JP4654662B2 - Packaging using gas barrier film laminate having heat treatment resistance - Google Patents

Description

The present invention relates to a package using a gas barrier film laminate in which the initial gas barrier properties are not easily deteriorated even when heat treatment such as heat sterilization is performed, and more specifically, packaging material for retort food and medical packaging suitably used as materials, the initial gas barrier properties even in the heat treatment in the heat sterilization treatment or cooking such as boiling sterilization or retort sterilization is to withstands the gas barrier film laminate having a heat treatment resistance It relates to the package used .

  In recent years, packaging materials used for packaging foods, pharmaceuticals, etc. have the function of preventing the influence of oxygen, water vapor, and other gases that alter the contents, in order to suppress the alteration of the contents and retain their functions and properties. It is required to have a gas barrier property that prevents these permeations. Therefore, conventionally, as a packaging material used for packaging foods and pharmaceuticals, a material using a metal foil such as an aluminum foil that is less affected by temperature, humidity, etc. as a gas barrier layer has been generally used.

  However, packaging materials using metal foil such as aluminum foil are not easily affected by temperature and humidity, and have high gas barrier properties. When it was later disposed of, it had to be treated as an incombustible material, and further, there were various drawbacks such as the inability to use a metal detector for inspection.

  Therefore, in order to overcome these drawbacks, for example, as described in Patent Documents 1 and 2, etc., inorganic materials such as silicon oxide and aluminum oxide are formed on the polymer film by thin film forming means such as vacuum deposition and sputtering. A vapor deposition film formed by forming a vapor deposition thin film of an oxide has been developed. These vapor-deposited films are known to have transparency and gas barrier properties against oxygen, water vapor, etc., and are used in various packaging fields as packaging materials having both transparency and gas barrier properties that cannot be obtained with metal foil or the like. Used in.

  On the other hand, as a method for imparting post-processing suitability to the deposited film as described above, a water-soluble polymer having a hydroxyl group and one or more kinds of metal alkoxides as the second layer on the inorganic oxide deposited thin film or After post-processing by applying a coating agent mainly composed of a metal alkoxide hydrolyzate or an aqueous solution containing at least one of tin chloride, or a water / alcohol mixed solution, followed by heat drying. A technique for reducing the deterioration of the gas barrier property has also been proposed (see, for example, Patent Document 3).

The gas barrier film according to this proposal has excellent gas barrier properties, transparency and suitability for post-processing, and is therefore widely used in the packaging field. The gas barrier coating layer is composed of a metal alkoxide hydrolyzate and a water-soluble film. Since it is mainly composed of a polymer, it forms a hard film. When a gas barrier film formed by partially laminating such a hard coating layer is used as a packaging material for medical products and retort foods, heat treatment related to boil sterilization, retort sterilization, and cooking, etc. When applied, the packaging material expands due to the effect of heat at that time, but the hard coating layer on the gas barrier film is difficult to follow the deformation associated with the expansion of the other constituent layers, so cracks and peeling occur. This is a cause of deterioration in the initial gas barrier properties.
U.S. Pat. No. 3,442,686 Japanese Patent Publication No.63-28017 Japanese Patent Laid-Open No. 7-164591

  The present invention has been made in view of the situation as described above, and has heat treatment resistance that makes it difficult for the initial gas barrier property to deteriorate even when heat treatment such as boil sterilization, retort sterilization, and heat cooking is performed. The object is to provide a gas barrier film laminate.

In order to achieve the above object, the invention according to claim 1 is characterized in that an applied power is 120 W, a processing time is 0.1 sec, a processing gas is argon, a processing unit pressure is applied to at least one surface of the plastic film substrate layer. Plasma pretreatment layer formed by plasma treatment using reactive ion etching (RIE) with each set to 2.0 Pa, an inorganic oxide vapor deposition layer, a water-soluble polymer and one or more metal alkoxides or their hydrolysis A gas barrier composite coating layer formed by applying a coating agent mainly composed of an aqueous solution containing water or a water / alcohol mixed solution and heating and drying is sequentially provided. On the gas barrier composite coating layer, a two-component curing type is provided. Functional plastic via an adhesive layer made of polyurethane adhesive and having a thickness in the range of 1.5 to 4.5 μm Click film layer is a packaging body using the gas barrier film laminate having a heat treatment resistance, characterized in that it is laminated and integrated.

