JP6868207B2 - Packaging body consisting of film, laminated film and laminated film - Google Patents

Description

The present invention relates to a film including a resin layer and a vapor-deposited layer provided on the resin layer. The present invention also relates to a laminated film provided with the above film and a package made of the laminated film.

Conventionally, a laminated film in which a plurality of films are laminated has been used as a member constituting a packaging body such as a pouch. The laminated film was laminated in the order of, for example, a first base material layer / a printing layer / an adhesive layer / a thin-film deposition layer / a second base material layer / an adhesive layer / a sealant layer from the outer surface side to the inner surface side. Contains multiple layers. In addition, "/" represents the boundary between layers. The printing layer is a layer that constitutes a pattern, a display, or the like of a package. The print layer is provided on the inner surface side of the first base material layer in order to prevent the print layer from peeling off or bleeding. The thin-film deposition layer is a layer for enhancing the gas barrier property of the laminated film and contains an inorganic substance such as aluminum. The thin-film deposition layer is formed by depositing an inorganic substance on the surface of the second base material layer.

The above-mentioned laminated film includes a first film including a first base material layer and a printing layer, a second film including a second base material layer and a vapor deposition layer, and a third film including a sealant layer. , Manufactured by laminating through an adhesive layer.

Further, for example, Patent Document 1 proposes to form a thin-film deposition layer by depositing aluminum on the surface of the sealant layer.

Japanese Unexamined Patent Publication No. 2001-179878

As a result of intensive research by the present inventors, it was found that when a vapor-deposited layer is provided on the film constituting the sealant layer, wrinkles are likely to occur on the film.

The present invention has been made in consideration of such a point, and an object of the present invention is to provide a film and a laminated film capable of suppressing the occurrence of wrinkles.

The present invention includes a resin layer including a first surface and a second surface, and a vapor-deposited layer provided on the second surface of the resin layer, and the resin layer constitutes the first surface. 1 layer and at least one hard layer having a density higher than that of the first layer and having a density of 0.934 g / cm ^{3 or more, and the total thickness of the hard layers.} Is a film having a thickness of 60% or more of the total thickness of the resin layer.

In the film according to the present invention, the density of the at least one hard layer ^{may be 0.941 g / cm 3} or more.

In the film according to the present invention, the density of the first layer ^{may be 0.925 g / cm 3} or less.

In the film according to the present invention, preferably, the resin layer contains polyethylene or a copolymer of ethylene and α-olefin, and does not contain a lubricant.

In the present invention, a resin layer including a first surface and a second surface, a vapor-deposited layer provided on the second surface of the resin layer, and a base material layer laminated on the vapor-deposited layer via an adhesive layer. The resin layer has a density higher than that of the first layer constituting the first surface and the first layer, and has a density of 0.934 g / cm ³ or more. A laminated film including at least one hard layer having a total thickness of the hard layer, which is 60% or more of the total thickness of the resin layer.

In the laminated film according to the present invention, the adhesive layer may contain an ether-based adhesive.

The present invention is a package including the above-mentioned laminated film.

According to the present invention, it is possible to suppress the occurrence of wrinkles in the film and the laminated film.

It is a front view which shows the bag in embodiment of this invention. FIG. 5 is a cross-sectional view showing a case where the bag shown in FIG. 1 is viewed along the line II-II. It is sectional drawing which shows an example of the layer structure of the laminated film which constitutes a bag. It is sectional drawing which shows an example of the layer structure of the 1st film of a laminated film. It is sectional drawing which shows the other example of the layer structure of the 1st film of a laminated film. It is a figure which shows an example of the manufacturing process of the 1st film. It is a figure which shows an example of the manufacturing process of a laminated film. It is a front view which shows the bag in the state which the upper part is sealed. It is a front view which shows one modification of a bag.

An embodiment of the present invention will be described with reference to FIGS. 1 to 8. In the drawings attached to the present specification, the scale, aspect ratio, etc. are appropriately changed from those of the actual product and exaggerated for the convenience of illustration and comprehension.

In addition, the terms such as "orthogonal" and "identical" and the values of length and angle used in the present specification to specify the shape and geometric conditions and their degrees are bound by a strict meaning. Instead, the interpretation will include the range in which similar functions can be expected.

(bag)
FIG. 1 is a front view showing a case where the package 10 according to the present embodiment is viewed from the front surface side. Further, FIG. 2 is a cross-sectional view showing a case where the package shown in FIG. 1 is viewed along the line II-II. In the present embodiment, an example in which the package 10 is a four-sided seal bag will be described. In addition, in this specification, a "packaging body" is not only a package body in a state after the contents are contained and sealed, but also a state in which the contents are not contained and sealed (contents). It is a concept that also includes a package (state before the product is filled). In FIG. 1, the package 10 in a state before the contents are filled is shown. Further, in FIG. 8 described later, the package 10 in a state after the contents are contained and sealed is shown.

The contents contained in the package 10 are not particularly limited. As will be described later, according to the present embodiment, it is possible to increase the lamination strength of the laminated film constituting the package 10. Therefore, a heavy content, for example, 100 g or more, preferably 200 g or more, more preferably 300 g or more, can be stored in the package 10.

