JP2013116609A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate which includes a metal vapor deposition film in a layer configuration, has appearance equivalent to a matte surface of aluminium foil, and excellent interlayer adhesion.SOLUTION: The laminate includes: the metal vapor deposition film having a substrate and a metal vapor deposition membrane; and an exterior film which has a transparent substrate and a print layer that is partially formed on one surface of the transparent substrate, and which is arranged so that the surface of the side of the print layer is oriented toward the side of the metal vapor deposition film. An intermediate layer is interposed between the metal vapor deposition film and the exterior film. The intermediate layer is formed of a transparent resin having a dispersed pigment, and the pigment has titanium oxide having a concentration of 5.7-35 mass%.

Description

  The present invention relates to a laminate including an aluminum vapor deposition film in a layer structure.

Conventionally, as a packaging material for packaging foods, pharmaceuticals, etc., a laminated body in which a sealant layer is laminated on an exterior film on which images such as letters and figures for explaining contents to be packaged are printed and heat sealability is given has been used. Yes. The laminated body is provided with other layers according to required functions and the like. In particular, a laminate containing an aluminum foil in its layer structure is excellent in barrier properties against water vapor, oxygen, light, etc., and is therefore widely used in applications that require high stability during storage of contents. .
As a laminate including an aluminum foil in the layer structure, there is a laminate in which a transparent resin film such as a polyethylene terephthalate film is used as an exterior film so that the aluminum foil can be visually recognized from the outside in order to give a high-class feeling due to a unique metallic luster. . Such a laminate is generally produced by printing on one side of a transparent resin film and sequentially laminating an aluminum foil, a sealant layer, etc. on the printed surface.
In general, aluminum foil has a glossy surface on one side and a matte surface on the other side in the manufacturing process. In other words, aluminum foil is generally manufactured by a method in which two foils are stacked, supplied to a rolling mill in that state, rolled with a rolling roll, and then peeled off into two sheets. The polished surface becomes a glossy glossy surface, and the surface where the aluminum foils are in contact with each other produces a fine unevenness and becomes a matte surface.
In the laminated body, the aluminum foil is usually arranged so that the matte surface faces the resin film, that is, the matte surface can be seen during packaging. This is because when the glossy surface is directed outward, the metallic luster increases, but the reflection of light also increases, making it difficult to recognize printing. Also, in terms of consumer preference, matte surfaces are often preferred.

In recent years, in the field of light packaging that does not require as high a barrier property as aluminum foil, instead of aluminum foil, a metal film (metal vapor deposition) is deposited on the surface of the base material in order to reduce environmental impact and cost. In some cases, a metal vapor-deposited film on which a film is formed is used.
However, the metal-deposited film has a strong luster that is equal to or greater than the glossy surface of the aluminum foil on both the base material side and the opposite side. Therefore, when a metal vapor deposition film is used instead of an aluminum foil in a laminate using a transparent resin film as an exterior film, printing becomes difficult to recognize due to light reflection.
Therefore, when a metal vapor-deposited film is used for a laminate for packaging, a white ink having a high concealment ratio is often applied to the entire surface of the exterior film to conceal the metallic luster. Therefore, the conventional laminated body using a metal vapor deposition film is insufficient in a high-class feeling compared with the thing using an aluminum foil. In addition, as white ink used for such a use, what contains the titanium oxide which is a white pigment in the density | concentration of about 25-35 mass% in conversion of solid content in white ink is common.

On the other hand, as a method for suppressing the reflection of light rays on the film surface, there is a method of forming irregularities on the film surface. According to this method, since the light is scattered by the unevenness, a unique matte feeling (mat feeling) is obtained.
As a method of forming irregularities on the film surface, for example, there is a method of applying matte ink such as mat varnish. As the matte ink, ink containing silica particles is mainly used. When such matte ink is applied, a layer having irregularities on the surface is formed by the silica particles, and light is scattered by the irregularities, so that a unique matte feeling (mat feeling) is obtained.
In Patent Document 1, a concavo-convex pattern is formed by embossing on the surface of a base film made of a transparent thermoplastic resin, and ink is filled in the concave portion of the concavo-convex pattern, and only the convex portion of the concavo-convex pattern is coated. A decorative film is disclosed in which a coating layer is formed and a pattern printing layer is formed on the surface of the coating layer with an ink using a curable resin as a binder. The decorative film is said to be excellent in texture. In addition, a pattern printing layer is formed on the back surface of the base film, and a transparent layer made of a transparent film is formed so as to cover the pattern printing layer, or a metal deposition film such as a half mirror is attached to the metal deposition. It is said that a complicated pattern can be created by forming a film layer.

