JP2006192901A - Vapor deposition film for boil sterilization and retort sterilization, and for packaging container which holds contents including moisture, and packaging material using this vapor deposition film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a highly practical vapor deposition film for boil sterilization and retort sterilization which excels in transparency, has high gas barrier nature and does not undergo degradation of physical properties after boil sterilization or retort sterilization, which has boil resistance and retort resistance without generation of delamination or the like, a vapor deposition film for a packaging container which holds contents including moisture, and a packaging material using this vapor deposition film. <P>SOLUTION: The vapor deposition film for boil sterilization and retort sterilization and for a packaging container holding contents including moisture made by laminating a primer layer 2 including a composite comprising a silane coupling agent or a hydrolyzate of the silane coupling agent having an organic functional group which can react with at least one of hydroxy group of a polyol and an isocyanate group of an isocyanate compound, a polyol and an isocyanate compound, an inorganic oxide thin film layer 3 which consists of an inorganic oxide with a thickness of 5-300 nm and a coating layer 4, sequentially on at least one side of a plastic substrate 1 which consists of a plastic material. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  TECHNICAL FIELD The present invention relates to a vapor deposition film for packaging containers that contains contents for boil sterilization, retort sterilization, and moisture, and a packaging material using the vapor deposition film.

  In recent years, packaging materials used for packaging foods, non-foods, pharmaceuticals, etc. contain oxygen, water vapor, and other contents that permeate the packaging material in order to suppress alteration of the contents and maintain their functions, properties, and quality. It is necessary to prevent the influence of a gas that alters an object, and it is required to have a gas barrier property that blocks these various gases. Therefore, conventionally, a packaging material using a metal foil made of a metal such as aluminum, which is less affected by temperature and humidity, as a gas barrier layer has been generally used.

  However, packaging materials using metal foils made of metal such as aluminum are excellent in gas barrier properties, but the contents cannot be confirmed through the packaging materials, and are non-combustible when discarded after use. Have disadvantages such as having to be treated as a metal detector and being unable to use a metal detector during inspection.

  Therefore, as a packaging material that has overcome these drawbacks, for example, silicon oxide, oxidation, etc., on a polymer film, such as described in Patent Documents 1 and 2, by a means such as vacuum deposition or sputtering. A film in which a deposited film of an inorganic oxide such as aluminum or magnesium oxide is formed has been developed. These vapor-deposited films are known to have transparency and gas barrier properties such as oxygen and water vapor, and have both transparency and gas barrier properties that cannot be obtained with metal foil, etc. As suitable.

  However, even a vapor-deposited film suitable for the packaging material described above is rarely used as a single vapor-deposited film as a packaging container or packaging material, and prints characters, designs, etc. on the surface of the vapor-deposited film as post-processing after vapor deposition. Or the packaging body is completed through various processes, such as bonding with a film etc. and shape processing to the packaging bodies, such as a container. In particular, packaging materials used for boil sterilization, retort sterilization, autoclave sterilization, and the like are sterilized through various processes, and therefore, care must be taken when designing packaging materials.

Therefore, after making a bag by laminating it with a sealant film using the above-mentioned vapor-deposited film, etc., filling the contents and attempting boil sterilization or retort sterilization resulted in delamination in a part of the seal part after sterilization. As a result, it became clear that the appearance was poor, the gas barrier property was lowered from the portion, and the contents were deteriorated.
U.S. Pat. No. 3,442,686 Japanese Patent Publication No.63-28017

  That is, as conditions used as a packaging material in such a case, transparency capable of directly seeing through the contents, high gas barrier properties for blocking gas etc. affecting the contents, and boil sterilization and retort It is required to have boil resistance, retort resistance, and autoclave resistance, such as no gas barrier deterioration after sterilization and autoclave sterilization, and no delamination, etc. No packaging material has been found.