Hereinafter, the configuration of the package 10 will be described. The package 10 includes an upper portion 11, a lower portion 12, and a side portion 13, and has a rectangular contour. The names such as "upper part", "lower part" and "side part", and the terms such as "upper side" and "lower part" are based on the state in which the portion indicated by reference numeral 11 in FIG. 1 is located above on the paper surface. It merely represents the position and direction of each component of the package 10. The posture of the package 10 when used is not limited by the names and terms in the present specification.

As shown in FIGS. 1 and 2, the package 10 includes a laminated film 20 that constitutes the front surface 15 of the package 10 and a laminated film 20 that constitutes the back surface 16 of the package 10. The laminated film 20 on the front surface 15 and the laminated film 20 on the back surface 16 are joined to each other by a sealing portion such as a lower sealing portion 12a.

The sealing portion is a portion where the inner surface 20x of the laminated film 20 on the front surface 15 and the inner surface 20x of the laminated film 20 on the back surface 16 are joined. In the plan view of the package 10 as shown in FIG. 1, the seal portion is hatched.

As shown in FIG. 1, the sealing portion has an outer edge sealing portion extending along the outer edge of the package 10. The outer edge seal portion includes a lower seal portion 12a extending along the lower portion 12 and a pair of side seal portions 13a extending along the pair of side portions 13. In the package 10 in the state before the contents are filled, as shown in FIG. 1, the upper portion 11 of the package 10 has an opening 11b. After the contents are contained in the package 10, the inner surface 20x of the laminated film 20 on the front surface 15 and the inner surface 20x of the laminated film 20 on the back surface 16 are joined at the upper portion 11 to form the upper seal portion 11a and the package. 10 is sealed.

The method for forming the sealing portion is not particularly limited as long as the packaging bodies 10 can be sealed by joining the laminated films 20 facing each other. For example, the inner surface of the laminated film 20 may be melted by heating or the like, and the inner surfaces may be welded to each other to form a sealing portion. Alternatively, the sealing portion may be formed by adhering the inner surfaces 20x of the laminated films 20 facing each other with an adhesive or the like.

(Layer structure of laminated film)
Next, the layer structure of the laminated film 20 will be described. FIG. 3 is a cross-sectional view showing an example of the layer structure of the laminated film 20.

As shown in FIG. 3, the laminated film 20 includes a first film 30 and a second film 40 laminated on the first film 30 via an adhesive layer 50. The first film 30 is located on the inner surface 20x side, and the second film 40 is located on the outer surface 20y side opposite to the inner surface 20x. Hereinafter, the first film 30, the second film 40, and the adhesive layer 50 will be described in detail.

(1st film)
FIG. 4 is a cross-sectional view showing an example of the layer structure of the first film 30. The first film 30 includes a resin layer 31 and a thin-film deposition layer 32 provided on the resin layer 31. The resin layer 31 is located on the inner surface 30x side corresponding to the inner surface 20x of the laminated film 20, and the thin-film deposition layer 32 is located on the outer surface 30y side opposite to the inner surface 30x.

[Resin layer]
The resin layer 31 includes a first surface 31x located on the inner surface 30x side of the first film 30, and a second surface 31y located on the opposite side of the first surface 31x. Further, the resin layer 31 includes a first layer 31a, a second layer 31b, and a third layer 31c that are arranged in order from the first surface 31x side to the second surface 31y side. The first layer 31a constitutes the first surface 31x of the resin layer 31, that is, the inner surface 20x of the laminated film 20. Hereinafter, the background of forming the resin layer 31 with a plurality of layers in this way will be described.

In the step of forming the vapor-deposited layer 32 on the resin layer 31, the vapor-deposited material constituting the vapor-deposited layer 32 is heated and vaporized or sublimated to adhere to the surface of the resin layer 31. As a result, the temperature of the resin layer 31 rises, and the resin layer 31 thermally expands. Therefore, for example, when the vapor-deposited layer 32 is formed on the resin layer 31 while transporting the film-shaped resin layer 31, it is conceivable that wrinkles occur in the resin layer 31 in the width direction orthogonal to the transport direction of the resin layer 31. Be done. In the transport direction of the resin layer 31, wrinkles are less likely to occur because tension is applied to the resin layer 31.

As a method of suppressing the occurrence of wrinkles in the resin layer 31, it is conceivable to form the resin layer 31 using a hard material. For example, in polyethylene, which is generally known as a material constituting the resin layer 31 which is a sealant layer, the higher the density, the higher the hardness. Therefore, it is considered that by forming the resin layer 31 using polyethylene having a high density, it is possible to suppress the thermal expansion of the resin layer 31 and thereby suppress the occurrence of wrinkles in the resin layer 31.

On the other hand, in polyethylene, the higher the density, the higher the melting point and the lower the heat sealability. Therefore, it is considered that when the density of the polyethylene constituting the resin layer 31 becomes high, the sealing strength at the time of heat sealing becomes low in the laminated film 20 in which the resin layer 31 functions as a sealant layer.

In consideration of such a background, in the present embodiment, the resin layer 31 has at least a density higher than that of the first layer 31a in addition to the first layer 31a constituting the first surface 31x. It is proposed to further include one hard layer. In the example shown in FIG. 4, the second layer 31b is a hard layer having a density higher than that of the first layer 31a. By providing the hard layer, it is possible to suppress the occurrence of wrinkles in the resin layer 31. Further, by making the density of the first layer 31a constituting the inner surface 20x of the laminated film 20 lower than the density of the hard layer, the heat sealability of the laminated film 20 can be ensured.

