JP5873234B2 - Oxygen-absorbing laminated film and packaging container - Google Patents

Description

  The present invention relates to an oxygen-absorbing laminated film in which a predetermined layer is coextruded, an oxygen-absorbing laminated body obtained by laminating a base resin layer on the oxygen-absorbing laminated film, and a gas-barrier oxygen absorbing film obtained by laminating a gas-barrier film. More particularly, the oxygen-absorbing structure comprising a coextruded film including an oxygen-absorbing layer and a odor barrier layer and absorbing residual oxygen in the container and preventing odor The present invention relates to laminated films and the like and packaging containers made of them.

  In order to remove oxygen in the package containing contents such as foods that are considered to be undesirably oxidatively deteriorated, there is a deoxygenation packaging method in which the contents are stored and sealed in a gas barrier container together with a sachet of oxygen absorbent. Are known. However, when the contents are heated in a microwave oven or the like, it is necessary to remove the oxygen absorbent in advance. Ideally, it is desirable that the contents can be heated by directly putting the container into the microwave oven. For this reason, various oxygen-absorbing laminates in which oxygen-absorbing layers are laminated have been developed.

  For example, as a container for storing oxygen-sensitive products, an outer set and an inner set are included, the outer set includes an inorganic barrier layer, and the inner set includes an oxygen scavenging layer and a heat seal layer having a predetermined oxygen permeability. There is a packaging material in which the oxygen scavenging layer is composed of an oxidizable organic component such as polyamide and a metal compound such as cobalt (Patent Document 1). In the embodiment, polyethylene terephthalate and aluminum foil are bonded as an outer set with a polyurethane-based adhesive, and the inner set is composed of a layer composed of MXD6 and cobalt and a heat seal layer. A packaging material in which the set is bonded with a polyurethane adhesive is disclosed.

  Further, from the inside of the package to the outside of the package, the inner layer of the olefin resin / the first layer of the oxygen barrier resin / the oxygen absorbing laminate / the cyclic olefin copolymer layer / the second layer of the oxygen barrier resin There is also an oxygen-absorbing package characterized by having a laminated structure of an / olefin-based resin outer surface layer (Patent Document 2). The oxygen-absorbing laminate is composed of a resin composition of an oxidizing resin and a transition metal-based catalyst. The oxidizing resin includes a carbon side chain such as acid-modified low-density polyethylene as an oxidizing resin, and has a main chain or a side chain. A resin is disclosed that includes at least one functional group selected from the group consisting of a carboxylic acid group, a carboxylic anhydride group, a carboxylic ester group, a carboxylic amide group, and a carbonyl group. The oxidizing resin has at least one functional group selected from the group consisting of a carboxylic acid group, a carboxylic acid anhydride group, a carboxylic acid ester group, a carboxylic acid amide group, and a carbonyl group. Is an electron-withdrawing group that activates tertiary carbon atoms and becomes an adsorption site for transition metal catalyst components, shortening the induction period in the generation of radicals and addition of oxygen, and deterioration of the resin under normal conditions In the presence of a small amount of a transition metal catalyst that does not generate oxygen, the oxygen absorbing ability is exhibited. In the examples, the acid-modified low density polyethylene is kneaded at a cobalt concentration of 5000 ppm.

  A plastic multilayer comprising an inner layer and an outer layer made of a thermoplastic resin, an oxygen absorbing layer between the inner layer and the outer layer, and an inorganic film layer provided on a surface of the inner layer and / or the outer layer. There is also a container (Patent Document 3). When an oxygen absorption layer comprising a thermoplastic resin and an oxidation catalyst captures oxygen, the resin deteriorates to generate cracks. When an inorganic film layer is provided on the oxygen absorption layer, the cracks are transmitted to the inorganic film layer, and gas It is made in view of the point that the barrier property is lowered, and according to the above configuration, it is possible to highly prevent the permeation of carbon dioxide gas and trap the residual oxygen in the resin.

  Furthermore, the resin composition is composed of at least three layers of a co-extrusion film-forming film, and the first layer constituting the surface layer of the above-mentioned co-extrusion film-forming film contains a thermoplastic resin and a white colorant. The second layer constituting the intermediate layer of the coextruded film-forming film is an oxygen-absorbing laminate of a resin composition containing an oxidizing resin and a transition metal catalyst, Further, the third layer constituting the back layer of the co-extruded film-forming film is composed of a transparent or translucent resin layer made of a resin composition containing a thermoplastic resin. There is also (patent document 4). The oxygen-absorbing laminate includes a radical generator and a photosensitizer. After filling and packaging the contents, the inner surface of the packaging bag is irradiated with ultraviolet light, and then the opening is heat sealed to form a seal portion. When formed and sealed, the ultraviolet light easily reaches the oxygen-absorbing laminate, whereby the transition metal catalyst constituting the oxygen-absorbing laminate acts on the oxidizing resin, and the oxidizing resin It is said to bind and absorb oxygen etc. in the packaging bag.

There is also an oxygen scavenger using cerium oxide having oxygen defects (Patent Document 5). Since iron-based oxygen scavengers require water during the reaction, they cannot fully demonstrate their performance when storing foods that dislike water, such as dried foods and electronic components, react to metal detectors, and microwave ovens. The cerium oxide represented by CeO _x (where x is a positive number less than 2) does not require moisture during the reaction and does not require oxygen in the atmosphere. It absorbs and does not react with metal detectors. It is said that ignition can be suppressed especially when the specific surface area is 0.6 m ² / g or less. There is also disclosed a deoxygenation functional film in which the cerium oxide is laminated with a gas barrier layer and a gas permeable layer.

  In addition, there is also one in which an oxygen-absorbing laminate is used as a container lid. For example, an inorganic oxide vapor-deposited film and a gas barrier coating film are provided on one surface of the base film, and a printed pattern layer and a laminating adhesive layer are further formed on the gas barrier coating film. There is a lid for aseptic cooked rice filling and packaging container characterized in that a heat-sealable resin layer is provided through the adhesive layer for laminating one after another (Patent Document 6). Can produce aseptically packaged cooked rice using a lid material that is excellent in strength, heat resistance, moisture resistance, heat sealability, pinhole resistance, puncture resistance, transparency, etc., and can prevent permeation of oxygen, water vapor, etc. That's it. Aseptically prepared by filling rice cooked aseptically at normal pressure into a packaging container consisting of a plastic tray sterilized in an aseptic atmosphere, and then opening and closing the opening with a plastic lid etc. It is used for filling packed rice.

Japanese Patent No. 2785405 JP 2002-137347 A Japanese Patent Laid-Open No. 2003-20023 JP 2006-224399 A Patent 4001614 Japanese Patent Laid-Open No. 2005-8160

A laminate having a heat seal layer as the innermost layer can be used as a packaging container by making a bag. It can also be used as a lid for a container body. For example, aseptic cooked rice filling and packaging containers have the advantage that they can be heated in a microwave oven or the like, and are frequently used in recent years. An example of such a lid member is a laminate having a heat seal layer described in Patent Document 6, for example. However, the lid for aseptic rice filling and packaging container described in Patent Document 6 has a gas barrier property that prevents permeation of oxygen, water vapor, and the like from the outside of the hermetically packaged container. It is not possible to remove oxygen inside the container generated from For this reason, it is desired that oxygen absorptivity can be imparted for the purpose of long-term storage.

  On the other hand, the packaging materials described in Patent Documents 1 to 5 as the packaging material for laminating the oxygen absorption layer include aluminum foil laminated and bonded as a gas barrier layer in the packaging material described in Patent Document 1, and if the aluminum foil is contained, Heating with a range becomes difficult. The oxygen-absorbing package described in Patent Document 2 is originally intended for blow molded containers and tube containers. Therefore, it does not have a heat seal layer and cannot be used as a lid for a sterile cooked rice filling and packaging container. Similarly, the plastic multilayer container described in Patent Document 3 is also intended for containers, and does not have a heat seal layer and cannot be used as a lid.

  Furthermore, the film described in Patent Document 4 contains a radical generator and a photosensitizer as an oxygen-absorbing laminate, and it is necessary to irradiate the inner surface of the packaging bag with ultraviolet light after filling and packaging the contents. is there.

  In addition, the deoxygenation functional film described in Patent Document 5 is obtained by laminating the deoxygenation layer made of cerium oxide with a gas permeable layer and a gas barrier layer, but the deoxygenation layer made of cerium oxide has oxygen absorption performance. Although there is an odor, it may change the flavor of the contents.

Furthermore, the multilayer film can be used as a packaging container by bag making and needs to have processability.
In view of the above situation, to provide an oxygen-absorbing laminated film that has no odor, has oxygen absorbability, can be heated in a microwave oven as a cooking device, and is useful as a packaging material for containers, a lid material, etc. With the goal.

Another object of the present invention is to provide an oxygen-absorbing laminated film having processability.
It is another object of the present invention to provide an oxygen-absorbing laminate and a gas-barrier oxygen-absorbing laminate in which such an oxygen-absorbing laminate film is further secured with gas barrier properties.

  Furthermore, it aims at providing the packaging container and cover material which consist of the said oxygen absorptive laminated | multilayer film, an oxygen absorptive laminated body, and a gas-barrier oxygen absorptive laminated body.

  In the present invention, a resin in which a photosensitizer is blended with a cyclized conjugated diene polymer has oxygen absorptivity, and an odor is generated at the time of oxygen absorption, but a odor barrier layer blended with mesoporous silica is laminated. It is possible to prevent deterioration of the flavor of the contents, and because the cyclized conjugated diene polymer has oxygen absorption performance even without moisture, it can be suitably used for oxygen absorption of contents that dislike moisture, oxygen absorption If the layer, odor barrier layer, and heat seal layer are co-extruded film-forming films via a thermoplastic resin layer, it is possible to avoid the odor that occurs when using a laminating adhesive, and the polyamide resin as the base resin layer The inventors have found that mechanical strength can be secured by laminating a resin or polyethylene terephthalate, and the present invention has been completed.

That is, the present invention is a coextrusion in which a thermoplastic resin layer (I), an oxygen absorbing layer, a thermoplastic resin layer (II), a odor barrier layer (I), and a heat seal layer are laminated in this order from the outer layer to the inner layer. the film,
Or, a thermoplastic resin layer (I), an oxygen absorbing layer, a thermoplastic resin layer (II) and a heat seal layer having a taste barrier property laminated in this order from the outer layer to the inner layer,
The oxygen absorbing layer includes a resin composition containing a photosensitizer in a cyclized conjugated diene polymer,
The odor barrier layer or the heat seal layer having odor barrier properties comprises a resin containing 0.01 to 1% by mass of mesoporous silica,
The mesoporous silica provides an oxygen-absorbing laminated film having an oil absorption of 201 ml / 100 g or more and 595 ml / 100 g or less .

The mesoporous silica is
After firing, at least one peak of the X-ray diffraction pattern exhibits a d-interval greater than 1.8 nm and has a benzene adsorption capacity greater than 15 g per 100 g material at 6.7 kPa (50 torr) and 25 ° C., porous, A non-layered crystal phase substance having a composition represented by the following formula (1):

（式中、Ｍは１種以上のイオンであり、
ｎは酸化物として表わされるＭを除いた組成の電荷であり、
ｑはＭの重量モル平均原子価であり、
ｎ／ｑはＭのモル数またはモル分率である。）
または、
直径が少なくとも１．３ｎｍの均一な寸法の細孔の六方構造配列を有し、焼成後、１．８ｎｍより大きいｄ₁₀₀値で示され得る六方構造の電子回折パターンを示す無機質、多孔質の上記記式（１）で示す組成の結晶相物質、
または、
酸化物のモル比で表して下記組成を有する反応混合物を結晶化した結晶相物質を焼成処理したものである、上記酸素吸収性積層フィルムを提供するものである。

(Wherein M is one or more ions,
n is the charge of the composition excluding M expressed as an oxide,
q is the weight molar average valence of M;
n / q is the number of moles or mole fraction of M. )
Or
Inorganic, porous, having a hexagonal structure array of uniformly sized pores with a diameter of at least 1.3 nm and exhibiting a hexagonal structure electron diffraction pattern that can be exhibited with a d ₁₀₀ value greater than 1.8 nm after firing A crystalline phase substance having a composition represented by the formula (1),
Or
The oxygen-absorbing laminated film is obtained by firing a crystal phase substance obtained by crystallizing a reaction mixture having the following composition expressed by a molar ratio of oxides.

[Table 1]
Composition of the reaction mixture ┌──────────────────┬─────────┐
│Component │Ratio │
├──────────────────┼─────────┤
│Solvent / SiO ₂ │1-1500 │
├──────────────────┼─────────┤
│OH ^- / SiO ₂ │0~10 │
├──────────────────┼─────────┤
│ (M _{e / 2} O + R _{f / 2} O) / SiO ₂ │0.01-20 │
├──────────────────┼─────────┤
│M _{e / 2} O / SiO ₂ │0-10 │
├──────────────────┼─────────┤
│R _{f / 2} O / SiO ₂ │0.01 ~ 2.0 │
└──────────────────┴─────────┘
(Wherein M is one or more ions, e and f are the weight average valences of M and R, respectively, the solvent is an alcohol or diol having 1 to 6 carbon atoms, or water, and R is , The total organic matter used to help the synthesis of the substance,
Formula: R ₁ R ₂ R ₃ R ₄ Q ⁺ (where Q is nitrogen or phosphorus, R ₁ , R ₂ , R ₃ and at least one is an aryl group or alkyl group having 6 to 36 carbon atoms) , R ₁ , R ₂ , R and R ₄ are each selected from hydrogen and an alkyl group having 1 to 5 carbon atoms). )
Furthermore, the present invention provides an oxygen-absorbing laminate, wherein a base resin layer is laminated on the outside of the thermoplastic resin layer (I) of the oxygen-absorbing laminate film.

The present invention also provides a gas barrier oxygen-absorbing laminate, wherein a gas barrier film is laminated on the inside or outside of the base resin layer of the oxygen-absorbing laminate.
Furthermore, the present invention provides a packaging container formed by bag-making the above oxygen-absorbing laminated film, oxygen-absorbing laminated body, or gas-barrier oxygen-absorbing laminated body.

  In addition, a container comprising a container body and a lid, wherein the lid is the oxygen-absorbing laminated film, the oxygen-absorbing laminated body, or the gas-barrier oxygen-absorbing laminated body. A container is provided.

  Since the oxygen-absorbing laminated film of the present invention uses a resin composition containing a photosensitizer in a cyclized conjugated diene polymer, the oxygen-absorbing power is strong and has a odor barrier layer. The flavor of the contents is not deteriorated.

In addition, the oxygen-absorbing laminated film of the present invention can heat the contents using a microwave oven or the like.
Since the oxygen-absorbing laminated film of the present invention is a coextruded film, no odor is generated by the laminating adhesive, and the contents are excellently stored.

  Since the innermost layer of the oxygen-absorbing laminated film of the present invention is a heat seal layer, it can be made into a packaging container by itself and can be used as a part of the container as a lid.

  The oxygen-absorbing laminated film of the present invention can be further laminated with a gas barrier film or the like, and is excellent in content retention over a long period of time.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing which shows an example of the layer structure of the oxygen absorptive laminated | multilayer film which concerns on this invention, thermoplastic resin layer (I) (20), oxygen absorption layer (10), thermoplastic resin toward an inner layer from an outer layer It consists of layer (II) (20), odor barrier layer (I) (30), and a heat seal layer (50). BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing which shows an example of the layer structure of the oxygen absorptive laminated | multilayer film which concerns on this invention, thermoplastic resin layer (I) (20), oxygen absorption layer (10), thermoplastic resin toward an inner layer from an outer layer It consists of layer (II) (20) and a heat seal layer (40) having odor barrier properties. FIG. 2 is a schematic cross-sectional view showing an example of a layer configuration of the oxygen-absorbing laminated film according to the present invention, outside the outermost thermoplastic resin layer (I) (20) of the oxygen-absorbing laminated film shown in FIG. Furthermore, it is a figure which shows the aspect by which the odor barrier layer (II) (30) and the thermoplastic resin layer (III) (20) were laminated | stacked. FIG. 3 is a schematic cross-sectional view showing an example of a layer configuration of an oxygen-absorbing laminated film according to the present invention, outside the outermost thermoplastic resin layer (I) (20) of the oxygen-absorbing laminated film shown in FIG. Furthermore, it is a figure which shows the aspect by which the odor barrier layer (II) (30) and the thermoplastic resin layer (III) (20) were laminated | stacked. It is a schematic sectional drawing which shows an example of a layer structure of the oxygen absorptive laminated body concerning this invention, and a base resin layer (60) is laminated adhesive (80) in the outermost layer of the oxygen absorptive laminated film shown in FIG. It is a figure which shows the aspect laminated | stacked by. It is a schematic sectional drawing which shows an example of a layer structure of the oxygen absorptive laminated body concerning this invention, and a base resin layer (60) is laminated adhesive (80) in the outermost layer of the oxygen absorptive laminated film shown in FIG. It is a figure which shows the aspect laminated | stacked by. FIG. 6 is a schematic cross-sectional view showing an example of the layer configuration of the gas-barrier oxygen-absorbing laminate according to the present invention, in which a gas-barrier film (70) is laminated on the outside of the oxygen-absorbing laminate shown in FIG. It is a figure which shows the aspect laminated | stacked by (). FIG. 7 is a schematic cross-sectional view showing an example of a layer configuration of the gas-barrier oxygen-absorbing laminate according to the present invention, in which a gas-barrier film (70) is laminated on the outer side of the oxygen-absorbing laminate shown in FIG. It is a figure which shows the aspect laminated | stacked by (). It is a schematic block diagram which shows an example of a low temperature plasma chemical vapor deposition apparatus. It is a schematic block diagram which shows an example of a winding-type vacuum deposition apparatus.

