JP2007069411A - Packaging laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a packaging laminate having gas barrier properties constituted so as to prevent not only a deterioration in adhesion or gas barrier properties but also the taste deterioration of content caused by an ink component even if heat treatment is applied under high temperature and high-pressure water is applied by reinforcing the adhesion of a gas barrier vapor deposition thin film layer and reducing the retorting and impact to the vapor deposition thin film layer. <P>SOLUTION: The packaging laminate is constituted by integrally stacking at least an inorganic vapor deposition thin film layer and an inorganic filler-containing resin thin film layer 5 between a plastic base material 2 for an inner layer and a plastic base material 1 for an outer layer so that the inorganic filler-containing resin thin film layer 5 is positioned on the side of the plastic base material for the outer layer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a packaging material having a laminated structure that is suitably used for packaging foods, pharmaceuticals, and the like that require heat treatment with high-temperature and high-pressure water, and more particularly to a packaging laminate having excellent hot water resistance.

  In recent years, packaging materials used for the packaging of foods and pharmaceuticals have been developed from oxygen, water vapor, and other gases that alter the contents of the package so that the functions and properties of the package are suppressed and their functions and properties are maintained. It is necessary to have a function of preventing the influence of the gas, and it is required to have a gas barrier property and the like for blocking the permeation of these gases and the like. Therefore, conventionally, as a packaging material requiring gas barrier properties, a material using a metal foil made of aluminum or the like, which is less affected by temperature, humidity, etc., as a gas barrier layer has been employed.

  Packaging materials using metal foil made of aluminum or the like as a gas barrier layer are less affected by temperature and humidity and have high gas barrier properties. However, they must be treated as non-combustible materials when discarded after use. There was a problem such as having to be.

  Therefore, as a packaging material for overcoming these disadvantages, a metal film such as aluminum or an inorganic oxide such as silicon oxide or aluminum oxide is formed on a polymer film by a thin film forming means such as a vacuum deposition method or a sputtering method. A transparent vapor deposition film formed by forming a vapor deposition thin film layer has been developed. These transparent vapor-deposited films are known to have gas barrier properties against oxygen, water vapor and the like, and are suitable as packaging materials.

  On the other hand, the need for various heat cooking and heat sterilization is increasing in foods and pharmaceuticals, etc., and as a packaging material for wrapping these, even if sterilization is performed under high temperature and high pressure water It is strongly desired that various performances such as initial gas barrier properties and adhesion can be maintained. In view of safety and convenience, development of transparent packaging materials having hot water resistance and barrier properties is also demanded.

  However, if the conventional transparent vapor-deposited film as described above is used as a packaging material and heat cooking or heat sterilization treatment is performed under high-temperature and high-pressure water, the adhesion and gas barrier properties originally possessed by this film can be maintained. It will disappear. As the cause, it is considered that the adhesion between the deposited thin film layer and the substrate is poor, and the crack resistance to the treatment of the deposited thin film layer under high temperature and high pressure water is low.

  One of the causes of poor adhesion is considered to be that a weak surface bonding layer (Weaku Boundary Layer (WBL)) is unevenly distributed on the outermost surface of the substrate. Further, in the case of a vapor deposition film in which a vapor deposition thin film layer is formed on a PET substrate, a hydrolysis layer exists on the surface of the PET substrate, and if a vapor deposition thin film layer is formed thereon, It is considered that a chemical bond that can sufficiently withstand heat treatment with high-temperature and high-pressure water cannot be obtained between the material and the deposited thin film layer.

  In addition, the gas barrier property cannot be maintained because the load (retort impact) applied to the deposited thin film layer induced by the heat treatment with high-temperature and high-pressure water cannot be absorbed in that part, and cracks caused by the load cannot be prevented. This is considered to be because the gas barrier property is lowered.

In order to solve the adhesion problem as described above, plasma treatment has been conventionally applied to the surface of the substrate. For example, an attempt has been made to improve the adhesion by performing metal oxide deposition after performing plasma treatment on a plastic substrate by in-line pretreatment. However, when plasma processing is performed in-line, an electrode for applying a voltage for generating plasma is disposed on the opposite side rather than on the drum side where the substrate is located. As a result, since the base material is installed on the anode side, a high self-bias cannot be obtained, and as a result, a high treatment effect cannot be exhibited.