Hereinafter, the materials constituting each layer of the resin layer 31 will be described in detail. First, a configuration common to each layer of the resin layer 31 will be described.

Each layer of the resin layer 31 contains, for example, polyethylene or a copolymer of ethylene and α-olefin. For example, each layer of the resin layer 31 may be composed of polyethylene or a copolymer of ethylene and α-olefin. Alternatively, the resin layer 31 may be composed of a material in which polyethylene is mixed with a copolymer of ethylene and α-olefin.

Polyethylene is classified into, for example, low-density polyethylene (hereinafter, also referred to as LDPE), medium-density polyethylene (hereinafter, also referred to as MDPE), and high-density polyethylene (hereinafter, also referred to as HDPE). The LDPE, density of 0.910 g / cm ³ or more and 0.925 g / cm ³ or less of polyethylene. MDPE is polyethylene having a density of 0.926 g / cm ³ or more and 0.940 g / cm ^{3 or less.} HDPE is polyethylene having a density of 0.941 g / cm ³ or more and 0.965 g / cm ^{3 or less.} LDPE is obtained, for example, by polymerizing ethylene at a high pressure of 1000 atm or more and less than 2000 atm. MDPE and HDPE can be obtained, for example, by polymerizing ethylene at medium or low pressures of 1 atm or more and less than 1000 atm. In addition, MDPE and HDPE may partially contain a copolymer of ethylene and α-olefin.

The copolymer of ethylene and α-olefin is, for example, linear low-density polyethylene (hereinafter, also referred to as LLDPE). LLDPE is obtained by copolymerizing an α-olefin with a linear polymer obtained by polymerizing ethylene at medium pressure or low pressure to introduce a short chain branch. Examples of the α-olefin include butene-1 (C ₄ ), hexene-1 (C ₆ ), 4-methylpentene (C ₆ ), octene-1 (C ₈ ) and the like. The density of LLDPE is, for example, 0.915 g / cm ³ or more and 0.945 g / cm ³ or less.

Hereinafter, examples of materials constituting each layer of the resin layer 31 will be described.

The first layer 31a is made of LDPE, LLDPE, or a mixed resin of LDPE and LLDPE. The second layer 31b is made of HDPE, MDPE and LLDPE. Alternatively, the second layer 31b is made of a mixed resin in which at least two of MDPE, HDPE and LLDPE are combined. Preferably, the second layer 31b is HDPE. The third layer 31c is made of LDPE, LLDPE, or a mixed resin of LDPE and LLDPE.

The second layer 31b, which is a hard layer, has a density of ^{0.934 g / cm 3 or more.} For example, when the second layer 31b is HDPE, the density of the second layer 31b is 0.941 g / cm ³ or more. Further, the ratio of the thickness T2 of the second layer 31b, which is a hard layer, to the thickness T0 of the entire resin layer 31 is 60% or more. As a result, it is possible to suppress the occurrence of wrinkles when the vapor-deposited layer 32 is formed on the resin layer 31.

Preferably, the density of the first layer 31a constituting the inner surface 30x of the first film 30, that is, the inner surface 20x of the laminated film 20, is the lowest in each layer of the resin layer 31. For example, the density of the first layer 31a is a 0.925 g / cm ³ or less, more preferably 0.918 g / cm ³ or less. Thereby, the heat sealability of the first film 30 and the laminated film 20 can be improved. For example, the melting point of the inner surface 20x of the laminated film 20 can be lowered. This makes it easier to weld the inner surfaces 20x of the laminated film 20 to each other.

The thickness T0 of the entire resin layer 31 is preferably 20 μm or more, more preferably 25 μm or more. The thickness T0 is preferably 40 μm or less, and more preferably 35 μm or less.
The thickness T1 of the first layer 31a is preferably 4 μm or more, more preferably 5 μm or more. The thickness T1 is preferably 8 μm or less, more preferably 7 μm or less.
The thickness T2 of the second layer 31b is preferably 12 μm or more, more preferably 15 μm or more. The thickness T2 is preferably 24 μm or less, more preferably 21 μm or less.
The thickness T3 of the third layer 31c is preferably 4 μm or more, more preferably 5 μm or more. The thickness T3 is preferably 8 μm or less, more preferably 7 μm or less.

As long as the resin layer 31 has a density higher than that of the first layer 31a and includes at least one hard layer having a density of ^{0.934 g / cm 3 or more, the specific resin layer 31 is specific.} The layer structure is not particularly limited. For example, although not shown, the resin layer 31 has a density higher than that of the first layer 31a and the first layer 31a, and has a density of 0.934 g / cm ³ or more. It may be composed of a layer 31b. In this case, the thickness T2 of the second layer 31b is 60% or more of the thickness T0 of the entire resin layer 31.

Alternatively, the resin layer 31 may include four or more layers. For example, as shown in FIG. 5, in the resin layer 31, the first layer 31a, the second layer 31b, the third layer 31c, and the fourth layer are arranged in order from the first surface 31x side to the second surface 31y side. Includes 31d and a fifth layer 31e. In this case, for example, the first layer 31a, the third layer 31c and the fifth layer 31e are made of LDPE, LLDPE, or a mixed resin of LDPE and LLDPE. The second layer 31b and the fourth layer 31d are made of a resin having a density higher than that of the first layer 31a and a density of 0.934 g / cm ³ or more, for example, HDPE, MDPE, or MDPE and HDPE. It consists of a mixed resin. That is, in the example shown in FIG. 5, the second layer 31b and the fourth layer 31d are hard layers. In this case, the total ratio of the thickness T2 of the second layer 31b and the thickness T4 of the fourth layer 31d to the thickness T0 of the entire resin layer 31 is 60% or more.