In the first aspect of the present invention, the thermoplastic resin layer (I), the oxygen absorbing layer, the thermoplastic resin layer (II), the odor barrier layer (I), and the heat seal layer are laminated in this order from the outer layer to the inner layer. Coextruded film or coextruded film in which a thermoplastic resin layer (I), an oxygen absorbing layer, a thermoplastic resin layer (II), and a heat seal layer having odor barrier properties are laminated in this order from the outer layer to the inner layer The oxygen absorbing layer includes a resin composition comprising a cyclized conjugated diene polymer and a photosensitizer, and the heat seal having the odor barrier layer or the odor barrier property. layer, a resin containing a mesoporous silica 0.01 wt%, the mesoporous silica, oxygen intake oil absorption is equal to or less than 201 ml / 100 g or more and 595ml / 100g It is a sex laminated film.

The second aspect of the present invention is an oxygen-absorbing laminate in which a base resin layer is laminated on the outside of the thermoplastic resin layer (I) of the oxygen-absorbing laminate film.
The third aspect of the present invention is a gas barrier oxygen-absorbing laminate, wherein a gas barrier film is laminated on the inside or outside of the base resin layer of the oxygen-absorbing laminate. Hereinafter, the present invention will be described in detail.

(1) Layer structure of oxygen-absorbing laminated film, etc. The oxygen-absorbing laminated film of the present invention is a coextruded film having a layer structure shown in FIG. 10), a thermoplastic resin layer (II) (20), a odor barrier layer (I) (30), and a heat seal layer (50). In the present invention, the thermoplastic resin layer (I) and the thermoplastic resin layer (II) may be the same or different.

  Moreover, as shown in FIG. 2, it has thermoplastic resin layer (I) (20), oxygen absorption layer (10), thermoplastic resin layer (II) (20), and odor barrier property toward an inner layer from an outer layer. A coextruded film in which the heat seal layer (40) is laminated in this order may be used. Since it is a coextruded film, four layers are laminated without using a laminating adhesive, and it is particularly suitable as a packaging container for stored items in which the solvent odor contained in the laminating adhesive is a problem.

  As shown in FIGS. 3 and 4, the oxygen-absorbing laminated film of the present invention is further provided on the outer side of the outermost thermoplastic resin layer (I) (20), and further with the odor barrier layer (II) (30) and the heat. The plastic resin layers (III) and (20) may be laminated by coextrusion. In the present invention, the odor barrier layer (I) and the odor barrier layer (II) may be the same or different.

  Moreover, the oxygen-absorbing laminated film of the present invention has a base resin layer (60) laminated on the outermost layer of the oxygen-absorbing laminated film shown in FIGS. 1 to 4 via a laminating adhesive (80). 5, It can also be set as the oxygen absorptive laminated body shown in FIG. By laminating the base resin layer (60), the mechanical strength can be increased and the puncture resistance can be ensured.

  Further, as shown in FIGS. 7 and 8, a gas barrier film (70) can be laminated on the outside of the oxygen-absorbing laminate to form a gas-barrier oxygen-absorbing laminate. Such a gas barrier film (70) can be bonded via a laminating adhesive (80). The gas barrier property can be secured by the gas barrier film (70).

  Moreover, although not shown in figure, the printing layer may be formed inside the said gas-barrier film (70). As a result, the design can be improved in addition to the content display, and white solid printing or the like can be performed when a higher light-shielding property is required.

(2) Oxygen-absorbing layer The oxygen-absorbing layer constituting the oxygen-absorbing laminated film of the present invention includes a resin composition containing a photosensitizer in a cyclized conjugated diene polymer, and the resin composition The product contains 10 to 100% by mass of the cyclized conjugated diene polymer, more preferably 20 to 90% by mass, and particularly preferably 30 to 70% by mass.

(i) Cyclic conjugated diene polymer The cyclized conjugated diene polymer used in the present invention is obtained by subjecting a conjugated diene polymer to a cyclization reaction as a raw material. Compared to the case of using a resin whose main component is a chain conjugated diene polymer, the oxygen absorbing layer is made of a resin made of a cyclized conjugated diene polymer, which is less generated by an oxygen absorption reaction. There are few decomposition products of a molecular weight substance, generation | occurrence | production of the film odor derived from the decomposition product can be suppressed effectively, and it is excellent in health and safety.

  As the conjugated diene polymer forming such a cyclized conjugated diene polymer, a polymer obtained by polymerizing a conjugated diene monomer, or a copolymer obtained by copolymerizing with a comonomer copolymerizable with the conjugated diene monomer. is there.

  Examples of such conjugated diene monomers include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-pentadiene, 2 -Methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene and the like. These monomers may be used alone or in combination of two or more. Among these, it is particularly preferable to use isoprene.

  Examples of other monomers copolymerizable with the conjugated diene monomer include styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, and p-tert. Aroma such as butyl styrene, α-methyl styrene, α-methyl-p-methyl styrene, o-chloro styrene, m-chloro styrene, p-chloro styrene, p-bromo styrene, 2,4-dibromo styrene, vinyl naphthalene Group vinyl monomers; chain olefin monomers such as ethylene, propylene and 1-butene; cyclic olefin monomers such as cyclopentene and 2-norbornene; 1,5-hexadiene, 1,6-heptadiene, 1,7 Non-conjugated diene monomers such as octadiene, dicyclopentadiene, 5-ethylidene-2-norbornene; (meth) a (Meth) acrylic acid esters such as methyl crylate and ethyl (meth) acrylate; other (meth) acrylic acid derivatives such as (meth) acrylonitrile and (meth) acrylamide; These monomers may be used alone or in combination of two or more. Specific examples of the conjugated diene polymer include natural rubber (NR), styrene-butadiene rubber (SBR), polyisoprene rubber (IR), polybutadiene rubber (BR), isoprene-isobutylene copolymer rubber (IIR), ethylene- Examples thereof include propylene-diene copolymer rubber (EPDM) and butadiene-isoprene copolymer rubber (BIR). Among these, polyisoprene rubber and polybutadiene rubber are preferable, and polyisoprene rubber is more preferable.

  The content of the conjugated diene monomer unit in the conjugated diene polymer is appropriately selected within a range not impairing the effects of the present invention, but is usually 40 mol% or more, preferably 60 mol% or more, more preferably 80 mol. % Or more. Especially, what consists only of a conjugated diene monomer unit is especially preferable. If the content of the conjugated diene monomer unit is too small, it may be difficult to obtain a suitable range of unsaturated bond reduction rate.

  The polymerization method of the conjugated diene polymer may be in accordance with a conventional method, for example, solution polymerization or emulsification using an appropriate catalyst such as a Ziegler polymerization catalyst, an alkyl lithium polymerization catalyst or a radical polymerization catalyst containing titanium as a catalyst component. Performed by polymerization.

  The conjugated diene polymer cyclized product used in the present invention can be obtained by subjecting the conjugated diene polymer to a cyclization reaction in the presence of an acid catalyst. As an acid catalyst, a well-known thing can be used, for example, sulfuric acid; fluoromethanesulfonic acid, difluoromethanesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, the alkylbenzene which has a C2-C18 alkyl group Organic sulfonic acid compounds such as sulfonic acid, their anhydrides and alkyl esters; boron trifluoride, boron trichloride, tin tetrachloride, titanium tetrachloride, aluminum chloride, diethylaluminum monochloride, ethylammonium chloride, aluminum bromide, Lewis acids such as antimony pentachloride, tungsten hexachloride, iron chloride; and the like. These acid catalysts may be used alone or in combination of two or more. Among these, organic sulfonic acid compounds are preferable, and p-toluenesulfonic acid and xylenesulfonic acid are more preferable. The usage-amount of an acid catalyst is 0.05-10 weight part normally per 100 weight part of conjugated diene polymers, Preferably it is 0.1-5 weight part, More preferably, it is 0.3-2 weight part.

  The cyclization reaction is usually performed by dissolving the conjugated diene polymer in a hydrocarbon solvent. The hydrocarbon solvent is not particularly limited as long as it does not inhibit the cyclization reaction. For example, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene; n-pentane, n-hexane, n-heptane, n -Aliphatic hydrocarbons such as octane; Alicyclic hydrocarbons such as cyclopentane and cyclohexane; and the like. The boiling point of these hydrocarbon solvents is preferably 70 ° C. or higher. The solvent used for the polymerization reaction of the conjugated diene polymer and the solvent used for the cyclization reaction may be of the same type. In this case, an acid catalyst for cyclization reaction can be added to the polymerization reaction solution after completion of the polymerization reaction, and the cyclization reaction can be carried out following the polymerization reaction. The amount of the hydrocarbon solvent used is such that the solid content concentration of the conjugated diene polymer is usually 5 to 60% by weight, preferably 20 to 40% by weight.

  The cyclization reaction can be carried out under any pressure of pressure, reduced pressure and atmospheric pressure, but it is desirable to carry out under atmospheric pressure from the viewpoint of easy operation. When the cyclization reaction is performed in a dry air flow, particularly in an atmosphere of dry nitrogen or dry argon, side reactions caused by moisture can be suppressed. The reaction temperature and reaction time in the cyclization reaction are not particularly limited. The reaction temperature is usually 50 to 150 ° C., preferably 70 to 110 ° C., and the reaction time is usually 0.5 to 10 hours, preferably 2 to 5 hours. After carrying out the cyclization reaction, the acid catalyst is deactivated and the acid catalyst residue is removed by a conventional method, and then the hydrocarbon solvent is removed to obtain a solid conjugated diene polymer cyclized product.

  The cyclization rate of the cyclized conjugated diene polymer, that is, the peak area of protons derived from double bonds before and after the cyclization reaction of the conjugated diene polymer by proton NMR analysis, The ratio of double bonds remaining in the cyclized product is determined, and the value represented by the calculation formula = (100−ratio of double bonds remaining in the cyclized product) is preferably 30 to 95%. More preferably, it is 50 to 90%, and most preferably 55 to 85%.

If it is less than 30%, the glass transition temperature may be lowered and the adhesive strength may be reduced. Conversely, if it exceeds 95%, the conjugated diene polymer cyclized product may be difficult to produce.
The weight average molecular weight of the conjugated diene polymer cyclized product is a standard polystyrene conversion value measured by GPS, and is usually 1,000 to 1,000,000, preferably 10,000 to 700,000, more preferably 30,000. 000-500,000. The weight average molecular weight of the conjugated diene polymer cyclized product can be adjusted by appropriately selecting the weight average molecular weight of the conjugated diene polymer subjected to cyclization. If the weight average molecular weight of the conjugated diene polymer cyclized product is too small, it is difficult to form into a film and the mechanical strength may be lowered. When the weight average molecular weight of the conjugated diene polymer cyclized product is too large, the solution viscosity at the time of the cyclization reaction increases, and it becomes difficult to handle and the processability at the time of extrusion molding may be lowered.

  The gel (toluene insoluble content) of the conjugated diene polymer cyclized product is usually 10% by weight or less, preferably 5% by weight or less, but it is particularly preferable that the conjugated diene polymer cyclized product has substantially no gel. If the amount of gel is large, the smoothness of the film may be impaired.

(ii) Photosensitizer The oxygen absorbing layer constituting the oxygen-absorbing laminated film of the present invention contains a photosensitizer.
When the cyclized conjugated diene polymer is irradiated with ultraviolet rays, the hydrogen at the allylic position is easily radicalized by the photosensitizer and an oxygen absorption reaction is initiated.

  Such a photosensitizer is not particularly limited. For example, benzophenone, o-methoxybenzophenone, acetophenone, o-methoxyacetophenone, methyl ethyl ketone, acetonaphthenequinone, valerophenone, hexanophenone, α-phenylbutyrophenone, dibenzos Examples include beron, benzoin, p-diacetylbenzene, 4-aminobenzophenone and the like.

The addition amount of the photosensitizer is preferably 0.01 to 1% by mass with respect to the cyclized conjugated diene polymer.
(iii) Thermoplastic resin A thermoplastic resin can be mix | blended with the oxygen absorption layer of this invention in 0-90 mass%. Examples of such thermoplastic resins include polyolefin resins, polyamide resins, polyester resins, polyvinyl alcohol resins, and ethylene-vinyl alcohol copolymer resins such as EVOH. Examples of polyolefin resins include polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, polyisoprene, polybutadiene, polymethylpentene, and other olefin homopolymers, ethylene-propylene random copolymers, and ethylene-propylene blocks. Copolymer, ethylene-propylene-polybutene-1 copolymer, copolymer of ethylene and α-olefin such as ethylene-cyclic olefin copolymer, ethylene-α, β-unsaturated carboxylic acid copolymer, ethylene -Α, β-unsaturated carboxylic acid ester copolymer, ionic cross-linked product of ethylene-α, β-unsaturated carboxylic acid copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer part or Other ethylene copolymers such as fully saponified products, these polyolefins Resin and the like can be exemplified graft-modified graft modified polyolefin resin and an acid anhydride such as maleic anhydride. Examples of the polyester resin include polyethylene terephthalate, and examples of the polyamide resin include nylon-6, nylon-6,6, nylon-6,12, and the like. Furthermore, examples of the polyvinyl alcohol-based resin include polyvinyl alcohol, ethylene-vinyl acetate copolymer parts or complete garments.

  The oxygen-absorbing layer used in the present invention can be composed of the cyclized conjugated diene polymer and the photosensitizer. However, film formation is facilitated by blending a thermoplastic resin within the above range, and Adhesion between the oxygen absorbing layer and other layers can be improved.

(Iv) Other blends The oxygen-absorbing layer constituting the oxygen-absorbing laminated film of the present invention has an antioxidant, a lubricant, a plasticizer, an antistatic agent, and a colorant as long as the object of the present invention is not impaired. A known additive such as an agent can be added at any time. In addition, what is necessary is just to determine these compounding quantities according to the kind of additive, a required function, etc.

  Among them, the antioxidant is added to prevent oxidation and gelation of the copolymer during film formation and to control oxygen absorption performance. For example, 2,6-di- (t-butyl) -4-methylphenol, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, Phenol-based antioxidants such as 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane Agents, phosphoric acid antioxidants such as triphenyl phosphite, tris (dinoniphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, sulfur such as dilauryl 3,3-thiodipropionate A system antioxidant or the like can be preferably used.

  The addition amount of the antioxidant is preferably 0.001 to 1% by mass with respect to the cyclized conjugated diene polymer. If it is less than 0.001% by mass, it is not preferable because the function of preventing the oxidation and gelation of the copolymer and the control function of oxygen absorption performance cannot be expressed. If it exceeds 1% by mass, the compatibility with the copolymer is poor. Since it will isolate | separate, it is not preferable.

In the present invention, the film thickness of the oxygen absorbing layer is preferably 5 to 100 μm, more preferably 10 to 30 μm.
(3) Odor Barrier Layer The odor barrier layer used in the oxygen-absorbing laminated film of the present invention is made of a resin containing 0.01 to 1% by mass of mesoporous silica. The mesoporous silica has an oil absorption of 201 ml. / 100g or more and 595ml / 100g or less .

(I) Resin As resin which mix | blends the said mesoporous silica, a thermoplastic resin can be widely used. This is because production by coextrusion is easy. As such a thermoplastic resin, various polyolefin resins that can be melted by heat and fused to each other can be used. Specifically, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene -Ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-α / olefin copolymer polymerized using metallocene catalyst, polypropylene, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer Polyolefin resins such as methylpentene polymer, polybutene polymer, polyethylene or polypropylene modified with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, Vinyl acetate Resins, poly (meth) can be exemplified an acrylic resin, resins such as polyvinyl chloride resin.

(Ii) Mesoporous silica The mesoporous silica used in the present invention is a porous silica material having pores having a pore diameter of 2 to 50 nm. In general, porous materials can adsorb other molecules in the pores and can be cracked or hydrocracked, and can be used as adsorbents for deodorization, catalysts, carriers for enzymes, carriers for fragrances and physiologically active substances, and others. In particular, if the pore diameter is 2 to 50 nm, the pore diameter is larger than that of conventional zeolite, and large molecules that could not be adsorbed by zeolite can also be adsorbed.

  As the mesoporous silica having a pore diameter of 2 to 50 nm used in the present invention, for example, a honeycomb mesoporous silica porous body made of honeycomb silica having a pore diameter of 2 to 50 nm can be suitably used. Note that the maximum dimension of the vertical cross section of the pores is defined as the dimension of the pores. For example, in the case of a hexagonal structure, the distance between two opposing surfaces is the maximum dimension of the pores.