Further, an invention according to claim 2, wherein, in the package using the gas barrier film laminate having a heat treatment resistance according to claim 1 Symbol placement, the inorganic oxide vapor-deposited thin film layer, aluminum oxide, silicon oxide, It consists of either magnesium or a mixture thereof.

Furthermore, the invention according to claim 3 is the packaging body using the gas barrier film laminate having heat treatment resistance according to any one of claims 1 or 2 , wherein the metal alkoxide is tetraethoxysilane or triisosilane. It is characterized by being either propoxyaluminum or a mixture thereof.

Furthermore, the invention according to claim 4 is a package using the gas barrier film laminate having heat treatment resistance according to any one of claims 1 to 3 , wherein the coating agent is a water-soluble polymer component. It includes at least one of polyvinyl alcohol or poly (vinyl alcohol-o-ethylene), cellulose, and starch.

The gas barrier film laminate having the heat treatment resistance of the present invention is less deteriorated in gas barrier properties even when heat is applied by heat treatment in retort sterilization, boil sterilization, heat cooking, etc., such as boil sterilization and retort sterilization. It is suitably used as a heat-treated medical packaging material for which heat sterilization is performed, a retort food packaging material for which heat cooking is performed, and a packaging material for electronic members.

  An embodiment of the present invention will be described below with reference to the drawings.

  1 and 2 are explanatory views showing a cross-sectional configuration of a gas barrier film laminate having heat treatment resistance according to the present invention. A gas barrier film laminate 10 having heat treatment resistance shown in FIG. 1 has a plasma pretreatment layer 4 formed on one surface of a plastic film substrate layer 1 by plasma treatment using reactive ion etching (RIE). And an inorganic oxide vapor-deposited thin film layer 2 and a coating agent mainly composed of an aqueous solution or water / alcohol mixed solution containing a water-soluble polymer and one or more metal alkoxides or hydrolysates thereof, and dried by heating. The gas barrier composite coating layer 3 is sequentially provided, and the gas barrier composite coating layer 3 is made of a two-component curable polyurethane adhesive and has a thickness in the range of 1.5 to 4.5 μm. A functional plastic film layer 7 is laminated and integrated through an agent layer 6.

  On the other hand, the gas barrier film laminate 20 having heat treatment resistance shown in FIG. 2 has a primer layer 24 made of a composite of an acrylic polyol, an isocyanate compound and a silane coupling agent on one surface of the plastic film substrate layer 1. And an inorganic oxide vapor-deposited thin film layer 2 and a coating agent mainly composed of an aqueous solution or water / alcohol mixed solution containing a water-soluble polymer and one or more metal alkoxides or hydrolysates thereof, and dried by heating. The gas barrier composite coating layer 3 is sequentially provided, and the gas barrier composite coating layer 3 is made of a two-component curable polyurethane adhesive and has a thickness in the range of 1.5 to 4.5 μm. A functional plastic film layer 7 is laminated and integrated through an agent layer 6.

  The plastic film base material layer 1 constituting each of the gas barrier laminates 10 and 20 having heat treatment resistance is made of a plastic material and is transparent in order to make use of the transparency of the inorganic oxide deposited thin film layer 2 described later. It is preferable. Examples of the plastic film base layer 1 include polyester films made of polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefin films made of polyethylene, polypropylene, etc., polystyrene films, polyamide films, polycarbonate films, polyacrylonitrile. A film, a polyimide film, etc. are mentioned. These plastic films may be stretched or unstretched, but those having excellent mechanical strength and dimensional stability are preferred. Among these, a polyethylene terephthalate film or a polyamide film arbitrarily stretched in the biaxial direction is preferably used.

  Moreover, this plastic film base material layer 1 has a well-known various additive and stabilizer on the surface on the opposite side to the surface on which the inorganic oxide vapor-deposited thin film layer 2 is provided, for example, an antistatic agent, an ultraviolet ray inhibitor, a plasticizer, A treatment layer made of a lubricant or the like may be provided.