By the way, as a result of intensive research by the present inventors, when the resin layer 31 contains a lubricant, the lamination strength between the first film 30 including the resin layer 31 and the vapor-deposited layer 32 and the second film 40 Was found to decrease. Based on this finding, in the present embodiment, the resin layer 31 may be configured so that the resin layer 31 does not contain a lubricant.

As a cause of the decrease in the lamination strength between the first film 30 and the second film 40 due to the lubricant, for example, a phenomenon in which the lubricant emerges on the surface of the resin layer 31 over time, a so-called bleed-out phenomenon, is considered. Be done. Specifically, due to the occurrence of the bleed-out phenomenon, the lubricant is present at the interface between the first film 30 and the adhesive layer 50, and the adhesive strength of the adhesive layer 50 is reduced. is there. Naturally, other causes are also possible.

Lubricants are additives used to increase the slipperiness of a film. Examples of lubricants include hydrocarbon-based lubricants, fatty acid-based lubricants, fatty acid amide-based lubricants, ester-based lubricants, alcohol-based lubricants, and metal soap-based lubricants.

Examples of the hydrocarbon-based lubricant include natural paraffin, paraffin wax, synthetic paraffin, and polyethylene wax. Paraffin is _{a general term for hydrocarbons represented by C n} H _{2n + 3} (n is a natural number).
Examples of fatty acid-based lubricants include stearic acid, palmitic acid, myristic acid, and arachidic acid.
Examples of the fatty acid amide-based lubricant include stearic acid amide, partiminic acid amide, oleic acid amide, and erucic acid amide.
Examples of the ester-based lubricant include butyl stearate and glycol monostearate.
Examples of the alcohol-based lubricant include cetyl alcohol, stearyl alcohol, polyethylene glycol and the like.
Examples of the metal soap-based lubricant include those in which an acid such as lauric acid or stearic acid is combined with a metal. For example, barium stearate, calcium stearate, zinc stearate, magnesium stearate and the like.

The fact that the resin layer 31 does not contain a lubricant means that the resin layer 31 is analyzed by, for example, Fourier transform infrared spectroscopy (FTIR) or X-ray photoelectron spectroscopy (XPS), and a peak peculiar to the lubricant appears in the analysis result. Proven by not.

The resin layer 31 may contain additives other than the lubricant. Examples of additives include antioxidants, antiblocking agents, neutralizing agents and the like.

Examples of antioxidants include phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, vitamin E-based antioxidants, amine-based antioxidants, and the like.

Examples of phenolic antioxidants include 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxy) benzene and n-octadecyl-β- ( 4'-Hydroxy-3', 5'-di-t-butylphenyl) propionate, stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, tris (3,5-di-) t-Butyl-4-hydroxybenzyl) -isocyanurate, 1,6-hexanediol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol bis-3- (3-t-Butyl-4-hydroxy-5-methylphenyl) propionate, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 4,4'-butylidenebis ( 3-Methyl-6-t-butylphenol), 3,9-bis [1,1-dimethyl-2- [β- (3-t-butyl-4-hydroxy-5-methylfienyl) propionyloxy] ethyl] 2,4,8,10-Tetraoxaspiro [5,5] -Undecane, bis- [3,3-bis- (4'-hydroxy-3'-t-butylphenyl) -butylphenyl) -butanoic acid] -glycol ester, Butyl hydroxytoluene (BHT) and the like can be mentioned.
Examples of phosphorus-based antioxidants include tris (2,4-di-t-butylphenyl) phosphite, distearylpentaerythritol diphosphite, and cyclic neopentanetetraylbis (2,6-di-t). -Butyl-4-methylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, triphenylphosphite (TPP) and the like can be mentioned.
Examples of the sulfur-based antioxidant include dioctadecyl-disulfide and disstearylthiodipropionate (DSTDP).
Examples of the vitamin E-based antioxidant include 2,5,7,8-tetramethyl-2 (4', 8', 12'-trimethyltridecyl) chroman-6-ol.
Examples of the amine-based antioxidant include Fennyrou β-naphthylamine (PBN) and the like.

The anti-blocking agent, for example, forms irregularities on the surface of the resin layer 31, thereby suppressing the first films 30 including the resin layer 31 from coming into close contact with each other when the first film 30 is wound into a roll. It plays the action. Examples of anti-blocking agents include calcium carbonate, silicon dioxide, synthetic zeolite and the like.

The neutralizing agent has the effect of suppressing the reaction between the polyethylene or the copolymer of ethylene and the α-olefin and the additive. Examples of the neutralizing agent include calcium stearate.

[Embedded layer]
The thin-film deposition layer 32 is a layer formed by depositing an inorganic substance on the outer surface 30y of the resin layer 31. Examples of inorganic substances include metals such as aluminum and inorganic oxides such as aluminum oxide and silicon oxide. The thickness of the thin-film deposition layer 32 is, for example, 5 nm or more and 100 nm or less.

