JP2021130208A - Aluminum vapor deposition film and laminate using the same - Google Patents

Abstract

To provide an aluminum vapor deposition film which can be firmly bonded to a plastic film through an olefin resin layer which is an adhesive resin by extrusion lamination without performing anchor coating treatment with respect to the aluminum vapor deposition film.SOLUTION: An aluminum vapor deposition film is provided in which a vapor deposition layer whose composition changes continuously from a metal aluminum layer to an aluminum oxide layer is laminated on at least one surface of a base material film surface through an anchor metal vapor deposition layer, and in which an orientation index X of (200) plane of the vapor deposition layer defined by formula (1) is 1 to 20%: X=[I200/(I111+I200)]×100(%) (1) (I111: integrated intensity of (111) plane measured by an X-ray diffraction method, I200: integrated intensity of (200) plane measured by the X-ray diffraction method).SELECTED DRAWING: None

Description

The present invention relates to an aluminum-deposited film and a laminate in which an aluminum-deposited film and a plastic film are bonded by an extrusion laminating method.

Thin-film deposition films with various thin films such as metals and metal oxides formed on the surface of plastic films are used for packaging foods, pharmaceuticals, industrial products, etc., for decoration of electrical appliances, electronic equipment materials, building materials, etc. Widely used in applications. In particular, metallized film made by the vacuum deposition method is widely used for packaging because it has excellent gas barrier performance, light blocking performance, decorativeness, etc., and has the best balance in manufacturing cost, productivity, and gas barrier performance. Aluminum vapor deposition film is widely used.

When an aluminum vapor-deposited film is used for packaging, it is used as a laminate with a surface layer material or a sealant film. As a processing method for the film laminate, an extrusion lamination method using a molten adhesive resin, a two-component curable urethane system A dry laminating method using an adhesive or the like is widely used. Of these, the extrusion laminating method, which is advantageous in terms of manufacturing cost and productivity, is preferably used, but in the extrusion laminating method, the adhesion between the aluminum vapor deposition layer and the adhesive resin is important.

By the way, as a method of heating a material in a vacuum vapor deposition method, there are a crucible heating method by electron beam heating and induction heating, and a resistance heating method by a boat. Of these, the crucible heating method using electron beam heating or induction heating requires replenishment of the evaporative material in the crucible when the evaporative material is insufficient, and the inside of the vapor deposition tank is opened to the atmosphere each time the evaporative material is replenished. Must be vacuumed again. On the other hand, in the resistance heating method, the wire-shaped evaporation material can be continuously provided to the heating source from inside and outside the vacuum chamber, and the vapor deposition can be performed for a long time while keeping the vapor deposition tank in a high vacuum state. Further, since the heat load due to the heating source is smaller than that of the crucible heating method, it is a vacuum deposition method that can achieve a high film formation rate.

However, the thin-film deposition film formed by the resistance heating method at a high film formation rate seems to have different properties (crystal orientation, crystal size, etc.) from the thin-film deposition film formed by the pot heating method. The adhesion between the aluminum vapor deposition layer and the adhesive resin, which is the above-mentioned problem, tends to be low. In the portion where the adhesion is low, the aluminum vapor deposition layer reacts with the moisture in the atmosphere to form a hydroxide, so that the metallic luster is lost and the gas barrier performance is deteriorated in the laminated body laminated by the extrusion lamination method. was there.

Therefore, by further providing a two-component curing type water-resistant coating layer on the surface of the aluminum-deposited layer of the aluminum-deposited film, it is possible to secure adhesion and prevent the aluminum from changing to hydroxide (Patent Document). 1).

Further, when the aluminum vapor-deposited film and the plastic film are bonded together by the extrusion laminating method, a method of raising the heating and melting temperature of the extruded resin layer to a high temperature or an anchor coat layer is provided between the aluminum vapor-deposited layer and the extruded adhesive resin layer. The method (Patent Document 2) and the adhesive resin have been devised (Patent Document 3).

Japanese Unexamined Patent Publication No. 2001-162711 Japanese Unexamined Patent Publication No. 2013-126719 Japanese Unexamined Patent Publication No. 2015-128894

However, the technique of Patent Document 1 has a problem that it leads to an increase in cost and a decrease in productivity.