  In order to obtain a high self-bias, a DC discharge method can be used. However, if a high bias voltage is obtained by this method, the plasma mode changes from glow to arc, so that uniform processing over a large area is possible. I couldn't do it.

  On the other hand, taste deterioration due to transfer of the ink component to the packaged contents (contents) may also be a problem in packaging materials using gas barrier vapor-deposited films. In other words, printing ink used for forming an ink layer applied to a packaging material has a unique odor caused by pigments, binders, and other components (hereinafter referred to as odor components), and may be an oil-based ink. In addition, since an organic solvent is used in addition to these, the flavor (odor, taste) of the contents may be impaired when the odor component in the ink layer of the packaging material is transferred to the package. The influence of this odor component becomes more prominent when heat treatment such as boiling and retort is performed.

  In conventional packaging materials using aluminum foil, the ink layer formed there is positioned on the side that does not touch the aluminum foil package (contents), and the transfer of the ink components to the contents It can be stopped. On the other hand, the gas barrier property that the laminated structure becomes a multilayer structure of substrate / barrier vapor deposition thin film layer / ink layer / adhesive layer / pinhole agent layer / pinhole resistant material layer / adhesive layer / sealant layer When the transparent vapor-deposited film was used as a packaging material, the ink layer was positioned on the content side of the vapor-deposited thin film layer, and thus the transfer of the ink component could not be stopped.

For this reason, Patent Document 1 proposes a packaging material having a configuration in which a barrier layer is disposed in the middle and an ink component is blocked. That is, a gas barrier transparent vapor deposition film for packaging comprising an exterior material layer / ink layer / adhesive layer / base material / barrier vapor deposition thin film layer / adhesive layer / pinhole resistant layer / adhesive layer / sealing material layer Although proposed, in the configuration according to this proposal, the adhesive layer and the barrier layer (barrier vapor deposition thin film layer) are close to each other, and the fluctuation of the adhesive layer during the retorting process is directly transmitted to the barrier layer. As a result, a load is applied to the barrier layer, which causes barrier deterioration.
JP 2003-170536 A

  The present invention has been made in order to solve the above-described problems, and has a structure capable of strengthening the adhesion of a gas barrier vapor-deposited thin film layer and reducing the retort impact on the vapor-deposited thin film layer. A laminate for packaging with gas barrier properties, in which adhesiveness, gas barrier properties, etc. are not deteriorated even when subjected to heat treatment below, and the taste deterioration of the contents due to ink components can also be prevented The purpose is to provide the body.

  In order to achieve the above-described problems, the invention according to claim 1 is characterized in that at least an inorganic vapor-deposited thin film layer and an inorganic filler-containing resin thin film layer are formed of a plastic substrate for an inner layer and a plastic substrate for an exterior. It is a laminated body in which the inorganic filler-containing resin thin film layer is laminated and integrated so as to be positioned on the exterior plastic substrate side.

  The invention described in claim 2 is the laminate for packaging according to claim 1, wherein the resin thin film layer containing the inorganic filler contains 5 to 60% by volume of fine powder of the inorganic filler. It is characterized by.

  Furthermore, the invention according to claim 3 is the laminate for packaging according to claim 1 or 2, characterized in that the inorganic filler is an inorganic pigment such as titanium oxide or barium nitrate.

  Furthermore, the invention according to claim 4 is the packaging laminate according to any one of claims 1 to 3, wherein the plastic substrate is polyethylene, polypropylene, polyamides, polyesters, polycarbonate, polyacrylonitrile, polystyrene. It is made of a plastic material having at least one of polyvinyl chloride, cellulose, triacetyl cellulose, polyvinyl alcohol, and polyurethane as a component, a copolymer component, or a chemical modification thereof as a component. And

  Furthermore, the invention according to claim 5 is the laminate for packaging according to any one of claims 1 to 4, wherein reactive ions are provided on the side on which the inorganic vapor-deposited thin film layer of the plastic substrate for the inner layer is laminated. A pretreatment using plasma in an etching (RIE) mode is performed.