As the mesoporous silica used in the present invention, those having a pore diameter of 2 to 50 nm can be widely used, and those having a specific surface area of 300 to 1300 m ² / g can be preferably used. This is because, within this range, the odor removal property of the oxygen absorption layer composed of the polyamide resin and the transition metal catalyst is particularly excellent.

  As the mesoporous silica used in the present invention, for example, a honeycomb mesoporous silica porous body having a pore diameter of 2 to 50 nm synthesized using a surfactant micelle as a template can be preferably used. For example, cetyltrimethylammonium hydroxide, cetyltrimethylphosphonium chloride, octadecyltrimethylphosphonium chloride, benzyltrimethylammonium hydroxide, cetylpyridinium chloride, myristyltrimethylammonium bromide, decyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide and dimethyldioxide hydroxide When precipitated hydrated silica having an ultimate particle size of 0.02 μm is added to a surfactant solution such as dodecylammonium, the silica binds to the outer periphery of the surfactant in a honeycomb shape. When the crystalline phase material thus obtained is fired, it becomes mesoporous silica from which the surfactant has been removed. By appropriately selecting the surfactant to be used, the diameter of the pores formed in a honeycomb shape can be selected.

  The mesoporous silica used in the present invention may be a commercial product. For example, mesoporous silica manufactured by Taiyo Kagaku Co., Ltd., trade names “TMPS-1.5”, “TMPS-2.7”, “TMPS-4” and the like can be suitably used.

  The mesoporous silica used in the present invention may further contain a noble metal such as platinum or palladium, or a mixture thereof. Such components can be present in the composition by cocrystallization.

The mesoporous silica used in the present invention may be composed of, for example, the following crystal phase substances (a) and (b). That is,
(A) after firing, at least one peak of the X-ray diffraction pattern exhibits a d-interval greater than 1.8 nm and has a benzene adsorption capacity of more than 15 g per 100 g of substance at 6.7 kPa (50 torr) and 25 ° C., A porous, non-layered crystalline phase material having a composition represented by the following formula (1):

（式中、Ｍは１種以上のイオンであり、
ｎは酸化物として表わされるＭを除いた組成の電荷であり、
ｑはＭの重量モル平均原子価であり、
ｎ／ｑはＭのモル数またはモル分率である。）
または、
（ｂ） 直径が少なくとも１．３ｎｍの均一な寸法の細孔の六方構造配列を有し、焼成後、１．８ｎｍより大きいｄ₁₀₀値で示され得る六方構造の電子回折パターンを示す無機質、多孔質の上記式（１）で示す組成の結晶相物質である。

(Wherein M is one or more ions,
n is the charge of the composition excluding M expressed as an oxide,
q is the weight molar average valence of M;
n / q is the number of moles or mole fraction of M. )
Or
(B) An inorganic, porous material having a hexagonal structure array of uniformly sized pores having a diameter of at least 1.3 nm and exhibiting an electron diffraction pattern of a hexagonal structure that can be represented by a d ₁₀₀ value greater than 1.8 nm after firing. It is a crystalline phase substance having a composition represented by the above formula (1).

Since the crystalline phase substance is an inorganic, porous crystalline phase substance having a composition represented by the above formula (1), which exhibits a hexagonal structure electron diffraction pattern that can be expressed by a d ₁₀₀ value greater than 1.8 nm after firing. An organic compound having a large molecular size, in particular an aromatic hydrocarbon having a substituted or unsubstituted polycyclic aromatic component, a bulky naphthene compound, or a highly substituted compound having a bulky configuration, for example It can be usefully used for conversion or catalyst having a molecular size of 1.3 nm or more.

  The pore size of the crystalline phase substance is not a strict crystallographic size, but an effective pore size determined by sorption measurement. A preferred method for determining the pore size is to use the conventionally known argon physisorption. That is, the mass of argon adsorbed on the sample is measured by changing the relative pressure on the sample at a constant temperature, and the adsorption isotherm is plotted. The point corresponding to the rapid change in the isotherm gradient indicates the filling of the pores and can be applied to known mathematical relationships to determine the pore size. Further, in a pore structure having a diameter of 6.0 nm or more, the Kelvin equation represented by the following equation (2) can be applied.

（式中、γは吸着質の表面張力であり、Ｖは吸着質のモル体積、θは接触角（通常は実用上の理由により０とする）、Ｒは気体定数、Ｔは絶対温度、ｒｋは毛管凝縮（細孔）の半径、Ｐ／Ｐ０は相対圧力（物理吸着等温式から）である。）
上記ケルビン式は、細孔構造における吸着を毛管凝縮現象として取り扱い、吸着が起こる圧力を表面張力と吸着質（ここではアルゴン）の接触角とにより細孔直径に関係付けたものである。ケルビン式が基にする原理は、直径が５から１００ｎｍの範囲の細孔において有効である。ケルビン式を適切に適用できない細孔壁部の吸着質の表面層の効果を修正して細孔直径を正確に測定するため、細孔寸法の測定に使用されるケルビン式の特別の適用として、ドリモアおよびヒール（Ｄ．Ｄｏｌｌｉｍｏｒｅ ａｎｄ Ｇ．Ｒ．Ｈｅａｌ）の「ジェイ・アプライド・ケム（Ｊ．Ａｐｐｌｉｅｄ Ｃｈｅｍ．）、１４巻、１０８頁、１９６４年」を適用する。ドリモアとヒールの方法は脱着等温線に適用するために導出されたものであるが、単にデータを逆に入れることにより吸着等温線にも良好に適用することができる。

(Where γ is the surface tension of the adsorbate, V is the molar volume of the adsorbate, θ is the contact angle (usually 0 for practical reasons), R is the gas constant, T is the absolute temperature, rk Is the radius of capillary condensation (pores) and P / P0 is the relative pressure (from the physical adsorption isotherm).
The Kelvin equation treats adsorption in the pore structure as a capillary condensation phenomenon, and relates the pressure at which adsorption occurs to the pore diameter by the surface tension and the contact angle of the adsorbate (here argon). The principle based on the Kelvin formula is valid for pores with diameters ranging from 5 to 100 nm. As a special application of the Kelvin method used to measure the pore size, to correct the effect of the surface layer of the adsorbate on the pore wall to which the Kelvin method cannot be applied properly, D. Dollimore and GR Heal, “J. Applied Chem., 14, 108, 1964” applies. The Drymore and heel methods were derived for application to the desorption isotherm, but can be successfully applied to the adsorption isotherm by simply putting the data in reverse.

The crystalline phase material used in the present invention includes a high sorption capacity and an extremely large pore opening, and the maximum dimension of the vertical cross section of the pore is defined as the dimension of the pore. In the case of a hexagonal structure, the distance between two opposing surfaces is the maximum dimension of the pore. The crystal phase substance is a substance having regularity sufficient to give at least one peak in a diffraction pattern by, for example, X-ray, electron, or neutron diffraction after firing. As the crystalline phase material used in the present invention, an open channel that can be easily observed with an electron diffraction and a transmission electron microscope can have a hexagonal structure arrangement. In particular, a transmission electron micrograph with a sample of material in the proper orientation shows a hexagonal arrangement of large channels, and the corresponding electron diffraction pattern gives an arrangement of nearly hexagonal structures with diffraction maxima. The d ₁₀₀ interval of the electron diffraction pattern is the interval between adjacent points of the hk0 projection of the hexagonal structure lattice, and the repetitive distance a ₀ between channels observed with an electron microscope is related by the following equation (3).

この電子回折パターンで観察されるこのｄ₁₀₀間隔は、物質のＸ線回折パターンにおける低角度ピークのｄ間隔に相当する。このパターンは、独特の１００、１１０、２００、２１０等の反射である六方構造のｈｋ０部分集合とこれの対称の関係にある反射とで表示することができる。ここで、チャンネルの六方構造（ヘキサゴナル）配列とは、数学的に完全なヘキサゴナル対称のみでなく、物質中のほとんどのチャンネルが最も近い六つのチャンネルによって実質的に等距離で取り囲まれていることを意味する。なお、上記結晶相物質の細孔の寸法は、１．３〜２０ｎｍのメソポーラス範囲であり、電子回折および透過電子顕微鏡で容易に観察しうる開口したチャンネルがほぼ六方構造配列の結晶相物質を焼成処理したものである。

This d ₁₀₀ interval observed in the electron diffraction pattern corresponds to the d interval of the low angle peak in the X-ray diffraction pattern of the material. This pattern can be displayed with the hk0 subset of the hexagonal structure, which is a unique reflection of 100, 110, 200, 210, etc., and the reflection in a symmetrical relationship therewith. Here, the hexagonal arrangement of channels means not only mathematically perfect hexagonal symmetry but also that most channels in a substance are surrounded by the nearest six channels at substantially equal distances. means. The pore size of the crystalline phase material is in the mesoporous range of 1.3 to 20 nm, and the crystalline phase material having open channels that can be easily observed with electron diffraction and transmission electron microscopy is fired. It has been processed.

  The crystalline phase substance used in the present invention gives an X-ray diffraction pattern having a hexagonal structure having several distinct maximum values in an extremely low angle region, but only in the low angle region of the X-ray diffraction pattern. It may have two distinct peaks.

The crystalline material used in the present invention has, in its fired form, a position where the d interval corresponding to the d ₁₀₀ value of the electron diffraction pattern of the material is greater than about 1.8 nm (Cuθ radiation at 4.909 degrees 2θ). Shows an X-ray diffraction pattern having at least one peak. In addition, the d interval has at least two peaks at a position larger than about 1 nm (8.82 degrees 2θ in CuKα line), and at least one peak is at a position where the d interval is larger than 1.8 nm. Preferably, it exhibits an X-ray diffraction pattern having a relative intensity greater than about 20% of the strongest peak and no peak at a position where the d interval is smaller than 1 nm. More preferably, the peak does not have a peak at a d-interval position smaller than 1 nm with a relative intensity greater than about 10% of the strongest peak. In a preferred hexagonal structure arrangement, at least one peak of the X-ray pattern has a d spacing corresponding to the d ₁₀₀ value of the electron diffraction pattern of the material.

  In the present specification, the X-ray diffraction data is based on a STAG PAD automatic diffraction apparatus using a θ-θ crystal structure, a CuKα ray, and an energy dispersive X-ray detector. Both incident X-ray and diffracted X-ray beams are collimated with a double slit incident and diffractive collimation system. The slit sizes used are 0.5, 1.0, 0.3 and 0.2 mm, respectively, starting from the X-ray tube source. Different slit systems have different peak intensities.

The diffraction data was recorded by scanning 2θ step by step with a counting time of 0.04 degrees every 10 seconds (θ is a Bragg angle). The interlayer spacing d is calculated in nm, and the relative intensity I / I _{0 of} the line minus the background (I ₀ is 1/100 of the strongest line) is derived using the profile fitting routine, and the intensity Are not corrected due to the Lorentz effect and polarization effect. In addition, relative intensity expresses vs (very strong) by 75-100, s (strong) by 50-74, m (medium) by 25-49, and w (weak) by 0-24.

  Diffraction data listed as a single line consists of many overlapping lines that appear to be resolvable or partially resolvable under specific conditions such as experimental high resolution and crystallographic exchange. Should be understood. In general, crystallographic changes may include minor changes in unit cell parameters and / or changes in crystal symmetry without substantial structural changes. These mild effects, including changes in relative strength, include cation content, skeletal structure, state and degree of pore filling, thermal and / or hydrothermal history, and particle size / shape effects, structural irregularities, Or as a result of differences in peak width / shape variations due to other factors known in the prior art of X-ray diffraction.

  The crystalline phase material used in the present invention exhibits an equilibrium benzene adsorption capacity of greater than about 15 g per 100 g of crystals at 6.7 kPa (50 torr) and 25 ° C. Equilibrium benzene adsorption capacity is measured on samples that show no pore blockage due to accompanying impurities. Water can be removed by a dehydration method such as heat treatment. Inorganic amorphous materials such as silica and organic materials can be removed by acid, base or other chemical agents and / or physical methods (eg, calcination), so that they do not adversely affect the materials of the present invention. In addition, obstacles can be removed.

  The crystalline phase material constituting the mesoporous silica used in the present invention is obtained by firing a crystalline phase material obtained by crystallizing a reaction mixture having the composition shown in the following table, expressed in terms of a molar ratio of oxides. Also good.

[Table 2]
Composition of the reaction mixture ┌──────────────────┬─────────┐
│Component │Ratio │
├──────────────────┼─────────┤
│Solvent / SiO ₂ │1-1500 │
├──────────────────┼─────────┤
│OH ^- / SiO ₂ │0~10 │
├──────────────────┼─────────┤
│ (M _{e / 2} O + R _{f / 2} O) / SiO ₂ │0.01-20 │
├──────────────────┼─────────┤
│M _{e / 2} O / SiO ₂ │0-10 │
├──────────────────┼─────────┤
│R _{f / 2} O / SiO ₂ │0.01 ~ 2.0 │
└──────────────────┴─────────┘
In the above composition, M is one or more ions, e and f are weight average valences of M and R, respectively, the solvent is an alcohol or diol having 1 to 6 carbon atoms, or water, and R Is the total organic matter used to help the synthesis of the substance,
Formula: R ₁ R ₂ R ₃ R ₃ Q + (where Q is nitrogen or phosphorus, and at least one of R ₁ , R ₂ , R ₃ and R ₄ is —C ₆ H ₁₃ , —C ₁₀ H ₂₁ , -C ₁₆ H ₃₃ and -C ₁₈ H _37, an aryl group or an alkyl group having 6 to ₃₆ carbon atoms, each of R ₁ , R ₂ , R ₃ and R ₄ being hydrogen and 1 to 5 carbon atoms A total organic substance consisting of an organic inducer having an alkyl group of

  Examples of R include cetyltrimethylammonium, cetyltrimethylphosphonium, octadecyltrimethylphosphonium, benzyltrimethylammonium, cetylpyridinium, myristyltrimethylammonium, decyltrimethylammonium, dodecyltrimethylammonium, and dimethyldidodecylammonium compounds. . These are referred to as organic inducers.

In addition to the organic inducer represented by R,
Formula: R ₁ R ₂ R ₃ R ₄ Q ⁺ (wherein Q is nitrogen or phosphorus, and R ₁ , R ₂ , R ₃ and R ₄ are selected from hydrogen and an alkyl group having 1 to 5 carbon atoms) You may use together the additional organic inducer which has. Such additional organic inducers include tetramethylammonium, tetraethylammonium, tetrapropylammonium and tetrabutylammonium compounds.

  The crystalline substance having the composition of the formula (1) has a composition represented by the following formula (4) based on an anhydride in an as-synthesized form.

（式中、Ｍは１種以上のイオンであり、
ｎは酸化物として表わされるＭを除いた組成の電荷であり、
ｑはＭの重量モル平均原子価であり、
Ｒは、イオンとしてＭに含まれず、物質の合成において助けるために使用される全有機物、ｒはＲの係数、即ち、Ｒのモル数またはモル分率である。）
ＭとＲの成分は結晶化の際にそれらが存在する結果として物質に取り込まれており、容易に除去することができ、またはＭについては、後結晶化法などにより交換することができる。例えば、合成したままの形態の物質の元のＭ、例えば、ナトリウムまたは塩素のイオンは、イオン交換によって他のイオンに交換する。好ましい交換イオンは、金属イオン、水素イオン、水素前駆体、例えば、アンモニウムイオン、およびこれらの混合物である。特に好ましいイオンは、炭化水素転化反応のために触媒活性を仕立てるものである。これは、元素周期表のＩＡ族（例えば、Ｋ）、ＩＩＡ族（例えば、Ｃａ）、ＶＩＩＡ族（例えば、Ｍｎ）、ＶＩＩＩＡ族（例えば、Ｎｉ）、ＩＢ族（例えば、Ｃｕ）、ＩＩＢ族（例えば、Ｚｎ）、ＩＩＩＢ族（例えば、Ｉｎ）、ＩＶＢ族（例えば、Ｓｎ）およびＶＩＩＢ族（例えば、Ｆ）の金属、希土類金属、および水素、ならびにこれらの混合物を包含する。

(Wherein M is one or more ions,
n is the charge of the composition excluding M expressed as an oxide,
q is the weight molar average valence of M;
R is not included as an ion in M and is the total organic matter used to assist in the synthesis of the material, r is the coefficient of R, ie the number of moles or mole fraction of R. )
The M and R components are incorporated into the material as a result of their presence during crystallization and can be easily removed or M can be replaced by post-crystallization methods or the like. For example, the original M, eg, sodium or chlorine ions, of the as-synthesized form of the material are exchanged for other ions by ion exchange. Preferred exchange ions are metal ions, hydrogen ions, hydrogen precursors such as ammonium ions, and mixtures thereof. Particularly preferred ions are those that tailor catalytic activity for the hydrocarbon conversion reaction. This is because the group IA (eg K), IIA (eg Ca), VIIA (eg Mn), VIIIA (eg Ni), IB (eg Cu), IIB ( For example, Zn), Group IIIB (eg In), Group IVB (eg Sn) and Group VIIB (eg F) metals, rare earth metals, and hydrogen, and mixtures thereof.