Further, in the techniques of Patent Documents 2 and 3, by raising the heating and melting temperature of the extruded resin layer to a high temperature, the aluminum vapor-deposited film is thermally shrunk, cracks are generated in the aluminum layer, and the gas barrier performance and the metallic luster are deteriorated. There is a problem that the base film of the aluminum-deposited film and the aluminum-deposited layer are peeled off, and the adhesion between the base film of the aluminum-deposited film and the aluminum-deposited layer is lowered. Attempting to provide an anchor coat layer leads to an increase in cost, and the isocyanate-based curing agent contained in the anchor coating agent reacts with the additive of the resin layer extruded without the curing reaction, and sufficient adhesion is obtained. There is a problem that cannot be done.

An object of the present invention is to solve these problems, and even if the aluminum vapor-deposited film is not subjected to an anchor coating treatment, the plastic is formed through an olefin resin layer which is an adhesive resin by extrusion laminating. It is an object of the present invention to provide an aluminum vapor-deposited film that can be firmly bonded to a film, and a laminate in which an aluminum vapor-deposited surface and a plastic film are firmly bonded by an olefin resin layer.

In order to achieve the above object, the present invention has the following configuration.

That is, in the present invention, a thin-film deposition layer whose composition changes continuously from the metal-aluminum layer to the aluminum oxide layer is laminated on at least one surface of the base film surface via an anchor metal vapor-deposited layer, and is defined by the formula (1). It is an aluminum vapor deposition film in which the orientation index X of the (200) plane of the vapor deposition layer is 1 to 20%.

X = [I200 / (I111 + I200)] × 100 (%) ... (1)
(I111: Integrated intensity of the (111) plane measured by the X-ray diffraction method, I200: Integrated intensity of the (200) plane measured by the X-ray diffraction method).

Further, the metal of the anchor metal vapor deposition layer is copper, and it is preferable that the ^{amount of copper adhered is 30 to 120 ng / cm 2.}

The thickness of the aluminum oxide layer is preferably 4 to 15 nm.

Further, it is preferable that the pure water contact angle on the surface of the vapor-deposited layer is less than 10 °.

Further, the present invention is a laminate in which a plastic film is bonded to the vapor-deposited layer side of the aluminum vapor-deposited film described above via a polyolefin resin layer, and the adhesion strength thereof is 1N / 15 mm or more.

According to the present invention, the aluminum vapor-deposited film and the aluminum-deposited surface and the plastic film can be firmly bonded to the plastic film via the olefin resin layer by extrusion laminating processing. A laminate is obtained.

The present invention will be described in detail below.

The aluminum-deposited film of the present invention is obtained by laminating a vapor-deposited layer whose composition continuously changes from a metallic aluminum layer to an aluminum oxide layer on at least one surface of a base film surface via an anchor metal vapor-deposited layer.

As described in the background technology, the thin-film deposition film formed by the resistance heating method at a high film formation rate has different properties (crystal orientation, There is a problem with the adhesion between the aluminum vapor deposition layer and the adhesive resin due to crystal size, etc.), but by providing a vapor deposition layer that continuously changes the composition from the metallic aluminum layer to the aluminum oxide layer, a high film formation rate can be achieved. While maintaining, the adhesion between the aluminum vapor deposition layer and the adhesive resin can be maintained.

The base plastic film used for the aluminum vapor deposition film is not particularly limited as long as it has vapor deposition processing suitability, but typical examples are polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and polybutylene 2,6-naphthalate. Polyester, polyvinyl alcohol, ethylene / vinyl acetate copolymer saponified product, polystyrene, polycarbonate, polyethylene, polyolefin such as polypropylene, polyamide such as 6 nylon and 12 nylon, aromatic polyamide, homopolymer such as polyimide or co-weight Examples include films and sheets made of coalesced materials. The base plastic film used for the aluminum vapor deposition film of the present invention is excellent in vapor deposition processing suitability, dimensional stability, and heat resistance, and a biaxially stretched polyethylene terephthalate film is preferably used from the viewpoint of economy.

The surface of these base plastic films may be subjected to surface modification treatment such as corona treatment, flame treatment, plasma treatment, and anchor coating. Further, the thickness of these plastic films is selected in the range of 6 to 50 μm from the viewpoint of vapor deposition processability and economy according to the purpose, and the range of 8 to 38 μm is preferable from the viewpoint of processability as a packaging material. , 9-18 μm is more preferred.