  Furthermore, the invention according to claim 6 is the laminate for packaging according to any one of claims 1 to 5, wherein the water-soluble polymer compound, the metal alkoxide and / or its hydrolyzate are formed on the inorganic vapor deposition thin film layer. A composite coating layer having at least one of a decomposed product and / or a polymer thereof as a component is provided.

  Furthermore, the invention according to claim 7 is characterized in that, in the packaging laminate according to claim 6, the water-soluble polymer compound has at least one of polyvinyl alcohol, cellulose, and starch as a component. .

  Furthermore, the invention according to claim 8 is characterized in that, in the packaging laminate according to claim 6, the metal alkoxide is a silane alkoxide.

  In the laminate for packaging of the present invention, the adhesion between the plastic substrate and the vapor-deposited thin film layer is strengthened, and the vapor-deposited thin film layer is protected from retort impact by the resin thin film layer containing an inorganic filler. Even if the heat treatment by is performed, the adhesion and gas barrier properties that were possessed before the treatment are unlikely to deteriorate.

  Also, since the inorganic filler-containing resin thin film layer is laminated in such a way that the gas barrier inorganic vapor-deposited thin film layer is always positioned between the package and the package, the components of the inorganic filler-containing resin thin film layer are packaged. Without shifting to the object side, it is possible to accurately prevent the taste deterioration of the packaged goods.

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

FIG. 1 is an explanatory view showing a schematic cross-sectional configuration of the packaging laminate of the present invention. In this laminate for packaging, the inorganic filler-containing resin thin film layer 3 and the inorganic filler-containing resin thin film layer 5 are interposed between the plastic substrate 2 for the inner layer and the plastic substrate 1 for the exterior. The layer 5 is laminated and integrated so that the layer 5 is located on the exterior plastic substrate 1 side. In the figure, 4 indicates a gas barrier composite coating layer, and 7 indicates an adhesive layer.

  The plastic substrates 1 and 2 are made of a plastic material, and are preferably transparent film-like substrates if possible in order to make use of the transparency of the inorganic vapor-deposited thin film layer 3.

  Specific examples of the plastic substrates 1 and 2 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, polyacrylic. A nitrile film, a polyimide film, etc. are mentioned. Furthermore, the plastic film which consists of polyvinyl chloride, a cellulose, a triacetyl cellulose, polyvinyl alcohol, and polyurethanes can also be mentioned. Moreover, the plastic film which consists of a material which has at least 1 or more types of the above materials as a component, or has in a copolymerization component, or has those chemical modifications in a component can also be mentioned.

  These plastic substrates 1 and 2 may be stretched or unstretched, but those having excellent mechanical strength and dimensional stability are preferred. Among the films described above, a polyethylene terephthalate film or a polyamide film arbitrarily stretched in the biaxial direction is preferably used.

  Various well-known additives and stabilizers such as an antistatic agent, an anti-ultraviolet agent, a plasticizer, a lubricant and the like are provided on the surface of the plastic substrate 2 for the inner layer where the inorganic vapor-deposited thin film layer 3 to be described later is not provided. The thin film which consists of may be formed.

  Further, the thickness is not particularly limited, but when an inorganic vapor-deposited thin film layer 3, a resin thin film layer 5 containing an inorganic filler, and a plastic substrate 1 for exterior are laminated and integrated thereabove. In consideration of the workability of the material, it is practically in the range of 3 to 200 μm, preferably in the range of about 6 to 30 μm.

  The surface of the plastic substrate 2 for the inner layer may be pretreated by reactive ion etching (RIE) using plasma in order to enhance the adhesion with the inorganic vapor-deposited thin film layer 3 formed thereon. It is particularly effective. By performing this RIE process, the generated radicals and ions can be used to chemically add functional groups to the surface of the plastic substrate 2, and the surface is ion etched to physically remove impurities and the like. It is possible to smooth the surface by skipping. By performing such surface treatment, a dense inorganic vapor-deposited thin film made of metal or inorganic oxide can be formed. And the adhesiveness of the plastic substrate 2 and the inorganic vapor-deposited thin film layer 3 can be strengthened, and further, the deterioration of the gas barrier property and the generation of cracks in the inorganic vapor-deposited thin film layer 3 are prevented, and the delamination is also performed. Generation can be reduced as much as possible.