  The substance having the composition defined by the above formula can be prepared using a reaction mixture having the following composition.

[Table 3]
Composition of the reaction mixture ┌──────────────────┬─────────┐
│Component │Ratio │
├──────────────────┼─────────┤
│Solvent / SiO ₂ │1-1500 │
├──────────────────┼─────────┤
│OH ^- / SiO ₂ │0~10 │
├──────────────────┼─────────┤
│ (M _{e / 2} O + R _{f / 2} O) / SiO ₂ │0.01-20 │
├──────────────────┼─────────┤
│M _{e / 2} O / SiO ₂ │0-10 │
├──────────────────┼─────────┤
│R _{f / 2} O / SiO ₂ │0.01 ~ 2.0 │
└──────────────────┴─────────┘
Examples of the organic inducer represented by R include cetyltrimethylammonium, cetyltrimethylphosphonium, octadecyltrimethylphosphonium, benzyltrimethylammonium, cetylpyridinium, myristyltrimethylammonium, decyltrimethylammonium, dodecyltrimethylammonium and dimethyl. Compounds such as didodecyl ammonium can be preferably used, and these are hydroxides, halides, and silicates. As a result, cetyltrimethylammonium hydroxide obtained by hydroxylating cetyltrimethylammonium, an organic inducer, and myristyltrimethylammonium bromide obtained by brominating myristyltrimethylammonium become surfactants, and micelles are used in the solvent. This forms a template for the growth and growth of the desired ultra-porous material nuclei.

  The reaction mixture preferably further contains an additional organic inducer such as tetramethylammonium, tetraethylammonium, tetrapropylammonium and tetrabutylammonium compounds in addition to the organic inducer.

  In addition, an organic adjuvant may be further included to change the pore size of the crystalline phase material. The organic adjuvants are: (1) C5-C20 aromatic hydrocarbons and amines and their halogen-substituted and C1-C14 alkyl-substituted derivatives; (2) C5-C20 cyclic and polycyclic Of aliphatic hydrocarbons and amines and their halogen-substituted and C1-C14 alkyl-substituted derivatives; (3) linear and branched aliphatic hydrocarbons and amines having 3 to 16 carbon atoms and their halogen-substituted derivatives Either can be used. In addition, as a halogen substituent of such an organic adjuvant, bromine is preferable.

  The C1-C14 alkyl substituent may be a linear or branched aliphatic chain such as, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, and combinations thereof. This organic adjuvant includes, for example, p-xylene, trimethylbenzene, triethylbenzene and triisopropylbenzene.

  Moreover, it is preferable to use at least partially an organic silicate such as a quaternary ammonium silicate as the silicon source. Examples of this include, but are not limited to, tetramethylammonium silicate and tetraethylorthosilicate.

  In order to produce the crystalline material, the reaction mixture is generally treated at a temperature of 25 to 250 ° C., preferably 50 until the required crystals are formed, generally from 5 minutes to 14 days, more preferably from 1 to 300 hours. Maintain at ˜175 ° C. and preferably pH 9-14. Thereby, a crystallized solid can be obtained.

Next, a part or all of the used organic component contained in the crystallized solid is removed.
The crystallized solid is used after calcining, especially in its metal, hydrogen and ammonium forms. This firing treatment is generally performed at a temperature of 400 to 750 ° C. for 1 minute to 20 hours, preferably 1 to 10 hours. Under reduced pressure, air, nitrogen, ammonia, etc. may be present at normal pressure.

In order to obtain a crystalline phase substance by the above, for example, a cetyltrimethylammonium hydroxide solution is used as an organic inducer, and this is mixed with a tetramethylammonium silicate solution, and then precipitated hydrated silica (free water about 6% by mass, water A crystal phase substance can be obtained by adding about 4.5% by mass of combined water, and having an ultimate particle size of 0.02 μm) and leaving it in a steam box at 95 ° C. overnight. After drying this at room temperature, it is baked at 540 ° C. for 1 hour in nitrogen and then baked in air for 6 hours. The calcined product had a surface area of 475 m ² / g and an equilibrium adsorption capacity (g / 100 g) of H ₂ O 8.3, cyclohexane 22.9, n-hexane 18.2 and benzene 21.5. The X-ray diffraction pattern of the fired product corresponds to 2θ (CuKα ray) with a d-interval of 10 Å (1.0 nm) units of 8.842 ° and 18 Å (1.8 nm) units to 4.908 °. And very strong relative intensity lines at d spacing of 3.78 ± 0.2 nm, and weak relative intensity lines at 2.16 ± 0.1 and 1.92 ± 0.1 nm. A transmission electron microscope (TEM) shows an image of a uniform hexagonal structure array and an electron diffraction pattern of a hexagonal structure with a d ₁₀₀ value of about 3.9 nm, with an average pore diameter of 3.22 nm.

Further, for example, a cetyltrimethylammonium hydroxide solution is used as an organic inducer, and a tetramethylammonium hydroxide solution is used in combination as an additional organic inducer, and precipitated hydrated silica (free water about 6% by mass, hydrated bond) A crystal phase substance can be obtained by adding about 4.5% by mass of water and adding an ultimate particle size of 0.02 μm) and leaving it in a steam box at 150 ° C. overnight. After drying this at room temperature, it is baked at 540 ° C. for 1 hour in nitrogen and then baked in air for 6 hours. The calcined product had a surface area of 993 m ² / g, and the equilibrium adsorption capacity (g / 100 g) was H ₂ O 7.1, cyclohexane 47.2, n-hexane 36.2, and benzene 49.5. The X-ray diffraction pattern of this fired product contains very strong relative intensity lines at d-interval 3.93 ± 0.2 nm, weak relative intensity lines at 2.22 ± 0.1 and 1.94 ± 0.1 nm. .
The average pore diameter of this crystalline material is 3.54 nm.

  The crystalline phase material used in the present invention may be tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal such as platinum or palladium, or a mixture thereof when performing a hydrogenation / dehydrogenation function. It can be used as a catalyst component in combination with such a hydrogenation component. Such components can be in the composition by co-crystallization and can be exchanged in the composition to some extent to a structure in which a Group IIIB element, such as aluminum, is impregnated or physically mixed. Such a component can be impregnated as it is, for example, in the case of platinum, the silicate may be treated with a solution containing platinum metal-containing ions. Accordingly, suitable platinum compounds for this purpose include various compounds including chloroplatinic acid, platinum chloride and platinum amine complexes.

  Furthermore, the crystalline material used in the present invention is preferably at least partially dehydrated when used as a catalyst component or adsorbent in an organic compound conversion process. This can be done by heating at a temperature of 200 to 595 ° C. for 30 minutes to 48 hours under atmospheric pressure, reduced pressure or increased pressure in an atmosphere such as air or nitrogen. Dehydration can be performed at room temperature by simply placing the material in a vacuum atmosphere, but it takes a long time to perform a sufficient amount of dehydration.

(Iii) Compounding ratio of mesoporous silica In the oxygen-absorbing laminated film of the present invention, the mesoporous silica is preferably compounded in the resin in an amount of 0.01 to 50% by mass, and in the present invention it is 0.01 to 1 % by mass. If it is less than 0.01% by mass, the odor removal effect may not be sufficient. The oxygen-absorbing laminated film of the present invention is a coextruded film and is characterized in that it can be laminated without using a dry laminate adhesive. If the content of mesoporous silica exceeds 50% by mass, the film forming property may be deteriorated.

In the oxygen-absorbing laminated film of the present invention, the thickness of the odor barrier layer is preferably 5 to 50 μm, more preferably 10 to 30 μm.
(Iv) Heat seal layer having odor barrier property In the oxygen-absorbing laminated film of the present invention, the odor barrier layer can be used as it is as a heat seal layer having odor barrier property. The resin constituting the odor barrier layer is a thermoplastic resin and has heat sealability. For this reason, the said odor barrier layer can be used as it is as a heat seal layer which has odor barrier property, and lamination | stacking of a heat seal layer can be avoided.

In the oxygen-absorbing laminated film of the present invention, the thickness of the heat seal layer having odor barrier properties is preferably 5 to 60 μm, more preferably 10 to 30 μm.
(4) Heat-seal layer As the heat-seal layer, polyolefin resins having various heat-seal properties that can be melted by heat and fused to each other can be used. Specifically, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene -Ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-α / olefin copolymer polymerized using metallocene catalyst, polypropylene, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer Polyolefin resins such as methylpentene polymer, polybutene polymer, polyethylene or polypropylene modified with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, Vinyl acetate Resins, poly (meth) acrylic resin, one or more films made of a resin such as polyvinyl chloride resin or sheet or coated film and the like can be used.

  In the present invention, a polyolefin-based resin can be preferably used. In particular, a polypropylene random copolymer using a single site metallocene catalyst is suitable. Specifically, it is a polypropylene random copolymer comprising a block or random copolymer of propylene and ethylene or propylene and 1-octene. It is because it is excellent in adhesiveness. The melt flow rate (MFR) of the resin constituting the heat seal layer is preferably 0.2 to 4.0 g / min, and more preferably 0.2 to 2.0. When it is less than 0.2 g / min, it is disadvantageous in terms of workability. On the other hand, if it exceeds 4.0 g / min, it is disadvantageous in terms of workability. In the present invention, the melt flow rate (MFR) is measured from a method based on JIS K6921, and the density is measured from a method based on JIS K7112.

The heat seal layer has a thickness of 5 to 60 μm, preferably 10 to 30 μm.
The heat seal layer may be a single layer or a multilayer composed of one of the above resins, or may be a multilayer of two or more layers.

  Further, the heat seal layer may be separated into a colored layer containing a pigment or a dye and a layer not containing the pigment, and the colored layer may be, for example, a white resin layer having excellent light shielding properties by kneading a white pigment or dye. it can.

  In the present invention, as the white colorant constituting the colored layer such as the white resin layer, one kind or a mixture of two or more kinds of white colorants such as inorganic or organic dyes and pigments are used. Is desirable. Specifically, for example, basic lead carbonate, basic lead sulfate, basic lead silicate, zinc white, zinc sulfide, lithopone, antimony trioxide, anatase type titanium oxide, rutile type titanium oxide, carbonic acid One or more of white pigments such as calcium, zinc oxide, barium sulfate, etc. can be used. These do not impair the cosmetics of the packaging container, and block or block the transmission of the sun, fluorescent lights, etc., and prevent light deterioration such as decomposition or alteration, discoloration, etc. of the contents filled and packed in the packaging bag be able to. In the colored layer, the blending amount of the colorant is 0.1 to 30% by mass, preferably 0.5 to 20% by mass with respect to the resin constituting the heat seal layer.

In this invention, it is not limited to the said white dye or a white pigment, A colored layer can be formed using the pigment and dye of another color.
When such a colored layer is formed, the thickness of the colored layer is 5 to 60 μm, preferably 10 to 40 μm. If it is this range, the effect by the target coloring can be acquired.

  When such a colored layer is formed, a heat seal layer having no colored layer as the innermost layer is formed. When inorganic titanium or the like is kneaded as a pigment or dye, the heat sealability is lowered, but the heat sealability can be ensured by forming a layer containing no pigment or dye in the innermost layer. In this case, the thickness of the layer containing no pigment or dye is 5 to 30 μm, preferably 5 to 30 μm. Sufficient heat sealability can be secured within this range.

(5) Thermoplastic resin layer In the oxygen-absorbing laminated film of the present invention, a thermoplastic resin layer is laminated when the above-described oxygen-absorbing layer and odor barrier layer are laminated.

  As the thermoplastic resin layer, various polyolefin resins that can be melted by heat and fused to each other can be used. Specifically, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene constituting the heat seal layer described above. -Acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-α / olefin copolymer polymerized using metallocene catalyst, polypropylene, ethylene-methyl methacrylate copolymer Polyolefin resins such as polymers, ethylene-propylene copolymers, methyl pentene polymers, polybutene polymers, polyethylene or polypropylene with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid and itaconic acid. Modified acid-modified poly Olefin resins, polyvinyl acetate resins, poly (meth) acrylic resin, a resin such as polyvinyl chloride resin can be used.

  Moreover, in this invention, when using a polyamide-type resin as an oxygen absorption layer, what can be closely_contact | adhered to a polyamide can be used suitably as a thermoplastic resin layer. Specifically, polymerized using olefin resin, low density polyethylene (LDPE), linear (linear) low density polyethylene (polymer polymerized using multisite catalyst, LLDPE), metallocene catalyst (single site catalyst). Ethylene-α / olefin copolymer, medium density polyethylene (MDPE), high density polyethylene (HDPE), polypropylene resin, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-acrylic acid Polyolefin resins such as ethyl copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, polyethylene or polypropylene are used for acrylic acid, methacrylic acid, maleic Acid-modified polyolefin resins modified with unsaturated carboxylic acids such as acid, maleic anhydride, fumaric acid, itaconic acid, polyvinyl acetate resins, poly (meth) acrylic resins, polyvinyl chloride resins, thermoplastic polyester resins In addition, one or more thermoplastic resins such as thermoplastic polyamide resins and others can be used. The thermoplastic resin is a polyolefin resin and has the same quality as the heat seal layer constituting the oxygen-absorbing laminated film of the present invention. Therefore, an oxygen absorption layer and a heat seal layer can be adhered by the thermoplastic resin.

  The resin constituting the thermoplastic resin layer having excellent adhesion to the above-described polyamide or the like preferably has a density of 0.88 to 0.92. The reason is that processability and adhesiveness are improved. As such a thermoplastic resin, a commercially available product may be used. For example, trade names “Modic M545” and “Modic APP P555” manufactured by Mitsubishi Chemical Corporation, trade names “Admer QF570” manufactured by Mitsui Chemicals, etc. There is.

  The thermoplastic resin layer can also be made into a colored layer by adding pigments or dyes thereto. In the oxygen-absorbing laminated film of the present invention, when a plurality of thermoplastic resin layers are laminated, they may be the same or different.

  In the oxygen-absorbing laminated film of the present invention, the innermost layer is a heat seal layer (50) or a heat seal layer (40) having a odor barrier property, and these are all thermoplastic resins. By laminating the thermoplastic resin layer (I) (20) on the outermost layer, since the innermost layer and the outermost layer are common, curling of the obtained oxygen-absorbing laminated film can be prevented. When the oxygen-absorbing laminated film is used as it is as a packaging material, or when another film is laminated on the oxygen-absorbing laminated film, if the flatness of the oxygen-absorbing laminated film is not maintained, Ear breakage occurs, making stable production difficult. In the present invention, stable processing can be performed by providing the thermoplastic resin layer (I) (20) as the outermost layer of the oxygen-absorbing laminated film.

Such a thermoplastic resin layer has a thickness of 3 to 15 μm, preferably 5 to 20 μm.
(6) Substrate resin layer In this invention, a base resin layer can be further laminated | stacked on the said oxygen absorptive laminated film, and it can be set as an oxygen absorptive laminated body. Such a base resin layer may be laminated by coextrusion, or a base resin film may be laminated via a laminating adhesive. This is because the odor barrier layer is laminated on the inner side of the oxygen absorbing layer, so that the transfer of odor to the contents by the laminating adhesive can be efficiently prevented.

As the base resin layer, a polyamide resin or a polyester resin such as polyethylene terephthalate or polyethylene naphthalate is used.
The polyamide-based resin may be an aliphatic polyamide, an aromatic polyamide, or a composition in which these are mixed. Specific examples of preferred polyamides include polycaproamide (nylon 6), poly-ε-aminoheptanoic acid (nylon 7), poly-ε-aminononanoic acid (nylon 9), polyundecanamide (nylon 11), polylaurin Lactam (nylon 12), polyethylenediamine adipamide (nylon 2.6), polytetramethylene adipamide (nylon 4.6), polyhexamethylene adipamide (nylon 6/6), polyhexamethylene sebacamide (Nylon 6 · 10), Polyhexamethylene dodecamide (Nylon 6 · 12), Polyoctamethylene dodecamide (Nylon 6 · 12), Polyoctamethylene adipamide (Nylon 8.6), Polydecamethylene adipamide (Nylon 10/6), polydecamethylene sebacamide (nylon 10/10), Polydodecamethylene dodecamide (nylon 12 and 12), metaxylenediamine-6 nylon (MXD6) and the like may be used, and a copolymer containing these as main components may be used. Examples thereof include caprolactam / Laurin lactam copolymer, caprolactam / hexamethylene diammonium adipate copolymer, laurin lactam / hexamethylene diammonium adipate copolymer, hexamethylene diammonium adipate / hexamethylene diammonium sebacate copolymer And ethylene diammonium adipate / hexamethylene diammonium adipate copolymer, caprolactam / hexamethylene diammonium adipate / hexamethylene diammonium sebacate copolymer, and the like. It is also effective to blend these polyamides with plasticizers such as aromatic sulfonamides, p-hydroxybenzoic acid, esters, elastomer components with low elastic modulus, and lactams as film flexibility modifiers. is there. The polyamide-based resin preferably has a density of 1.14 to 1.22 g / m ³ . The reason is that it is excellent in processability such as extrusion characteristics.