The aluminum vapor-deposited film in the present invention is obtained by laminating a vapor-deposited layer whose composition continuously changes from a metallic aluminum layer to an aluminum oxide layer on a base plastic film via an anchor metal vapor-deposited layer. The method for forming the anchor metal vapor deposition layer on the base plastic film is not particularly limited, but a certain amount can be stably formed by a sputtering method targeting a specific metal. preferable. Among them, the planar magnetron type sputtering method is more preferable from the viewpoint of discharge stability because it is easy to input a large amount of power.

The metal of the anchor metal vapor deposition layer in the present invention is selected from magnesium, silicon, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, palladium, silver, tin, tantalum, tungsten and the like. However, copper is preferable because of its economy and ease of vapor deposition by the above-mentioned sputtering.

When the metal of the anchor metal vapor deposition layer is copper, the amount of adhesion thereof is preferably in the range of 30 to ^{120 ng / cm 2.} If it is less than 30 ng / cm ^2, the adhesion strength between the base plastic film and the metallic aluminum layer may be insufficient. Further, even if it exceeds 120 ng / cm ² , the effect reaches a plateau and the plasma intensity for sputtering is strong, so that the base plastic film may be deteriorated or the reddish appearance due to copper may become a problem. From an economic point of view, a more preferable amount of adhesion is in the range of ^{40 to 90 ng / cm 2.} In the planar magnetron type sputtering, the amount of the anchor metal vapor deposition layer adhered can be controlled by the discharge voltage, the discharge pressure and the film transport speed.

The thin-film deposition layer in the present invention has a different surface orientation from that of the thin-film deposition layer formed by the crucible heating method by electron beam heating or induction heating, especially when the film formation rate is high when the film is formed by the resistance heating method. Become. That is, in the present invention, when the integrated intensities of the (111) plane and the (200) plane of the aluminum vapor deposition layer in the X-ray diffraction measurement are I111 and I200, respectively, the vapor deposition layer defined by the following formula (1) It is important that the orientation index X of the (200) plane is 1 to 20%.

X = [I200 / (I111 + I200)] × 100 (%) ... (1).

X is controlled by the film formation rate of the aluminum vapor deposition layer. That is, the faster the film formation rate, the larger the film formation rate, and the lower the film formation rate, the smaller the film formation rate. In the crucible heating method using electron beam heating or induction heating, the film formation rate is low, so it is less than 1%, and even in the resistance heating method, if the film formation rate is reduced, it is less than 1%, so sufficient productivity cannot be obtained.

If X exceeds 20%, the adhesion is insufficient even if a thin-film deposition layer whose composition changes continuously from the metallic aluminum layer to the aluminum oxide layer is provided. In addition, in order to exceed 20%, the film formation rate must be increased, but as a result, the base film loses heat, aluminum abnormally evaporates, and pinholes occur, resulting in appearance. It becomes a problem.

As a method for producing a thin-film deposition layer in which the composition changes continuously from the metallic aluminum layer to the aluminum oxide layer, a method in which a thin-film deposition layer in which the composition changes continuously from the metallic aluminum layer to the aluminum oxide layer is formed in a vacuum chamber is preferable. That is, the base film is generally long, supplied in roll form, unwound from the roll in a vacuum chamber, vapor-deposited, and wound again in roll form, which is common in the early stages of vapor deposition. A metallic aluminum layer is formed, oxygen is introduced in the latter half of the vapor deposition, and aluminum oxide is formed by the reaction of metallic aluminum and oxygen. Since the oxygen introduced in the latter half of the vapor deposition diffuses from the winding side to the unwinding side of the base film, the metallic aluminum layer and the aluminum oxide layer are not formed as being strictly separated, but as a base material. The reaction of oxygen continuously proceeds from the metallic aluminum layer to the aluminum oxide layer according to the position of the vapor deposition zone through which the film passes, forming an inclined structure in which the composition continuously changes in the film thickness direction. The thickness of the aluminum oxide layer can be controlled by the film transport rate, the aluminum deposition rate, and the amount of oxygen supplied.