Japanese Patent Laid-Open No. 06-087201

However, when matte ink is applied to the exterior film side surface of the laminate, which is a laminate of a transparent exterior film and a metal vapor-deposited film, a matte feel can be obtained, but it is less aesthetic than the matte surface of aluminum foil. . Therefore, when this is used as a packaging material, a high-class feeling will be inferior compared with the case where the laminated body using aluminum foil is used.
In addition, if a matte ink layer is provided on the surface, the ink may be rubbed or peeled off due to friction during the packaging process or in the distribution stage, resulting in poor appearance and difficulty in recognizing display etc. Occurs. The decorative film disclosed in Patent Document 1 has a pattern printed layer on the surface, and therefore, when this is used as a packaging material, the same problem occurs.
Although it is conceivable to provide a matte ink layer between the layers of the laminate, in this case, as described above, the aesthetic appearance is poor, and furthermore, the matte ink layer surface has irregularities, so the exterior film and the sealant layer There also arises a problem that the adhesion between them is hindered.
It is also conceivable to reduce the concealment rate by applying a white ink that has been used in the past with a transfer amount lower than that for the purpose of concealment. However, according to the study of the present inventor, when white ink is applied with a low transfer amount, for example, when the gravure printing plate depth is reduced, white spots are scattered, resulting in poor appearance.

  The present invention has been made in view of the above circumstances, and is a laminate including a metal vapor deposition film in a layer structure, and has an appearance equivalent to the matte surface of an aluminum foil, and also has adhesion between layers. An object is to provide a good laminate.

The present invention for solving the above problems has the following aspects.
[1] A metal vapor deposition film having a substrate and a metal vapor deposition film;
It has a transparent substrate and a printed layer partially formed on one side of the transparent substrate, and is disposed on the metal vapor-deposited film with the surface on the printed layer side facing the metal vapor-deposited film side. An exterior film,
An intermediate layer is interposed between the metal deposited film and the exterior film,
The said intermediate | middle layer is comprised from the transparent resin in which the pigment was disperse | distributed, and contains a titanium oxide by the density | concentration of 5.7-35 mass% as said pigment.
[2] The laminate according to [1], wherein the layer constituting the surface opposite to the exterior film side is a sealant layer.
[3] The laminate according to [1] or [2], which is a packaging material.

  ADVANTAGE OF THE INVENTION According to this invention, it is a laminated body provided with a metal vapor deposition film in a layer structure, Comprising: The laminated body which has the external appearance equivalent to the matte surface of aluminum foil, and favorable adhesiveness between layers can be provided.

It is a schematic sectional drawing which shows one Embodiment of the laminated body of this invention.

<Laminated body>
The laminate of the present invention comprises a metal vapor deposition film having a base material and a metal vapor deposition film,
It has a transparent substrate and a printed layer partially formed on one side of the transparent substrate, and is disposed on the metal vapor-deposited film with the surface on the printed layer side facing the metal vapor-deposited film side. An exterior film,
An intermediate layer is interposed between the metal deposited film and the exterior film,
The intermediate layer is made of a transparent resin in which a pigment is dispersed, and contains titanium oxide at a concentration of 5.7 to 35% by mass as the pigment.

In the laminate of the present invention, the exterior film has a printing layer partially formed on a transparent substrate, and there is a region where the printing layer is not formed, that is, a light-transmitting region that transmits light. The intermediate layer is mainly composed of a transparent resin. Therefore, when the said laminated body is seen from the exterior film side, the metal vapor deposition film of a metal vapor deposition film can be visually recognized from the said translucent area | region.
The metal vapor deposition film has a strong metallic luster equal to or greater than the glossy surface of the aluminum foil. Therefore, when the exterior film and the metal vapor-deposited film are directly laminated, the appearance of the translucent area of the exterior film is a metallic luster that is significantly stronger than the matte surface of aluminum (hereinafter abbreviated as “AL”) foil. It will have something. By providing an intermediate layer in which a specific pigment is dispersed at a specific concentration between the metal vapor-deposited film and the exterior film, the appearance of the translucent region is similar to the appearance of the matte surface of the metal foil.
As described above, the matte surface of the metal foil is reproduced in the translucent region that is the background of the printed layer of the exterior film, so that images such as characters and figures provided as the printed layer can be easily recognized. Moreover, compared with the case where white ink is applied to the entire surface of the exterior film in order to conceal the metal vapor deposition film as in the prior art, it has a high-grade appearance.
Moreover, since the laminated body of this invention uses the metal vapor deposition film instead of AL foil, it is low cost and has little environmental impact. In the case of using the AL foil, the AL foil itself is expensive, and the number of bonding increases at the time of manufacture, which increases the cost.
Moreover, the titanium oxide mix | blended with an intermediate | middle layer does not inhibit the laminate strength between an exterior film and a metal vapor deposition film. Therefore, the laminate of the present invention also has good adhesion between layers.

