JP2001064423A - Vapor-deposited film and packing material by using the vapor-deposited film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vapor-deposited film excellent in transparency, having a high gas-barrier properties, hardly causing deterioration even after a boil sterilization or a retort sterilization, having high boiling resistance and retort resistance without causing delamination or the like, and having a high practicality, and further to provide a packing material by using the vapor-deposited film. SOLUTION: This vapor-deposited film is obtained by laminating a primer layer 2 composed of a composite at least comprising a silicone substantially having a reactive group, a polyol and an isocyanate compound, a vapor- deposited layer 3 having 5-300 nm thickness and composed of an inorganic oxide, in order at least on one surface of a plastic substrate composed of a plastic material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate for packaging used in the field of packaging of foods, non-foodstuffs, pharmaceuticals, and the like, and is particularly used in the field of packaging requiring sterilization such as boil sterilization, retort sterilization and autoclave sterilization. The present invention relates to a vapor-deposited film and a packaging material using the vapor-deposited film.

[0002]

2. Description of the Related Art In recent years, packaging materials used for packaging foods, non-foodstuffs, pharmaceuticals, etc., include oxygen, which penetrates the packaging material, in order to suppress deterioration of contents and maintain their functions, properties and quality. It is necessary to prevent the influence of water vapor and other gases that alter the contents, and it is required to have a gas barrier property that blocks these various gases (gases). Therefore, conventionally, a packaging material using a metal foil made of a metal such as aluminum, which is less affected by temperature, humidity, and the like, as a gas barrier layer has been generally used.

[0003] However, a packaging material using a metal foil made of a metal such as aluminum has excellent gas barrier properties, but the contents cannot be checked through the packaging material. However, there is a problem in that a metal detector cannot be used during the inspection.

[0004] To overcome these disadvantages, as packaging materials, for example, inorganic materials such as silicon oxide, aluminum oxide and magnesium oxide as described in US Pat. No. 3,442,686 and JP-B-63-28017 are disclosed. A film has been developed in which an oxide is formed on a polymer film by forming a vapor-deposited film by a forming method such as a vacuum vapor deposition method or a sputtering method. These vapor-deposited films are known to have transparency and gas barrier properties against oxygen, water vapor, etc., and are suitable as packaging materials having both transparency and gas barrier properties that cannot be obtained with metal foils and the like. I have.

[0005]

However, even a film suitable for the above-mentioned packaging material is rarely used alone as a vapor deposition film as a packaging container or a packaging material. A package is completed through various processes such as printing or laminating characters and pictures on the surface or laminating the film with a film or the like, and shape processing into a package such as a container. In particular, packaging materials used for boil sterilization, retort sterilization, autoclave sterilization, and the like are sterilized through various processes, so that careful attention must be paid to the design of the packaging materials.

[0006] Then, after the above-mentioned vapor-deposited film or the like is bonded to a sealant film and made into a bag, the contents are filled and boil sterilization and retort sterilization are attempted. After sterilization, delamination occurs in a part of the seal portion. It has been found that there are problems such as poor appearance and deterioration of the gas barrier properties from the portion, resulting in deterioration of the contents.

In other words, the conditions used as a packaging material in such a case include transparency that allows the contents to be directly seen through, high gas barrier properties that block gases that affect the contents, and the like. It is required to have a boil resistance, a retort resistance and an autoclave resistance such that the gas barrier property does not deteriorate even after boil sterilization, retort sterilization and autoclave sterilization, and delamination does not occur.

[0008] Therefore, in the present invention, excellent transparency,
A highly vapor-deposited film having high gas barrier properties, no deterioration in physical properties even after boil sterilization or retort sterilization, high boil resistance without occurrence of delamination, and retort resistance, and a highly practical vapor-deposited film having the retort resistance. It is an object to provide a packaging material.

[0009]

Means for Solving the Problems The present invention has been made to achieve the above object, and the invention described in claim 1 provides a plastic substrate made of a plastic material, at least one surface of which is provided with a substantially reactive group. A primer layer comprising a composite containing at least a silicone, a polyol and an isocyanate compound, and a vapor-deposited film characterized by sequentially laminating a vapor-deposited thin film layer of an inorganic oxide having a thickness of 5 to 300 nm.