  As a gas species for performing the pretreatment by RIE, a treatment gas such as argon, oxygen, nitrogen, or hydrogen can be used. These processing gases may be used alone or in combination of two or more. In addition, the processing may be performed continuously using two processing units.

In addition, pretreatment conditions by RIE indicated by processing speed, energy level, and the like should be appropriately set according to the type of plastic substrate, packaging application, discharge device characteristics, and the like. However, plasma self bias value of, 200V or 2000V or less, Ed = Ed values defined in plasma density × treatment time strongly be below 100V · s · m ^-2 higher 10000V · s · m ^-2 request Is done. Even with a value slightly lower than this, a certain degree of adhesion can be exhibited, but the advantage is lower than that of the untreated product. On the other hand, if the value is high, a strong treatment is applied excessively, the surface of the plastic substrate is deteriorated, and the adhesiveness is lowered. Regarding the type of gas for plasma and its mixing ratio, etc., depending on the application, type of plastic substrate, device characteristics, etc. These conditions should be set accordingly.

  On the other hand, the inorganic vapor-deposited thin film layer 3 having gas barrier properties is laminated on the plastic substrate 2 pretreated by such treatment. The inorganic vapor-deposited thin film layer 3 is made of metal, an inorganic oxide such as aluminum oxide or silicon oxide. The thickness is generally preferably in the range of 5 to 300 nm, but the specific value may be selected appropriately in consideration of the intended use as a packaging material. However, if the 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 layer may not be sufficiently achieved. Further, when the thickness exceeds 300 nm, the thin film cannot be kept flexible, and there is a problem because it may cause cracks due to external factors such as bending and pulling after film formation. A thickness in the range of 10 to 150 nm is more preferable.

  As a method of forming the inorganic vapor-deposited thin film layer 3 on the plastic substrate 2, thin film forming means such as a vacuum vapor deposition method, a sputtering method, an ion plating method, and a plasma vapor deposition method (CVD) can be employed. However, considering productivity, the vacuum deposition method is the best at present. As a heating means of the vacuum evaporation method, it is preferable to use any one of an electron beam heating method, a resistance heating method, and an induction heating method, but the electron beam heating method is more preferable in consideration of the wide selection of evaporation materials. . Further, in order to improve the adhesion between the inorganic vapor-deposited thin film layer 3 and the plastic substrate 2 and the denseness of the inorganic vapor-deposited thin film layer 3, it is also possible to perform vapor deposition using a plasma assist method or an ion beam assist method.

  Formation of the inorganic vapor-deposited thin film layer 3 by such a method may be performed by the same film forming machine (in-line film forming machine) in-line with the above-described pretreatment by RIE. By in-line film formation, the process can be shortened and an inexpensive packaging laminate can be provided.

  Next, the composite coating layer 4 formed on the inorganic vapor-deposited thin film layer 3 will be described. The composite coating layer 4 is a coating layer having a gas barrier property. For example, 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 is used. Formed using. More specifically, a coating obtained by mixing a water-soluble polymer dissolved in an aqueous (water or water / alcohol mixed) solvent with a metal alkoxide directly or hydrolyzed beforehand. Using an agent, this is coated on the inorganic vapor-deposited thin film layer 3 and then dried by heating. Below, each component contained in this coating agent is demonstrated in detail.

  Examples of the water-soluble polymer used in the coating agent include polyvinyl alcohol, polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, and sodium alginate. In particular, when polyvinyl alcohol (hereinafter abbreviated as PVA) is used, excellent gas barrier properties can be expressed. The PVA here is generally obtained by saponifying polyvinyl acetate, and a complete PVA in which only a few percent of acetate groups remain from a so-called partially saponified PVA in which several tens of percent of acetate groups remain. Can be used.

The metal alkoxide is a compound represented by a general formula, M (OR) _n M: metal such as Si, Ti, Al, Zr, or alkyl group such as R: CH ₃ or C ₂ H ₅ . Specifically, tetraethoxysilane [Si (OC ₂ H ₅ ) ₄ ], triisopropoxyaluminum [Al (O-2
'-C ₃ H ₇ ) ₃ ] and the like. Among them, tetraethoxysilane and triisopropoxyaluminum are preferable because they are relatively stable in an aqueous solvent after hydrolysis. In addition, since the composite film layer formed with the coating agent which consists of a mixture of a metal alkoxide and a water-soluble polymer is a hydrogen bond, there exists a possibility that it may swell and melt | dissolve in water. Therefore, in order to prevent this, it is preferable to add a silane coupling agent to the metal alkoxide in the coating agent.