When the vapor deposition layer 32 is made of a metal such as aluminum, the vapor deposition layer 32 has a light-shielding property. On the other hand, when the vapor deposition layer 32 is made of an inorganic oxide such as aluminum oxide or silicon oxide, the vapor deposition layer 32 has transparency. In the following description, the thin-film metal vapor deposition layer is also referred to as a metal thin-film deposition layer, and the thin-film deposition layer made of an inorganic oxide is also referred to as a transparent thin-film deposition layer.

Since the vapor deposition layer 32 is located on the inner surface 20x side of the laminated film 20 with respect to the print layer 42, the visibility of the print layer 42 from the outer surface 20y side is not hindered by the vapor deposition layer 32. Therefore, from the viewpoint of visual recognition of the print layer 42, the vapor deposition layer 32 may be either a metal vapor deposition layer or a transparent vapor deposition layer.

Examples of the method for forming the vapor deposition layer 32 include a physical vapor deposition method (PVD method) such as a vacuum vapor deposition method, a sputtering method, and an ion plating method, or a plasma chemical vapor deposition method, heat. Examples thereof include a chemical vapor deposition method, a chemical vapor deposition method such as a photochemical vapor deposition method, and a CVD method.

[Gas barrier coating film]
It is known that the inorganic oxide constituting the transparent thin-film deposition layer becomes colored as its thickness increases. Therefore, in order to maintain the transparency of the transparent thin-film vapor deposition layer, it is preferable that the thickness of the transparent thin-film deposition layer is a predetermined value or less. For example, the thickness of the transparent thin-film deposition layer is 5 nm or more and 15 nm or less. In this case, it is considered that the transparent vapor deposition layer is likely to be damaged such as cracks due to the small thickness. Further, it is considered that the gas barrier property becomes insufficient due to the small thickness of the transparent thin-film deposition layer. Therefore, when the vapor deposition layer 32 is a transparent vapor deposition layer, it is preferable to provide a gas barrier coating film on the surface of the vapor deposition layer 32 opposite to the resin layer 31 (that is, the second film 40 side). By providing the vapor-deposited layer 32 with a gas-barrier coating film, it is possible to prevent damage such as cracking from occurring in the vapor-deposited layer 32, and it is possible to enhance the gas-barrier property. When the gas barrier coating film is provided on the transparent vapor deposition layer, the gas barrier coating film is transparent. Further, the gas barrier coating film may be provided on the metal vapor deposition layer.

The gas barrier coating film is a layer that functions as a layer that suppresses the permeation of oxygen gas, water vapor, and the like. The gas barrier coating film is of the general formula R ¹ _n M (OR ² ) _m (where R ¹ and R ² represent organic groups having 1 to 8 carbon atoms, M represents a metal atom, and n. Represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents the valence of M). It is obtained by a gas barrier composition containing a resin and / or an ethylene / vinyl alcohol copolymer and further polycondensing by the solgel method in the presence of a solgel method catalyst, acid, water and an organic solvent.

As the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m , at least one or more of a partial hydrolyzate of the alkoxide and a condensate of the hydrolysis of the alkoxide can be used. Further, the partial hydrolyzate of the alkoxide may be one in which all of the alkoxy groups are hydrolyzed, one or more hydrolyzed, and a mixture thereof. As the condensate of hydrolysis of the alkoxide, one having a dimer or more of the partially hydrolyzed alkoxide, specifically, one having a 2 to hexamer is used.

In the above-mentioned ^{alkoxide represented by the general formula R 1} _n M (OR ² ) _m , silicon, zirconium, titanium, aluminum, or the like can be used as the metal atom represented by M. In the present embodiment, preferred metals include, for example, silicon and titanium. Further, in the present invention, the alkoxide may be used alone or by mixing alkoxides of two or more different metal atoms in the same solution.

Further, in the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m ^{, specific examples of the organic group represented by R 1} include, for example, a methyl group, an ethyl group, an n-propyl group, and i. Alkyl groups such as −propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-octyl group and others can be mentioned. Further, in the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m ^{, specific examples of the organic group represented by R 2} include, for example, a methyl group, an ethyl group, an n-propyl group, and i. -Propyl group, n-butyl group, sec-butyl group, etc. can be mentioned. In addition, these alkyl groups may be the same or different in the same molecule.

When preparing the above gas barrier composition, for example, a silane coupling agent or the like may be added. As the above-mentioned silane coupling agent, a known organic reactive group-containing organoalkoxysilane can be used. In this embodiment, an organoalkoxysilane having an epoxy group is particularly preferably used, and specifically, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, or , Β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be used. The above-mentioned silane coupling agent may be used alone or in combination of two or more.

(2nd film)
The second film 40 includes at least a base material layer 41. As shown in FIG. 3, the second film 40 may further include a printing layer 42 provided on the inner surface 20x side of the base material layer 41.

As the material constituting the base material layer 41, for example, polyethylene terephthalate, plastics such as polypropylene and nylon, and the like can be used. The base material layer 41 has high heat resistance required when forming a seal portion by heat welding. When the base material layer 41 is plastic, it may be stretched uniaxially or biaxially. The thickness of the base material layer 41 is, for example, 4 μm or more and 50 μm or less.