A second aspect of the present invention is a plastic substrate comprising a plastic material, a primer layer comprising a composite containing at least a polyol containing isocyanate and an isocyanate compound, and having a thickness of 5 to 300.
a vapor-deposited film characterized by sequentially laminating vapor-deposited thin film layers made of an inorganic oxide having a thickness of 10 nm.

The invention according to claim 3 is characterized in that the polyol is an acrylic polyol.
The deposited film described above.

According to a fourth aspect of the present invention, there is provided the vapor-deposited film according to the first, second or third aspect, wherein the silicone is a linear silicone or a ladder silicone.

According to a fifth aspect of the present invention, there is provided the vapor-deposited film according to the first, second, third or fourth aspect, wherein the thickness of the primer layer is in the range of 0.01 to 2 μm. is there.

According to a sixth aspect of the present invention, there is provided the vapor-deposited film according to any one of the first to fifth aspects, wherein the inorganic oxide is aluminum oxide, silicon oxide, magnesium oxide or a mixture thereof. It was done.

According to a seventh aspect of the present invention, there is provided the vapor-deposited film according to any one of claims 1 to 6, wherein a coating layer is laminated on the vapor-deposited film of the inorganic oxide. is there.

The invention according to claim 8 is the vapor-deposited film according to any one of claims 7 to 7, wherein the coating layer comprises an aqueous polymer comprising a metal alkoxide and / or a hydrolyzate thereof.

According to a ninth aspect of the present invention, there is provided the vapor-deposited film according to the eighth aspect, wherein the metal alkoxide comprises one of tetraethoxysilane, triisopropoxyaluminum, and a mixture thereof. It is.

According to a tenth aspect of the present invention, there is provided the vapor-deposited film according to the seventh aspect, wherein the coating layer comprises a water-soluble polymer and silver chloride.

[0019] The invention of claim 11 is the vapor deposition film according to claim 8, 9 or 10, wherein the water-soluble polymer is polyvinyl alcohol.

A twelfth aspect of the present invention is characterized in that a heat seal layer is laminated on an inorganic oxide vapor-deposited thin film layer or a coating layer of the vapor-deposited film via an adhesive.
11. The packaging material according to any one of 11.

[0021]

According to the present invention, after a primer layer having excellent dimensional stability and adhesion is provided on a plastic substrate even after boil sterilization or retort sterilization, a vapor-deposited thin film layer made of an inorganic oxide having excellent gas barrier properties is provided. , A highly practical vapor-deposited film free from delamination and gas barrier property deterioration even after boiling sterilization or retort sterilization, and a packaging material using this vapor-deposited film can be obtained.

[0022]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail with reference to the drawings. FIG. 1 is a cross-sectional view illustrating a vapor deposition film of the present invention. First, the deposited film of the present invention shown in FIG. 1 will be described. The plastic substrate 1 in FIG. 1 is a film made of a plastic material, on which a primer layer 2 substantially composed of a compound such as silicone, polyol and isocyanate compound having a reactive group, and a vapor-deposited thin film layer composed of an inorganic oxide 3. The coating layer 4 is sequentially laminated.
In this case, the coating layer 4 may not be provided depending on the required quality.

The above-mentioned plastic substrate 1 is a film made of a plastic material, and is preferably a transparent film in order to make use of the transparency of the deposited thin film layer. For example, polyethylene terephthalate (PET), polyester films such as polyethylene naphthalate, polyolefin films such as polyethylene and polypropylene, polystyrene films, polyamide films, polyvinyl chloride films, polycarbonate films, polyacrylonitrile films, polyimide films, and the like are used. Either stretched or unstretched may be used, and those having mechanical strength and dimensional stability are preferred. These are processed into a film and used. Also, on the surface of the plastic substrate 1,
Various additives and stabilizers generally used, for example, antistatic agents, ultraviolet inhibitors, plasticizers, lubricants and the like may be used.