  In addition, such coating agents may contain known additives such as isocyanate compounds, silane coupling agents, or dispersants, stabilizers, viscosity modifiers, and colorants, as long as the gas barrier properties are not impaired. It is also possible to add.

  As a method for applying the coating agent, conventionally known methods such as a dipping method, a roll coating method, a screen printing method, a spray method, and a gravure printing method that are usually used can be used.

  The thickness of the composite coating layer 4 varies depending on the optimum conditions depending on the type of coating agent, processing machine, processing conditions, and the like. When the thickness after drying is less than 0.01 μm, it is difficult to obtain a uniform coating film and a sufficient gas barrier property may not be obtained. On the other hand, if the thickness exceeds 50 μm, cracks are likely to occur in the film, which may be a problem. The thickness is preferably in the range of 0.01 to 50 μm, more preferably in the range of 0.1 to 10 μm.

  Next, the resin film layer 5 containing an inorganic filler will be described. This inorganic filler-containing resin thin film layer 5 is formed by using a coating agent containing a resin for forming a film as a main component and containing an inorganic filler therein. For example, after coating the inorganic deposition thin film layer 3 in a thin film with a coating agent obtained by kneading an inorganic filler with a resin component such as polyurethane and further mixing an organic solvent for giving a viscosity suitable for coating, It is formed by heating and drying.

  This inorganic filler-containing resin thin film layer 5 is a deposited thin film caused by rocking in the constituent layers of the packaging laminate induced by heat treatment with high-temperature and high-pressure water, for example, rocking in the adhesive layer It is a layer that plays a role of absorbing and mitigating the impact on the layer. The reason why the substance having the role of absorbing and relaxing the impact is used as the inorganic filler is that it can be uniformly dispersed in the polymer and can relieve the stress. Hereinafter, the inorganic filler component contained in the coating agent described above will be described in more detail.

  Specific examples of the inorganic filler include titanium oxide, calcium hydroxide, calcium carbonate, and barium sulfate. These inorganic fillers are finely powdered so as to be well dispersed in the coating agent. The particle size of the inorganic filler is not particularly limited.

  The proportion of the inorganic filler in the coating agent is preferably about 5 to 60% by volume. More preferably, the ratio may be 10 to 25% by volume. When the proportion of the inorganic filler is less than 5% by volume, the effect of absorbing retort impact is insufficient, and when it exceeds 60% by volume, uniform dispersion is difficult.

  On the other hand, as a coating method for the coating agent, conventionally known methods such as a dipping method, a roll coating method, a screen printing method, a spray method, a gravure printing method and the like that are usually used can be used.

In addition, the optimum conditions for the thickness vary depending on the type of coating agent, processing machine, processing conditions, and the like. When the thickness after drying is less than 0.01 μm, it is difficult to obtain a uniform coating film and a sufficient gas barrier property may not be obtained. On the other hand, when the thickness exceeds 50 μm, cracks are likely to occur in the deposited thin film layer, which may be a problem. Preferably it may be in the range of 0.01 to 50 μm, more preferably 0.1 to 10 μm.

  The resin thin film layer 5 containing an inorganic filler can also serve as a white printing layer generally used for packaging materials by using, for example, titanium oxide as the inorganic filler. In addition, an inorganic filler containing both a gas barrier coating function and a retort / impact absorption mitigation function is formed by forming this resin thin film by further adding an inorganic filler to the coating agent constituting the composite coating layer 4 described above. It is good also as a resin thin film layer.

  As described above, the inorganic vapor-deposited thin film layer 3, the composite coating layer 4, and the resin thin film layer 5 are sequentially laminated on the plastic substrate 2 for the inner layer, and further laminated through the adhesive layer 7. Is a plastic substrate 1 for exterior use. This plastic substrate 1 for exterior is a part which is located outside when the package is manufactured using the laminate for packaging of the present invention and bears the exterior part.