Generally, a natural oxide film having a thickness of about 3 nm is formed on the surface of a metallic aluminum layer formed by thin-film deposition on a base plastic film due to oxygen in the atmosphere or the like. It is necessary to form aluminum oxide layers by a reactive vapor deposition method such as Therefore, stable adhesion can be obtained.

The thickness of the aluminum oxide layer and the metallic aluminum layer is the composition distribution (so-called depth profile) of aluminum and oxygen obtained by X-ray photoelectron spectroscopy or Auger electron spectroscopy at the sputtering depth and the vapor deposition thickness in a transmission electron microscope. It can be calculated from the correlation with the measurement, and the thickness of the aluminum oxide layer is preferably in the range of 5 to 15 nm, and more preferably in the range of 6 to 12 nm from the viewpoint of vapor deposition processing suitability and economy. If the thickness of the aluminum oxide layer is less than 5 nm, the adhesion to the adhesive resin by the extrusion lamination may be insufficient. If the thickness of the aluminum oxide layer exceeds 15 nm, the layer in which metallic aluminum and aluminum oxide are mixed becomes thick, the color tone becomes brown, and the metallic luster may be insufficient.

The thickness of the metallic aluminum layer is preferably in the range of 20 to 50 nm, and more preferably in the range of 25 to 45 nm from the viewpoint of vapor deposition processing suitability and economy. If it is less than 20 nm, the light blocking property and metallic luster may be insufficient, and even if it exceeds 50 nm, the characteristics do not improve, and the heat load during the vapor deposition process increases, causing problems such as heat loss of the base film. May occur.

Further, by forming the aluminum oxide layer, the wettability of the vapor-deposited surface of the aluminum-deposited film is improved. The pure water contact angle of the aluminum-deposited surface measured in accordance with JIS R3257 (1997) is preferably 10 ° or less.

In the present invention, the plastic film laminated with the vapor-deposited surface of the aluminum vapor-deposited film is not particularly limited, and typical examples are polyester and polyethylene such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and polybutylene 2,6-naphthalate. , A film made of polyolefin such as polypropylene.

These films are printed as needed, and the printed surface is laminated with the vapor-deposited surface of the aluminum-deposited film. In this case, an unstretched polypropylene film, a linear low-density polyethylene film, or the like is laminated as a sealant film on the base plastic film side of the aluminum-deposited film. Further, in the aluminum-deposited film laminate of the present invention, an unstretched polypropylene film, a linear low-density polyethylene film, or the like may be laminated with the vapor-deposited surface of the aluminum-deposited film as the innermost sealant film. In this case, it is used by directly printing on the base plastic film side of the aluminum vapor-deposited film or by laminating another printed plastic film.

The adhesive resin used for the extrusion laminating process is not particularly limited as long as it adheres to both the vapor-deposited surface of the aluminum vapor-deposited film and the laminated plastic film and can be firmly bonded, and has adhesion, appearance, and economy. Although it depends on the sex, olefin resins such as polyethylene, polypropylene, ethylene / methacrylic acid copolymer, ethylene / vinyl acetate copolymer, and maleic acid-modified polyolefin resin are used. In the present invention, polyethylene with less decomposition of the acid component and less damage to the aluminum vapor deposition layer is more preferably used. The conditions for extrusion laminating may be general extrusion laminating conditions, and ozone treatment and corona treatment may be performed as necessary. In the present invention, strong bonding can be achieved without performing anchor coating treatment, but it is not excluded that anchor coating treatment is performed for the purpose of stronger bonding.

In the aluminum-deposited film laminate of the present invention, the adhesion strength between the vapor-deposited layer and the adhesive resin layer is preferably 1N / 15 mm or more. If the adhesion strength is less than 1N / 15 mm, peeling is likely to occur during use, which may limit the application and the composition of the laminate. It is preferably 1.1 N / 15 mm or more.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not necessarily limited thereto. The physical properties in Examples and Comparative Examples were measured as follows.

(1) Aluminum vapor deposition layer (200) plane orientation index For the plane orientation of the aluminum vapor deposition layer, the integrated strength of the (111) plane and the (200) plane is measured by a horizontal X-ray diffractometer (Rigaku SMARTLAB 3FD). Asked by doing.