The thickness of the plastic substrate 1 is suitable as a packaging material, other layers may be laminated, and a primer layer 2, a vapor-deposited thin film layer 3 made of an inorganic oxide, and a coating layer 4 are formed. Considering the workability of the case, practically 3
It is preferable to set it to 6 to 30 μm in the range of to 200 μm depending on the use. Further, in consideration of mass productivity, it is desirable to form a continuous long film so that each layer can be formed continuously.

The primer layer 2 of the present invention is provided on a plastic substrate 1 made of a plastic film, and enhances the adhesion between the plastic substrate 1 and the deposited thin film layer 3 made of an inorganic oxide. Or retort sterilization,
An object is to prevent delamination from occurring after heat treatment such as autoclave sterilization. After careful examination,
In order to achieve the above object, the primer layer must be substantially composed of a composite containing at least a silicone, a polyol and an isocyanate compound having a reactive group.

Further, the composite constituting the primer layer will be described in detail. The polyol is a polymer terminal
It has one or more hydroxyl groups and is reacted with an isocyanate group of an isocyanate compound to be added later.
Among them, a polyol obtained by polymerizing an acrylic acid derivative monomer or an acrylic polyol which is a polyol obtained by copolymerizing an acrylic acid derivative monomer and another monomer is particularly preferable.

As the polyol, an acrylic acid derivative monomer such as ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, or hydroxybutyl methacrylate is homopolymerized or copolymerized, and a polyol or the acrylic acid derivative monomer and another monomer such as styrene are added. Polymerized acrylic polyols are preferred. In consideration of the reactivity with the isocyanate compound, the acrylic polyol preferably has a hydroxyl value of 5 to 200 (KOH mg / g).

The silicone constituting the primer layer may be substantially in a state before the reaction with a polyol having a reactive group or the like, or may be one which has been reacted in advance with a polyol or the like as described below.

The silicone-containing polyol is obtained by reacting a polyol having a reactive organic functional group in a part of the side chain of the silicone with the polyol. Ladder silicones which are said to be ladder-shaped are particularly preferred.

The ratio of acrylic polyol to silicone is
Silicone is used in a weight ratio of SiO _{2 in} the range of 1/1 to 100
It is preferably in the range of 0/1, more preferably 2
/ 1 to 100/1.

The dissolving and diluting solvent may be any solvent that can be dissolved and diluted, for example, esters such as ethyl acetate and butyl acetate, alcohols such as methanol, ethanol and isopropyl alcohol, ketones such as methyl ethyl ketone, toluene and xylene. And the like can be used alone or arbitrarily blended with aromatic hydrocarbons.

Further, the isocyanate compound is added in order to increase the adhesion to the base material and the inorganic oxide by a urethane bond formed by reacting with a polyol such as an acrylic polyol, and mainly acts as a crosslinking agent or a curing agent. . Specific examples of the isocyanate compound exhibiting the above function include aromatic tolylene diisocyanate (TD
I) or diphenylmethane diisocyanate (MDI),
Monomers such as aliphatic xylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), one of these polymers or derivatives, or two or more of these can be used.

Here, the compounding ratio of the acrylic polyol containing silicone in the side chain and the isocyanate compound may result in poor curing when the amount of the isocyanate compound is too small, and when the amount is too large, blocking and the like may occur, resulting in processing problems. is there. Therefore, the blending ratio of the acrylic polyol and the insocyanate compound is preferably such that the NCO groups derived from the isocyanate compound are not more than 50 times the OH groups derived from the acrylic polyol, and particularly preferred is N
This is a case where CO groups and OH groups are blended in equivalent amounts. The mixing method may be a commonly used method.

The primer layer in the present invention is formed by preparing a composite solution in which a polyol containing isocyanate in the side chain and an isocyanate compound are appropriately mixed, coating the plastic substrate 1 and drying and curing. Specifically, the composite solution for forming the primer layer is prepared by mixing and reacting a silicone having an arbitrary reactive organic functional group with an acrylic polyol in advance, in addition to using a solution in which silicone has already been grafted with a silicone. A method of preparing a composite solution by adding a diluent and diluting the mixture to an arbitrary concentration, followed by mixing with an isocyanate compound to prepare a composite solution.