  Therefore, in the present invention, it has excellent transparency, high gas barrier properties, no deterioration of physical properties after boil sterilization or retort sterilization, no delamination, etc., high boil resistance and retort resistance practicality It is an object to provide a high vapor deposition film and a packaging material using the vapor deposition film.

  The present invention is for achieving the above-mentioned object. The invention of claim 1 is directed to an organic functional group that reacts with at least one of a hydroxyl group of a polyol or an isocyanate group of an isocyanate compound on at least one side of a plastic substrate made of a plastic material. A silane coupling agent or a hydrolyzate of a silane coupling agent, a primer layer containing a composite of a polyol and an isocyanate compound, an inorganic oxide thin film layer comprising an inorganic oxide having a thickness of 5 to 300 nm, and a coating The layers are sequentially laminated to form a vaporized film for boil sterilization and retort sterilization.

  According to the second aspect of the present invention, there is provided a silane coupling agent having an organic functional group that reacts with at least one of a hydroxyl group of a polyol or an isocyanate group of an isocyanate compound on at least one surface of a plastic substrate made of a plastic material. Contains moisture characterized by sequentially laminating a decomposition layer, a primer layer containing a composite of a polyol and an isocyanate compound, an inorganic oxide thin film layer made of an inorganic oxide having a thickness of 5 to 300 nm, and a coating layer This is a vapor deposition film for a packaging container that contains the contents.

  The invention according to claim 3 is the vapor-deposited film according to claim 1 or 2, wherein the organic functional group contained in the silane coupling agent is any one of an isocyanate group, an amino group, and a mercapto group. It is what.

  The invention according to claim 4 is the vapor deposition film according to any one of claims 1 to 3, wherein the polyol is an acrylic polyol.

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

  The invention according to claim 6 is the deposited film according to any one of claims 1 to 5, wherein the inorganic oxide is aluminum oxide, silicon oxide, magnesium oxide or a mixture thereof. is there.

  The invention according to claim 7 is the vapor-deposited film according to any one of claims 1 to 6, wherein the coating layer comprises a water-soluble polymer and a metal alkoxide and / or a hydrolyzate thereof. is there.

  The invention according to claim 8 is the vapor-deposited film according to claim 7, wherein the metal alkoxide is composed of tetraethoxysilane, triisopropoxyaluminum, or a mixture thereof.

  The invention according to claim 9 is the vapor-deposited film according to claim 7 or 8, wherein the water-soluble polymer is made of polyvinyl alcohol.

  The invention of claim 10 is a packaging material characterized in that a heat seal layer is laminated on the coating layer of the vapor deposition film according to any one of claims 1 to 9 via an adhesive layer.

  According to the present invention, after providing a primer layer excellent in dimensional stability and adhesion even after boiling and retort sterilization on a plastic substrate, an inorganic oxide thin film layer excellent in gas barrier properties is laminated. Therefore, even after use as a boil-killing bacterium or retort sterilization, or for use in packaging containers that contain water-containing contents, highly practical vapor-deposited films that do not cause delamination or deteriorate gas barrier properties A packaging material using this deposited film is obtained.

Hereinafter, the best mode for carrying out the invention will be described in more detail with reference to the drawings.
1 and 2 are cross-sectional views illustrating a deposited film according to an embodiment of the present invention. A plastic substrate 1 in FIG. 1 is a film made of a transparent plastic material, on which a primer layer 2 made of a composite of a silane coupling agent having an organic functional group, a polyol and an isocyanate compound, and an inorganic oxide are deposited. The inorganic oxide thin film layers 3 formed by, for example, are sequentially stacked.

  The vapor deposition film shown in FIG. 2 is obtained by further laminating a coating layer 4 on the inorganic oxide thin film layer 3 of the vapor deposition film shown in FIG.