In the laminate of the present invention, the layer constituting the surface opposite to the exterior film side is preferably a sealant layer. Thereby, the said laminated body becomes what has heat-sealability. In this case, for example, the laminate can be easily processed into a bag shape by superposing the sealant layer side on the inside and heat-sealing the peripheral edge or the like.
As a metal vapor deposition film, when a base material contains a heat-adhesive resin and the metal vapor deposition film is provided on one side, the base material of the metal vapor deposition film functions as a sealant layer.
A sealant layer may be further provided on the side opposite to the exterior film side of the metal vapor-deposited film. In this case, the base material of the metal vapor deposition film may or may not contain a heat-adhesive resin. Moreover, a metal vapor deposition film may be provided only on one side, or may be provided on both sides.
Hereinafter, the laminated body of the present invention will be described with reference to the accompanying drawings and the embodiments. However, the present invention is not limited to the following embodiments.

[First embodiment]
1st embodiment of the laminated body of this invention is described. FIG. 1 is a schematic cross-sectional view of a laminate 1 according to the present embodiment.
The laminate 1 includes a metal vapor deposition film 10 and an exterior film 20.
The metal vapor deposition film 10 includes a base material 11 and a metal vapor deposition film 12 formed on one surface of the base material 11.
The exterior film 20 includes a transparent substrate 21 and a printing layer 22 partially formed on one surface of the transparent substrate 21. The exterior film 20 is disposed on the surface of the metal vapor-deposited film 10 on the side of the AL vapor-deposited film 12 with the surface on the printed layer 22 side facing the metal vapor-deposited film 10 side.
An intermediate layer 30 is provided between the metal vapor deposition film 10 and the exterior film 20.
A sealant layer 40 is provided on the metal vapor deposition film 10 on the side opposite to the intermediate layer 30 side.

(Metal vapor deposition film 10)
As the base material 11 of the metal vapor deposition film 10, a resin film is usually used. As a resin constituting the resin film, polyesters such as polyethylene terephthalate, polyamide, polypropylene, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, Examples include polycarbonate and polyacetal. The resin film may be a single-layer film made of any one or a mixture of two or more of these resins, or may be a multilayer film obtained by multilayer co-extrusion of two or more resins.
The resin film may be an unstretched film or a stretched film. A stretched film is preferable from the viewpoint of difficulty in elongation during heating.
The substrate 11 may be a coat film obtained by coating a resin film with a barrier resin or the like.
The substrate 11 may be a laminated film in which two or more kinds are selected from the resin film and the coat film and laminated by a dry lamination method or the like. The laminated film may be a laminated film of one or more kinds of resin films and one or more kinds of coated films, may be a laminated film of two or more kinds of resin films, or may be composed of two or more kinds of coated films. A laminated film may be used.
The substrate 11 is preferably a biaxially stretched polyester film, a biaxially stretched polyamide film or a biaxially stretched polypropylene film from the viewpoint of heat resistance and versatility.
As a metal which comprises the metal vapor deposition film 12, aluminum, magnesium, etc. are mentioned, for example. Among these, aluminum is preferable from versatility.

The thickness of the metal vapor-deposited film 10 is preferably 9 to 50 μm, and more preferably 12 to 40 μm.
The thickness of the metal vapor-deposited film 12 is preferably 200 to 1000 mm, and more preferably 400 to 800 mm. If the thickness of the metal vapor deposition film 12 is 400 mm or more, the light shielding property and the gas barrier property are good.