Various additives such as tertiary amines, imidazole derivatives, metal salt compounds of carboxylic acids, quaternary ammonium salts, quaternary phosphonium salts, and other curing accelerators; Phyto-based antioxidants, leveling agents, flow regulators, catalysts, crosslinking reaction accelerators, fillers, etc. are added as required.

The primer layer 2 is formed by applying the composite solution to a printing method such as offset printing, gravure printing, silk screen printing, roll coating, knife edge coating, or the like.
It is formed by coating on the substrate 1 using a coating method such as gravure coating, and then drying the coating film, removing the solvent and the like, and curing.

The thickness of the primer layer 2 only needs to be such that a uniform coating film is formed, and is generally preferably in the range of 0.01 to 2 μm. When the thickness is less than 0.01 μm, it is difficult to obtain a uniform coating film, and the adhesion may be reduced. On the other hand, when the thickness exceeds 2 μm, it is not preferable because it is difficult to maintain flexibility in the coating film due to the thickness, and the coating film may be cracked by external factors. Particularly preferred is a range of 0.05 to 0.5 μm.

Next, the deposited thin film layer 3 made of an inorganic oxide is
Any material may be used as long as it is made of a deposited film of an inorganic oxide such as aluminum oxide, silicon oxide, tin oxide, magnesium oxide, or a mixture thereof, and has transparency and a gas barrier property against oxygen, water vapor, and the like. Among them, aluminum oxide and silicon oxide are particularly preferable.

The optimum thickness of the vapor-deposited thin film layer 3 varies depending on the type and composition of the inorganic compound to be used, but is generally preferably in the range of 5 to 300 nm, and the value is appropriately selected. However, if the film thickness is less than 5 nm, a uniform film may not be obtained or the film thickness may not be sufficient, and the function as a gas barrier material may not be sufficiently achieved. When the film thickness exceeds 300 nm, it is difficult to maintain flexibility in the thin film, and the thin film may be cracked by external factors such as bending and pulling after film formation. Preferably, 10 to 150 nm
Within the range.

Various means can be used to form the vapor-deposited thin film layer 3 made of an inorganic oxide on the primer layer 2, but it is generally formed by a vacuum vapor deposition method. Other thin film forming methods such as a sputtering method, an ion plating method, and a plasma vapor deposition method (CVD) can also be used. However, in consideration of productivity, the vacuum evaporation method is the most excellent. Any of an electron beam heating method, a resistance heating method, and an induction heating method may be appropriately used as a heating means of the vacuum deposition apparatus using the vacuum deposition method. In order to improve the adhesion between the deposited thin film layer and the plastic substrate and the denseness of the deposited thin film layer, a plasma assist method or an ion beam assist method can be used. In addition, in order to increase the transparency of the deposited thin film layer, reactive deposition in which oxygen gas is blown or the like may be performed at the time of deposition.

The coating layer 4 provided on the evaporated thin film layer 3 made of an inorganic oxide is for protecting the evaporated thin film layer 3.
In addition, it is provided to provide high gas barrier properties.

Examples of the coating layer which imparts a high gas barrier property as the coating layer 4 include a layer made of a water-soluble polymer and one or more metal alkoxides and / or hydrolysates. It is formed by applying a solution comprising silane, triisopropoxyaluminum, or a mixture thereof. Other examples of the coating layer that imparts high gas barrier properties include those made of a water-soluble polymer and tin chloride, and those coated with a solution of the water-soluble polymer made of polyvinyl alcohol. Specifically, a solution obtained by dissolving a water-soluble polymer and tin chloride in an aqueous (water or water / alcohol mixture) solvent, or a solution obtained by directly or preliminarily hydrolyzing a metal alkoxide is mixed with the solution. It is formed by coating the solution on the inorganic oxide deposited thin film layer 3 and drying by heating. Each component forming the coating layer 4 will be described in more detail.