The integrated intensity was detected by irradiating an arbitrary portion of one aluminum vapor-deposited film with measured X-rays (wavelength 0.15418 nm (CuKα)), the horizontal axis is the Bragg diffraction angle 2θ (deg), and the vertical axis is the diffraction intensity. It was calculated from the X-ray diffraction pattern of (cps). Using the acquired Bragg diffraction angle 2θ (deg) and numerical data obtained by subtracting the baseline component (cps) from the diffraction intensity (cps), the integrated intensity was obtained as the area of each peak by numerical analysis software. At this time, the Bragg diffraction angle region, which is 10% or more of the peak intensity after subtracting the baseline component, was calculated, and the obtained value was multiplied by (100/90) to obtain the integrated intensity (cps · deg). When another peak overlapped with the target peak in the diffraction pattern, the peak was divided by the dedicated software and the numerical value of the target peak was used.

Here, the diffraction of the (111) plane was observed at a Bragg angle of about 38.4 °, and the diffraction of the (200) plane was observed at a Bragg angle of about 44.3 °. When the integrated intensities of the observed planes (111) and (200) are I111 and I200, respectively, the orientation index X (%) of the plane (200) represented by the following formula was obtained.

X = [I200 / (I111 + I200)] × 100 (%).

(2) Pure water contact angle on the aluminum vapor deposition surface The pure water contact angle on the aluminum vapor deposition surface is 0.4 μL of pure water at room temperature using a contact angle meter CA-X manufactured by Kyowa Interface Science Co., Ltd., and aluminum vapor deposition. It was dropped on the surface, and the contact angle (°) 3 seconds after the dropping was determined.

(3) Copper adhesion amount (ng / cm ² )
A sample cut into 10 cm squares was prepared from an aluminum vapor deposition film, and after immersing this sample in 20 ml of nitrate for 24 hours, the absorbance of copper (wavelength 324.8 nm) of the obtained solution was measured by an atomic absorption spectrophotometer (Co., Ltd.). ) AA-6300 type manufactured by Shimadzu Corporation) was used to measure, and the amount of copper adhered was calculated using a standard sample with a known dissolved amount (concentration) of copper as a calibration curve. These calculations were performed using four different cut samples, and the average value of the obtained values was taken as the copper adhesion amount (ng / cm ² ).

(4) Thickness of thin-film deposition layer After sampling the thin-film aluminum film by the micro-sampling method, a focused ion beam processing device (FB-2000 manufactured by Hitachi, Ltd.) is used to scan the cross section of the thin-film aluminum film in the thickness direction. After being exposed by the beam, the cross-section of the thin-film aluminum vapor deposition layer was observed on the exposed cross section with an electric field emission type transmission electron microscope (HF-2200 manufactured by Hitachi, Ltd., hereinafter referred to as TEM). The thickness of the aluminum-deposited layer was determined as the arithmetic mean of the thicknesses obtained at two points in the thickness direction in the cross-sectional observation.

(5) Thickness of Metal Aluminum Layer and Aluminum Oxide Layer Film Using a fully automatic scanning X-ray photoelectron spectroscopy analyzer (Quantera SXM manufactured by Physical Electricals), X-ray source AlKα, X-ray output 25.1 W, photoelectron extraction Surface analysis was performed at an angle of 45 °. From the vapor deposition surface side of the aluminum vapor deposition film, sputtering is performed with Ar ion energy of 1 keV using Ar ions, and narrow-range photoelectron spectra of carbon, oxygen, and aluminum elements are measured at regular sputtering times, and C1s, O1s, and Al2p are measured. The composition ratio of each element was calculated from the narrow region photoelectron peak area intensity ratio and the relative sensitivity coefficient, and the composition distribution in the depth direction was obtained based on the following method.

First, paying attention to the carbon concentration on the base plastic film side, the sputter time corresponding to the intermediate (1/2) concentration of the peak concentration of the carbon concentration is regarded as the spatter time reaching the interface between the vapor deposition layer and the base plastic film. bottom. The signal derived from the anchor metal layer at the interface was small and ignored. The thickness of the total vapor-deposited layer obtained by TEM observation in item (4) was related to the sputtering time corresponding to the interface, and the sputtering depth corresponding to the sputtering time was calculated.

