or zinc is particularly preferable from the viewpoint of heat resistance, water resistance and transparency. As the polyvalent metal compound, a calcium compound or a zinc compound is preferable for the above-mentioned reasons.
Further, as the polyvalent metal compound, for example, a simple substance of the polyvalent metal, an oxide, a hydroxide, a carbonate, an organic acid salt (for example, an acetate) or an inorganic acid salt, an ammonium complex of the polyvalent metal oxide, or 2 to 2 to Examples include quaternary amine complexes, or carbonates or organic acid salts thereof. Among these polyvalent metal compounds, alkaline earth metals, cobalt, nickel, copper, zinc, aluminum or silicon oxides, hydroxides, from the viewpoint of gas barrier properties, resistance to high temperature steam and hot water, and manufacturability, It is preferred to use chlorides, carbonates or acetates, ammonium complexes of copper or zinc or carbonates thereof. Among these, zinc oxide, aluminum oxide, calcium hydroxide, calcium carbonate, zinc acetate and calcium acetate are preferable, and zinc oxide or calcium carbonate is particularly preferable, from the viewpoint of industrial productivity.

When the second coating layer (B) is formed by drying a coating film composed of the second coating liquid (b) containing the polyvalent metal compound, the form of the polyvalent metal compound is particulate. However, it may be in the form of non-particulates or may be dissolved, but it is preferably in the form of particles from the viewpoint of dispersibility, gas barrier property and productivity. The average particle size of such particles is not particularly limited, but from the viewpoint of gas barrier properties and coating suitability, the average particle size is preferably 5 μm or less, more preferably 1 μm or less, and 0.1 μm or less. Is particularly preferable.

The second coating layer (B) may contain various additives in addition to the polyvalent metal compound, if necessary, as long as the effects of the present invention are not impaired. As the additive, for example, when the second coating layer (B) is formed by drying a coating film composed of the second coating liquid (b) containing a polyvalent metal compound, the second coating is used. It contains a resin that is soluble or dispersible in the solvent used in the liquid (b), a dispersant that is soluble or dispersible in the solvent, a surfactant, a softener, a stabilizer, a film-forming agent, a thickener, and the like. May be good. Among the above, it is preferable to contain a resin that is soluble or dispersible in the solvent used for the second coating liquid (b). As a result, the coatability and film forming property of the second coating liquid (b) are improved. Examples of such resins include alkyd resins, melamine resins, acrylic resins, urethane resins, polyester resins, phenol resins, amino resins, fluororesins, epoxy resins, isocyanate resins and the like.

Further, it is preferable to contain a dispersant that is soluble or dispersible in the solvent used for the second coating liquid (b). This improves the dispersibility of the polyvalent metal compound. As the dispersant, an anionic surfactant or a nonionic surfactant can be used.
Examples of the surfactant include (poly) carboxylate, alkyl sulfate ester salt, alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulphosuccinate, alkyldiphenyl ether disulfonate, alkyl phosphate, and aromatic. Phosphoric acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene alkyl ester, alkylallyl sulfate ester salt, polyoxyethylene alkyl phosphate ester, sorbitan alkyl ester, glycerin fatty acid ester, sorbitan fatty acid ester, citrus fatty acid Various surfactants such as esters, polyethylene glycol fatty acid esters, polyoxyethylene sorbitan alkyl esters, polyoxyethylene alkyl allyl ethers, polyoxyethylene derivatives, polyoxyethylene sorbitol fatty acid esters, polyoxy fatty acid esters, polyoxyethylene alkyl amines, etc. Be done. These surfactants may be used alone or in combination of two or more.

When the additive is contained in the second coating layer (B), the mass ratio of the polyvalent metal compound to the additive (polyvalent metal compound: additive) is 30:70 to 99: 1. It is preferably within the range, preferably within the range of 50:50 to 98: 2.

The thickness of the second coating layer (B) is preferably in the range of 0.01 to 5 μm, more preferably in the range of 0.03 to 3 μm, and further preferably in the range of 0.1 from the viewpoint of gas barrier properties. The range is ~ 1.2 μm. Even when the coating layer contains a plurality of the second coating layers (B), the total preferable thickness of the second coating layers (B) in the coating layer is the same as described above.

(Method for forming the second coating layer (B))
Examples of the method for forming the second coating layer (B) include a coating method and a dipping method. Among these, the coating method is preferable from the viewpoint of productivity. Hereinafter, a case where the second coating layer (B) is formed by the coating method will be described.

The formation of the second coating layer (B) by the coating method can be specifically formed by drying a coating film composed of the second coating liquid (b) containing a polyvalent metal compound.