Specific examples of the water-soluble polymer used to form the coating layer of the present invention include polyvinyl alcohol, polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, sodium alginate and the like. In particular, polyvinyl alcohol (hereinafter, referred to as
PVA) has the best gas barrier properties. The PVA referred to here is generally obtained by saponifying polyvinyl acetate, and includes a range from so-called partially saponified PVA in which acetic acid groups remain to several tens% to complete PVA in which only a few% of acetic acid groups remain. .

Tin chloride is stannous chloride (SnCl ₂ ),
Stannic chloride (SnCl ₄ ) or a mixture thereof may be used, and either anhydrous or hydrated can be used.

Further, the metal alkoxide is represented by a general formula such as tetraethoxysilane [Si (OC ₂ H ₅ ) ₄ ], triisopropoxy aluminum [Al (O-2′-C ₃ H ₇ ) ₃ ], M (OR) n (M: Si, Ti, Al, Zr
And R: an alkyl group such as CH ₃ and C ₂ H ₅ ). Among them, tetraethoxysilane and triisopropoxyaluminum are preferable because they are relatively stable in an aqueous solvent after hydrolysis.

The above-mentioned components can be used alone or in combination to form a coating layer. Further, as long as the gas barrier properties of the coating layer are not impaired, an isocyanate compound, a silane coupling agent, a dispersing agent and a stabilizer can be used. , A viscosity modifier, a colorant and the like. Additives may be added.

For example, the isocyanate compound added to the coating layer 4 has two or more isocyanate groups (NCO groups) in its molecule. For example, tolylene diisocyanate (hereinafter referred to as TDI), triphenylmethane triisocyanate ( There are monomers such as TTI) and tetramethylxylene diisocyanate (hereinafter referred to as TMXDI), and polymers and derivatives thereof.

In order to form the coating layer 4, conventionally known means such as a commonly used dipping method, roll coating method, screen printing method, spraying method and the like can be used. The thickness of the coating layer 4 varies depending on the type of the coating agent forming the coating layer and the processing conditions, and the thickness after drying may be 0.01 μm or more.
When the thickness is 0 μm or more, cracks easily occur in the film.
The range of 01 to 50 μm is preferred.

If necessary, another layer is laminated on the deposited thin film layer 3 or the coating layer 4. For example, it is a printing layer, an intervening film, a heat seal layer, or the like. The printing layer is formed for practical use as a packaging bag or the like, and various pigments are added to conventionally used ink binder resins such as urethane, acrylic, nitrocellulose, rubber, and vinyl chloride. , A layer composed of an ink to which an additive such as an extender, a plasticizer, a desiccant, a stabilizer and the like are added, and on which characters, pictures, and the like are formed. As a forming method, for example, an offset printing method, a gravure printing method,
A well-known printing method such as a silk screen printing method, and a coating method such as a roll coat, a knife edge coat, and a gravure coat can be used. Thickness is 0.1 ~ 2.0μ
m is fine.

If necessary, an intervening film is provided. The intervening film is provided to increase the breaking strength during sterilization of the boil and retort, and is generally a biaxially oriented nylon film, a biaxially oriented polyethylene terephthalate film, a biaxially oriented polypropylene in terms of mechanical strength and thermal stability. It is a kind selected from the film.
The thickness is determined according to the material, required quality, and the like, but is generally in the range of 10 to 30 μm. As a forming method, lamination can be performed by a method such as a dry lamination method in which an adhesive such as a two-component curable urethane-based resin is used.

The heat sealing layer is provided as a sealing layer when forming a bag-like package. For example, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer or a metal thereof A film made of a kind of resin such as a crosslinked product is used. The thickness is determined according to the purpose, but is generally in the range of 15 to 200 μm. As a forming method, it is general to use a dry laminating method or the like in which a film for forming a heat seal layer is bonded using an adhesive such as a two-component curable urethane resin.