  The plastic film substrate layer 1 may be a single plastic film as described above, or may have a multilayer structure in which these films are laminated. Further, the thickness is not particularly limited, but in consideration of suitability as a packaging material, further, an inorganic oxide vapor-deposited thin film layer 2 and a gas barrier composite coating layer 3 described later, a two-component curable polyurethane adhesive Considering processability when forming the agent layer 6 and further the functional plastic film layer 7, it is practically 3 to 200 μm, preferably 6 to 30 μm.

  In the present invention, a plasma pretreatment layer 4 (see FIG. 1) formed by plasma treatment using reactive ion etching (RIE) on at least one surface of the plastic film substrate layer 1 having such a configuration. Or the primer layer 24 (refer FIG. 2) which consists of a composite of an acrylic polyol, an isocyanate compound, and a silane coupling agent is provided.

  The plasma pretreatment layer 4 and the primer layer 24 are layers provided for further strengthening the adhesion between the plastic film substrate layer 1 and the inorganic oxide vapor deposition layer 3.

  The plasma pretreatment layer 4 formed on the surface of the plastic film substrate layer 1 by plasma treatment using RIE can place functional groups on the surface by radicals and ions generated during the treatment (chemical effect). In addition, it is possible to perform smoothing simultaneously with the removal of impurities by ion etching (physical effect), and a smooth surface free of impurities can be obtained while the functional group is located. Therefore, it is possible to form a dense inorganic oxide deposited thin film layer 2 on the plasma pretreatment layer 4 and the primer layer 24. As a result, the adhesion between the plastic film substrate layer 1 and the inorganic oxide vapor-deposited thin film layer 2 can be strengthened, and the inorganic oxide vapor deposition described later is applied when heat treatment is applied or when an external force is applied. Peeling of the thin film layer 2 and generation of cracks are almost eliminated, and a decrease in gas barrier properties is suppressed.

  On the other hand, the primer layer 24 is also a layer provided to reinforce the adhesion between the plastic film substrate layer 1 and the inorganic oxide vapor-deposited thin film layer 2 in the same manner as the plasma pretreatment layer 4. And a composite of an isocyanate compound and a silane coupling agent.

  Acrylic polyol is a polymer compound obtained by polymerizing an acrylic acid derivative monomer or a polymer compound obtained by copolymerizing an acrylic acid derivative monomer and other monomers, and has a hydroxyl group at the terminal, It is for making it react with the isocyanate group of an isocyanate compound. Among them, those obtained by polymerizing acrylic acid derivative monomers such as ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate alone, and acrylic polyols obtained by copolymerizing with other monomers such as styrene are preferably used. In consideration of the reactivity with the isocyanate compound, those having a hydroxyl number between 5 and 200 (KOHmg / g) are preferred.

  The isocyanate compound reacts with the acrylic polyol and is added to further enhance the adhesion between the plastic film substrate layer 1 and the inorganic oxide vapor-deposited thin film layer 2 by a urethane bond formed at that time. Acts as an agent or curing agent. Examples of the isocyanate compound having such an action include aromatic tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), aliphatic xylene diisocyanate (XDI), hexadiene isocyanate (HMDI), and isophorone diisocyanate (IPDI). Monomers such as these and polymers and derivatives thereof are preferably used. These can be used alone or in admixture of two or more.

  The blending ratio of these acrylic polyol and isocyanate compound is not particularly limited, but if the isocyanate compound is too small, curing may be poor, and if it is too much, blocking or the like may occur. As the blending ratio of the acrylic polyol and the insocyanate compound, the isocyanate group derived from the isocyanate compound is preferably 50 times or less of the hydroxyl group derived from the acrylic polyol. Particularly preferred is a case where an isocyanate group and a hydroxyl group are blended in equal amounts. As the mixing method, a known method can be used and is not particularly limited.

  The silane coupling agent preferably has a functional group that reacts with the hydroxyl group of the acrylic polyol or the isocyanate group of the isocyanate compound. For example, those containing an isocyanate group such as γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β- (aminoethyl)- Those containing amino groups such as γ-aminopropyltriethoxysilane, γ-phenylaminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Such as those containing an epoxy group, etc., and these can be used alone or in admixture of two or more.