Moreover, as a polyester-type resin, a polyethylene terephthalate can be used conveniently. The polyester resin preferably has a specific gravity of 1.00 to 1.41 g / m ³ . The reason is because it is excellent in extrusion suitability.

In the present invention, the film thickness of the base resin layer is preferably 5 to 25 μm, more preferably 5 to 15 μm.
In forming the base resin layer, for example, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, mold release properties, flame retardancy, antifungal properties, strength, etc. Various plastic compounding agents and additives can be added for the purpose of improvement and modification, and the addition amount can be arbitrarily added from a very small amount to several tens of percent depending on the purpose. Can do.

  In the above, as a general additive, for example, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a pigment, and the like can be used. In this case, a modifying resin or the like can also be used.

(7) Gas barrier film In the present invention, various gas barrier films capable of preventing permeation of oxygen and water vapor can be laminated.

(A) Polyvinyl alcohol In this invention, polyvinyl alcohol can be used conveniently as a gas barrier film. Although there is no restriction | limiting in the thickness of the gas-barrier film which consists of polyvinyl alcohol, Preferably it is 15-25 micrometers.

  On the other hand, although polyvinyl alcohol can be used as a single layer film, since it is a water-soluble polymer, it may be a laminated film in which a coating film made of polyvinyl alcohol is formed on a substrate film having excellent water resistance. As such a base film, the base film described in the section of a gas barrier laminate film described later can be suitably used. Thereby, water resistance is securable. Examples of such a polyvinyl alcohol resin include “RS-110 (degree of saponification = 99%, degree of polymerization = 1,000)” manufactured by Kuraray Co., Ltd., and “Kuraray Poval LM-20SO ( “Saponification degree = 40%, polymerization degree = 2,000)”, “GOHSENOL NM-14 (degree of saponification = 99%, polymerization degree = 1,400)” manufactured by Nippon Synthetic Chemical Industry Co., Ltd. Can do.

(B) Ethylene / vinyl alcohol copolymer In the present invention, an ethylene / vinyl alcohol copolymer can also be suitably used as the gas barrier film. Although there is no restriction | limiting in the thickness of the gas-barrier film which consists of an ethylene vinyl alcohol copolymer, Preferably it is 10-30 micrometers.

  On the other hand, the ethylene / vinyl alcohol copolymer can be used as a single layer film, but may be a laminated film in which a coating film made of an ethylene / vinyl alcohol copolymer is formed on a base film. As such a base film, the base film described in the section of a gas barrier laminate film described later can be suitably used. Thereby, the various characteristics according to a base film, such as a mechanical characteristic, can be improved. Examples of such an ethylene / vinyl alcohol copolymer include “Eval EP-F101 (ethylene content; 32 mol%)” manufactured by Kuraray Co., Ltd., “Soarnol D2908 (ethylene content; 29 mol) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.” %) "And the like.

(C) Gas barrier laminated film As a gas barrier film used in the present invention, a vapor deposition film formed by vapor-depositing an organosilicon compound, a metal or a metal oxide is provided on one surface of a base film, and a general film is formed on the vapor deposition film. Formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, and n represents an integer of 0 or more. M represents an integer of 1 or more, and n + m represents a valence of M.), and a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. Further, a gas barrier laminated film provided with a gas barrier coating film made of a gas barrier composition obtained by polycondensation by a sol-gel method can also be used. The gas barrier coating film is formed by a polyvinyl alcohol resin or ethylene / vinyl alcohol copolymer and at least one alkoxide chemically reacting with each other to form a strong three-dimensional network composite polymer layer. The film acts synergistically, has excellent gas barrier properties that prevent permeation of oxygen, water vapor, and the like, and also has excellent hot water resistance.

(I) Base film As the base film constituting the gas barrier laminate film, polyethylene resin, polypropylene resin, cyclic polyolefin resin, fluorine resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin) , Acrylonitrile-butadiene-styrene copolymer (ABS resin), polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, polycarbonate resin, polyethylene terephthalate, polyethylene naphthalate and other polyester resins, polyimide Resin, Polyamideimide resin, Polyarylphthalate resin, Silicone resin, Polysulfone resin, Polyphenylene sulfide resin, Polyethersulfone resin, Polyurethane resin, Acetal resin, Cellulos Various resins such as a resin and the like can be used. In particular, a polyester resin or a polyamide resin can be preferably used. As a film thickness of a base film, it is 6-100 micrometers, More preferably, it is 9-50 micrometers.

(Ii) Surface treatment In the present invention, a deposited film is formed by vapor-depositing an organosilicon compound, a metal or a metal oxide on one surface of the above-mentioned base film. Also good. Thereby, the adhesiveness with the vapor deposition film or the gas barrier coating film can be improved. Such surface treatments include corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, etc., and other pretreatments, etc. is there.

(Iii) Vapor deposition film formed by vapor-depositing organosilicon compound, metal or metal oxide Examples of the vapor deposition film in the present invention include a chemical vapor deposition method, a physical vapor deposition method or a combination thereof, It can be produced by forming a single-layer film consisting of one layer of a vapor-deposited film obtained by vapor-depositing a metal or metal oxide, or a multilayer film or a composite film consisting of two or more layers.

  Examples of the chemical vapor deposition method include chemical vapor deposition methods such as plasma chemical vapor deposition method, low temperature plasma chemical vapor deposition method, thermal chemical vapor deposition method, and photochemical vapor deposition method (Chemical Vapor Deposition method), CVD method). Specifically, a vapor deposition monomer gas such as an organosilicon compound is used as a raw material on one surface of a base film, and an inert gas such as argon gas or helium gas is used as a carrier gas. As described above, a vapor deposition film such as silicon oxide can be formed by using a low temperature plasma chemical vapor deposition method using an oxygen gas or the like and using a low temperature plasma generator or the like.

  In the above, as a low temperature plasma generator, generators, such as high frequency plasma, pulse wave plasma, and microwave plasma, can be used, for example. In view of obtaining highly active and stable plasma, it is preferable to use a high-frequency plasma generator.

An example of a method for forming a deposited film by the low temperature plasma chemical vapor deposition method will be described with reference to FIG. 9 which is a schematic configuration diagram of a low temperature plasma chemical vapor deposition apparatus.
In the present invention, the base film 201 is fed out from the unwinding roll 223 disposed in the vacuum chamber 222 of the plasma chemical vapor deposition apparatus 221, and the base film 201 is further fed at a predetermined speed via the auxiliary roll 224. Then, it is conveyed onto the circumferential surface of the cooling / electrode drum 225. On the other hand, a gas mixture for vapor deposition is prepared by supplying vapor deposition monomer gas such as oxygen gas, inert gas, organosilicon compound, etc. from the gas supply devices 226, 227 and the raw material volatilization supply device 228, etc. Is introduced into the vacuum chamber 222 through the raw material supply nozzle 229. The mixed gas composition for vapor deposition is supplied onto the substrate film 201 conveyed on the circumferential surface of the cooling / electrode drum 225, and plasma is generated and irradiated by glow discharge plasma 230 to form a vapor deposited film. . Next, when the base film 201 on which the vapor deposition film is formed as described above is wound around the winding roll 234 via the auxiliary roll 233, a vapor deposition film formed by vapor-depositing an organosilicon compound by plasma chemical vapor deposition is formed. Can do. A predetermined power is applied to the cooling / electrode drum 225 from a power source 231 disposed outside the vacuum chamber 222, and a magnet 232 is disposed in the vicinity of the cooling / electrode drum 225 to promote plasma generation. Has been. Since a predetermined voltage is applied from the power source to the cooling / electrode drum in this way, glow discharge plasma is generated in the vicinity of the opening of the raw material supply nozzle in the vacuum chamber and the cooling / electrode drum. The glow discharge plasma is derived from one or more gas components in the mixed gas. When the base film is conveyed at a constant speed in this state, the glow discharge plasma causes the cooling / electrode drum surface to be A deposited film formed by depositing an organosilicon compound can be formed on the base film. In FIG. 9, reference numeral 235 represents a vacuum pump.

In the present invention, the vacuum chamber is depressurized by a vacuum pump and adjusted to a vacuum degree of 1 × 10 ⁻¹ to 1 × 10 ⁻⁸ Torr, preferably a vacuum degree of 1 × 10 ⁻³ to 1 × 10 ⁻⁷ Torr. It is preferable to do.

The raw material volatilization supply device volatilizes the organic silicon compound as the raw material, mixes it with oxygen gas, inert gas, etc. supplied from the gas supply device, and introduces this mixed gas into the vacuum chamber through the raw material supply nozzle. . At this time, the content of the organosilicon compound in the mixed gas is preferably 1 to 40%, the oxygen gas content is 10 to 70%, and the inert gas content is preferably 10 to 60%. For example, the mixing ratio of organosilicon compound: oxygen gas: inert gas can be about 1: 6: 5 to 1:17:14. Note that the degree of vacuum in the vacuum chamber when supplying the organosilicon compound, the inert gas, the oxygen gas, and the like is 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably 1 × 10 ⁻¹ to 1 × 10 ⁻² Torr is preferable, and the conveying speed of the base film is 10 to 300 m / min, preferably 50 to 150 m / min. Formation of the vapor deposition film formed by vapor-depositing the organosilicon compound obtained in this way is formed on the base film in the form of a thin film in the form of SiO _x while oxidizing the plasma-formed source gas with oxygen gas. Therefore, the deposited film is a dense continuous layer having a small gap and a high flexibility. Therefore, the barrier property of the deposited film is an inorganic oxide such as silicon oxide formed by a conventional vacuum deposition method or the like. Compared with a deposited film of a product, it is much higher, and a sufficient barrier property can be obtained with a thin film thickness. Moreover, since the surface of the base film is cleaned by SiO _X plasma and polar groups and free radicals are generated on the surface of the base film, the adhesion between the deposited film to be formed and the base film is high. It will be a thing. Further, the degree of vacuum at the time of forming the deposited film is 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably 1 × 10 ⁻¹ to 1 × 10 ⁻² Torr. Since the degree of vacuum when forming a vapor-deposited film of inorganic oxide such as silicon oxide is lower than 1 × 10 ⁻⁴ to 1 × 10 ⁻⁵ Torr, The vacuum state setting time can be shortened, the degree of vacuum is easily stabilized, and the film forming process is also stabilized.

In the present invention, a vapor deposition film formed using a vapor deposition monomer gas such as an organosilicon compound chemically reacts with a vapor deposition monomer gas such as an organosilicon compound and oxygen gas, and the reaction product is a base film. Is formed into a dense and flexible thin film, and is usually an oxidation represented by the general formula SiO _x (where X represents a number from 0 to 2). It is a continuous thin film mainly composed of silicon. The silicon oxide vapor deposition film is a silicon oxide vapor deposition represented by the general formula SiO _x (where X represents a number from 1.3 to 1.9) in terms of transparency and barrier properties. A thin film mainly composed of a film is preferable. The value of X varies depending on the molar ratio of vapor deposition monomer gas and oxygen gas, plasma energy, etc. Generally, the gas permeability decreases as the value of X decreases, but the film itself is yellow. The transparency becomes worse.

In the present invention, the silicon oxide vapor-deposited film is mainly composed of silicon oxide, and further contains at least one compound of carbon, hydrogen, silicon or oxygen, or a compound composed of two or more elements by chemical bonding or the like. It consists of a vapor deposition film. For example, when a compound having a C—H bond, a compound having a Si—H bond, or a carbon unit is in the form of graphite, diamond, fullerene, or the like, the raw material organosilicon compound or a derivative thereof is further added. It may be contained by a chemical bond or the like. Examples thereof include hydrocarbons having a CH ₃ site, hydrosilica such as SiH ₃ silyl and SiH ₂ silylene, and hydroxyl derivatives such as SiH ₂ OH silanol. In this invention, it is preferable that it is a vapor deposition film containing an organosilicate compound as said vapor deposition film. In addition to the above, the type, amount, etc. of the compound contained in the deposited film can be changed by changing the conditions of the deposition process. Under the present circumstances, as content which said compound contains in a vapor deposition film, it is 0.1 to 50%, Preferably it is 5 to 20%. If the content is less than 0.1%, the impact resistance, spreadability, flexibility, etc. of the vapor-deposited film will be insufficient, and scratches, cracks, etc. will easily occur due to bending, etc., and high barrier properties will be stabilized. On the other hand, it may be difficult to maintain, and if it exceeds 50%, the barrier property may be lowered.

  Furthermore, in the present invention, in the vapor deposition film obtained by vapor-depositing an organosilicon compound, it is preferable that the content of the compound decreases from the surface of the vapor deposition film in the depth direction. As a result, the impact resistance and the like are enhanced by the above-mentioned compound on the surface of the deposited film, and on the other hand, at the interface with the substrate film, the content of the above-mentioned compound is small, so that the tight adhesion between the substrate film and the deposited film is Will be strong.

  In the present invention, the deposited film is formed in the depth direction using a surface analyzer such as an X-ray photoelectron spectrometer (XPS), a secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy, SIMS), or the like. The above physical properties can be confirmed by analyzing by ion etching or the like and conducting elemental analysis of the deposited film.

  In the present invention, the thickness of the deposited film is preferably about 50 to 4000 mm, more preferably 100 to 1000 mm. If it is thicker than 4000 mm, cracks or the like may occur in the film. On the other hand, if it is less than 50 mm, it may be difficult to achieve a barrier effect. The film thickness can be measured by a fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name, RIX2000 type) manufactured by Rigaku Corporation. As a means for changing the film thickness of the vapor deposition film, it can be performed by a method of increasing the volume velocity of the vapor deposition film, that is, a method of increasing the amount of monomer gas and oxygen gas or a method of slowing the vapor deposition rate. .

  In the present invention, the vapor deposition film formed by vapor-depositing an organosilicon compound, metal or metal oxide may be not only one layer of the vapor deposition film but also a multilayer film in which two or more layers are laminated and used. The materials may be used alone or as a mixture of two or more thereof, and a vapor deposition film mixed with different materials may be formed.

  In the present invention, examples of the vapor deposition monomer gas such as an organosilicon compound include 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, Dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, etc. Etc. can be used. Among these, it is particularly preferable to use 1,1,3,3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material because of its handleability and the characteristics of the formed continuous film. In the above, as the inert gas, for example, argon gas, helium gas, or the like can be used.

  On the other hand, in the present invention, a vapor deposition film formed by vapor-depositing an organosilicon compound, a metal, or a metal oxide can also be formed by physical vapor deposition. As such a physical vapor deposition method, for example, an organic silicon compound by a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum deposition method, a sputtering method, an ion plating method, or an ion cluster beam method, A vapor deposition film formed by vapor deposition of metal or metal oxide can be formed.

  Specifically, an organic silicon compound, a metal or a metal oxide is used as a raw material, this is heated and vaporized, and this is vapor-deposited on one of the substrate films, or a raw material is a metal or metal Using an oxidation reaction vapor deposition method in which oxygen is introduced and oxidized to be deposited on one side of the base film, and further, a plasma assisted oxidation reaction vapor deposition method in which the oxidation reaction is supported by plasma is used. A vapor deposition film can be formed. In addition, as a heating method of the vapor deposition material, for example, a resistance heating method, a high frequency induction heating method, an electron beam heating method (EB), or the like can be used. A method for forming a vapor deposition film by physical vapor deposition will be described with reference to FIG. 10 showing a schematic configuration diagram showing an example of a winding type vacuum vapor deposition apparatus.

  First, the base film 201 fed out from the unwinding roll 243 is guided to the cooled coating drum 246 through the guide rolls 244 and 245 in the vacuum chamber 242 of the wind-up type vacuum evaporation apparatus 241. The evaporation source 248 heated by the crucible 247, for example, metal aluminum or aluminum oxide is evaporated on the substrate film 201 guided on the cooled coating drum 246, and if necessary, An oxygen gas or the like is ejected from the oxygen gas outlet 249 and a vapor deposition film formed by depositing, for example, aluminum oxide is formed through the masks 250 and 250 while supplying the oxygen gas. When the base film 201 on which the deposited film is formed is sent out through the guide rolls 251 and 252 and wound around the take-up roll 253, a deposited film can be formed by physical vapor deposition. First, a first-layer deposited film is formed by using the above-described winding-type vacuum deposition apparatus, and then a deposition film is further formed thereon, or the above-described winding-type vacuum deposition apparatus is connected in series. Then, the vapor deposition film may be continuously formed to form the vapor deposition film composed of two or more multilayer films.

The deposited film formed by depositing a metal or a metal oxide may basically be a thin film deposited with a metal oxide, such as silicon (Si), aluminum (Al), magnesium (Mg), Metal oxides such as calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y) The deposited film can be used. Preferably, a vapor-deposited film of a metal oxide such as silicon (Si) or aluminum (Al) can be used. Therefore, the metal oxide vapor deposition film can be referred to as a metal oxide such as silicon oxide, aluminum oxide, magnesium oxide, and the like, for example, SiO _x , AlO _x , MgO. MO _X (in the formula, M represents a metal element, the value of X is in the range respectively of a metal element different.) as _X, etc. represented by.