  As mentioned above, although the schematic structure of the laminated body for packaging of this invention was demonstrated, the thing of the structure laminated | stacked other structural layers, such as an interposition film layer and a sealant layer, in addition to each structural layer mentioned above may be sufficient. .

  The intervening film layer is provided to increase the bag breaking strength and puncture strength of the produced packaging body when the packaging body is produced using the packaging laminate of the present invention. From the viewpoint of strength and thermal stability, a biaxially stretched nylon film, a biaxially stretched polyethylene terephthalate film, a biaxially stretched polypropylene film, or the like is applied. The thickness is determined according to the material and the required quality, but generally only needs to be in the range of 10 to 30 μm.

  Further, the sealant layer is provided so as to serve as an adhesive layer when forming a bag-like package or the like. For example, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, ethylene -It consists of resin thin film layers, such as a methacrylic acid ester copolymer, an ethylene-acrylic acid copolymer, an ethylene-acrylic acid ester copolymer, and those metal crosslinked products. The thickness is determined according to the purpose, but is generally in the range of 15 to 200 μm.

  Moreover, it is also possible to laminate | stack a printing layer, an interposition film layer, a sealant layer, etc. as needed also to the surface in which the inorganic vapor deposition thin film layer 3 of the plastic base material 1 is not laminated | stacked.

  Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to these examples.

First, pretreatment by reactive ion etching (RIE) using plasma was performed on one side of a 12 μm thick biaxially stretched polyethylene terephthalate (PET) film. At this time, a high frequency power source with a frequency of 13.56 MHz was used for the electrodes, the self-bias value was 800 V, and the Ed value was 450 V / s / m ² . Argon / oxygen mixed gas was used as the processing gas.

  Subsequently, an inorganic vapor-deposited thin film layer made of aluminum oxide with a thickness of 20 nm is formed on the PET film that has been pretreated using RIE mode plasma in the above-described process by reactive vapor deposition using an electron beam heating method. A deposited film was produced by forming a film.

Next, on the inorganic vapor-deposited thin film layer of this vapor-deposited film, a solution prepared by mixing A liquid and B liquid having the following composition in a mixing ratio (volume%) at a ratio of 6: 4 is prepared, and the thin film is formed by gravure coating Was applied and dried to form a composite coating layer having a thickness of 0.4 μm.
<Liquid A>: Hydrolyzed solution having a solid content of 3% by volume (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>: A 3% by volume water / isopropyl alcohol solution of polyvinyl alcohol (90:10 by weight ratio of water: isopropyl alcohol).

Furthermore, on the composite film layer, a C solution having the following composition was prepared, a thin film was applied by a gravure coating method, and dried to form a resin thin film layer containing an inorganic filler having a thickness of 1 μm.
<C liquid>: A solution obtained by kneading urethane resin and titanium oxide and diluting with an organic solvent (isopropyl alcohol: methyl ethyl ketone: toluene = 1: 3: 2). The titanium oxide component ratio was 35% by volume.

Subsequently, with respect to the barrier laminate obtained in the above step, a plastic base material for exterior (made of PET, thickness is formed on the resin thin film layer containing the inorganic filler. μm), and on the plastic substrate for the inner layer, stretched nylon (thickness 15 μm) and unstretched polypropylene (thickness 70 μm) in this order by dry lamination using a two-component curable polyurethane adhesive By laminating, the packaging laminate according to Example 1 was produced.

  A packaging laminate according to Example 2 was produced in the same manner as in Example 1 except that the content of the inorganic filler component was 10% by volume.

  A packaging laminate according to Example 3 for comparison was produced in the same manner as in Example 1 except that the resin thin film layer containing the inorganic filler was not formed.