  In these silane coupling agents, an organic functional group present at one end interacts in a composite composed of an acrylic polyol and an isocyanate compound to form a strong film. Also, the silane coupling agent containing a functional group that reacts with the hydroxyl group of acrylic polyol or the isocyanate group of the isocyanate compound forms a covalent bond, forms a stronger film, and is generated by hydrolysis of the alkoxy group at the other end. The silanol group has a strong interaction with the metal in the inorganic oxide and the highly active hydroxyl group on the surface of the inorganic oxide, and exhibits excellent adhesion with the inorganic oxide deposited thin film layer 2. . Therefore, you may use what hydrolyzed the said silane coupling agent with the metal alkoxide. Moreover, there is no problem even if the alkoxy group of the silane coupling agent is a chloro group, an acetoxy group or the like, and these alkoxy groups, chloro groups, acetoxy groups, etc. are hydrolyzed to form silanol groups. Can also be used.

  The mixing ratio of the acrylic polyol and the silane coupling agent is preferably from 1/1 to 100/1, more preferably from 2/1 to 50/1, by weight.

  Further, the thickness of the primer layer 24 having such a structure is not particularly limited as long as it can form a uniform coating film, but generally 0.01 to 2 μm in dry film thickness. It is preferable to be in the range. 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, if the thickness exceeds 2 μm, it is difficult to maintain flexibility in the coating film, and if an external force is applied, the coating film may be cracked, which is not preferable.

  Examples of the method for forming the primer layer 24 include known printing methods such as offset printing, gravure printing, and silk screen printing, and known coating methods such as roll coating, knife edge coating, and gravure coating. . As drying conditions, generally used conditions are employed.

  On the other hand, the inorganic oxide vapor-deposited thin film layer 2 is provided on each of the plasma pretreatment layer 4 and the primer layer 24 provided for improving adhesion (FIGS. 1 and 2). 2). Hereinafter, the inorganic oxide deposited thin film layer 2 will be described in detail.

  The inorganic oxide vapor-deposited thin film layer 2 is a vapor-deposited thin film made of an inorganic oxide such as aluminum oxide, silicon oxide, tin oxide, magnesium oxide, or a mixture thereof, and has transparency and gas barrier properties against oxygen, water vapor, etc. It is a layer which has. Considering expression of heat treatment resistance to various heat treatments such as heat sterilization treatment and cooking, among these, a thin film layer made of aluminum oxide or silicon oxide is particularly preferable. However, the constituent material of the inorganic oxide vapor-deposited thin film layer in the present invention is not limited to the above-mentioned inorganic oxide, and other inorganic oxides can be used as long as the material meets the above conditions. .

  The optimum thickness of the inorganic oxide vapor-deposited thin film layer 2 varies depending on the type and configuration of the inorganic oxide used, but generally the range of 5 to 300 nm is desirable, and the value is appropriately selected within this range. obtain. However, if the thickness is less than 5 nm, it may be difficult to obtain a uniform layer or the thickness may not be sufficient, and the gas barrier function may not be sufficiently achieved. Further, when the thickness exceeds 300 nm, it is difficult to maintain flexibility, and there is a problem because cracks may occur when a force such as bending or pulling is applied after film formation. More preferably, the thickness is in the range of 10 to 150 nm.

  There are various methods for forming the inorganic oxide vapor-deposited thin film layer 2 on the plasma pretreatment layer 4 and the primer layer 24, but generally a normal vacuum vapor deposition method can be employed. In addition, other thin film forming methods such as sputtering, ion plating, and plasma vapor deposition (CVD) can also be used. However, considering productivity, the vacuum deposition method is the best at present. In addition, it is preferable to use any one of an electron beam heating method, a resistance heating method, and an induction heating method as the heating means of the vacuum evaporation method, but considering the wide range of selectivity of the evaporation material, the electron beam heating method is used. More preferably, it is used. Further, in order to further improve the adhesion to the plasma pretreatment layer 4 and the primer layer 24 and the denseness of the thin film, this layer can be formed by using a plasma assist method or an ion beam assist method. In order to increase transparency, it is possible to use reactive vapor deposition performed by blowing various gases such as oxygen.