  In addition, as the range of the value of X, silicon (Si) exceeds 0 and 2 or less, aluminum (Al) exceeds 0 and 1.5 or less, magnesium (Mg) exceeds 0 and 1 or less, calcium (Ca ) Is greater than 0 and less than or equal to 1, potassium (K) is greater than 0 and less than or equal to 0.5, tin (Sn) is greater than 0 and less than or equal to 2, sodium (Na) is greater than 0 and less than or equal to 0.5, and boron (B) is 0 to 1, 5 or less, Titanium (Ti) is more than 0 to 2 or less, Lead (Pb) is more than 0 to 1 or less, Zirconium (Zr) is more than 0 to 2 or less, Yttrium (Y) is more than 0 to 1 .5 or less. In the above, when X = 0, it is a complete metal, and the upper limit of the range of X is a completely oxidized value. Generally, examples other than silicon (Si) and aluminum (Al) are poor. Therefore, in the present invention, silicon or aluminum is preferable as M. In this case, the value of X is 1.0 to 2.0 for silicon (Si) and 0.5 to 1.5 for aluminum (Al). It is a range. In addition, although the film thickness of the said vapor deposition film changes with kinds etc. of the metal to be used or a metal oxide, it can be arbitrarily selected within the range of 50 to 2000 mm, preferably 100 to 1000 mm, for example. Moreover, the vapor deposition film formed by vapor-depositing a metal or metal oxide is used as a metal or metal oxide to be used in one kind or a mixture of two or more kinds to constitute a vapor deposition film mixed with different materials. You can also

Furthermore, in the present invention, for example, a composite film composed of two or more layers of different kinds of vapor-deposited films can be formed by using both physical vapor deposition and chemical vapor deposition.
As a composite film composed of two or more layers of the above-mentioned different kinds of vapor-deposited films, first, a chemical vapor deposition method is used on a base film, and it is dense and flexible and can relatively prevent the occurrence of cracks. A composite film comprising two or more layers is provided by providing a vapor deposition film obtained by vapor-depositing an organosilicon compound, and then providing a vapor deposition film obtained by vapor-depositing a metal or metal oxide by physical vapor deposition on the vapor deposition film. It is preferable to constitute a vapor deposition film composed of a film. Contrary to the above, on the base film, a vapor deposition film formed by vapor-depositing a metal or metal oxide is first provided by a physical vapor deposition method, and then a dense film is formed by a chemical vapor deposition method. It is also possible to provide a vapor-deposited film made of a composite film composed of two or more layers by providing a vapor-deposited film formed by vapor-depositing an organosilicon compound that is rich in flexibility and can relatively prevent the occurrence of cracks.

(Iv) Gas barrier coating film The gas barrier coating film used in the present invention has a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² are organic having 1 to 8 carbon atoms). Represents a group, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M. It contains the above alkoxide, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and further polycondensed by a sol-gel method in the presence of a sol-gel method catalyst, acid, water, and an organic solvent. A coating film made of a gas barrier composition, which is coated on the vapor deposition film on the base film to provide a coating film, and has a melting point of 20 to 180 ° C. and the base film. Heat treatment at the following temperature for 10 seconds to 10 minutes It can be formed.

  In addition, the gas barrier composition is applied onto the deposited film on the base film, and two or more coating films are stacked, at a temperature of 20 ° C. to 180 ° C. and below the melting point of the base film. You may heat-process for 10 seconds-10 minutes, and may form the composite polymer layer which laminated | stacked two or more gas barrier coating films.

As the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m , at least one of alkoxide partial hydrolyzate and alkoxide hydrolysis condensate can be used. The partial hydrolyzate is not limited to the one in which all of the alkoxy groups are hydrolyzed, and may be one in which one or more are hydrolyzed, or a mixture thereof, and further a hydrolysis condensate. As a dimer or more of a partially hydrolyzed alkoxide, specifically, a dimer or hexamer may be used.

In the general formula R ¹ _n M (OR ² ) _m , R ¹ is an alkyl group having 1 to 8, preferably 1 to 5, more preferably 1 to 4 carbon atoms which may have a branch. For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-octyl group, etc. Can be mentioned.

In the general formula R ¹ _n M (OR ² ) _m , R ² is an alkyl group having 1 to 8 carbon atoms, more preferably 1 to 5, and particularly preferably 1 to 4 which may have a branch. Yes, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, and the like. When a plurality of (OR ² ) are present in the same molecule, (OR ² ) may be the same or different.

Examples of the metal atom represented by M in the general formula R ¹ _n M (OR ² ) _m include silicon, zirconium, titanium, aluminum, and the like.
In the present invention, silicon is preferable. In this case, as an alkoxide that can be preferably used in the present invention, when n = 0 in the general formula R ¹ _n M (OR ² ) _m , the general formula Si (ORa) ₄ (wherein Ra is Represents an alkyl group having 1 to 5 carbon atoms). In the above, Ra includes a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and the like. Specific examples of such an alkoxysilane include tetramethoxysilane Si (OCH ₃ ) ₄ , tetraethoxysilane Si (OC ₂ H ₅ ) ₄ , tetrapropoxysilane Si (OC ₃ H ₇ ) ₄ , tetrabutoxysilane Si ( OC ₄ H ₉₎ can be exemplified ₄ like.

In the case where n is 1 or more, the general formula RbnSi (ORc) _4-m (wherein m represents an integer of 1, 2, 3 and Rb and Rc are a methyl group, an ethyl group, An alkylalkoxysilane represented by n-propyl group, n-butyl group, etc.) can be used. Examples of such an alkylalkoxysilane include methyltrimethoxysilane CH ₃ Si (OCH ₃ ) ₃ , methyltriethoxysilane CH ₃ Si (OC ₂ H ₅ ) ₃ , dimethyldimethoxysilane (CH ₃ ) ₂ Si (OCH). _{3) 2,} dimethyl diethoxy silane _{(CH 3) 2 Si (OC} 2 H 5) 2, may use other like. In the present invention, the above alkoxysilane, alkylalkoxysilane and the like may be used alone or in combination of two or more.

  In the present invention, a polycondensation product of the above alkoxysilane can also be used, and specifically, for example, polytetramethoxysilane, polytetraemethoxysilane, and the like can be used.

In the present invention, a zirconium alkoxide in which M is Zr can also be suitably used as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m . For example, tetramethoxyzirconium Zr (OCH ₃ ) ₄ , tetraethoxyzirconium Zr (OC ₂ H ₅ ) ₄ , tetra ipropoxyzirconium Zr (iso-OC ₃ H ₇ ) ₄ , tetra n butoxyzirconium Zr (OC ₄ H ₉ ) ₄ , etc. can be exemplified.

Further, as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , a titanium alkoxide in which M is Ti can be preferably used. For example, tetramethoxytitanium Ti (OCH ₃ ) ₄ , tetra Examples include ethoxytitanium Ti (OC ₂ H ₅ ) ₄ , tetraisopropoxytitanium Ti (iso-OC ₃ H ₇ ) ₄ , tetra-n-butoxytitanium Ti (OC ₄ H ₉ ) ₄ , and others.

As the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , an aluminum alkoxide in which M is Al can be used. For example, tetramethoxyaluminum Al (OCH ₃ ) ₄ , tetraethoxyaluminum _{Al (OC 2 H 5) 4} , tetraisopropoxy aluminum _{Al (is0-OC 3 H 7} ) 4, tetra-n-butoxy aluminum _{Al (OC 4 H 9) 4} , may use other like.

  In the present invention, two or more of the alkoxides may be used in combination. For example, when alkoxysilane and zirconium alkoxide are mixed and used, the toughness, heat resistance and the like of the resulting gas barrier laminate film can be improved, and a decrease in the retort resistance of the film during stretching can be avoided. Under the present circumstances, the usage-amount of a zirconium alkoxide is the range of 10 mass parts or less with respect to 100 mass parts of said alkoxysilanes. When the amount exceeds 10 parts by mass, the formed gas barrier coating film tends to gel, and the brittleness of the film increases, and the gas barrier coating film tends to peel off when the base film is coated. This is not desirable.

  In addition, when alkoxysilane and titanium alkoxide are mixed and used, the thermal conductivity of the resulting gas barrier coating film is lowered, and the heat resistance is remarkably improved. Under the present circumstances, the usage-amount of a titanium alkoxide is the range of 5 mass parts or less with respect to 100 mass parts of said alkoxysilane. When the amount exceeds 5 parts by mass, the brittleness of the formed gas barrier coating film increases, and the gas barrier coating film may be easily peeled off when the base film is coated.

  As the polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer used in the present invention, a polyvinyl alcohol resin or an ethylene / vinyl alcohol copolymer can be used alone, respectively, or polyvinyl alcohol A single resin and an ethylene / vinyl alcohol copolymer can be used in combination. In the present invention, physical properties such as gas barrier properties, water resistance, weather resistance, and the like can be remarkably improved by using a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer.

  When the polyvinyl alcohol resin and the ethylene / vinyl alcohol copolymer are used in combination, the blending ratio of each is polyvinyl alcohol resin: ethylene / vinyl alcohol copolymer = 10: 0. It is preferable that the position is from 05 to 10: 6.

  The content of the polyvinyl alcohol resin and / or the ethylene / vinyl alcohol copolymer is in the range of 5 to 500 parts by mass, preferably 20 to 200 parts by mass with respect to 100 parts by mass of the total amount of the alkoxide. The blending ratio of When it exceeds 500 parts by mass, the brittleness of the gas barrier coating film becomes large, and the water resistance and weather resistance of the resulting barrier film may be lowered. On the other hand, if it is less than 5 parts by mass, the gas barrier property may be lowered.

  In the polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer, as the polyvinyl alcohol resin, one obtained by saponifying polyvinyl acetate can be generally used. Polyvinyl alcohol resins include partially saponified polyvinyl alcohol resins in which several tens of percent of acetate groups remain, completely saponified polyvinyl alcohols in which no acetate groups remain, and modified polyvinyl alcohol resins in which OH groups have been modified. Well, not particularly limited. Examples of such a polyvinyl alcohol resin include “RS-110 (degree of saponification = 99%, degree of polymerization = 1,000)” manufactured by Kuraray Co., Ltd., and “Kuraray Poval LM-20SO ( “Saponification degree = 40%, polymerization degree = 2,000)”, “GOHSENOL NM-14 (degree of saponification = 99%, polymerization degree = 1,400)” manufactured by Nippon Synthetic Chemical Industry Co., Ltd. Can do.

  As the ethylene / vinyl alcohol copolymer, a saponified product of a copolymer of ethylene and vinyl acetate, that is, a product obtained by saponifying an ethylene-vinyl acetate random copolymer can be used. For example, it is not particularly limited, and includes a partially saponified product in which several tens mol% of acetic acid groups remain to a complete saponified product in which only several mol% of acetic acid groups remain or no acetic acid groups remain. However, it is preferable to use a saponification degree that is preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more from the viewpoint of gas barrier properties. In addition, the content of the repeating unit derived from ethylene in the ethylene / vinyl alcohol copolymer (hereinafter also referred to as “ethylene content”) is usually 0 to 50 mol%, preferably 20 to 45 mol%. It is preferable. Examples of such an ethylene / vinyl alcohol copolymer include “Eval EP-F101 (ethylene content; 32 mol%)” manufactured by Kuraray Co., Ltd., “Soarnol D2908 (ethylene content; 29 mol) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.” %) "And the like.

The gas barrier composition used in the present invention has the general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M is Represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M.) And a gas barrier obtained by polycondensation by the sol-gel method in the presence of a sol-gel method catalyst, acid, water, and an organic solvent. Composition. In preparing the gas barrier composition, a silane coupling agent or the like may be added.

  As the silane coupling agent that can be suitably used in the present invention, known organic reactive group-containing organoalkoxysilanes can be widely used. For example, an organoalkoxysilane having an epoxy group is suitable. For example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, or β- (3,4-epoxy). (Cyclohexyl) ethyltrimethoxysilane or the like can be used. Such silane coupling agents may be used alone or in combination of two or more. In addition, the usage-amount of a silane coupling agent exists in the range of 1-20 mass parts with respect to 100 mass parts of said alkoxysilanes. If 20 parts by mass or more is used, the gas barrier coating film to be formed has increased rigidity and brittleness, and the insulation and workability of the gas barrier coating film may be lowered.

  The sol-gel catalyst is a catalyst mainly used as a polycondensation catalyst, and a basic substance such as tertiary amine that is substantially insoluble in water and soluble in an organic solvent is used. For example, N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine, etc. can be used. In the present invention, N, N-dimethylbenzylamine is particularly preferred. The usage-amount is 0.01-1.0 mass part per 100 mass parts of total amounts of an alkoxide and a silane coupling agent.

  The “acid” used in the gas barrier composition is mainly used as a catalyst for hydrolysis of an alkoxide, a silane coupling agent or the like in the sol-gel method. For example, mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid, organic acids such as acetic acid and tartaric acid, and the like can be used. The amount of the acid used is preferably 0.001 to 0.05 mol based on the total molar amount of the alkoxide and the alkoxide content of the silane coupling agent (for example, silicate moiety).

  Furthermore, in the gas barrier composition, water can be used in a proportion of 0.1 to 100 mol, preferably 0.8 to 2 mol, relative to 1 mol of the total molar amount of the alkoxide. When the amount of water exceeds 2 mol, the polymer obtained from the alkoxysilane and the metal alkoxide becomes spherical particles, and the spherical particles are three-dimensionally crosslinked to form a porous polymer having a low density, Such a porous polymer cannot improve the gas barrier property of the gas barrier laminate film. Moreover, when the amount of the water is less than 0.8 mol, the hydrolysis reaction may hardly proceed.

  Furthermore, as an organic solvent used in said gas-barrier composition, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol, etc. can be used, for example. The polyvinyl alcohol-based resin and / or the ethylene / vinyl alcohol copolymer is preferably handled in a state of being dissolved in a coating solution containing the alkoxide, silane coupling agent, or the like. It can be selected appropriately. For example, when a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer are used in combination, it is preferable to use n-butanol. An ethylene / vinyl alcohol copolymer solubilized in a solvent can also be used. For example, trade name “Soarnol” manufactured by Nippon Synthetic Chemical Industry Co., Ltd. can be preferably used. The amount of the organic solvent used is usually 30 to 500 with respect to 100 mass of the total amount of the alkoxide, silane coupling agent, polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer, acid and sol-gel catalyst. Part by mass.

In the present invention, the gas barrier laminate film can be produced by the following method.
First, an alkoxide such as alkoxysilane, a silane coupling agent, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, a sol-gel catalyst, an acid, water, an organic solvent, and, if necessary, a metal alkoxide Etc. are mixed to prepare a gas barrier composition. By mixing, the gas barrier composition (coating liquid) starts and proceeds with a polycondensation reaction.

  Next, the gas barrier composition is applied onto the deposited film on the base film by a conventional method and dried. By this drying step, polycondensation of the alkoxide such as alkoxysilane, metal alkoxide, silane coupling agent, polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer further proceeds, and a coating film is formed. . On the first coating film, the above coating operation may be further repeated to form a plurality of coating films composed of two or more layers.

  Next, the base film coated with the gas barrier composition is heated at 20 ° C. to 180 ° C. and below the melting point of the base film, preferably at a temperature in the range of 50 ° C. to 160 ° C. for 10 seconds to 10 minutes. Process. Thereby, a barrier film in which one or two or more gas barrier coating films of the gas barrier composition are formed on the vapor deposition film can be produced.

  A barrier film obtained by using an ethylene / vinyl alcohol copolymer alone or both a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer is excellent in gas barrier properties after hydrothermal treatment. On the other hand, when a barrier film is produced using only a polyvinyl alcohol-based resin, a first coating film is formed by previously applying a gas barrier composition using a polyvinyl alcohol-based resin, On the coating film, a gas barrier composition containing an ethylene / vinyl alcohol copolymer is applied to form a second coating film, and when these composite layers are formed, the gas barrier properties after hydrothermal treatment It is possible to produce a barrier film with improved resistance.

  Further, a coating film is formed by the gas barrier composition containing the ethylene / vinyl alcohol copolymer, or the gas barrier composition containing a combination of the polyvinyl alcohol resin and the ethylene / vinyl alcohol copolymer is applied. Even if a film is formed and a plurality of these films are laminated, it becomes an effective means for improving the gas barrier property of the barrier film.

The production method of the gas barrier laminate film used in the present invention will be described in more detail using alkoxysilane as the alkoxide.
The alkoxysilane and metal alkoxide blended as the gas barrier composition are hydrolyzed by the added water. During the hydrolysis, the acid acts as a hydrolysis catalyst. Next, protons are taken from the hydroxyl groups generated by the hydrolysis by the action of the sol-gel catalyst, and the hydrolysis products are dehydrated and polycondensed. At this time, the silane coupling agent is simultaneously hydrolyzed by the acid catalyst, and the alkoxy group becomes a hydroxyl group.