  The plastic substrate 1 described above is a film made of a plastic material, and a transparent film is preferable in order to make use of the transparency of the inorganic oxide thin film layer. For example, polyethylene terephthalate (PET), polyester film such as polyethylene naphthalate, polyolefin film such as polyethylene and polypropylene, polystyrene film, polyamide film, polyvinyl chloride film, polycarbonate film, polyacrylonitrile film, polyimide film, etc. are used. Either stretched or unstretched, and those having mechanical strength and dimensional stability are preferred. In particular, polyethylene terephthalate arbitrarily stretched in the biaxial direction is preferably used. Various known additives and stabilizers such as an antistatic agent, an ultraviolet ray preventing agent, a plasticizer, and a lubricant may be used on the surface of the plastic substrate 1.

  The thickness of the plastic substrate 1 is not particularly limited, but is suitable as a packaging material, may be laminated with other layers, the primer layer 2, the inorganic oxide thin film layer 3, or the coating layer 4 In consideration of the workability when forming the film, it is practically in the range of 3 to 200 μm, and preferably 6 to 30 μm depending on the application.

  In consideration of mass productivity, it is desirable to use 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 improves the adhesion between the plastic substrate 1 and the inorganic oxide thin film layer 3 made of an inorganic oxide. It is intended to prevent the occurrence of delamination after heat treatment such as sterilization, retort sterilization, and autoclave sterilization. As a result of intensive studies, the primer layer 2 can be used as a primer layer 2 to achieve the above-mentioned purpose. The silane coupling agent having an organic functional group or a hydrolyzate thereof must be a composite of a polyol and an isocyanate compound. There is.

  Furthermore, the composite which comprises the primer layer 2 is demonstrated in detail. As examples of the silane coupling agent, a silane coupling agent containing any organic functional group can be used. For example, vinyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropyltrimethoxysilane, A silane coupling agent such as sidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, or one or more of hydrolysates thereof can be used.

  Further, among these silane coupling agents, those having a functional group that reacts with a hydroxyl group of a polyol or an isocyanate group of an isocyanate compound are particularly preferable. For example, those containing isocyanate groups such as γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, those containing mercapto groups such as γ-mercaptopropyltriethoxysilane, and γ-aminopropyltriethoxysilane , Γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, and γ-phenylaminopropyltrimethoxysilane.

  Further, those containing an epoxy group such as γ-glycidoxypropyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrimethoxysilane, vinyltris (β-methoxyethoxy) silane A silane coupling agent such as that obtained by adding an alcohol or the like to a hydroxyl group may be used, and one or more of these may be used.

  These silane coupling agents have a silane cup containing a functional group in which an organic functional group present at one end exhibits an interaction in a composite composed of a polyol and an isocyanate compound, or reacts with a hydroxyl group of a polyol or an isocyanate group of an isocyanate compound. By forming a covalent bond by using a ring agent, a stronger primer layer is formed, and the alkoxy group at the other end or the silanol group generated by hydrolysis of the alkoxy group is a metal in inorganic oxide or inorganic By exhibiting a strong interaction with a highly polar hydroxyl group or the like on the surface of the oxide, high adhesion with the inorganic oxide can be exhibited, and the desired physical properties can be obtained. Therefore, a silane coupling agent hydrolyzed with a metal alkoxide as the primer layer may be used.

  Moreover, there is no problem even if the alkoxy group of the silane coupling agent is a chloro group, an acetoxy group, etc., and these alkoxy groups, chloro groups, acetoxy groups, etc. are hydrolyzed to form silanol groups. If present, it can be used in this composite.

  A polyol has two or more hydroxyl groups at the polymer terminal and is reacted with an isocyanate group of an isocyanate compound added later. As this polyol, an acrylic polyol which is a polyol obtained by polymerizing an acrylic acid derivative monomer or a polyol obtained by copolymerizing an acrylic acid derivative monomer and other monomers is preferable. Among them, an acrylic polyol obtained by polymerizing an acrylic acid derivative monomer such as ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, or hydroxybutyl methacrylate, or an acrylic polyol obtained by copolymerizing the acrylic acid derivative with another monomer such as styrene is preferable. Used. In consideration of the reactivity with the isocyanate compound and the compatibility with the silane coupling agent, the hydroxyl value of the acrylic polyol is preferably between 5 and 200 (KOHmg / g).