The printed layer 42 is a layer printed on the base material layer 41 in order to show product information or give an aesthetic impression to the package 10. The print layer 42 expresses characters, numbers, symbols, figures, patterns, and the like.

The laminated film 20 may further include a functional layer. As the functional layer, an appropriate one can be selected according to the required performance such as water vapor and other gas barrier properties, light shielding properties, and various mechanical strengths. For example, when the functional layer is a gas barrier layer, the above-mentioned vapor deposition layer, gas barrier coating film, or the like can be provided between the base material layer 41 and the printing layer 42. In this case, a transparent vapor deposition layer is provided as the vapor deposition layer so as not to obstruct the visibility of the print layer 42. Further, in order to impart mechanical strength, a support may be provided as a functional layer. As the support, the same one as that of the base material layer 41 can be used.

(Adhesive layer)
The adhesive layer 50 contains an adhesive for adhering the first film 30 and the second film 40. Examples of the adhesive include an ether-based adhesive and an ester-based adhesive.

Examples of the ether-based adhesive include polyether polyurethane and the like. Polyether polyurethane is produced by the reaction of a polyether polyol with an isocyanate. Examples of the isocyanate include aromatic isocyanates such as tolylene diisocyanate (TDI) and xylylene diisocyanate (XDI), aliphatic isocyanates such as hexamethylene diisocyanate (HMDI), and alicyclic isocyanates such as isophorone diisocyanate (IPDI). The isocyanate compound of the above, or an adduct or multimer of the above-mentioned various isocyanate compounds can be used.

Examples of the ester-based adhesive include polyester polyurethane and polyester. Polyester polyurethane is formed by the reaction of polyester polyol and isocyanate. The example of isocyanate is the same as that of the above-mentioned ether-based adhesive.

The effect reaction of the ether-based adhesive proceeds faster than the effect reaction of the ester-based adhesive. Therefore, by using an ether-based adhesive, the time required for the aging step for curing the adhesive can be shortened. On the other hand, the adhesive strength of the ether-based adhesive is more likely to decrease due to the influence of the bleed-out of the lubricant than the adhesive strength of the ester-based adhesive. Here, according to the present embodiment, since the resin layer 31 does not contain a lubricant, there is no concern that the adhesive strength of the ether-based adhesive will be reduced due to the influence of the lubricant.

Method for Producing First Film Next, an example of the method for producing the first film 30 will be described with reference to FIG.

First, the material constituting the resin layer 31 is prepared. Subsequently, the film-shaped resin layer 31 is produced by extruding the material by a melt extrusion method such as an inflation method or a casting method (T-die method). Preferably, the inflation method is used. As a result, a film having a lower draw ratio can be produced as compared with the case of using the casting method.

Subsequently, as shown in FIG. 6, the thin-film deposition apparatus 35 is used to deposit the inorganic material on the film-shaped resin layer 31 to form the thin-film deposition layer 32. In this way, the first film 30 including the resin layer 31 and the vapor deposition layer 32 can be obtained. Here, according to the present embodiment, the resin layer 31 includes a hard layer having a thickness of 60% or more with respect to the thickness T0 of the entire resin layer 31. Therefore, it is possible to prevent the resin layer 31 from thermally expanding due to the temperature rise of the resin layer 31 in the vapor deposition process. Alternatively, even if thermal expansion occurs in the resin layer 31, since the resin layer 31 is highly rigid, it is possible to prevent the resin layer 31 from being deformed such as wrinkles.

Then, the first film 30 is wound to obtain a roll body 30R. At this time, the tension at the time of winding the first film 30 is appropriately adjusted to suppress the winding tightness of the first film 30. For example, the tension when winding the first film 30 is lowered toward the outside of the roll body 30R. As a result, even when the resin layer 31 does not contain a lubricant, it is possible to prevent the first film 30 from wrinkling or the like.

Method for Manufacturing Laminated Film Next, an example of a method for manufacturing the laminated film 20 will be described with reference to FIG. 7.

First, the above-mentioned first film 30 and the second film 40 in which the printing layer 42 is formed on the film-like base material layer 41 are prepared. Subsequently, as shown in FIG. 7, the first film 30 and the second film 40 are laminated via the adhesive layer 50 by the dry laminating method. Thereby, the laminated film 20 including the first film 30 and the second film 40 can be obtained.

By the way, when the resin layer 31 contains a lubricant, it is conceivable that the lubricant appears on the surface of the resin layer 31 due to the bleed-out phenomenon. Further, when the first film 30 is wound around the roll body 30R, the surface of the resin layer 31 opposite to the vapor deposition layer 32 comes into contact with the surface of the vapor deposition layer 32. Therefore, it is conceivable that the lubricant appearing on the surface of the resin layer 31 adheres to the surface of the vapor deposition layer 32. In this case, the lubricant is present at the interface between the first film 30 and the adhesive layer 50, and the adhesive strength (lamination strength) between the first film 30 and the second film 40 is lowered. There are concerns.

On the other hand, according to the present embodiment, since the resin layer 31 does not contain a lubricant, it is possible to prevent the lubricant from appearing on the surface of the vapor-deposited layer 32. As a result, it is possible to suppress a decrease in the lamination strength between the first film 30 and the second film 40.