(Exterior film 20)
As the transparent base material 21 of the exterior film 20, one having a haze measured by JISK7105 of 0.5 to 10% is preferable.
As the transparent substrate 21, a resin film is preferable. Examples of the resin constituting the resin film include polyesters such as polyethylene terephthalate, polyamide, polypropylene, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polycarbonate, and polyacetal. The resin film may be a single-layer film made of any one or a mixture of two or more of these resins, or may be a multilayer film obtained by multilayer co-extrusion of two or more resins.
The resin film may be an unstretched film or a stretched film. A stretched film is preferable from the viewpoint of difficulty in elongation during heating.
The transparent substrate 21 may be a coat film obtained by coating a resin film with a barrier resin or the like.
The transparent substrate 21 may be a laminated film in which two or more of the resin film and the coat film are selected and laminated by a dry lamination method or the like. The laminated film may be a laminated film of one or more kinds of resin films and one or more kinds of coated films, may be a laminated film of two or more kinds of resin films, or may be composed of two or more kinds of coated films. A laminated film may be used.
The transparent substrate 21 is preferably a biaxially stretched polyester film, a biaxially stretched polyamide film or a biaxially stretched polypropylene film from the viewpoint of heat resistance and versatility.
The thickness of the transparent substrate 21 is preferably 6 to 50 μm, and more preferably 9 to 40 μm.

The printing layer 22 can be formed by applying colored ink so that an image of a desired character, figure, or the like is formed, and drying.
The colored ink is not particularly limited and can be appropriately selected from known ones.
The colored ink usually contains a resin (vehicle), a colorant such as a colored pigment or a dye, and a solvent for dissolving or dispersing the resin and the colorant, and further contains an additive as necessary.
As resins contained in the colored ink, urethane resin, urethane urea resin, acrylic modified urethane resin, acrylic modified urethane urea resin, polyamide, acrylic resin, styrene-acrylic copolymer resin, styrene-maleic acid copolymer resin, ethylene -Acrylic acid copolymer resin, ethylene-vinyl acetate copolymer resin, polyester, shellac, rosin modified maleic acid resin, amine modified urethane resin, maleic acid modified polypropylene, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride- Examples thereof include acrylic acid copolymer resins, chlorinated polypropylene resins, cellulose resins, nitrocellulose resins, hydroxyethyl cellulose resins, hydroxypropyl cellulose resins, and butyral resins. These may be used individually by 1 type and may use 2 or more types together. Among these, urethane resin, urethane urea resin, acrylic resin, chlorinated polypropylene resin, and amine-modified urethane resin are preferable from the viewpoint of versatility and adhesiveness.
Examples of the solvent include water, isopropyl alcohol, methyl ethyl ketone, ethyl acetate, toluene and the like. These may be used alone or in combination of two or more.
Examples of additives include extender pigments, neutralizers, leveling agents, antifoaming agents, waxes, silane coupling agents, rust preventives, preservatives, and plasticizers. These may be used individually by 1 type and may use 2 or more types together.
As the colored ink, it is preferable to use a resin having good adhesion to the transparent substrate 21. For example, when the transparent substrate 21 is a biaxially stretched polyester film or a biaxially stretched polyamide film, one containing a urethane resin is preferable, and when it is a biaxially stretched polypropylene film, it contains a chlorinated polypropylene resin. Those that do are preferred.
In addition, the colored ink is more preferably a water-based ink from the viewpoint of reducing the burden on the environment. In this case, the resin contained in the aqueous ink is preferably aqueous (water-soluble or water-dispersible), and more preferably an aqueous urethane resin or an amine-modified urethane resin.
The colored ink can be applied by a known printing method such as gravure printing.
As a drying method, any of heat drying, vacuum drying, and drying combining these may be used. Heat drying may be either hot air drying or infrared irradiation.
The thickness of the printing layer 22 is preferably 0.1 to 5 μm, and more preferably 0.5 to 3 μm. If the thickness of the printing layer 22 is 0.1 μm or more, it can be sufficiently colored, and if it is 5 μm or less, the printing layer 22 can be easily formed.