Next, paying attention to the oxygen concentration in the aluminum oxide layer, the sputter depth calculated from the sputter time corresponding to the intermediate (1/2) concentration of the peak oxygen concentration is regarded as the interface between the aluminum oxide layer and the metallic aluminum layer. I did it.

As a result of the above analysis, when it is confirmed that an aluminum oxide layer of about 3 nm is formed on the surface of the metallic aluminum layer, natural oxidation due to oxidation after the metallic aluminum layer is taken out into the atmosphere. It was judged to be due to the membrane.

(6) Appearance (metallic luster)
The appearance was visually inspected to confirm the metallic luster. Those with a bright metallic luster were evaluated as acceptable (○), those with a slightly brownish and dull metallic luster that could not be used practically were evaluated as (Δ), and those without metallic luster were evaluated as (×).

(7) Laminate strength A cut sample cut into a width of 15 mm and a length of 150 mm was prepared from the laminate by extrusion lamination described in the following item (8), and "Tencilon" (RTG-1210) manufactured by Orientec Co., Ltd. The aluminum vapor-deposited film and the biaxially stretched polypropylene film were peeled off by a T-type peeling method at a tensile speed of 300 mm / min, and the laminate strength was measured.

(8) Extrusion Laminating An aluminum vapor deposition film is set on the first paper feed side of the extrusion laminating machine, and a biaxially stretched polypropylene film with a thickness of 20 μm is set on the second paper feed side. ) "Sumikasen" (registered trademark) L420) is extruded between the vapor deposition layer side of the aluminum vapor deposition film and the biaxially stretched polypropylene film so as to have a thickness of 8 μm at a resin temperature of 300 ° C., and sandwiched between these two films by a nip roll. They were joined to create a laminate.

(Example 1)
A roll-to-roll using a biaxially stretched polyethylene terephthalate film ("Lumilar (registered trademark)" P60 manufactured by Toray Co., Ltd.) having a thickness of 12 μm, a width of 2 m, and a length of 60,000 m is used as the base film of the aluminum vapor-deposited film. -Using a roll vacuum vapor deposition machine, a planar magnetron type discharge electrode targeting copper is installed between the film feeding section and the vapor deposition section, and a voltage supplied by a high-frequency power supply (frequency 60 kHz) is applied to generate plasma. A copper vapor deposition layer of 80 ng / cm ^{2 was formed on the film.} Furthermore, the metal aluminum wire is continuously supplied to the boat heated by the resistance heating method to evaporate it, and the film transfer speed is 480 m / min, and the metal aluminum layer thickness is 35 nm and the aluminum oxide layer thickness is 10 nm. Formed. On the base film, on a cooled rotating drum, films having a composition corresponding to the position of the base film in the traveling direction are sequentially formed in the thickness direction, and oxygen is supplied from the position where the vapor deposition is last received. , A thin-film deposition layer was formed that continuously changed from a metallic aluminum layer to an aluminum oxide layer. The plane orientation index X was 12.4%.

(Example 2)
In Example 1, the evaporation rate of the aluminum wire was reduced to a film transfer rate of 360 m / min and a plane orientation index of 4.2%. An aluminum-deposited film was obtained by adjusting the thickness of the metallic aluminum layer and the aluminum oxide layer to be close to those of Example 1.

(Example 3)
An aluminum-deposited film was obtained in the same manner as in Example 1 except that the amount of oxygen supplied was reduced so that the thickness of the aluminum oxide layer was 6 nm.

(Example 4)
In Example 1, the supply speed of the aluminum wire was reduced, the film transport speed was 420 m / min, and the plane orientation index was 8.5%. The oxygen supply amount was adjusted so that the film thickness of the aluminum oxide layer was 14 nm, and an aluminum-deposited film was obtained.

(Example 5)
Similar to Example 1, the metallic aluminum layer and the aluminum oxide layer were continuously vapor-deposited to obtain an aluminum-deposited film, except that a ^{45 ng / cm 2} copper-deposited layer was formed on the PET film in Example 1. rice field.

(Comparative Example 1)
In Example 1, only the metallic aluminum layer was deposited without supplying oxygen. As the aluminum oxide layer on the surface of the vapor-deposited layer, only a natural oxide film having a thickness of 3 nm was observed.