  In addition, the opening of the epoxy group also occurs due to the action of the base catalyst, generating a hydroxyl group. In addition, a polycondensation reaction between the hydrolyzed silane coupling agent and the hydrolyzed alkoxide also proceeds. In the reaction system, polyvinyl alcohol resin, ethylene / vinyl alcohol copolymer, or polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer are present, so polyvinyl alcohol resin and ethylene / vinyl alcohol copolymer are present. Reaction with the hydroxyl group of the polymer also occurs. In addition, the polycondensate to be generated includes, for example, an inorganic part composed of a bond such as Si—O—Si, Si—O—Zr, Si—O—Ti, and the like, and an organic part resulting from the silane coupling agent. It is a composite polymer containing.

  In the above reaction, for example, a linear polymer having a partial structural formula represented by the following formula (III) and further having a portion derived from a silane coupling agent is first formed.

このポリマーは、ＯＲ基（エトキシ基などのアルコキシ基）が、直鎖状のポリマーから分岐した形で有する。このＯＲ基は、存在する酸が触媒となって加水分解されてＯＨ基となり、ゾルゲル法触媒（塩基触媒）の働きにより、まず、ＯＨ基が、脱プロトン化し、次いで、重縮合が進行する。すなわち、このＯＨ基が、下記の式（Ｉ）に示されるポリビニルアルコール系樹脂、または、下記の式（ＩＩ）に示されるエチレン・ビニルアルコール共重合体と重縮合反応し、Ｓｉ−Ｏ−Ｓｉ結合を有する、例えば、下記の式（ＩＶ）に示される複合ポリマー、あるいは、下記の式（Ｖ）及び（ＶＩ）に示される共重合した複合ポリマーを生じると考えられる。

This polymer has an OR group (an alkoxy group such as an ethoxy group) branched from a linear polymer. The OR group is hydrolyzed to become an OH group using an existing acid as a catalyst, and the OH group is first deprotonated by the action of a sol-gel catalyst (base catalyst), and then polycondensation proceeds. That is, this OH group undergoes a polycondensation reaction with a polyvinyl alcohol-based resin represented by the following formula (I) or an ethylene / vinyl alcohol copolymer represented by the following formula (II) to form Si—O—Si. For example, it is considered that a composite polymer represented by the following formula (IV) or a copolymerized composite polymer represented by the following formulas (V) and (VI) is formed.

上記の反応は常温で進行し、ガスバリア性組成物は、調製中に粘度が増加する。このガスバリア性組成物を、基材フィルム上の前記蒸着膜の上に塗布し、加熱して溶媒および重縮合反応により生成したアルコールを除去すると重縮合反応が完結し、基材フィルム上の前記蒸着膜の上に透明な塗布膜が形成される。なお、上記の塗布膜を複数層積層する場合には、層間の塗布膜中の複合ポリマー同士も縮合し、層と層との間が強固に結合する。

The above reaction proceeds at room temperature, and the viscosity of the gas barrier composition increases during preparation. When this gas barrier composition is applied onto the vapor deposition film on the base film and heated to remove the solvent and the alcohol produced by the polycondensation reaction, the polycondensation reaction is completed, and the vapor deposition on the base film is completed. A transparent coating film is formed on the film. In addition, when laminating | stacking two or more said coating films, the composite polymer in the coating film of an interlayer is also condensed, and a layer couple | bonds firmly between layers.

  Furthermore, the surface of the vapor deposition film in which the organic reactive group of the silane coupling agent or the hydroxyl group generated by hydrolysis deposits the organic silicon compound, metal or metal oxide on the base film. Since it bonds to the hydroxyl group of the base film, the adhesion between the substrate film or the surface of the vapor deposition film and the coating film is also good. Thus, in the present invention, the vapor deposition film formed by vapor-depositing an organosilicon compound, a metal or a metal oxide and the gas barrier coating film are, for example, a chemical bond, a hydrogen bond, or a hydrolytic or co-condensation reaction. Since a coordination bond or the like is formed, the adhesion between the deposited film and the gas barrier coating film is improved, and a better gas barrier effect can be exhibited by the synergistic effect of the two layers.

In the present invention, when the amount of water added is adjusted to 0.8 to 2 mol, preferably 1.0 to 1.7 mol, relative to 1 mol of alkoxides, the above linear polymer is used. Is formed. Such a linear polymer has crystallinity and has a structure in which a large number of minute crystals are embedded in an amorphous part. Such a crystal structure is the same as that of a crystalline organic polymer (for example, vinylidene chloride or polyvinyl alcohol), and a polar group (OH group) is partially present in the molecule, and the molecular aggregation energy is high. Since the rigidity is also high, it is particularly excellent in gas barrier properties (blocking and blocking permeation of O ₂ , N ₂ , H ₂ O, CO ₂ , etc.). Furthermore, the hydroxyl group can be chemically bonded to the thermoplastic resin layer to form a strong laminated structure.

  Examples of the method for applying the gas barrier composition of the present invention include, for example, once by a roll coater such as a gravure roll coater, spray coat, spin coat, dipping, brush, bar code, applicator or the like. A coating film having a dry film thickness of 0.01 to 30 μm, preferably about 0.1 to 10 μm, can be formed by applying a plurality of times. Further, under a normal environment, 50 to 300 ° C., preferably The gas barrier coating film of the present invention is formed by performing condensation at a temperature of 70 to 200 ° C. by heating and drying for 0.005 to 60 minutes, preferably 0.01 to 10 minutes. Can do.

Such a gas barrier laminate film has a thickness of 12 to 30 μm.
(8) Printed layer In this invention, you may form a printed layer in any layer which comprises an oxygen absorptive laminated | multilayer film, Preferably it is forming a printed layer in a gas barrier film. According to the back printing, the printed layer can be protected.

  The printing layer is composed of one or more ordinary ink vehicles as the main component, and if necessary, a plasticizer, a stabilizer, an antioxidant, a light stabilizer, an ultraviolet absorber, a curing agent, and a crosslinking agent. Add one or more additives such as additives, lubricants, antistatic agents, fillers, etc., add colorants such as dyes and pigments, and use solvents, diluents, etc. An ink composition obtained by kneading to prepare an ink composition can be used. As such an ink vehicle, known ones such as sesame oil, drill oil, soybean oil, hydrocarbon oil, rosin, rosin ester, rosin modified resin, shellac, alkyd resin, phenolic resin, maleic resin, Natural resin, hydrocarbon resin, polyvinyl chloride resin, polyacetic acid resin, polystyrene resin, polyvinyl butyral resin, acrylic or methacrylic resin, polyamide resin, polyester resin, polyurethane resin, epoxy resin, urea resin , Melamine resin, amino alkyd resin, nitrocellulose, ethyl cellulose, chlorinated rubber, cyclized rubber, etc. can be used alone or in combination.

The printing method may be a printing method such as relief printing, screen printing, transfer printing, flexographic printing, or the like in addition to gravure printing.
(9) Laminating adhesive In the above, a laminating adhesive can be used for laminating the base resin layer and the gas barrier film. Examples of laminating adhesives include polyvinyl acetate adhesives, homopolymers such as ethyl acrylate, butyl, and 2-ethylhexyl ester, or co-polymerization of these with methyl methacrylate, acrylonitrile, styrene, and the like. Polyacrylic acid ester adhesives composed of coalescence, cyanoacrylate adhesives, ethylene copolymer adhesives composed of copolymers of ethylene and monomers such as vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid, Cellulose adhesive, polyester adhesive, polyamide adhesive, polyimide adhesive, amino resin adhesive made of urea resin or melamine resin, phenol resin adhesive, epoxy adhesive, polyurethane adhesive, Reactive (meth) acrylic adhesive, chloroprene rubber, nitrile rubber It can be used rubber-based adhesives consisting of styrene-butadiene rubber, a silicone-based adhesive, an alkali metal silicate, inorganic adhesive made of a low-melting-point glass or the like, an adhesive other like.

  The composition system of the above-mentioned adhesive may be any composition form such as an aqueous type, a solution type, an emulsion type, and a dispersion type, and the property is any of film / sheet form, powder form, solid form, etc. Further, the bonding mechanism may be any of a chemical reaction type, a solvent volatilization type, a heat melting type, and a hot pressure type.

The adhesive can be applied by, for example, a roll coating method, a gravure roll coating method, a kiss coating method, a coating method such as others, or a printing method, and the coating amount is 0.1 to 10.0 g. / M ² (dry explosion condition) is desirable.

(10) Production method of oxygen-absorbing laminated film An oxygen-absorbing laminated film comprising the coextruded film of the present invention is prepared by preparing a resin constituting the thermoplastic resin layer, oxygen-absorbing layer, odor barrier layer, and heat seal layer. Then, by co-extrusion molding using a T-die co-extruder, an inflation co-extruder, etc., the thermoplastic resin layer, oxygen absorbing layer, thermoplastic resin layer, odor barrier layer, heat seal layer It is possible to produce an oxygen-absorbing laminated film comprising a five-layer coextrusion film-forming film laminated in order.

  Also, the resin constituting the thermoplastic resin layer, the oxygen absorbing layer, and the heat seal layer having odor barrier properties is prepared, and these are coextruded using a T-die coextrusion machine, an inflation coextrusion machine, etc. By doing so, an oxygen-absorbing laminated film comprising a four-layer coextrusion film-forming film laminated in the order of the thermoplastic resin layer, the oxygen-absorbing layer, the thermoplastic resin layer, and the resin layer constituting the heat seal layer is produced. be able to.

  Furthermore, in the present invention, according to a conventional method, a base resin layer or a gas barrier film may be laminated on the oxygen-absorbing laminated film via a laminating adhesive, and mechanical strength may be improved by laminating the base resin layer. In addition, oxygen permeability and water vapor permeability can be reduced by laminating gas barrier films. In addition, what laminated | stacked the base resin layer on the said oxygen absorptive laminated film is called an oxygen absorptive laminated body, and what laminated | stacked the gas barrier film further is called a gas barrier absorptive oxygen absorptive laminated body.

(11) Manufacturing method of packaging container The packaging container of the present invention can be manufactured by bag-making the oxygen-absorbing laminated film, the oxygen-absorbing laminated body, and the gas-barrier oxygen-absorbing laminated body. The bag body uses the above-mentioned oxygen-absorbing laminated film, oxygen-absorbing laminated body, or gas-barrier oxygen-absorbing laminated body, and the heat seal layer faces are overlapped to face each other. It can be manufactured by forming a seal portion by sealing. As the bag-making method, the oxygen-absorbing laminated film according to the present invention as described above is folded or overlapped so that the surface of the inner layer is opposed, and the peripheral end portion thereof is, for example, a side seal type, Two-side seal type, three-side seal type, four-side seal type, envelope-attached seal type, joint-attached seal type (pillow seal type), pleated seal type, flat bottom seal type, square bottom seal type, gusset type, etc. The packaging container according to the present invention can be manufactured by heat sealing according to the form. In addition, for example, a self-supporting packaging bag (standing pouch) is also possible.

  In the above, the heat sealing method can be performed by a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, an ultrasonic seal, and the like.

  In the present invention, if, for example, the contents are filled from the opening of the bag body and then vacuum-packed while degassing and depressurizing the air in the container, it remains in the packaging container. Oxidation due to oxygen or the like can be efficiently prevented.

(12) Applications The oxygen-absorbing laminate film, oxygen-absorbing laminate, and gas-barrier oxygen-absorbing laminate according to the present invention have strength and the like, have excellent durability, and are moisture-proof, heat-sealable, and puncture-resistant. In addition, it has excellent barrier properties to prevent permeation of oxygen gas, water vapor, etc., and has the contents of filling and packaging, storage and the like.

  The oxygen-absorbing laminated film, oxygen-absorbing laminated body, and gas-barrier oxygen-absorbing laminated body of the present invention can be formed as described above and used as a packaging container. It can also be used as a lid for packaging containers composed of a container body and a lid. The container body is a polypropylene saddle-shaped or boat-shaped container, and the contents of the above-mentioned oxygen-absorbing laminated film, oxygen-absorbing laminated body, and gas-barrier oxygen-absorbing laminated body are covered with a fringe at the opening. After storing, the lid material can be heat sealed to form a packaging container. Examples of the contents include sterile cooked rice. If sterile cooked rice is stored in the packaging container of the present invention, oxygen in the container is absorbed and removed by the oxygen-absorbing layer, and permeation of oxygen and water vapor can be prevented by the gas barrier film, and the storage stability of the contents is excellent. .

  In the oxygen-absorbing laminated film of the present invention, the coextruded film is a thermoplastic resin layer (I) having a thickness of 5 to 15 μm, an oxygen-absorbing layer having a thickness of 10 to 30 μm, and a thermoplastic resin layer having a thickness of 5 to 15 μm ( II), a odor barrier layer having a film thickness of 5 to 50 μm, and a heat seal layer having a film thickness of 5 to 60 μm, and having a substantially symmetrical thickness around the oxygen absorption layer, and curling the oxygen-absorbing laminated film Can be suppressed. For this reason, when laminating a polyamide-based resin or a gas barrier film, the lamination is easy and the processability is excellent.

EXAMPLES Next, although an Example is given and this invention is demonstrated concretely, these Examples do not restrict | limit this invention at all.
(Production Example 1)
Preparation of cyclized diene copolymer 300 parts by mass of polyisoprene having 80% cis-1,4-structure isoprene unit in a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas introduction tube Was dissolved in 700 parts by mass of toluene. After complete dissolution, 2.4 parts by mass of p-toluenesulfonic acid was added to carry out a cyclization reaction.

  The obtained cyclized diene copolymer was pelletized, and 100 parts by mass of the cyclized diene copolymer was used as a sensitizer, 1 part by mass of benzophenone, and as an antioxidant, 2-t-butyl-6- (3-t-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate 0.05 parts by mass was mixed to obtain a cyclized diene copolymer.

Example 1
First, the following resin compositions (a) to (f) were coextruded at a set temperature of 190 ° C. using a three-type five-layer top-blown air-cooled inflation coextrusion film forming machine to form a corona on one side. After the treatment, an oxygen-absorbing laminated film having a total thickness of 55 μm consisting of three types and five layers was produced.

(A) Polyethylene (manufactured by Prime Polymer Co., Ltd., trade name “SP4020”) as the first layer (thermoplastic resin layer),
(B) As a second layer (oxygen absorbing layer), a kneaded product comprising 30 parts by mass of the cyclized diene copolymer of Production Example 1 and 70 parts by mass of a polyethylene resin,
(C) Polyethylene (manufactured by Prime Polymer Co., Ltd., trade name “SP4020”) as the third layer (thermoplastic resin layer),
(D) As the fourth layer (odor barrier layer), mesoporous silica (manufactured by Taiyo Kagaku Co., Ltd., trade name “TMPS-1.5”, average pore diameter 1.8 nm, specific surface area 1019.0 m ² / g, fine 1 mass of polyethylene with a pore volume of 0.373 cm ³ / g, a bulk specific gravity of 0.281 g / cm ³ , an average particle diameter of 3.2 μm, and an oil absorption of 201 ml / 100 g is manufactured by Prime Polymer Co., Ltd., trade name “SP4020”). % Kneaded resin,
(E) Polyethylene (manufactured by Prime Polymer Co., Ltd., trade name “SP4020”) was used as the fifth layer (heat seal layer).

  In the oxygen-absorbing laminated film, the first layer (a) is 5 μm, the second layer (b) is 20 μm, the third layer (c) is 5 μm, the fourth layer (d) is 20 μm, ) To 5 μm.

  To this oxygen-absorbing laminated film, a stretched polyamide film (product name “N-1202” manufactured by Toyobo Co., Ltd.) having a thickness of 25 μm and a gas barrier film (product name “IB-PET-PUB” manufactured by Dai Nippon Printing Co., Ltd.) are dried. Lamination was performed to obtain a gas barrier oxygen-absorbing laminate in which the gas barrier film was the outermost layer.

(Example 2)
In the same manner as in Example 1, the following resins (a) to (e) were coextruded at a set temperature of 190 ° C. using a three-layer, five-layer, top-blown air-cooled inflation co-extrusion film forming machine to form a film, After performing corona treatment on one side, an oxygen-absorbing laminated film having a total thickness of 55 μm consisting of 3 types and 5 layers was produced.

(A) Polyethylene (manufactured by Prime Polymer Co., Ltd., trade name “SP4020”) as the first layer (thermoplastic resin layer),
(B) As a second layer (oxygen absorbing layer), a kneaded product comprising 30 parts by mass of the cyclized diene copolymer of Production Example 1 and 70 parts by mass of a polyethylene resin,
(C) Polyethylene (manufactured by Prime Polymer Co., Ltd., trade name “SP4020”) as the third layer (thermoplastic resin layer),
(D) As the fourth layer (odor barrier layer), mesoporous silica (manufactured by Taiyo Kagaku Co., Ltd., trade name “TMPS-4”, average pore diameter 4.2 nm, specific surface area 1159.0 m ² / g, pore volume 1.020 cm ³ / g, bulk specific gravity 0.184 g / cm ³ , average particle diameter 11.0 μm, oil absorption 595 ml / 100 g) is added in an amount of 1% by mass to polyethylene (manufactured by Prime Polymer, trade name “SP4020”). Kneaded resin,
(E) Polyethylene (manufactured by Prime Polymer Co., Ltd., trade name “SP4020”) was used as the fifth layer (heat seal layer).