(Intermediate layer 30)
The intermediate layer 30 is a layer composed of a transparent resin in which a pigment is dispersed, and contains titanium oxide at a concentration of 5.7 to 35% by mass as the pigment. In addition, this density | concentration is a density | concentration of solid content conversion, and can be calculated | required from the compounding quantity of the component mix | blended with the material used for formation of the intermediate | middle layer 30. FIG.
The transparent resin constituting the intermediate layer 30 includes urethane resin, urethane urea resin, acrylic modified urethane resin, acrylic modified urethane urea resin, polyamide, acrylic resin, styrene-acrylic copolymer resin, and styrene-maleic acid copolymer resin. , Ethylene-acrylic acid copolymer resin, ethylene-vinyl acetate copolymer resin, polyester, shellac, rosin modified maleic acid resin, amine modified urethane resin, maleic acid modified polypropylene, vinyl chloride-vinyl acetate copolymer resin, chloride Examples thereof include vinyl-acrylic acid copolymer resins, chlorinated polypropylene resins, cellulose resins, nitrocellulose resins, hydroxyethyl cellulose resins, hydroxypropyl cellulose resins, butyral resins. These may be used individually by 1 type and may use 2 or more types together.
Among these, urethane resin, urethane urea resin, acrylic resin, chlorinated polypropylene resin, and amine-modified urethane resin are preferable from the viewpoint of versatility and adhesiveness.
In addition, as the transparent resin constituting the intermediate layer 30, it is preferable to use a resin having good adhesion to the transparent substrate 21 in consideration of the material constituting the transparent substrate 21. Further, from the viewpoint of adhesive strength, the resin constituting the intermediate layer 30 and the resin constituting the printing layer 22 are preferably the same.

As titanium oxide, what is marketed as a pigment can be used.
The concentration of titanium oxide in the intermediate layer 30 is preferably 5.7 to 35% by mass, and more preferably 11.6 to 27.5% by mass. If it is 5.7-35 mass%, the external appearance equivalent to the matte surface of AL foil will be obtained. If it is less than 5.7% by mass, the metallic gloss of the metal vapor-deposited film 12 cannot be sufficiently suppressed, and images such as characters and figures on the printed layer 22 are difficult to visually recognize. If it exceeds 35% by mass, it may become too white and no metallic luster may be obtained, or the appearance may be impaired due to the formation of a dark white portion and a thin portion.

The intermediate layer 30 may contain components other than the transparent resin and titanium oxide as long as the effects of the present invention are not impaired.
As the other components, known additives can be used. However, it is preferable not to contain colorants such as colored pigments and dyes other than titanium oxide.
Specific examples of additives include neutralizers, leveling agents, antifoaming agents, waxes, silane coupling agents, rust preventives, preservatives, and plasticizers. These may be used individually by 1 type and may use 2 or more types together.

The thickness of the intermediate layer 30 is preferably 0.1 to 5 μm, and more preferably 0.5 to 2 μm.
Note that the thickness of the intermediate layer 30 indicates the thickness of the thickest portion. That is, the width from the portion of the exterior film 20 where the printed layer 22 is not provided, that is, the surface on the intermediate layer 30 side of the transparent base material 21 to the surface on the intermediate layer 30 side of the metal vapor-deposited film 10 is Is the thickness.

(Sealant layer 40)
The material constituting the sealant layer 40 is not particularly limited, and known materials can be used. For example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polyolefin such as polypropylene, Examples include ionomers, ethylene vinyl acetate copolymers, ethylene acrylic acid copolymers, ethylene copolymers such as ethylene methyl methacrylate copolymers, and the like. These may be used individually by 1 type and may use 2 or more types together.
The sealant layer 40 is usually formed using a resin film composed of any one or more of the above resins. As the resin film, an unstretched film is preferable. If it is an unstretched film, the laminated bodies 1 can be heat-sealed easily.
The thickness of the sealant layer 40 can be determined in consideration of the use of the laminate 1 and the like. For example, when used as a packaging material for packaging food, daily necessities, pharmaceuticals, etc., 10 to 200 μm is preferable, and 20 to 100 μm is more preferable. When the thickness is less than 10 μm, there is a possibility that sufficient sealing strength cannot be obtained when the laminate 1 is formed into a bag-like container by heat sealing.

(Manufacturing method of the laminated body 1)
The laminated body 1 can be manufactured, for example, by a manufacturing method including the following steps (1a) to (1c).
(1a) A step of forming the intermediate layer 30 on the surface of the exterior film 20 on the printed layer 22 side.
(1b) The process of laminating | stacking the surface at the side of the metal vapor deposition film 12 of the metal vapor deposition film 10 on the intermediate | middle layer 30 formed by said (1a).
(1c) The process of laminating | stacking the sealant layer 40 on the surface on the opposite side to the metal vapor deposition film 12 side of the metal vapor deposition film 10.