  The mixing ratio of the acrylic polyol and the silane coupling agent is preferably in the range of 1/1 to 1000/1 by weight ratio, more preferably in the range of 2/1 to 100/1. The dissolving and diluting solvent is not particularly limited as long as it 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, A mixture of aromatic hydrocarbons such as toluene and xylene alone and arbitrarily can be used. However, when an aqueous solution such as hydrochloric acid is used to hydrolyze the silane coupling agent, it is preferable to use a solvent in which alcohols such as isopropyl alcohol and ethyl acetate as a polar solvent are arbitrarily mixed as a cosolvent.

  Furthermore, an isocyanate compound is added in order to improve the adhesiveness with a plastic substrate or an inorganic oxide by a urethane bond formed by reacting with a polyol such as an acrylic polyol, and mainly functions as a crosslinking agent or a curing agent. Specific examples of isocyanate compounds that exhibit the above functions include aromatic tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), aliphatic xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), and isophorone diisocyanate. Monomers such as (IPDI), one of these polymers or derivatives, or two or more thereof can be used.

  Here, the blending ratio of the acrylic polyol and the isocyanate compound is not particularly limited, but if the isocyanate compound is too small, the curing may be poor, and if it is too much, blocking or the like occurs and processing problems occur. There is. Therefore, the mixing ratio of the acrylic polyol and the isocyanate compound is preferably that the NCO group derived from the isocyanate compound is 50 times or less of the OH group derived from the acrylic polyol, and particularly preferably the NCO group and the OH group are mixed in an equivalent amount. This is the case. As a mixing method, a known method can be used and is not particularly limited.

  The primer layer in the present invention is formed by preparing a composite solution in which a silane coupling agent, a polyol, and an isocyanate compound are mixed at an arbitrary concentration, coating the plastic substrate 1, and drying and curing it. Specifically, the primer agent for forming the primer layer is prepared by mixing a silane coupling agent and a polyol, adding a solvent and a diluent to dilute to an arbitrary concentration, and then mixing with an isocyanate compound. In addition to the above method, a mixture of a silane coupling agent and a polyol mixed in a solvent in advance is prepared by reacting the silane coupling agent and a polyol in advance and diluting to an arbitrary concentration by adding a solvent and a diluent, and then adding an isocyanate compound. There are methods.

  Various additives such as tertiary amines, imidazole derivatives, carboxylic acid metal salt compounds, quaternary ammonium salts, quaternary phosphonium salts, and other accelerators, phenol-based, sulfur-based, and phosphite-based materials. It is also possible to add antioxidants such as leveling agents, flow control agents, catalysts, crosslinking reaction accelerators, fillers and the like.

  The primer layer 2 is a plastic substrate 1 using a known printing method such as an offset printing method, a gravure printing method, a silk screen printing method, or a known coating method such as a roll coating, a knife edge coating, or a gravure coating. Then, the coating film is formed by drying, removing the solvent, and curing.

  The thickness of the primer layer 2 is not particularly limited as long as a uniform coating film can be formed, but generally it is 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 lowered. On the other hand, when the thickness exceeds 2 μm, the coating film cannot be kept flexible because it is thick, and the coating film may be cracked due to external factors, which is not preferable. Particularly preferred is a range of 0.05 to 0.5 μm.

  Next, the inorganic oxide thin film layer 3 made of an inorganic oxide is made of a vapor-deposited film of an inorganic oxide such as aluminum oxide, silicon oxide, tin oxide, magnesium oxide, or a mixture thereof. Any material having gas barrier properties such as water vapor may be used. Among them, aluminum oxide and silicon oxide are particularly preferable. However, the inorganic oxide thin film layer 3 of the present invention is not limited to the inorganic oxide described above, and any material that meets the above conditions can be used.