  Next, the gas barrier composite coating layer 3 provided on the inorganic oxide vapor deposition layer 2 will be described. The gas barrier composite coating layer 3 is a coating layer having a gas barrier property, and is a layer provided for developing an excellent gas barrier property in cooperation with the inorganic oxide vapor-deposited thin film layer 2. And a coating agent mainly comprising an aqueous solution or a water / alcohol mixed solution containing at least one metal alkoxide or a hydrolyzate thereof, and dried by heating.

  More specifically, a coating agent is prepared by mixing a water-soluble polymer dissolved in an aqueous (water or water / alcohol mixed) solvent with a metal alkoxide directly or previously hydrolyzed to form a coating agent. After coating on the oxide vapor-deposited thin film layer 2, it is formed by heating and drying. Hereinafter, each component contained in the coating agent will be described in more detail.

  Examples of the water-soluble polymer constituting the coating agent include polyvinyl alcohol, poly (vinyl alcohol-o-ethylene), polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, sodium alginate and the like. In particular, polyvinyl alcohol (hereinafter abbreviated as PVA) is preferable because excellent gas barrier properties can be expressed. PVA here is generally obtained by saponifying polyvinyl acetate. As PVA, for example, complete PVA in which only a few percent of acetic acid groups remain from so-called partially saponified PVA in which several tens percent of acetic acid groups remain can be used.

The metal alkoxide is a compound represented by the general formula, M (OR) n (M: metal such as Si, Ti, Al, Zr, R: alkyl group such as CH ₃ , C ₂ H _5, etc.) Specifically, tetraethoxysilane [Si (OC ₂ H ₅ ) ₄ ], triisopropoxy aluminum [Al (O-2′-C ₃ H ₇ ) ₃ ] and the like can be mentioned. Among these, tetraethoxysilane and triisopropoxyaluminum are preferable because they are relatively stable in an aqueous solvent after hydrolysis.

  In the coating agent, a known additive such as an isocyanate compound, a silane coupling agent, a dispersant, a stabilizer, a viscosity modifier, a colorant, or the like is added as necessary, as long as the gas barrier property is not impaired. Is also possible.

As a method for forming the gas barrier composite coating layer 3 using such a coating agent, a conventionally known method such as a dipping method, a roll coating method, a screen printing method, a spray method, or a gravure printing method may be used. Is possible.

  The thickness of the gas barrier composite coating layer 3 is not particularly limited, and the optimum condition varies depending on the type of coating agent, the type of processing machine, the difference in processing conditions, and the like. However, when the thickness after drying is 0.01 μm or less, a uniform film cannot be obtained and sufficient gas barrier properties may not be obtained. On the other hand, if the thickness exceeds 50 μm, cracks are likely to occur in the coating, which may be a problem. Therefore, the thickness may be in the range of 0.01 to 50 μm, more preferably 0.1 to 10 μm.

  The gas barrier film laminate having heat treatment resistance according to the present invention comprises a two-component curable polyurethane adhesive on the gas barrier composite coating layer 3 described above, and has a thickness of 1.5 to 4.5 μm. The functional plastic film layer 7 is further laminated and integrated through the adhesive layer 6 in the above.

  The functional plastic film layer 7 is a layer made of a plastic material that is laminated to give various functions required as a packaging material or the like to the gas barrier film laminate having heat treatment resistance according to the present invention. An intervening film or a sealant layer.

  The intervening film is provided to increase the bag breaking strength and piercing strength when used as a bag-like packaging material, and is generally a biaxially stretched nylon film or a biaxially stretched polyethylene in terms of mechanical strength and thermal stability. It is selected from terephthalate films and biaxially oriented polypropylene films. The thickness is determined according to the material and required quality, but is generally in the range of 10 to 30 μm.

  Further, the sealant layer is provided so as to function as an adhesive layer when a bag-like package or the like is produced. Specifically, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer And a resin such as a metal cross-linked product thereof. The thickness is determined according to the purpose, but is generally in the range of 15 to 200 μm.

  The adhesive layer 6 is formed by laminating and integrating the functional plastic film layer 7 having these functions on the gas barrier coating layer 3, and heat-sterilizing the gas barrier film laminate having the heat treatment resistance of the present invention. Even if heat treatment such as heat cooking is performed, this layer is provided in order to prevent the initial gas barrier property that was possessed before the heat treatment from being easily deteriorated.