Examples of the layer structure of the laminated film 20 including the first film 30 and the second film 40 described above include the following. In addition, "/" indicates the boundary between layers. When the vapor deposition layer is provided on the base material layer, the vapor deposition layer and the gas barrier coating film are transparent in consideration of the visibility of the printing layer.
-Base material layer / printing layer / adhesive layer / metal vapor deposition layer / resin layer / base material layer / printing layer / adhesive layer / gas barrier coating film / transparent vapor deposition layer / resin layer / base material layer / transparent vapor deposition layer / Gas barrier coating film / printing layer / adhesive layer / metal vapor deposition layer / resin layer / base material layer / transparent vapor deposition layer / gas barrier coating film / printing layer / adhesive layer / support / adhesive layer / metal vapor deposition layer / Resin layer

Manufacturing Method of Package Body The above-mentioned laminated films 20 are heat-sealed to form a sealing portion such as a lower sealing portion 12a and a side sealing portion 13a. Further, the heat-sealed laminated film 20 is cut into an appropriate shape to obtain the package 10 shown in FIG. Subsequently, the contents 18 are filled into the package 10 through the opening 11b of the upper portion 11. After that, the upper portion 11 is heat-sealed to form the upper seal portion 11a. In this way, as shown in FIG. 8, it is possible to obtain a package 10 filled with and sealed with the contents 18.

Here, according to the present embodiment, the first layer 31a of the resin layer 31 constituting the inner surface 20x of the laminated film 20 has a low density, so that the melting point of the inner surface 20x is lowered and the laminated film 20 is heat-sealed. You can improve your sex. Therefore, the sealing strength between the inner surfaces 20x of the laminated films 20 facing each other can be increased.

Further, according to the present embodiment, since the resin layer 31 does not contain a lubricant, the lamination strength between the first film 30 and the second film 40 is appropriately secured. Therefore, it is possible to prevent the strength of the seal portion (seal strength) from decreasing.

Further, according to the present embodiment, since the vapor deposition layer 32 is provided on the resin layer 31 which is the sealant layer, it is not necessary to provide a second base material layer for supporting the vapor deposition layer. Therefore, the package 10 is formed by laminating two films, the first film 30 including the resin layer 31 and the vapor deposition layer 32, and the second film 40 including the base material layer 41 and the printing layer 42. The laminated film 20 for this purpose can be realized. Therefore, the cost, man-hours, and the like required for the package 10 can be reduced as compared with the case where the package 10 is constructed by using the laminated film in which the three films are laminated.

It is possible to make various changes to the above-described embodiment. Hereinafter, a modified example will be described with reference to the drawings as necessary. In the following description and the drawings used in the following description, the same codes as those used for the corresponding parts in the above-described embodiment will be used for the parts that can be configured in the same manner as in the above-described embodiment. Duplicate explanations will be omitted. Further, when it is clear that the action and effect obtained in the above-described embodiment can be obtained in the modified example, the description thereof may be omitted.

(Modified example of packaging)
In the above-described embodiment, the example in which the package 10 is a four-sided seal bag is shown, but the specific configuration of the package 10 is not particularly limited. For example, as shown in FIG. 9, the package 10 has an upper seal portion 11a and a lower seal portion 12a, and a back seal portion 14a extending from a substantially central portion of the upper seal portion 11a toward a substantially central portion of the lower seal portion 12a. It may be a so-called pillow bag provided with.

Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the description of the following Examples as long as the gist of the present invention is not exceeded.

(Example 1)
By the inflation method, a film-like resin layer 31 including the first layer 31a, the second layer 31b, and the third layer 31c shown in FIG. 4 was produced. Table 1 shows the resin material used to form each layer, and the density and thickness of each layer.

Subsequently, a thin-film deposition layer 32 containing aluminum was formed on the surface of the film-like resin layer 31 on the third layer 31c side by the PVD method. In this way, the first film 30 including the resin layer 31 and the vapor deposition layer 32 was formed.

(Example 2)
By the inflation method, a film-like resin layer 31 including the first layer 31a, the second layer 31b, and the third layer 31c shown in FIG. 4 was produced. Table 2 shows the resin material used to form each layer, and the density and thickness of each layer.

Subsequently, a thin-film deposition layer 32 containing aluminum was formed on the surface of the film-like resin layer 31 on the third layer 31c side by the PVD method. In this way, the first film 30 including the resin layer 31 and the vapor deposition layer 32 was formed.

(Comparative Example 1)
By the inflation method, a film-like resin layer 31 including the first layer 31a, the second layer 31b, and the third layer 31c shown in FIG. 4 was produced. Table 3 shows the resin material used to form each layer, the density and thickness of each layer.

Subsequently, a thin-film deposition layer 32 containing aluminum was formed on the surface of the film-like resin layer 31 on the third layer 31c side by the PVD method. In this way, the first film 30 including the resin layer 31 and the vapor deposition layer 32 was formed.

(Comparative Example 2)
By the inflation method, a film-like resin layer 31 including the first layer 31a, the second layer 31b, and the third layer 31c shown in FIG. 4 was produced. Table 4 shows the resin material used to form each layer, the density and thickness of each layer.

Subsequently, a thin-film deposition layer 32 containing aluminum was formed on the surface of the film-like resin layer 31 on the third layer 31c side by the PVD method. In this way, the first film 30 including the resin layer 31 and the vapor deposition layer 32 was formed.