  The optimum thickness of the inorganic oxide thin film layer 3 varies depending on the type and configuration of the inorganic compound to be used, but generally it is 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. In addition, when the film thickness exceeds 300 nm, the inorganic oxide thin film layer cannot retain flexibility, and the inorganic oxide thin film layer may be cracked due to external factors such as bending and pulling after the film formation. . Preferably, it exists in the range of 10-150 nm.

  Various means can be used as the means for forming the inorganic oxide thin film layer 3 on the primer layer 2, but it is generally formed by vacuum deposition. Sputtering, ion plating, plasma vapor deposition (CVD), or the like can be used as means other than this vacuum vapor deposition. However, considering productivity, the vacuum deposition method is the best at present. Any one 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 evaporation apparatus by this vacuum evaporation method. In order to improve the adhesion between the inorganic oxide thin film layer and the plastic substrate and the denseness of the inorganic oxide thin film layer, a plasma assist method or an ion beam assist method can be used. Further, in order to increase the transparency of the inorganic oxide thin film layer, it is possible to carry out reactive vapor deposition in which oxygen gas or the like is blown during vapor deposition.

  The coating layer 4 provided on the inorganic oxide thin film layer 3 in the embodiment shown in FIG. 2 is for protecting the inorganic oxide thin film layer 3 and is used for providing a high gas barrier property. Is a layer.

  Regarding the coating layer 4, as a material for forming a coating layer that imparts high gas barrier properties, for example, a material composed of a water-soluble polymer and at least one metal alkoxide and / or a hydrolyzate thereof, and further, the metal alkoxide, A solution made of any of tetraethoxysilane, triisopropoxyaluminum, or a mixture thereof is applied and formed. Other examples of the coating layer that imparts high gas barrier properties include those comprising a water-soluble polymer and tin chloride, and further comprising a solution comprising the water-soluble polymer coated with polyvinyl alcohol. Specifically, a solution in which a water-soluble polymer and tin chloride are dissolved in an aqueous (water or water / alcohol mixed) solvent, or a solution in which a metal alkoxide is directly or previously hydrolyzed in the solution. The mixed solution is formed on the inorganic oxide thin film layer 3 by coating 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 for forming 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 here is generally obtained by saponifying polyvinyl acetate, and includes from so-called partially saponified PVA in which several dozen percent of acetate groups remain to complete PVA in which only several percent of acetate groups remain. There is no particular limitation.

The tin chloride may be stannous chloride (SnCl ₂ ), stannic chloride (SnCl ₄ ), or a mixture thereof, and may be used as an anhydride or a hydrate.

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

  Each of the above components can be used alone or in combination to form a coating layer, and further within the range that does not impair the gas barrier properties of the coating layer, isocyanate compound, silane coupling agent, dispersant, stabilizer, viscosity adjustment You may add additives, such as an agent and a coloring agent.

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

  Conventionally known means such as a dipping method, a roll coating method, a screen printing method, a spray method and the like that are usually used can be used for the coating method for forming the coating layer 4. The thickness of the coating layer varies depending on the type of coating agent for forming the coating layer and the processing conditions, but it is sufficient that the thickness after drying is 0.01 μm or more, but if the thickness is 50 μm or more, the film will crack. Since it becomes easy, the range of 0.01-50 micrometers is preferable.

  Further, another layer can be laminated on the inorganic oxide thin film layer 3 or the coating layer 4. For example, a printing layer, an intervening film, a heat seal layer, and the like. The printed layer is formed for practical use as a packaging bag, etc., 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 additives such as extender pigments, plasticizers, desiccants, stabilizers and the like are added, and characters, patterns, etc. are formed. As a forming method, for example, a known printing method such as an offset printing method, a gravure printing method, or a silk screen printing method, or a known coating method such as a roll coating, a knife edge coating, or a gravure coating can be used. The thickness may be 0.1 to 2.0 μm.