  In general, in a laminate in which the inorganic oxide vapor-deposited thin film layer and the gas barrier composite coating layer responsible for the development of gas barrier properties are sandwiched and laminated between a part of the laminate in the configuration as described above, These layers, which are hard and brittle, cannot follow the deformation based on the expansion due to the heat applied to the body, and there is a risk of the occurrence of cracks and peeling. On the other hand, the gas barrier film laminate having heat treatment resistance of the present invention has an inorganic oxide vapor-deposited thin film layer and a gas barrier composite coating layer sandwiched between the hard and brittle properties in the middle, Since the functional plastic film layer 6 is laminated and integrated through an adhesive layer having a thickness of 1.5 to 4.5 μm, which is composed of a curable polyurethane adhesive layer, Even if the adhesive layer works as a buffer layer against various forces applied during deformation, as a result, cracking and peeling are unlikely to occur in the inorganic oxide vapor-deposited thin film layer and gas barrier composite coating layer, and heat treatment is performed. Deterioration of gas barrier properties is difficult to occur.

Incidentally, the two-component curable polyurethane adhesive was selected from various adhesives because this adhesive has heat resistance, and the adhesive layer formed thereby is subjected to heat treatment. This is because even if it is broken, the adhesiveness is hardly lowered, and such actions and effects cannot be achieved by other adhesives. Further, if the thickness is less than 1.5 μm, not only is it difficult to form a uniform layer on the gas barrier composite coating layer 3, but the above-mentioned function cannot be expected, and the gas barrier is deteriorated. And cause delamination. Moreover, when the thickness exceeds 4.5 μm, deformation due to expansion and contraction of the adhesive layer due to heat during heat treatment increases, and the inorganic oxide vapor-deposited thin film layer 2 and the gas barrier composite coating layer 3 can follow these deformations. It will be lost, and cracks and peeling will easily occur.

  The two-component curable polyurethane adhesive layer 6 having such an action is composed of a main component having a hydroxyl group at the polymer terminal and a curing agent having an isocyanate group (polyisocyanate), and urethane is reacted by the reaction between the hydroxyl group and the isocyanate group. It is a layer formed by forming a bond and curing.

  As the main agent having a hydroxyl group at the polymer terminal, a polyester polyol having a terminal hydroxyl group comprising a polyol and a dicarboxylic acid, a polyester polyurethane polyol obtained from a polyester polyol and a diisocyanate, a polyether polyurethane polyol obtained from a polyether polyol and a diisocyanate, and a polyester polyol Examples thereof include a polyester polyether polyurethane polyol obtained from a mixture of polyether polyol and diisocyanate, all of which are bifunctional or trifunctional polyols. Among these, a polyester-based material is preferable as the main agent effective in imparting heat treatment resistance. These may be acid anhydride-modified.

  On the other hand, as a curing agent, an adduct obtained by adding diisocyanate to trimethylolpropane, a burette obtained by reacting water with diisocyanate, a polyfunctional compound having bond formation such as isocyanurate obtained by a polymer of diisocyanate. Polyisocyanates can be used alone or in combination of two or more. Diisocyanates include diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, aromatic diisocyanate such as tolylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate. And alicyclic diisocyanates such as hydrogenated 4,4′-diphenylmethane diisocyanate, methylcyclohexylene diisocyanate, isopropylidene dicyclohexyl-4,4′-diisocyanate, and the like.

  What is necessary is just to add the compounding ratio of a main ingredient and a hardening | curing agent so that the equivalent ratio of the hydroxyl group of a main ingredient / isocyanate group of a hardening | curing agent may become the range of 1 / 1-1 / 3.

  It is also possible to add additives such as silane coupling agents, titanate coupling agents, phosphoric acids and derivatives thereof, polybasic acid anhydrides and the like into the adhesive.