[0052]

EXAMPLES The vapor deposition film of the present invention will be described in more detail with reference to specific examples. During <composite solution prepared> A) diluent solvent (ethyl acetate), 1.1 eq of TDI as the isocyanate compound to acryl polyol containing 10% Si0 ₂ in terms of a ladder silicone in its side chain to the OH group of the acrylic polyol The mixed solution added so as to obtain a composite solution A is a solution obtained by adding a diluting solvent to a concentration of 2%.

[0053] B) in dilute solutions (ethyl acetate), polydimethylsiloxane having carbinol groups plus 10% Si0 ₂ in terms of relative Acrylic polyol-terminated
A composite solution B was prepared by adding TDI as an isocyanate compound in an amount equivalent to 1.1 to the OH group of the acrylic polyol and adding a diluting solvent to a concentration of 2%.

C) A mixed solution obtained by diluting a mixed solution in a diluting solvent (ethyl acetate) so that the NCO group is 1.1 equivalent to the OH group of the acrylic polyol so as to have a concentration of 2%. Let it be solution C.

<Example 1> As the plastic substrate 1,
On one surface of a biaxially stretched nylon film (ONY) having a thickness of 12 μm, a composite solution A was formed as a primer layer 2 to a thickness of 0.1 μm by a gravure coating method. (Dry Film Thickness) Next, metal aluminum is evaporated on the primer layer 2 by a vacuum evaporation apparatus using an electron beam heating method, oxygen gas is introduced therein, and aluminum oxide having a thickness of 20 nm is evaporated to form the evaporated thin film layer 3. Formed. Further, a coating agent having the following composition is applied thereon by a gravure coater, and dried at 100 ° C. for 1 minute with a drier to form a 0.3 μm thick coating layer 4.
Was obtained. The composition of the coating agent used was a mixture of a liquid and a liquid at a mixing ratio (wt%) of 60/40. Here, 89.6 g of hydrochloric acid (0.1N) was added to 10.4 g of tetraethoxysilane, and
The hydrolysis solution having a solid content of 3 wt% (in terms of SiO ₂ ) stirred and hydrolyzed for 3 minutes is 3 w of polyvinyl alcohol.
It is a t% water / isopropyl alcohol solution (90:10 by weight ratio of water: isopropyl alcohol).

Example 2 A vapor-deposited film of the present invention was obtained in the same manner as in Example 1, except that the composite solution B was used as the primer layer 2.

Comparative Example 1 A vapor-deposited film was obtained in the same manner as in Example 1, except that the primer layer 2 was not provided.

Comparative Example 2 A vapor-deposited film was obtained in the same manner as in Example 1, except that the composite solution C was used as the primer layer 2.

<Production of Packaging Material> An unstretched polypropylene film having a thickness of 70 μm as a heat seal layer on the side of the vapor-deposited thin film layer of each of the vapor-deposited films of Examples 1 and 2 and Comparative Examples 1 and 2 was bonded in a two-part curable urethane system. Lamination was carried out by a dry lamination method via an agent to obtain a packaging material.

<Test 1> Examples 1 and 2 and Comparative Example 1
A pouch having a three-sided seal portion was prepared from a packaging material using the vapor deposition film of No. 2 and water 400
g, and sterilized in boil at 90 ° C. for 30 minutes.
As an evaluation, the oxygen transmission rate (cc / m2) before and after boiling sterilization was performed.
/ Day), peel strength (gr / 15 mm), and the occurrence of delamination after boiling were observed by visual observation. Table 1 shows the results.