  In addition, the intervening film is provided to increase the bag breaking strength during boil and retort sterilization. Generally, from the viewpoint of mechanical strength and thermal stability, biaxially stretched nylon film, biaxially stretched polyethylene terephthalate film, biaxially stretched It is a kind selected from polypropylene films. 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 known method such as a dry laminating method in which an adhesive such as a two-component curable urethane resin is used.

  The heat seal layer is provided as a sealing layer when a bag-like package or the like is formed. 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 their metals A film made of one kind of resin such as a cross-linked 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 common to use a dry laminating method or the like in which a film forming a heat seal layer is bonded using an adhesive such as a two-component curable urethane resin. Can do.

  The vapor deposition film of this invention and the packaging material using this vapor deposition film are further demonstrated with a specific Example.

<Preparation of primer agent>
A) In a diluting solvent (ethyl acetate), 5 parts by weight of acrylic polyol is weighed and mixed with 1 part by weight of γ-isocyanatopropyltrimethoxysilane and stirred. Next, a primer solution A is prepared by diluting a mixed solution in which TDI is added as an isocyanate compound so that the amount of NCO groups is equal to the OH group of the acrylic polyol to a concentration of 2%.

  B) In an diluted solvent (ethyl acetate), 6 parts by weight of acrylic polyol is weighed and stirred with respect to 1 part by weight of N-β- (aminoethyl) -γ-aminopropyltriethoxysilane. Next, a primer solution B is obtained by diluting a mixed solution of TDI as an isocyanate compound so that NCO groups are equivalent in amount to OH groups of the acrylic polyol to a concentration of 2%.

C) In a diluting solvent (isopropyl alcohol / ethyl acetate), 2.5 parts by weight of acrylic polyol was mixed with 1 part by weight of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (hereinafter referred to as EETMS), and As a catalyst, a tin chloride (SnCl ₂ ) / methanol solution (prepared to 0.003 mol / g) is added to EETMS so as to be 1/135 mol and stirred. Next, a primer solution C is prepared by diluting a mixed solution in which TDI is added as an isocyanate compound so that the amount of NCO groups is equal to the OH group of the acrylic polyol to a concentration of 2%.

D) Acrylic polyol mixed with EETMS and tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ : hereinafter referred to as TEOS) in a dilute solvent (isopropyl alcohol / ethyl acetate) so as to have a molar ratio of 1: 1. Of EETMS and TEOS is weighed 1.25 times by weight, and a tin chloride (SnCl ₂ ) / methanol solution (prepared to 0.003 mol / g) is used as a catalyst in addition to EETMS and TEOS. Is added to the mixture so as to be 1/400 mol and stirred. 0.1N HCl was added thereto, stirred and hydrolyzed, and then a primer solution D was prepared by diluting a mixed solution in which TDI was added so that the NCO group was equivalent to the OH group of the acrylic polyol to a concentration of 2%. .

  E) In a diluting solvent (ethyl acetate), TDI as an isocyanate compound was added to the acrylic polyol so as to have an equivalent amount with respect to the OH group of the acrylic polyol, and the diluting solvent was added to a concentration of 2%. Primer E And

  F) TEOS equivalent to 0.1 part by weight is added to 1 part by weight of acrylic polyol in dilute solvent (isopropyl alcohol / ethyl acetate), 0.1N HCl is added thereto, and after stirring and hydrolysis, TDI is converted into acrylic polyol. A primer solution F was prepared by diluting a mixed solution of NCO groups so as to have an equal amount of NCO groups to 2% concentration.

<Example 1>
As a plastic substrate 1, a primer agent A as a primer layer 2 having a thickness of 0.2 μm (dry film thickness) was formed on one side of a 12 μm-thick biaxially stretched polyethylene terephthalate (PET) film. Next, metal aluminum was evaporated on the primer layer 2 by an electron beam heating vacuum deposition apparatus, oxygen gas was introduced therein, and aluminum oxide was deposited to form an inorganic oxide thin film layer 3 having a thickness of 20 nm. Further, a coating agent having the following composition was applied thereon with a gravure coater and dried at 100 ° C. for 1 minute with a dryer to obtain a deposited film having a coating layer 4 having a thickness of 0.3 μm. As the composition of the coating agent, one liquid and two liquids mixed at a blending ratio (wt%) of 60/40 was used. Here, 1 liquid is a hydrolyzed solution having a solid content of 3 wt% (in terms of SiO ₂ ) obtained by adding 89.6 g of hydrochloric acid (0.1N) to 10.4 g of tetraethoxysilane, and stirring and hydrolyzing for 30 minutes. It is a 3 wt% water / isopropyl alcohol solution of polyvinyl alcohol (water: isopropyl alcohol weight ratio 90:10).