Examples of the present invention will be specifically described below. The present invention is not limited to these examples.
<Preparation of primer solution>
First, γ-isocyanatopropyltrimethylsilane and acrylic polyol were mixed at a ratio of 1 to 10 parts by weight in a diluting solvent (ethyl acetate) and stirred. Next, a 7 to 3 mixture of xylylene diisocyanate and isophorone diisocyanate was added as an isocyanate compound so that the isocyanate groups of this isocyanate compound were equivalent to the hydroxyl groups of the acrylic polyol. Then, this mixed solution was diluted with ethyl acetate so that the total concentration of the added compounds was 2% by weight to obtain a primer solution.
<Preparation of gas barrier coating solution>
Liquid A and liquid B having the composition shown below were mixed at a blending ratio (wt%) of 6/4 to obtain a gas barrier coating solution.

<Liquid A>
Hydrolysis 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 for 30 minutes for hydrolysis.

<Liquid B>
3 wt% water / isopropyl alcohol solution of polyvinyl alcohol (water: isopropyl alcohol weight ratio 90:10).

  Next, a 12 μm thick biaxially stretched polyethylene terephthalate (PET) film is used as the plastic film base layer, and the applied power is 120 W on one side, the processing time is 0.1 sec, the processing gas is argon, and the processing unit pressure is Was set to 2.0 Pa, and plasma treatment using reactive ion etching (RIE) was performed to provide a plasma pretreatment layer. At this time, a high frequency power source having a frequency of 13.56 MHz was used for the electrodes.

  Subsequently, metal aluminum is evaporated by an electron beam heating method, oxygen gas is introduced therein, aluminum oxide having a thickness of 15 nm is deposited on the plasma pretreatment layer obtained in the above step by vacuum deposition, and inorganic oxidation is performed. A physical vapor deposition thin film layer was formed. Next, the gas barrier coating solution described above was applied onto the inorganic oxide vapor-deposited thin film layer by a gravure coating method and dried to form a gas barrier composite coating layer having a thickness of 0.4 μm to obtain a laminated film. This laminated film was designated as gas barrier film A.

  On the other hand, a biaxially stretched polyethylene terephthalate (PET) film having a thickness of 12 μm is used as a plastic film substrate layer, and a primer solution having the above-described composition is applied to one side thereof by a gravure coating method and dried to have a thickness of 0 A 1 μm primer layer was formed. Then, an inorganic oxide vapor-deposited thin film layer and a gas barrier composite coating layer were formed on the primer layer by the same method as the gas barrier film A, and this was used as a gas barrier film B.

On the other hand, a biaxially stretched polyethylene terephthalate (PET) film having a thickness of 12 μm is used as a plastic film substrate layer, and metal aluminum is evaporated on one side thereof by an electron beam heating method, and oxygen gas is introduced thereinto. Was deposited by vacuum deposition to form an inorganic oxide deposited thin film layer. Subsequently, the gas barrier coating solution described above was applied onto the inorganic oxide vapor-deposited thin film layer by a gravure coating method and dried to form a gas barrier composite coating layer having a thickness of 0.4 μm to obtain a laminated film. This laminated film was designated as gas barrier film C.
<Creation of two-component curable polyurethane adhesive>
Polyester polyurethane polyol is used as the main agent and isophorone diisocyanate (IPDI) adduct is used as the curing agent, and the mixture is mixed so that each functional group ratio is 1/1, so that the solid content is 30 wt%. It was diluted with ethyl acetate to obtain a two-component curable polyurethane adhesive.

  On the gas barrier composite coating layer of the gas barrier film A, a stretched nylon film (thickness 15 μm) and an unstretched polypropylene film (thickness 70 μm) are made of a two-component curable polyurethane adhesive having the above composition. The gas barrier film laminate having heat treatment resistance according to Example 1 was obtained by sequentially laminating sequentially through a 2.5 μm adhesive layer by a dry laminating method.

On the gas barrier composite coating layer of the gas barrier film B, a stretched nylon film (thickness 15 μm) and an unstretched polypropylene film (thickness 70 μm) are sequentially laminated under the same conditions as in Example 1 for reference. to obtain a gas barrier Furumu laminate having a heat treatment resistance according to the second embodiment.

  On the gas barrier composite coating layer of the gas barrier film A, the thickness of each adhesive layer is 1.5 μm, and the others have the heat treatment resistance according to Example 3 under the same conditions as in Example 1. A gas barrier film laminate was obtained.

  On the gas barrier composite coating layer of the gas barrier film A, each adhesive layer has a thickness of 3.0 μm, and the other conditions are the same as in Example 1 and have heat treatment resistance according to Example 4. A gas barrier film laminate was obtained.