As the polyvalent metal compound contained in the second coating liquid (b), the same compounds as described above can be used, and a calcium compound or a zinc compound is preferable.

The second coating liquid (b) may contain various additives in addition to the polyvalent metal compound, if necessary, as long as the effects of the present invention are not impaired. Examples of the additive include a resin that is soluble or dispersible in the solvent used in the second coating liquid (b), a dispersant that is soluble or dispersible in the solvent, other surfactants, softeners, and stables. Agents, film-forming agents, thickeners and the like can be mentioned.
Among the above, the second coating liquid (b) can be used as a solvent for the second coating liquid (b) for the purpose of improving the coatability and film forming property of the second coating liquid (b). It is preferable to use a mixture of meltable or dispersible resins. Examples of such a resin include those similar to those mentioned as various additives that may be contained in the second coating layer (B).
Further, as an additive, it is preferable to mix a soluble or dispersible dispersant with the solvent used in the second coating liquid (b) for the purpose of improving the dispersibility of the polyvalent metal compound. Examples of the dispersant include those similar to those mentioned above as various additives that may be contained in the second coating layer (B). When the second coating liquid (b) contains an additive, the mass ratio of the polyvalent metal compound to the additive (polyvalent metal compound: additive) is 30:70 to 99: 1. It is preferably within the range, and more preferably within the range of 50:50 to 98: 2.

Examples of the solvent used for the second coating liquid (b) include water, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, n-pentyl alcohol, dimethylsulfoxide, and dimethylformamide. , Dimethylacetamide, toluene, hexane, heptane, cyclohexane, acetone, methyl ethyl ketone, diethyl ether, dioxane, tetrahydrofuran, ethyl acetate, butyl acetate and the like. Further, these solvents may be used alone or in combination of two or more. Among these, methyl alcohol, ethyl alcohol, isopropyl alcohol, toluene, ethyl acetate, methyl ethyl ketone and water are preferable from the viewpoint of coatability. Further, from the viewpoint of productivity, methyl alcohol, ethyl alcohol, isopropyl alcohol and water are preferable. Since the first gas barrier layer (A) formed from the first coating liquid (a) has excellent water resistance, water can be used as the solvent used for the second coating liquid (b). ..

The second coating liquid (b) is applied to a surface on which the second coating layer (B) is laminated, for example, on the first coating layer (A) to form a coating film, and the coating film is formed. The second coating layer (B) can be formed by drying.

The coating method of the second coating liquid (b) is not particularly limited and can be appropriately selected from known coating methods. For example, a casting method, a dipping method, a roll coating method, a gravure coating method, a screen printing method, and a reverse method can be selected. Examples include a coating method, a spray coating method, a kit coating method, a die coating method, a metering bar coating method, a chamber doctor combined coating method, and a curtain coating method.

The amount of the second coating liquid (b) applied is set according to the thickness of the second gas barrier layer (B) to be formed. After applying the second coating liquid (b), the solvent of the second coating liquid (b) contained in the coating film is removed by drying to form the second gas barrier layer (B).

The drying method is not particularly limited, and examples thereof include a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method. Any of these methods may be used alone or in combination of two or more. The drying temperature is not particularly limited, but when the above-mentioned water or a mixed solvent of water and an organic solvent is used as the solvent, it is usually preferably 50 ° C. to 160 ° C. Further, the pressure at the time of drying is usually performed under normal pressure or reduced pressure, and it is preferable to perform at normal pressure from the viewpoint of equipment convenience. When the second coating layer (B) thus formed contains a polyvalent metal compound, and further, when the second coating liquid (b) contains other components such as additives, , Applicable other ingredients are included.

(Gas barrier film 13)
FIG. 3 is a schematic cross-sectional view of the gas barrier film according to the present embodiment.
In the gas barrier film 13 of FIG. 3, the adhesion layer 2 and the inorganic compound vapor deposition layer 3 are laminated on the film substrate 1, and further, the polycarboxylic acid-based polymer and the general formula ^R1Si (OR ² ) ₃ are used. 99.5: 0.5-80.0: 20. With at least one silicon-containing compound selected from the group consisting of the represented silane coupling agents, their hydrolysates and their condensates.
The first coating layer (A) 5 contained in a mass ratio of 0 (however, the mass of the silicon-containing compound is the mass in terms of the silane coupling agent), and the second coating layer containing a polyvalent metal compound. (B) 6 are sequentially laminated. The first coating layer (A) 5 and the second coating layer (B) 6 form a gas barrier layer 10c. These coating layers are similar to those described above.

Next, a laminated film for packaging using a gas barrier film will be described.