In the step (1a), the intermediate layer 30 is mixed, for example, with a transparent resin, titanium oxide, an optional additive, and a solvent so that the concentration in terms of solid content of titanium oxide is within a predetermined range. The coating agent can be prepared by coating the coating agent on the surface of the exterior film 20 on the printed layer 22 side and drying.
Any solvent can be used as long as it can dissolve or disperse the transparent resin and disperse titanium oxide. Examples thereof include water, isopropyl alcohol, methyl ethyl ketone, ethyl acetate, and toluene. These may be used alone or in combination of two or more.
The coating agent can be applied by a known coating method such as a gravure coating method, a micro gravure coating method, a roll coating method, a reverse roll coating method, a bar coating method, a kiss coating method, or a flow coating method.
As a drying method, any of heat drying, vacuum drying, and a combination of these may be used. Heat drying may be either hot air drying or infrared irradiation.

As a method for laminating the metal vapor-deposited film 10 in the step (1b), a known laminating method can be used, and examples thereof include a laminating method by a dry laminating method, an extrusion laminating method, a non-solvent laminating method, or a combination thereof.
Among these, the dry laminating method is preferable in terms of versatility and adhesive strength.
Examples of the adhesive used for dry lamination (hereinafter referred to as an adhesive for dry lamination) include urethane, acrylic, and epoxy. Among these, urethane is preferable from the viewpoint of versatility.
The application thickness of the adhesive is preferably 0.5 to 5 μm, and more preferably 1 to 3 μm.
As a method of laminating the sealant layer 40 in the step (1c), a known laminating method can be used. For example, the same method as the method exemplified in the step (1b) can be mentioned.
In addition, when the metal vapor deposition film 10 is laminated | stacked using an adhesive agent at a process (1b), between the intermediate | middle layer 30 of the obtained laminated body 1 and the metal vapor deposition film 10, the contact bonding layer which is not illustrated intervenes. . Similarly, when the sealant layer 40 is laminated using an adhesive in the step (1c), an adhesive layer (not shown) is interposed between the metal vapor-deposited film 10 and the sealant layer 40 of the obtained laminate 1. .

Moreover, the manufacturing method containing the following processes (2a)-(2c) as another manufacturing method of the laminated body 1 is mentioned.
(2a) A step of forming the intermediate layer 30 on the surface of the metal vapor deposition film 10 on the metal vapor deposition film 12 side.
(2b) The process of laminating | stacking the surface by the side of the printing layer 22 of the exterior film 20 on the intermediate | middle layer 30 formed by said (2a).
(2c) The process of laminating | stacking a sealant layer on the surface on the opposite side to the metal vapor deposition film 12 side of the metal vapor deposition film 10.

The step (2a) can be performed in the same manner as in the step (1a) except that the coating agent is applied to the surface of the metal vapor deposition film 10 on the metal vapor deposition film 12 side.
The step (2b) can be performed in the same manner as the step (1b) except that the exterior film 20 is used instead of the metal vapor deposition film 10.
Step (2c) can be carried out in the same manner as in step (1c).

As mentioned above, although the example of an embodiment was shown and explained, the layered product of the present invention is not limited to the above-mentioned embodiment.
For example, when the resin constituting the base material 11 of the metal vapor-deposited film 10 is the same as the resin listed as the material constituting the sealant layer 40, the base material 11 functions as the sealant layer. It does not have to be.
Moreover, you may arrange | position the metal vapor deposition film 10 so that the surface on the opposite side to the metal vapor deposition film 12 side may face the exterior film 20 side. In this case, however, a transparent substrate is used as the substrate 11. Examples of the transparent substrate include those similar to the transparent substrate 21.

The use of the laminate of the present invention is not particularly limited, and examples thereof include packaging materials and industrial materials. Among them, it is useful as a packaging material because the matte appearance of the AL foil is preferred.
It does not specifically limit as a usage method of the packaging material which consists of a laminated body of this invention. For example, when the surface opposite to the exterior film side is a sealant layer, it can be used as a bag-like container such as a stick-shaped bag, a three-sided bag, or a four-sided bag, or a lid for the container by heat sealing.
The contents when used as a packaging material are not particularly limited, but are packaged in the field of light packaging that does not require a barrier property as high as AL foil, such as snacks and other confectionery, cereals, tea leaves, Examples include food such as pet food, toiletry products, stationery, daily necessaries such as car supplies, and secondary packaging of pharmaceuticals such as PTP packaging.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.
The materials used for preparing the coating agent in the following examples are shown below.