On the gas barrier composite coating layer of the gas barrier film B, the thickness of each adhesive layer is 3.0 μm, and the heating according to Example 5 for reference is performed under the same conditions as in Example 1. A gas barrier film laminate having processing resistance was obtained.

  On the gas barrier composite coating layer of the gas barrier film A, the thickness of each adhesive layer is 0.8 μm, and the other conditions are the same as in Example 1, and the gas barrier according to Example 6 for comparison is used. A conductive film laminate was obtained.

  On the gas barrier composite coating layer of the gas barrier film B, the thickness of each adhesive layer is 0.8 μm, and the other conditions are the same as in Example 1, and the gas barrier according to Example 7 for comparison is used. A conductive film laminate was obtained.

  On the gas barrier composite coating layer of the gas barrier film A, the thickness of each adhesive layer is 6.0 μm, and the other conditions are the same as in Example 1, and the gas barrier according to Example 8 for comparison is used. A conductive film laminate was obtained.

  On the gas barrier composite coating layer of the gas barrier film B, the thickness of each adhesive layer is 6.0 μm, and the other conditions are the same as in Example 1, and the gas barrier according to Example 9 for comparison is used. A conductive film laminate was obtained.

On the gas barrier composite coating layer of the gas barrier film C, the thickness of each adhesive layer is 3.0 μm, and the other conditions are the same as in Example 1, and the gas barrier according to Example 10 for comparison is used. A conductive film laminate was obtained.
<Evaluation method>
Using the gas barrier film laminate according to each example, a pouch having four sides as seal portions was produced, and 200 g of water was filled as the contents. Thereafter, retort sterilization at 121 ° C. for 30 minutes was performed. In addition, the oxygen permeability before and after the retort treatment (unit: cm ³ / m ² / day, measurement condition: 30 ° C.-70% RH) was measured to evaluate the gas barrier properties. In addition, the state of the pouch after the retort treatment was visually observed to confirm the occurrence of delamination. The results are shown in Table 1.

It is explanatory drawing which shows an example of the cross-sectional structure of the gas-barrier film laminated body which has the heat processing tolerance of this invention. It is explanatory drawing which shows the other example of the cross-sectional structure of the gas-barrier film laminated body which has the heat processing tolerance of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Plastic film base material layer 2 ... Inorganic oxide vapor deposition thin film layer 3 ... Gas barrier composite coating layer 4 ... Plasma pretreatment layer 24 ... Primer layer 6 Adhesive layer 7 ..Functional plastic film layers 10, 20 ... gas barrier film laminate having heat treatment resistance

Claims (4)

On at least one surface of the biaxially stretched polyethylene terephthalate film, the applied power 120 W, 0.1 sec and the processing time, process gas using argon, a reactive ion etching using respectively set pressure to 2.0 Pa (RIE) Applying a coating agent mainly composed of an aqueous solution or water / alcohol mixed solution containing a plasma pretreatment layer formed by plasma treatment, an inorganic oxide vapor deposition layer, a water-soluble polymer and one or more metal alkoxides or hydrolysates thereof. And a gas barrier composite coating layer formed by heating and drying are sequentially provided, and the gas barrier composite coating layer is made of a two-component curable polyurethane adhesive and has a thickness of 1.5 to 4.5 μm. The functional plastic film layer is laminated and integrated through the adhesive layer in Package using the gas barrier film laminate having a heat treatment resistance.   The gas barrier film laminate having heat treatment resistance according to claim 1, wherein the inorganic oxide vapor-deposited thin film layer is made of any one of aluminum oxide, silicon oxide, magnesium oxide, or a mixture thereof. Packaging body.   3. The gas barrier film laminate having heat treatment resistance according to claim 1, wherein the metal alkoxide is either tetraethoxysilane, triisopropoxyaluminum, or a mixture thereof. Package used.   The said coating agent contains at least 1 or more types of polyvinyl alcohol or poly (vinyl alcohol-o-ethylene), a cellulose, and a starch as a water-soluble polymer component, The Claim 1 characterized by the above-mentioned. A package using a gas barrier film laminate having heat resistance to heat.

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