(Laminated film for packaging)
FIG. 4 is a schematic cross-sectional view of a laminated film for packaging according to an embodiment of the present invention. In the packaging laminated film 100 of FIG. 4, a gas barrier layer 10 and a heat-sealing polyester film 30 are laminated via an adhesive layer 20. The polyester film 30 having a heat-sealing property is used as a sealant layer.
As the gas barrier layer 10, any of the configurations of the gas barrier layers 10a, 10b, and 10c shown in FIGS. 1 to 3 described above can be applied. Further, the gas barrier layer 10 is not limited to these configurations.

The polyester film 30 having a heat-sealing property may be an amorphous polyester film, a polyester film obtained by polymerizing terephthalic acid, ethylene glycol, diethylene glycol, or a comonomer to have a heat-sealing property, or a butylene terephthalate unit. A polyester film that imparts heat-sealing properties by being used as the main constituent unit may be used. These may be a single layer or a multi-layer extruded film depending on the performance required for the packaging material.

The thickness of the polyester film 30 having a heat-sealing property is preferably 20 to 500 μm depending on the balance between the mechanical properties and the heat-sealing property. Further, 30 μm or more is more preferable, 300 μm or less, more preferably 150 μm or less is preferable.

As a method for forming a laminated film for packaging, a dry laminating method in which a barrier film and a sealant film are bonded with a one-component curable or two-component curable urethane adhesive, and a non-solvent dry laminating method in which a solvent-free adhesive is used for bonding. The above-mentioned resin can be formed by a known laminating method such as an extrusion laminating method in which the above-mentioned resin is heated and melted, extruded into a curtain shape, and bonded to each other. The dry laminating method is preferable for water treatment. Any laminating method can be used as long as the treatment is performed at a temperature of 85 ° C. or lower.

Further, in the present invention, since the laminated film is used for packaging, a printing layer may be provided at all. Generally, a print layer is provided between a barrier film and a polyester film having a heat-sealing property, and the print layer is further laminated on a gas barrier layer of the barrier film.

FIG. 5 is a schematic cross-sectional view of a packaging laminated film according to an embodiment of the present invention, showing the configuration of a packaging laminated film 110 having a printing layer. This is because the adhesion layer 2, the inorganic compound vapor deposition layer 3, and the composite coating layer 4 are laminated on the film base material 1, the printing layer 40 is formed on the adhesive layer 40, and the adhesive layer 20 is interposed above the printing layer 40. The polyester film layer 30 having a heat-sealing property is laminated.

In the above-mentioned laminated film for packaging, it is desirable for recycling that polyester accounts for 90% or more of the total weight. That is, if the total weight of the layer made of a raw material other than the polyester material such as the adhesive layer, the printing layer, and the gas barrier layer is less than 10%, more preferably 5% or less of the total weight, the substance is made of a single material. It is considered and easy to recycle.

Specific examples of the present invention will be described below.
First, each material will be described.

The adhesion layer 2 was prepared by the following procedure.
Coating solution 1: Adhesive solution manufactured by Mitsui Chemicals Co., Ltd. Main agent: Takelac A-525 (inner urethane resin precursor 50% by mass, ethyl acetate 50% by mass) / Hardener: Takenate A-52 (inner urethane resin curing) Agent 55% by mass, ethyl acetate 45% by mass) / Solvent: Ethyl acetate These components are mixed and applied at A-525: A-52: ethyl acetate = 9: 1: 165 (solid content concentration 3% by mass). Liquid 1 was prepared.

The composite coating layer 4 was prepared by the following procedure.
Coating solution 2: 10.4 parts by mass of tetraethoxysilane and 89.6 parts by mass of hydrochloric acid (concentration: 0.1N) were mixed, and the mixed solution was stirred for 30 minutes to obtain a hydrolyzed solution of tetraethoxysilane. .. On the other hand, polyvinyl alcohol was dissolved in a mixed solvent of water / isopropyl alcohol (water / isopropyl alcohol (mass ratio) = 90:10) to obtain a 3% by mass polyvinyl alcohol solution. 60 parts by mass of the hydrolyzed solution of tetraethoxysilane and 40 parts by mass of the polyvinyl alcohol solution were mixed to obtain a coating liquid 2 as a composite coating composition.

The first coating liquid (a) was prepared by the following procedure.
Coating liquid 3: PAA (polyacrylic acid) aqueous solution having a number average molecular weight of 200,000 (Aron A-10H manufactured by Toagosei, solid content concentration 25% by mass) / GPTMS (γ-glycidoxypropyltrimethoxysilane) / solvent: Water, isopropyl alcohol (IPA)
These components were blended at Aron A-10H: GPTMS: water: IPA = 10: 0.17: 66: 7 (solid content concentration 15% by mass) to prepare a coating liquid 3.
As GPTMS (γ-glycidoxypropyltrimethoxysilane), one manufactured by Shin-Etsu Chemical Co., Ltd. was used.