<Example 1>
Colored ink (N800LPGT manufactured by Toyo Ink Mfg. Co., Ltd.) is applied to a part of one side of a 20 μm thick biaxially oriented polypropylene (OPP) film with a gravure coater and dried with hot air for about 1 second at 80 ° C. An exterior film was produced by forming a 1 μm printed layer.
Next, the material A and the material B1 were mixed at a mass ratio of 93: 7 to prepare a coating agent. The coating agent was scooped with Zahn cup # 3 so that the cup was full, and the viscosity was adjusted. The viscosity was adjusted by adding the solvent so that the time from when the coating agent started to flow from the bottom of the cup to when all the coating agent in the cup flowed was about 15 seconds.
The coating agent whose viscosity was adjusted was applied onto the printed layer of the exterior film by a gravure coater and dried with hot air at 80 ° C. for about 1 second to form an intermediate layer to obtain an exterior film with an intermediate layer.
Next, a 12 μm thick AL vapor deposition film having an AL vapor deposition layer on one side of a biaxially stretched polyethylene terephthalate (PET) film, and an urethane dry laminate adhesive on the intermediate layer of the outer film with the intermediate layer. And bonded together. Thereafter, an unstretched polypropylene (CPP) film having a thickness of 30 μm as a sealant layer was bonded to the AL vapor-deposited film using an adhesive for urethane-based dry lamination to obtain a target laminate.
The following evaluation was performed about the obtained laminated body.

[1. appearance]
A control sample was prepared by bonding the matte surface of the AL foil onto the printed layer of the exterior film produced in the same manner as in Example 1 using an urethane dry laminate adhesive.
Each of the laminate and the control sample obtained above was visually observed from the exterior film side, and the appearance of the laminate was evaluated according to the following criteria.
(Evaluation criteria)
◯: Matte feeling was imparted evenly, and the matte surface appearance was the same as that of the control sample.
(Triangle | delta): Although a mat feeling is provided, compared with a control sample, there is some unevenness.
X: Matte feeling is not given. Or, a matte feeling is given, but there is a noticeable unevenness.

[2. Adhesion]
An evaluation sample was prepared by cutting a part of the outer-layer-equipped outer film produced when producing the laminate as described above to A4 size. The tape peeling test described below was performed on this evaluation sample.
(Tape peeling test)
The adhesion between the ink and the substrate was evaluated according to the following procedure using a commercially available cellophane tape (“Cellophane adhesive tape for packaging No. 405”, 18 mm width, manufactured by Nichiban Co., Ltd.).
A 10 cm cellophane tape is affixed to the image area on the ink surface. Next, the pasted cellophane tape is picked with fingers and peeled by 90 °. At this time, if the ink was not transferred onto the cellophane tape surface, it was determined as “pass”.
From the above measurement results, the adhesion of the intermediate layer to the exterior film was evaluated according to the following criteria.
(Evaluation criteria)
○: Ink does not transfer to the cellophane tape surface.
X: Ink is transferred to the surface of the cellophane tape.

[3. Lightness (L *)]
A spectrocolorimeter (SpectroEye manufactured by Gretagmacbeth) was used as an index of the metallic gloss level, and L * (lightness) in the CIE L * a * b * color system was measured from the exterior film side of the laminate. The measurement was performed at a portion where the printed layer was not formed.
In the present invention, the lightness (L *) is preferably 72 to 94, and more preferably 74 to 92. When the brightness (L *) is 72 or more and 94 or less, the appearance is close to the AL matte surface. In particular, when it is 74 or more and 92 or less, it becomes an appearance that almost reproduces the AL matte surface.

<Example 2>
A laminate was obtained in the same manner as in Example 1 except that the coating agent for forming the intermediate layer was prepared by mixing the material A and the material B1 at a mass ratio of 80:20.
About the obtained laminated body, evaluation similar to Example 1 was performed.

<Example 3>
A laminate was obtained in the same manner as in Example 1 except that the coating agent for forming the intermediate layer was a mixture of the material A and the material B1 at a mass ratio of 75:25.
About the obtained laminated body, evaluation similar to Example 1 was performed.