表５におけるシワのレベルの意味は下記のとおりである。
レベル１：シワが存在しない。
レベル２：シワは存在するが、包装体の用途において実質的に問題にならない。
レベル３：シワが多数存在し、包装体の用途において使用できない。 (Confirmation of wrinkles)
The appearances of the first film 30 of Examples 1 and 2 and the first film 30 of Comparative Examples 1 and 2 were visually confirmed, and the state of wrinkles was examined. The results are shown in Table 5.

The meanings of wrinkle levels in Table 5 are as follows.
Level 1: No wrinkles.
Level 2: Wrinkles are present, but are not substantially a problem in packaging applications.
Level 3: There are many wrinkles and it cannot be used for packaging purposes.

(Preparation of laminated film)
The laminated film 20 was produced by the dry laminating method using the first films 30 of Examples 1 and 2 and Comparative Examples 1 and 2. Specifically, the first film 30 and the second film 40 made of a stretched polypropylene film were laminated via an adhesive layer by a dry laminating method to prepare a laminated film 20. As the second film 40, a stretched polypropylene film having a thickness of 30 μm was used. As the adhesive layer 50, an ether-based adhesive was used. The thickness of the adhesive layer 50 was 2.5 μm. The laminated film 20 is laminated from the outer surface side to the inner surface side in the order of base material layer 41 / printing layer 42 / adhesive layer 50 / thin-film deposition layer 32 / resin layer 31.

(Preparation of packaging)
In addition, each of the laminated films obtained in Examples 1 and 2 was used to prepare a package shown in FIG. 9 filled with fried rice having a weight of 450 g as the content 18. At this time, the length S1 of the package 10 was set to 245 mm, and the length S2 was set to 165 mm. Next, the package 10 was cooled to freeze the internal contents 18. After that, a drop test was carried out 10 times in which the package 10 was freely dropped from a height of 1.2 m from a predetermined test table to cause the package 10 to collide with the test table, and whether or not the package 10 was torn. I confirmed. In the drop test, after dropping the package 10 with the back surface 16 (the surface on the side where the back seal portion 14a does not exist) positioned downward, the package body with the lower portion 12 positioned downward. The test process of dropping 10 was counted as one drop test. The number of samples was 2. That is, two packages 10 containing the first film 30 of Examples 1 and 2 were prepared, and each of the two packages 10 was subjected to a drop test 10 times.

As a result of the drop test, in the package 10 including the first film 30 of Examples 1 and 2, the phenomenon that the package 10 was broken was not observed.

10 Package 11 Upper 11a Upper seal 12 Lower 12a Lower seal 13 Side 13a Side seal 14a Back seal 15 Front surface 16 Back surface 17 Storage 18 Contents 20 Laminated film 30 First film 31 Resin layer 31a First Layer 31b Second layer 31c Third layer 31d Fourth layer 31e Fifth layer 32 Vapor deposition layer 40 Second film 41 Base material layer 42 Printing layer 50 Adhesive layer

Claims (9)

A resin layer containing the first surface and the second surface,
A thin-film deposition layer provided on the second surface of the resin layer is provided.
The resin layer includes a first layer, a second layer, and a third layer that are arranged in order from the first surface side to the second surface side.
The first layer is made of LDPE, LLDPE, or a mixed resin of LDPE and LLDPE, and constitutes the first surface of the resin layer.
The second layer, HDPE, MDPE, young properly is, MDPE, made mixed resin combining at least two of HDPE and LLDPE, and has a higher density than the density in the first layer And has a density of 0.941 g / cm ^{3 or more.}
The third layer is made of LDPE, LLDPE, or a mixed resin of LDPE and LLDPE, and constitutes the second surface of the resin layer.
The density of the first layer is the lowest in each layer of the resin layer.
A film in which the thickness of the second layer is 60% or more of the total thickness of the resin layer. The film according to claim 1, wherein the resin layer contains an additive other than a lubricant. The film according to claim 1 or 2, wherein the density of the first layer is 0.925 g / cm ^{3 or less.} The film according to any one of claims 1 to 3, wherein the resin layer does not contain a lubricant. The film according to any one of claims 1 to 4, wherein the thickness of the entire resin layer is 40 μm or less. A resin layer containing the first surface and the second surface,
A thin-film deposition layer provided on the second surface of the resin layer,
A base material layer laminated on the vapor-deposited layer via an adhesive layer is provided.
The resin layer includes a first layer, a second layer, and a third layer that are arranged in order from the first surface side to the second surface side.
The first layer is made of LDPE, LLDPE, or a mixed resin of LDPE and LLDPE, and constitutes the first surface of the resin layer.
The second layer, HDPE, MDPE, young properly is, MDPE, made mixed resin combining at least two of HDPE and LLDPE, and has a higher density than the density of said first layer And has a density of 0.941 g / cm ^{3 or more.}
The third layer is made of LDPE, LLDPE, or a mixed resin of LDPE and LLDPE, and constitutes the second surface of the resin layer.
The density of the first layer is the lowest in each layer of the resin layer.
A laminated film in which the thickness of the second layer is 60% or more of the total thickness of the resin layer. The laminated film according to claim 6, wherein the resin layer contains an additive other than a lubricant. The laminated film according to claim 6 or 7, wherein the adhesive layer contains an ether-based adhesive. A package including the laminated film according to any one of claims 6 to 8.

Images