The second coating liquid (b) was prepared by the following procedure.
Coating liquid 4: Zinc oxide-containing resin composition: K035A (Sumitomo Osaka Cement Co., Ltd. zinc oxide (ZnO) 16.6% by mass, urethane resin precursor 1.74% by mass, dispersant 1.66% by mass, toluene 72% by mass %, Methyl ethyl ketone 8% by mass) / Hardener: C-320 (75% by mass of urethane resin curing agent, 25% by mass of ethyl acetate) / Solvent: Toluene, Methyl ethyl ketone (MEK), IPA
These components were blended at K035A: C-320: toluene: MEK: IPA = 100: 3: 24: 3: 3 (solid content concentration 15% by mass) to prepare a coating liquid 4.

Using the above materials, laminated films for packaging of the following Examples and Comparative Examples were produced.

(Example 1)
A gravure coat is used on the corona-treated side of the biaxially stretched polybutylene terephthalate film (PBT, thickness 15 μm) which is a film base material, and the liquid of the above coating liquid 1 is used as an adhesion layer by a gravure roll coating method to a thickness of 0.1 g. It was applied to / m ² and dried by heating to cure. Next, as the inorganic compound vapor deposition layer, aluminum was evaporated while introducing oxygen by an electron beam vacuum vapor deposition method to form an AlOx vapor deposition film having a thickness of 10 nm. Next, the coating liquid 2 was applied as a composite film layer to a thickness of 0.3 g / m ² and dried by heating to obtain a transparent gas barrier film having the configuration shown in FIG.

Next, on the gas barrier layer of the obtained gas barrier film, heat-seal PET (NS-PET: manufactured by Nakamoto Pax, thickness 20 μm) is dried using a two-component adhesive (Mitsui Kagaku A525 / A52). Laminating by a laminating method, a laminated film for packaging of the present invention having a composition of [transparent gas barrier film / adhesive layer (4 g / m ² ) / heat seal PET] was obtained.

(Example 2)
A gravure coat is used on the corona-treated side of a biaxially stretched polybutylene terephthalate film (PBT, thickness 15 μm), which is a film base material, and the liquid of the above coating liquid 1 is applied as an adhesion layer by a gravure roll coating method to make polyester. The resin was cured by 0.1 g / m ² .
Next, the coating liquid 3 is applied as the first coating liquid (a) and dried by overheating, then the coating liquid 4 is applied as the second coating liquid (b) and heat-dried, and the adhesion layer (0.1 g / m ² ) is applied. ) / PAA (0.4 g / m ² ) / ZnO (0.4 g / m ² as ZnO). The laminated film for packaging of the present invention was obtained.

(Example 3)
A gravure coat is used on the corona-treated side of the biaxially stretched polybutylene terephthalate film (PBT, thickness 15 μm) which is a film base material, and the liquid of the above coating liquid 1 is applied as an adhesion layer by the gravure roll coating method to make polyester. The resin was cured by 0.1 g / m ² .
Next, as the inorganic compound vapor deposition layer, aluminum was evaporated while introducing oxygen by an electron beam vacuum vapor deposition method to form an AlOx vapor deposition film having a thickness of 10 nm. Next, the coating liquid 3 is applied as the first coating liquid (a) and overheated and dried, then the coating liquid 4 is applied as the second coating liquid (b) and heat-dried, and the adhesion layer (0.1 g / m ² ) is applied. ) / AlOx vapor-deposited film / PAA (0.4 g / m ² ) / ZnO (0.4 g / m ² as ZnO). A laminated film for packaging of the present invention having the structure shown is obtained.

(Example 4)
Amorphous PET (Hytron PG Tamapoli, thickness 30 μm) was applied on the gas barrier layer of the gas barrier film obtained in Example 1 by a dry laminating method using a two-component adhesive (Mitsui Kagaku A525 / A52). By laminating, a laminated film for packaging of a comparative example having a composition of [transparent gas barrier film / adhesive layer (4 g / m ² ) / amorphous PET] was obtained.

(Comparative example)
CPP (S East Cello, thickness 20 μm) was laminated on the gas barrier layer of the gas barrier film obtained in Example 1 by a dry laminating method using a two-component adhesive (Mitsui Chemicals A525 / A52). A laminated film for packaging of Comparative Example having a structure of transparent gas barrier film / adhesive layer (4 g / m ² ) / CPP] was obtained.