<Example 4>
A laminate was obtained in the same manner as in Example 1 except that the coating agent for forming the intermediate layer was a mixture of the material A and the material B1 at a mass ratio of 96.5: 3.5.
About the obtained laminated body, evaluation similar to Example 3 was performed.

<Comparative Example 1>
A laminate was obtained in the same manner as in Example 1 except that the coating agent for forming the intermediate layer was a mixture of the material A and the material B1 at a mass ratio of 98.5: 1.5.
About the obtained laminated body, evaluation similar to Example 1 was performed.

<Comparative example 2>
A laminate was obtained in the same manner as in Example 1 except that the coating agent for forming the intermediate layer was a mixture of the material A and the material B1 at a mass ratio of 50:50.
About the obtained laminated body, evaluation similar to Example 1 was performed.

<Comparative Example 3>
A laminate was obtained in the same manner as in Example 1 except that the coating agent for forming the intermediate layer was prepared by mixing the material A and the material B2 at a mass ratio of 50:50.
About the obtained laminated body, evaluation similar to Example 1 was performed.

<Comparative example 4>
A laminate was obtained in the same manner as in Example 1 except that the material C was used as the coating agent for forming the intermediate layer.
About the obtained laminated body, evaluation similar to Example 1 was performed.

Examples 1-4, the layer structure of the laminates obtained in Comparative Examples 1-4, the coating agent used to form the intermediate layer, the compounding ratio (mass ratio) of the materials used to prepare the coating agent, the intermediate layer Table 2 shows the evaluation results of thickness, type of pigment used, pigment concentration in terms of solid content in the intermediate layer, appearance, adhesion, and lightness (L *).
In addition, when the AL foil is directly laminated on the transparent base material (OPP) with the matte surface facing the transparent base material side, the AL foil is laminated directly with the gloss surface facing the transparent base material side In order to show the brightness when the AL vapor deposition film was directly laminated, three types of laminates having the layer configuration shown in Table 3 were prepared as Reference Examples 1 to 3, and the above-mentioned from the transparent substrate (OPP) side. The lightness (L *) was measured by the same procedure. The results are shown in Table 3.
In the layer configuration shown in Tables 2-3, DL indicates an adhesive layer formed using an adhesive for dry lamination.

As shown in the above results, the laminates of Examples 1 to 4 had a matte surface appearance of AL foil. Moreover, the adhesiveness between layers was also favorable.
On the other hand, the laminate of Comparative Example 1 in which titanium oxide was blended in the intermediate layer at a concentration of 2.5% was too strong in metallic luster and the matte appearance of the AL foil was not obtained.
The laminate of Comparative Example 2 in which titanium oxide was blended in the intermediate layer at a concentration of 54% had a white appearance.
The laminated body of Comparative Example 3 in which precipitated barium sulfate was blended at a concentration of 42% in the intermediate layer had almost the same whiteness as that of Example 1 in the state of the exterior film with the intermediate layer, but the AL vapor deposited film was laminated. In this state, the metallic luster was too strong, and the matte surface appearance of the AL foil was not obtained. This is thought to be due to the fact that the pigment itself, which is precipitated barium sulfate, has less hiding properties than titanium oxide.
The laminate of Comparative Example 4 in which the intermediate layer was formed using the material C, which is a mat varnish, had a matte feeling but was visually uneven and was inferior in aesthetics compared to the matte surface of the AL foil. . Furthermore, the adhesion of the intermediate layer to the exterior film was poor.

DESCRIPTION OF SYMBOLS 1 Laminated body 10 Metal vapor deposition film 11 Base material 12 Metal vapor deposition film 20 Exterior film 21 Transparent base material 22 Print layer 30 Intermediate layer 40 Sealant layer

Claims (3)

A metal vapor deposition film having a substrate and a metal vapor deposition film;
It has a transparent substrate and a printed layer partially formed on one side of the transparent substrate, and is disposed on the metal vapor-deposited film with the surface on the printed layer side facing the metal vapor-deposited film side. An exterior film,
An intermediate layer is interposed between the metal deposited film and the exterior film,
The said intermediate | middle layer is comprised from the transparent resin in which the pigment was disperse | distributed, and contains a titanium oxide by the density | concentration of 5.7-35 mass% as said pigment.   The laminated body of Claim 1 whose layer which comprises the surface on the opposite side to the said exterior film side is a sealant layer.   The laminate according to claim 1 or 2, which is a packaging material.

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