[0061]

[Table 1]

Laminate strength: T-type peeling, gf / 15 m
m, PECUT = polyethylene cut oxygen permeability; cc /
m ² / day, 30 ° C.-70% Rh Appearance: ○ = no delamination, Δ = partial delamination, × = delamination occurred on the entire surface

As shown in Table 1 above, the initial evaluation of Comparative Example 1 before sterilizing the boil shows that a primer layer is necessary. In addition, in the configuration with the primer layer, there was no problem in the adhesion and gas barrier properties in the initial evaluation before the sterilization of the boil, but the results after the boil showed that Examples 1 and 2 showed no deterioration in the gas barrier properties and high adhesion. You can see that it is maintained. On the other hand, according to Comparative Example 2, it can be seen that after retorting, delamination and the like occur, resulting in poor appearance, and insufficient adhesion between the plastic substrate and the deposited thin film layer. Therefore, the packaging materials of Examples 1 and 2 have higher gas barrier properties to block the gas and the like which affect the contents than those of Comparative Examples 1 and 2, there is no deterioration even after boiling sterilization, and delamination occurs. There is no boil resistance that meets all.

[0064]

As described above, according to the present invention, a versatile packaging material having excellent transparency and a high gas barrier property can be obtained. Because of its superiority, it can be widely used in the packaging field.

[Brief description of the drawings]

FIG. 1 is a sectional view of a vapor deposition film of the present invention.

[Explanation of symbols]

 1 plastic substrate 2 primer layer 3 evaporated thin film layer 4 coating layer

Continued on the front page (72) Inventor Masayuki Ohashi 1-5-1, Taito, Taito-ku, Tokyo Letterpress Printing Co., Ltd. F-term (reference) 3E086 AD01 BA04 BA15 BA24 BA40 BB01 BB22 BB41 BB51 CA03 CA28 4F006 AA12 AA17 AA22 AA35 AA36 AA38 AA39 AB37 AB39 AB74 BA01 BA05 CA07 DA01 DA04 4F100 AA05D AA17C AA18C AA19 AA19C AA20C AH03B AH08D AK01A AK01D AK07 AK21D AK25B AK25J AK48 AK51B AK52B AR00E AT00A BA03 BA04 BA05 BA07 BA10A BA10C BA10D BA10E CA02B CB00 EH46 EH66C EJ38 EJ65B GB15 GB23 JA20C JB05D JD02 JJ03 JL12E JM02C JN01 YY00C

Claims (12)

[Claims] 1. A primer layer comprising a composite material containing at least one of a silicone, a polyol and an isocyanate compound having a substantially reactive group on at least one surface of a plastic substrate made of a plastic material, and having a thickness of 5 to 300.
A vapor-deposited film characterized by sequentially laminating vapor-deposited thin film layers made of an inorganic oxide having a thickness of 10 nm. 2. A primer layer comprising a composite containing at least a polyol containing silicone and an isocyanate compound on at least one side of a plastic substrate comprising a plastic material, and a vapor-deposited thin film layer comprising an inorganic oxide having a thickness of 5 to 300 nm. A deposited film characterized by being laminated. 3. The vapor-deposited film according to claim 1, wherein the polyol is an acrylic polyol. 4. The method according to claim 1, wherein said silicone is a linear silicone or a ladder silicone.
Or the vapor deposition film of 3. 5. The method according to claim 1, wherein said primer layer has a thickness of 0.01 to 2
The vapor-deposited film according to claim 1, 2, 3, or 4, wherein the thickness is in a range of μm. 6. The vapor-deposited film according to claim 1, wherein the inorganic oxide is aluminum oxide, silicon oxide, magnesium oxide, or a mixture thereof. 7. The vapor-deposited film according to claim 1, wherein a film layer is laminated on the inorganic oxide vapor-deposited thin film layer of the vapor-deposited film. 8. The vapor-deposited film according to claim 7, wherein said coating layer comprises an aqueous polymer comprising a metal alkoxide and / or a hydrolyzate thereof. 9. The method according to claim 8, wherein said metal alkoxide comprises one of tetraethoxysilane, triisopropoxyaluminum, and a mixture thereof.
The vapor-deposited film as described. 10. The vapor-deposited film according to claim 7, wherein said coating layer comprises a water-soluble polymer and silver chloride. 11. The vapor-deposited film according to claim 8, wherein the water-soluble polymer is polyvinyl alcohol. 12. The packaging material according to claim 1, wherein a heat seal layer is laminated on the inorganic oxide vapor-deposited thin film layer or the coating layer of the vapor-deposited film via an adhesive. .