<Polyester material ratio>
The ratio of the film base material of the barrier film, which is a polyester material, and the polyester film having heat-sealing property to the obtained laminated film for packaging was calculated in% by weight.

<Evaluation as a packaging film>
Make a 10 cm x 15 cm three-way seal bag from the obtained laminated film for packaging, put 50 g of commercially available biscuit confectionery as the contents, seal it, and then put 10 bags each in a cardboard box between Tokyo and Osaka. Transported. After transportation, it was confirmed that the biscuits had damaged the appearance of the packaging bag. Those without holes in the packaging bag were marked with ◯, and those with holes were marked with x.
The results are shown in Table 1.

As shown in Table 1, in Examples 1 to 4, the ratio of the polyester material is 90% or more in terms of weight%, and it can be regarded as a single polyester material, and its applicability to chemical recycling is high. Also, in the evaluation as a packaging film, it can sufficiently withstand the transportation test of the contents and is expected to be versatile as a packaging film.
On the other hand, the polyester material ratio of the comparative film using CPP is less than 50%, and it is difficult to apply chemical recycling.

According to the laminated film for packaging of the present invention, by providing a packaging material composed of a laminated film containing only a polyester material as a main material, recycling by a single material is easy, and in particular, chemical recycling of polyester is easy. It is possible to provide a laminated film for packaging that can be performed. Furthermore, by using a film base material containing a polyester resin whose main constituent unit is butylene terephthalate, the heat-resistant water-resistant, impact-resistant, pressure-resistant, piercing resistance, and bending resistance required for packaging materials are imparted. However, by laminating a gas barrier layer as a barrier property and laminating a polyester film having a heat-sealing property as a sealing property, a packaging material satisfying the characteristics required for the packaging material is provided with only the polyester material as the main component. Can be done.

1 Film substrate 2 Adhesive layer 3 Inorganic compound vapor deposition layer 4 Composite coating layer 5 First coating layer (A)
6 Second coating layer (B)
10 Gas barrier layer 10a, 10b, 10c Gas barrier layer 11, 12, 13 Gas barrier film 20 Adhesive layer 30 Polyester film layer with heat sealability 40 Printing layer 100, 110 Laminated film for packaging

Claims (5)

A laminated film for packaging in which a gas barrier layer and a polyester film layer having a heat-sealing property are laminated in this order on a film base material containing a polyester resin having a butylene terephthalate unit as a main constituent unit .
The film base material of the first half is a stretched film,
The gas barrier layer includes an inorganic compound vapor deposition layer made of an inorganic compound, a composite coating layer made of a composition containing at least one of a hydroxyl group-containing polymer compound, a metal alkoxide, a silane coupling agent, or a hydrolyzate thereof. Are stacked one after another,
A laminated film for packaging, characterized in that polyester accounts for 90% or more of the total weight . A laminated film for packaging in which a gas barrier layer and a polyester film layer having a heat-sealing property are laminated in this order on a film base material containing a polyester resin having a butylene terephthalate unit as a main constituent unit.
The film base material of the first half is a stretched film,
The gas barrier layer is a polycarboxylic acid-based polymer (A1) and the general formula R. ¹ Si (OR ² ) ₃ (A1: A2) = 99.5: 0. The first coating layer contained in a mass ratio of 5 to 80.0: 20.0 (however, the mass of the silicon-containing compound is the mass in terms of the silane coupling agent), and the second containing the polyvalent metal compound. Consists of a coating layer of
A laminated film for packaging, characterized in that polyester accounts for 90% or more of the total weight. A laminated film for packaging in which a gas barrier layer and a polyester film layer having a heat-sealing property are laminated in this order on a film base material containing a polyester resin having a butylene terephthalate unit as a main constituent unit.
The film base material of the first half is a stretched film,
The gas barrier layer includes an inorganic compound vapor-deposited layer made of an inorganic compound, a polycarboxylic acid-based polymer (A1), and a general formula R. ¹ Si (OR ² ) ₃ (A1: A2) = 99.5: 0. The first coating layer contained in a mass ratio of 5 to 80.0: 20.0 (however, the mass of the silicon-containing compound is the mass in terms of the silane coupling agent), and the second containing the polyvalent metal compound. Consists of a coating layer of
A laminated film for packaging, characterized in that polyester accounts for 90% or more of the total weight. The packaging according to any one of claims 1 to 3, wherein the gas barrier layer and a polyester film layer having a heat-sealing property are bonded to each other with a one-component curing type or two-component curing type urethane adhesive. For laminated film. The laminated film for packaging according to any one of claims 1 to 4, wherein a printing layer is provided between the gas barrier layer and the polyester film layer.

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