For the barrier laminate obtained in Example 1, in the same manner as in Example 1 except that the laminate position of the plastic substrate for exterior, stretched nylon (15 μm) and unstretched polypropylene (70 μm) was reversed, A laminate for packaging according to Example 4 for comparison was prepared.
<Evaluation 1>
<Oxygen permeability after retort treatment>
A four-sided pouch was prepared using the packaging laminate obtained in each of the above examples, and tap water was filled as the contents. Next, a retort treatment at 121 ° C. for 30 minutes was performed on these water-filled pouches. After this treatment, water is extracted from the pouch, and the oxygen permeability after the retort treatment of the packaging laminate constituting the pouch is 30 ° C.-70% RH using Modern Control (MOCON OXTRAN 10 / 50A). Measured under atmosphere. This measurement was performed within 24 hours after the retort treatment. The results are shown in Table 1.
<Evaluation 2>
<Lamination strength after retort treatment>
The laminate strength between the plastic substrate / deposition film for packaging of the packaging laminate after the retort treatment was measured using a Tensilon universal testing machine RTC-1250 manufactured by Orientec Co. (conforms to JIS Z1707). However, the measurement was performed while the measurement site was wetted with water. The results are shown in Table 1.

次に、各実施例に係る包装用積層体を用い、大きさ１３０ｍｍ×１８０ｍｍの四方シール袋を作製し、内容物として蒸留水を２００ｍｌ充填し、密封した後、１２１℃、３０分の条件でレトルト処理を行った。その後内容物（蒸留水）をアジデントテクノロジー社製ＧＣ−ＭＳ分析装置にて分析した。その結果、実施例４の比較のために作製した包装用積
層体では印刷インキ由来の成分と推定されるピークが観察された。また、内容物について官能試験を行ったところ、実施例１〜３に係る包装用積層体により作製されたシール袋中の内容物には異味、異臭はなかったが、実施例４に係る包装用積層体により作製されたシール袋中の内容物には異味、異臭が感じられた。

Next, using a packaging laminate according to each example, a four-side sealed bag having a size of 130 mm × 180 mm was prepared, filled with 200 ml of distilled water as a content, sealed, and then at 121 ° C. for 30 minutes. Retort treatment was performed. Thereafter, the contents (distilled water) were analyzed with a GC-MS analyzer manufactured by Agilent Technologies. As a result, a peak presumed to be a component derived from printing ink was observed in the packaging laminate produced for comparison with Example 4. Moreover, when the sensory test was done about the content, the content in the sealing bag produced by the laminated body for packaging according to Examples 1 to 3 did not have a taste and odor, but for packaging according to Example 4. The contents in the sealed bag made of the laminate had a nasty taste and odor.

It is explanatory drawing which shows the general | schematic cross-section structure of the laminated body for packaging of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Plastic base material for exterior 2 ... Plastic base material 3 for inner layers ... Inorganic vapor deposition thin film layer 4 ... Composite film layer 5 ... Resin thin film layer 6 containing an inorganic filler ... Pretreatment surface by RIE

Claims (8)

  At least the inorganic vapor-deposited thin film layer and the inorganic filler-containing resin thin film layer are disposed between the plastic substrate for the inner layer and the plastic substrate for the exterior. A laminated body for packaging, which is laminated and integrated so as to be positioned.   2. The packaging laminate according to claim 1, wherein the inorganic filler-containing resin thin film layer contains a fine powder of an inorganic filler in a proportion of 5 to 60% by volume.   The packaging laminate according to claim 1 or 2, wherein the inorganic filler is an inorganic pigment such as titanium oxide or barium nitrate.   The plastic substrate has at least one of polyethylene, polypropylene, polyamides, polyesters, polycarbonate, polyacrylonitrile, polystyrene, polyvinyl chloride, cellulose, triacetyl cellulose, polyvinyl alcohol, and polyurethane as a component, or a co-polymer. The packaging laminate according to any one of claims 1 to 3, wherein the laminate is a plastic material having a polymerization component or a chemical modification thereof as a component.   5. The pretreatment using reactive ion etching (RIE) mode plasma is performed on the side of the inner layer plastic substrate on which the inorganic vapor deposition thin film layer is laminated. The laminated body for packaging in any one.   On the inorganic vapor-deposited thin film layer, a composite coating layer having at least one of a water-soluble polymer compound, a metal alkoxide and / or a hydrolyzate thereof and / or a polymer thereof as a component is provided. The laminated body for packaging according to any one of claims 1 to 5.   The packaging laminate according to claim 6, wherein the water-soluble polymer compound has at least one of polyvinyl alcohol, cellulose, and starch as a component.   The packaging laminate according to claim 6, wherein the metal alkoxide is a silane alkoxide.

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