<Example 2>
In Example 1, a vapor deposition film was obtained in the same manner except that silicon oxide having a thickness of about 40 nm was vapor deposited as the inorganic oxide thin film layer 3 by a resistance vapor deposition vacuum deposition method.

<Example 3>
A vapor deposition film was obtained in the same manner as in Example 1 except that the primer agent B was used as the primer layer 2.

<Example 4>
In Example 1, a vapor deposition film was obtained in the same manner except that the primer agent C was used as the primer layer 2.

<Example 5>
A vapor deposition film was obtained in the same manner as in Example 1 except that the primer agent D was used as the primer layer 2.

<Comparative example 1>
A vapor deposition film was obtained in the same manner as in Example 1 except that the primer layer 2 was not provided.

<Comparative example 2>
In Example 1, a vapor deposition film was obtained in the same manner except that the primer agent E was used as the primer layer 2.

<Comparative Example 3>
In Example 1, a vapor deposition film was obtained in the same manner except that the primer agent F was used as the primer layer 2.

<Manufacture of packaging materials>
An intervening film made of a biaxially stretched nylon film having a thickness of 15 μm is laminated on the coating layer side of the vapor deposited films of Examples 1 to 5 and Comparative Examples 1 to 3 by a dry laminating method through a two-component curable urethane adhesive. Furthermore, a packaging material was obtained by laminating a low-density polyethylene film having a thickness of 40 μm as a polyolefin heat seal layer on the intervening film by a dry laminating method through a two-component curable urethane adhesive.

<Test 1>
A pouch having a four-side seal portion is made of a packaging material using the vapor deposition films of Examples 1 to 5 and Comparative Examples 1 to 3, each filled with 150 g of water, and subjected to retort sterilization at 121 ° C. for 30 minutes. went. As an evaluation, the oxygen transmission rate (cc / m ² / day) before and after retort sterilization, the peel strength (gr / 15 mm) and the delamination occurrence after retort were observed. The peeled surface was observed by detecting the aluminum element from the plastic substrate and the sealant film with a fluorescent X-ray apparatus and estimating the peeled surface. The results are shown in Table 1.

  1) The peel strength was measured by pulling at a peel speed of 300 mm / min.

  2) The oxygen transmission rate was measured in an atmosphere of 30 ° C. and 70% RH using an oxygen transmission measuring device; OXTRAN-10 / 50A manufactured by Modern Control.

  3) In the evaluation of the peeling surface, AlO represents cohesive failure of the inorganic oxide thin film layer, and ADH represents peeling between the coating layer and the adhesive layer.

  4) After the retort sterilization, the appearance was observed by bending the pouch seal part by 180 °. When the inorganic oxide thin film layer was delaminated, the appearance was indicated by “x”, and when it was not delaminated, “◎” was indicated.

  As shown in Table 1 above, all the packaging materials have no problem in adhesion and gas barrier properties before retorting. However, looking at the results after retorting, it can be seen that the packaging materials of Examples 1 to 5 are not deteriorated in gas barrier properties and are peeled off by the adhesive layer even when viewed from the peeled surface, and maintain high adhesion. . On the other hand, when Comparative Examples 1 to 3 are seen, delamination or the like occurs after retorting, resulting in poor appearance, and observation of the peeled surface shows that the adhesion between the plastic substrate and the inorganic oxide thin film layer is insufficient. Therefore, the packaging materials of Examples 1 to 5 have a high gas barrier property that blocks the gas that affects the contents from those of Comparative Examples 1 to 3, and there is no deterioration after retort, and the occurrence of delamination, etc. Satisfies all retort resistance.