(Comparative Example 2)
In Example 1, a thin-film deposition layer that continuously changes from a metallic aluminum layer to an aluminum oxide layer was formed without providing a copper vapor deposition layer.

(Comparative Example 3)
In Example 1, the oxygen supply amount was increased and the plane orientation index X was set to 31.0%.

(Comparative Example 4)
An aluminum-deposited film was obtained in the same manner as in Example 1 except that the supply speed of the aluminum wire was reduced, the film transport speed was 200 m / min, and the plane orientation index was 0.4%.

(Reference example 1)
In Example 1, a metal-aluminum ingot is supplied to a pot heated by an induction heating method to evaporate the aluminum evaporation source, and only the metal-aluminum layer is vapor-deposited at a film transport speed of 240 m / min without supplying oxygen to form an aluminum-deposited film. Got The plane orientation index X was 0.1%.

(Reference example 2)
In Example 1, a metal aluminum ingot is supplied to a pot heated by an electron beam heating method to evaporate the aluminum evaporation source, and only the metal aluminum layer is vapor-deposited at a film transfer speed of 300 m / min without supplying oxygen to vaporize aluminum. I got a film.

Table 1 shows the production conditions of each Example, Comparative Example, and Reference Example, the aluminum-deposited film, and their characteristics.

As shown in Table 1, in the aluminum vapor deposition films of Examples 1 to 5, a vapor deposition layer whose composition continuously changes from the metal aluminum layer to the aluminum oxide layer is laminated via the copper vapor deposition layer which is an anchor metal vapor deposition layer. When the (200) plane orientation index of the vapor-deposited layer is in the range of 1 to 20%, the laminate peeling interface is between the vapor-deposited layer (Al) and the low-density polyethylene resin (PE), and the lamination strength is 1 N / 15 mm or more. It was possible to obtain an aluminum-deposited film laminate having stable lamination strength.

In Comparative Example 1, the vapor-deposited layer whose composition continuously changes from the metallic aluminum layer to the aluminum oxide layer was not laminated, and the lamination strength was low.

In Comparative Example 2, the anchor metal vapor deposition layer was not laminated, and the laminate peeling interface was between the vapor deposition layer (Al) and the base material PET film (PET), and the lamination strength was also low.

In Comparative Example 3, the (111) plane orientation, which is the main orientation of metallic aluminum, was lowered, and the original crystallinity of metallic aluminum could not be obtained. Therefore, the aluminum metallic luster as metallic aluminum was low.

In Comparative Example 4, the (111) plane orientation, which is the main orientation of metallic aluminum, is high, and metallic luster and original crystallinity can be obtained as metallic aluminum, but the film forming speed is low and the productivity is insufficient. It was something like that.

In the reference example, the (200) plane orientation index is as low as 0.1%, and the lamination strength is sufficient even though the vapor deposition layer whose composition changes continuously from the metallic aluminum layer to the aluminum oxide layer is not laminated. However, in each case, the film transport speed was low, and the productivity was insufficient as compared with the resistance heating method.

Claims (5)

A vapor-deposited layer whose composition continuously changes from the metallic aluminum layer to the aluminum oxide layer is laminated on at least one surface of the base film surface via an anchor metal vapor-deposited layer, and is (200) of the thin-film deposition layer defined by the formula (1). ) An aluminum-deposited film having a surface orientation index X of 1 to 20%.
X = [I200 / (I111 + I200)] × 100 (%) ... (1)
(I111: Integrated intensity of (111) plane measured by X-ray diffraction method, I200: Integrated intensity of (200) plane measured by X-ray diffraction method) The aluminum vapor-deposited film according to claim 1, wherein the metal of the anchor metal vapor-deposited layer is copper, and the amount of copper adhered is 30 to 120 ng / cm ^2. The aluminum-deposited film according to claim 1 or 2, wherein the thickness of the aluminum oxide layer is 4 to 15 nm. The aluminum-deposited film according to any one of claims 1 to 3, wherein the pure water contact angle on the surface of the vapor-deposited layer is less than 10 °. A laminate in which a plastic film is bonded to the vapor-deposited layer side of the aluminum-deposited film according to claims 1 to 4 via an adhesive resin layer, and the adhesion strength thereof is 1N / 15 mm or more.