  In the oxygen-absorbing laminated film, the first layer (a) is 5 μm, the second layer (b) is 20 μm, the third layer (c) is 5 μm, the fourth layer (d) is 20 μm, ) To 5 μm.

  In the same manner as in Example 1, a stretched polyamide film having a thickness of 25 μm (manufactured by Toyobo, trade name “N-1202”) and a gas barrier film (produced by Dai Nippon Printing Co., Ltd., trade name “IB”) were applied to this oxygen-absorbing laminated film. -PET-PUB ") was bonded together by dry lamination to obtain a gas barrier oxygen-absorbing laminate in which the gas barrier film was the outermost layer.

Example 3
In the same manner as in Example 1, the following resins (a) to (e) were coextruded at a set temperature of 190 ° C. using a three-layer, five-layer, top-blown air-cooled inflation co-extrusion film forming machine to form a film, After performing corona treatment on one side, an oxygen-absorbing laminated film having a total thickness of 55 μm consisting of 3 types and 5 layers was produced.

(A) Polyethylene (manufactured by Prime Polymer Co., Ltd., trade name “SP4020”) as the first layer (thermoplastic resin layer),
(B) Polyethylene (manufactured by Prime Polymer Co., Ltd., trade name “SP4020”) as the second layer (thermoplastic resin layer),
(C) As a third layer (oxygen absorbing layer), a kneaded product comprising 30 parts by mass of the cyclized diene copolymer of Production Example 1 and 70 parts by mass of a polyethylene resin,
(D) Polyethylene (manufactured by Prime Polymer Co., Ltd., trade name “SP4020”) as the fourth layer (thermoplastic resin layer),
(E) As the fifth layer (heat seal layer having odor barrier property), mesoporous silica (manufactured by Taiyo Kagaku Co., Ltd., trade name “TMPS-4”, average pore diameter 4.2 nm, specific surface area 1159.0 m ² / g, pore volume 1.020 cm ³ / g, bulk specific gravity 0.184 g / cm ³ , average particle diameter 11.0 μm, oil absorption 595 ml / 100 g) with respect to polyethylene (trade name “SP4020” manufactured by Prime Polymer Co., Ltd.) 1% by mass kneaded resin was used.

  In the oxygen-absorbing laminated film, the first layer (a) is 5 μm, the second layer (b) is 5 μm, the third layer (c) is 20 μm, the fourth layer (d) is 5 μm, ) Was set to 20 μm.

  In the same manner as in Example 1, a stretched polyamide film having a thickness of 25 μm (manufactured by Toyobo, trade name “N-1202”) and a gas barrier film (produced by Dai Nippon Printing Co., Ltd., trade name “IB”) were applied to this oxygen-absorbing laminated film. -PET-PUB ") was bonded together by dry lamination to obtain a gas barrier oxygen-absorbing laminate in which the gas barrier film was the outermost layer.

Example 4
After the following (A) to (G) are co-extruded at a set temperature of 190 ° C. using a four-kind seven-layer top-blown air-cooled inflation co-extrusion film forming machine and subjected to corona treatment on one side An oxygen-absorbing laminated film having a total thickness of 80 μm composed of 4 types and 7 layers was produced.

(A) Polyethylene (manufactured by Prime Polymer Co., Ltd., trade name “SP4020”) as the first layer (thermoplastic resin layer),
(B) As the second layer (odor barrier layer), mesoporous silica (manufactured by Taiyo Kagaku Co., Ltd., trade name “TMPS-4”, average pore diameter 4.2 nm, specific surface area 1159.0 m ² / g, pore volume 1.020 cm ³ / g, bulk specific gravity 0.184 g / cm ³ , average particle diameter 11.0 μm, oil absorption 595 ml / 100 g) is added in an amount of 1% by mass to polyethylene (manufactured by Prime Polymer, trade name “SP4020”). Kneaded resin,
(C) Polyethylene (manufactured by Prime Polymer Co., Ltd., trade name “SP4020”) as the third layer (thermoplastic resin layer),
(D) As a fourth layer (oxygen absorbing layer), a kneaded product comprising 30 parts by mass of the cyclized diene copolymer of Production Example 1 and 70 parts by mass of a polyethylene resin,
(E) Polyethylene (manufactured by Prime Polymer Co., Ltd., trade name “SP4020”) as the fifth layer (thermoplastic resin layer),
(F) As the sixth layer (odor barrier layer), mesoporous silica (manufactured by Taiyo Kagaku Co., Ltd., trade name “TMPS-4”, average pore diameter 4.2 nm, specific surface area 1159.0 m ² / g, pore volume 1.020 cm ³ / g, bulk specific gravity 0.184 g / cm ³ , average particle diameter 11.0 μm, oil absorption 595 ml / 100 g) is added in an amount of 1% by mass to polyethylene (manufactured by Prime Polymer, trade name “SP4020”). Kneaded resin,
(G) Polyethylene (manufactured by Prime Polymer Co., Ltd., trade name “SP4020”) was used as the seventh layer (heat seal layer).

  In the oxygen-absorbing laminated film, the first layer (a) is 5 μm, the second layer (b) is 20 μm, the third layer (c) is 5 μm, the fourth layer (d) is 20 μm, ) Was 5 μm, the sixth layer (f) was 20 μm, and the seventh layer (g) was 5 μm.

  In the same manner as in Example 1, a stretched polyamide film having a thickness of 25 μm (manufactured by Toyobo, trade name “N-1202”) and a gas barrier film (produced by Dai Nippon Printing Co., Ltd., trade name “IB”) were applied to this oxygen-absorbing laminated film. -PET-PUB ") was bonded together by dry lamination to obtain a gas barrier oxygen-absorbing laminate in which the gas barrier film was the outermost layer.

(Example 5)
First, the following resin compositions (a) to (f) were coextruded at a set temperature of 190 ° C. using a four-type, five-layer, top-blown air-cooled inflation coextrusion film forming machine to form a corona on one side. After carrying out the treatment, an oxygen-absorbing laminated film having a total thickness of 70 μm composed of 3 types and 5 layers was produced.

(A) Polyethylene (manufactured by Prime Polymer Co., Ltd., trade name “SP4020”) as the first layer (thermoplastic resin layer),
(B) As a second layer (oxygen absorbing layer), a kneaded product comprising 30 parts by mass of the cyclized diene copolymer of Production Example 1 and 70 parts by mass of a polyethylene resin,
(C) A resin obtained by kneading 30% milk white masterbatch containing 60% titanium oxide as a pigment in polyethylene (manufactured by Prime Polymer Co., Ltd., trade name “SP4020”) as a third layer (thermoplastic resin layer),
(D) As the fourth layer (odor barrier layer), mesoporous silica (manufactured by Taiyo Kagaku Co., Ltd., trade name “TMPS-1.5”, average pore diameter 1.8 nm, specific surface area 1019.0 m ² / g, fine 1 mass of polyethylene with a pore volume of 0.373 cm ³ / g, a bulk specific gravity of 0.281 g / cm ³ , an average particle diameter of 3.2 μm, and an oil absorption of 201 ml / 100 g is manufactured by Prime Polymer Co., Ltd., trade name “SP4020”). % Kneaded resin,
(E) Polyethylene (manufactured by Prime Polymer Co., Ltd., trade name “SP4020”) was used as the fifth layer (heat seal layer).

  In the oxygen-absorbing laminated film, the first layer (a) is 5 μm, the second layer (b) is 20 μm, the third layer (c) is 20 μm, the fourth layer (d) is 20 μm, ) To 5 μm.

  To this oxygen-absorbing laminated film, a stretched polyamide film (product name “N-1202” manufactured by Toyobo Co., Ltd.) having a thickness of 25 μm and a gas barrier film (product name “IB-PET-PUB” manufactured by Dai Nippon Printing Co., Ltd.) are dried. Lamination was performed to obtain a gas barrier oxygen-absorbing laminate in which the gas barrier film was the outermost layer.

(Comparative Example 1)
In the same manner as in Example 1, the following resins (a) to (e) were coextruded at a set temperature of 190 ° C. using a two-type five-layer top-blown air-cooled inflation coextrusion film forming machine, to form a film. After performing corona treatment on one side, an oxygen-absorbing laminated film having a total thickness of 55 μm consisting of two types and five layers was produced.

(A) Polyethylene (manufactured by Prime Polymer Co., Ltd., trade name “SP4020”) as the first layer (thermoplastic resin layer),
(B) As a second layer (oxygen absorbing layer), a kneaded product comprising 30 parts by mass of the cyclized diene copolymer of Production Example 1 and 70 parts by mass of a polyethylene resin,
(C) Polyethylene (manufactured by Prime Polymer Co., Ltd., trade name “SP4020”) as the third layer (thermoplastic resin layer),
(D) Polyethylene (manufactured by Prime Polymer Co., Ltd., trade name “SP4020”) as the fourth layer (thermoplastic resin layer),
(E) Polyethylene (manufactured by Prime Polymer Co., Ltd., trade name “SP4020”) was used as the fifth layer (heat seal layer).

  In the oxygen-absorbing laminated film, the first layer (a) is 5 μm, the second layer (b) is 20 μm, the third layer (c) is 5 μm, the fourth layer (d) is 20 μm, ) To 5 μm.

  In this comparative oxygen-absorbing laminated film, in the same manner as in Example 1, a stretched polyamide film having a thickness of 25 μm (trade name “N-1202” manufactured by Toyobo Co., Ltd.) and a gas barrier film (produced by Dai Nippon Printing Co., Ltd., product name “ IB-PET-PUB ") was bonded by dry lamination to obtain a comparative gas barrier oxygen-absorbing laminate having a gas barrier film as the outermost layer.

(Example 6)
Two gas barrier oxygen-absorbing laminates produced in Examples 1 to 5 were cut into a size of 130 mm × 170 mm, the heat seal layer was stacked as the innermost layer, and the other side was sealed with a seal width of 10 mm, leaving the filling port. And the packaging bag was manufactured.

After filling the packaging bag with 100 ml of air from the filling port, the filling port was heat-sealed and sealed to obtain a package.
This package was stored at 60 ° C. for 1 week and subjected to sensory evaluation for the presence or absence of odor. The results are shown in Table 4.

(Comparative Example 2)
A comparative package was obtained in the same manner as in Example 5 except that the comparative gas barrier oxygen-absorbing laminate obtained in Comparative Example 1 was used. In the same manner as in Example 5, the presence or absence of odor was subjected to sensory evaluation. The results are shown in Table 4.

(実施例７)
実施例１で製造したガスバリア性酸素吸収性積層体を使用して、紫外線を照射した後、１３０ｍｍ×１７０ｍｍの大きさに２枚切り取り、ヒートシール層を最内層として重ね、充填口を残して他をシール幅１０ｍｍで四方をシールして包装袋を製造した。

(Example 7)
Using the gas barrier oxygen-absorbing laminate produced in Example 1, after irradiating with ultraviolet rays, two sheets were cut into a size of 130 mm × 170 mm, the heat seal layer was stacked as the innermost layer, and the filling port was left behind. The four sides were sealed with a seal width of 10 mm to produce a packaging bag.

  200 ml of air was sealed in the packaging bag, and the filling port was heat-sealed and sealed to obtain a package. Then, about the residual oxygen concentration of the obtained package, (i) Immediately after filling, (ii) After storage for 3 days in a constant temperature bath of 23 ° C. and 50% RH, (iii) In a constant temperature bath of 23 ° C. and 50% RH After storage for 7 days, the time points were measured with a zirconia oxygen analyzer (manufactured by Toray). The results are shown in Table 5. The unit of Table 5 is%.

  The present invention has an oxygen collecting function of binding and absorbing oxygen existing in a head space or the like in a packaged product, or oxygen contained in contents or generated oxygen, and as a result, the packaged product. Oxygen that permeates from the outside is coupled with the function of blocking the permeation by the barrier substrate film, and the quality, freshness, etc. of the contents, for example, its state when filled and packaged is almost as it is or it is Maintained in the above state, furthermore, the odor generated during oxygen absorption can be removed by the odor barrier layer, and the packaged product can be stored, stored, displayed, etc. for a long period of time. Almost no change in quality such as odor is observed, it can protect the quality, freshness, etc. of the contents very well, and can be applied to packaging products of various forms. That.

10 ... oxygen absorbing layer,
20 ... thermoplastic resin layer (I), thermoplastic resin layer (II)
30 ... Odor barrier layer (I), Odor barrier property (II),
40 ... a heat seal layer having odor barrier properties,
50 ... heat seal layer,
60 ... base resin layer,
70: Gas barrier film,
80 ... Laminate adhesive layer

Claims (8)

From the outer layer toward the inner layer, the thermoplastic resin layer (I) made of polyolefin resin, the oxygen absorbing layer, the thermoplastic resin layer (II) made of polyolefin resin, the odor barrier layer (I), and the heat seal layer Co-extruded film that is laminated in order, the resin of the odor barrier layer and the resin of the heat seal layer are the same polyolefin resin,
Alternatively, from the outer layer toward the inner layer, a thermoplastic resin layer (I) made of a polyolefin resin, an oxygen absorbing layer, a thermoplastic resin layer (II) made of a polyolefin resin, and a heat seal layer having odor barrier properties A co-extruded film laminated in order,
The oxygen absorbing layer includes a resin composition containing a photosensitizer in a cyclized conjugated diene polymer,
The odor barrier layer or the heat seal layer having odor barrier properties comprises a resin containing 0.01 to 1% by mass of mesoporous silica,
The mesoporous silica has an oil absorption of 201 ml / 100 g or more and 595 ml / 100 g or less. The mesoporous silica is
After firing, at least one peak of the X-ray diffraction pattern exhibits a d-interval greater than 1.8 nm and has a benzene adsorption capacity greater than 15 g per 100 g material at 6.7 kPa (50 torr) and 25 ° C., porous, A non-layered crystal phase substance having a composition represented by the following formula (1):
[Equation 1]
Mn / q (SiO ₂ ) (1)
(Wherein M is one or more ions,
n is the charge of the composition excluding M expressed as an oxide,
q is the weight molar average valence of M;
n / q is the number of moles or mole fraction of M.
Or
Inorganic, porous, having a hexagonal structure arrangement of uniformly sized pores with a diameter of at least 1.3 nm and exhibiting a hexagonal structure electron diffraction pattern that, after firing, can be shown with a d ₁₀₀ value greater than 1.8 nm A crystalline phase substance having a composition represented by formula (1),
Or
The oxygen-absorbing laminated film according to claim 1, wherein a crystal phase substance obtained by crystallizing a reaction mixture having the following composition expressed in terms of a molar ratio of an oxide is fired .
[Table 1]

Composition of the reaction mixture ┌──────────────────┬─────────┐
│Component │Ratio │
├──────────────────┼─────────┤
│Solvent / SiO ₂ │1-1500 │
├──────────────────┼─────────┤
│OH ^- / SiO ₂ │0~10 │
├──────────────────┼─────────┤
│ (M _{e / 2} O + R _{f / 2} O) / SiO ₂ │0.01-20 │
├──────────────────┼─────────┤
│M _{e / 2} O / SiO ₂ │0-10 │
├──────────────────┼─────────┤
│R _{f / 2} O / SiO ₂ │0.01 ~ 2.0 │
└──────────────────┴─────────┘
(Wherein M is one or more ions, e and f are the weight average valences of M and R, respectively, the solvent is an alcohol or diol having 1 to 6 carbon atoms, or water, and R is , The total organic matter used to help the synthesis of the substance,
Formula: R ₁ R ₂ R ₃ R ₄ Q ⁺ (where Q is nitrogen or phosphorus, and at least one of R ₁ , R ₂ , R ₃ and R ₄ is an aryl group or alkyl group having 6 to 36 carbon atoms) And the rest of R ₁ , R ₂ , R ₃ and R ₄ are each selected from hydrogen and an alkyl group having 1 to 5 carbon atoms). )   The thermoplastic resin layer (III) comprising a odor barrier layer (II) and a polyolefin resin is further laminated on the outside of the thermoplastic resin layer (I) by coextrusion. Or the oxygen absorptive laminated film of 2.   An oxygen-absorbing laminate, wherein a base resin layer is laminated on the outside of the thermoplastic resin layer (I) of the oxygen-absorbing laminate film according to any one of claims 1 to 3.   The oxygen-absorbing laminate according to claim 4, wherein the base resin layer is a polyamide resin or a polyester resin.   A gas barrier oxygen-absorbing laminate, wherein a gas barrier film is laminated on the inside or outside of the base resin layer of the oxygen-absorbing laminate according to claim 5. A package in which the oxygen-absorbing laminated film according to any one of claims 1 to 3, the oxygen-absorbing laminated body according to claim 4 or 5, or the gas-barrier oxygen-absorbing laminated body according to claim 6 is formed into a bag. container. A container comprising a container body and a lid,
The lid material is the oxygen-absorbing laminated film according to any one of claims 1 to 3, the oxygen-absorbing laminated body according to claim 4 or 5, or the gas-barrier oxygen-absorbing laminated body according to claim 6. Characteristic packaging container.

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