<Example 6>
As a plastic substrate 1, a primer agent A as a primer layer 2 having a thickness of 0.2 μm (dry film thickness) was formed on one side of a 12 μm-thick biaxially stretched polyethylene terephthalate (PET) film. Next, metal aluminum was evaporated by an electron beam heating vacuum deposition apparatus, and oxygen gas was introduced therein, thereby forming an inorganic oxide thin film layer 3 made of aluminum oxide having a thickness of 20 nm on the primer layer 2. A polypropylene film having a thickness of 30 μm was laminated as a heat seal layer on the inorganic oxide thin film layer 3 of the obtained vapor-deposited film by dry lamination via a two-component curable urethane adhesive to obtain a packaging material.

<Comparative example 4>
In Example 6, a packaging material was obtained in the same manner as in Example 6 except that the primer layer 2 was not provided.

<Test 2>
The laminate strength (gr / 15 mm) between the inorganic oxide thin film layer and the heat seal layer (polypropylene film) was measured using the packaging material of Example 6 and the packaging material of Comparative Example 4 thus produced. . At the same time, the laminate strength (gr / 15 mm) was measured in the same manner while hanging a small amount of tap water on the peel surface of the inorganic oxide thin film layer and the heat seal layer. The peel strength was measured by pulling at a peel speed of 300 mm / min. The results are shown in Table 2.

It is sectional drawing of the vapor deposition film of this invention. It is sectional drawing which shows the other example of the vapor deposition film of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Plastic base material 2 ... Primer layer 3 ... Inorganic oxide thin film layer 4 ... Film layer.

Claims (10)

  A silane coupling agent having an organic functional group that reacts with at least one of a hydroxyl group of a polyol or an isocyanate group of an isocyanate compound, or a hydrolyzate of a silane coupling agent on at least one surface of a plastic substrate made of a plastic material, and a polyol, A vapor deposition film for boil sterilization and retort sterilization, wherein a primer layer containing a composite with an isocyanate compound, an inorganic oxide thin film layer made of an inorganic oxide, and a coating layer are sequentially laminated.   A silane coupling agent having an organic functional group that reacts with at least one of a hydroxyl group of a polyol or an isocyanate group of an isocyanate compound, or a hydrolyzate of a silane coupling agent on at least one surface of a plastic substrate made of a plastic material, and a polyol, A vapor deposition film for a packaging container containing a moisture-containing content, wherein a primer layer containing a composite with an isocyanate compound, an inorganic oxide thin film layer made of an inorganic oxide, and a coating layer are sequentially laminated.   The vapor-deposited film according to claim 1 or 2, wherein the organic functional group contained in the silane coupling agent is any one of an isocyanate group, an amino group, and a mercapto group.   The vapor-deposited film according to claim 1, wherein the polyol is an acrylic polyol.   The thickness of the said primer layer is the range of 0.01-2 micrometers, The vapor deposition film in any one of Claims 1-4 characterized by the above-mentioned.   The vapor-deposited film according to claim 1, wherein the inorganic oxide is aluminum oxide, silicon oxide, magnesium oxide, or a mixture thereof.   The said coating layer consists of a water-soluble polymer, a metal alkoxide, and / or its hydrolyzate, The vapor deposition film in any one of Claims 1-6 characterized by the above-mentioned.   The vapor-deposited film according to claim 7, wherein the metal alkoxide is composed of any of tetraethoxysilane, triisopropoxyaluminum, or a mixture thereof.   The vapor-deposited film according to claim 7 or 8, wherein the water-soluble polymer is made of polyvinyl alcohol.   A packaging material, wherein a heat seal layer is laminated on the coating layer of the vapor deposition film according to claim 1 through an adhesive layer.

Images