JP2006175780A - Gas-barrier laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas-barrier laminate which has excellent gas-barrier properties even if the gas-barrier laminate is left to stand in the atmosphere under a high-humidity condition over a long period of time, and which is suitable for a packing material. <P>SOLUTION: In this gas-barrier laminate where a gas-barrier layer is formed on at least one side of a substrate, the gas-barrier layer includes alkali metal silicate (A), colloidal silica (B), and colloidal silica (C); the mean particle diameter of the colloidal silica (B) is in the range of 1-50 nm; the mean particle diameter of the colloidal silica (C) is in the range of 10-1,000 nm; and the mean particle diameter of the colloidal silica (C) is 2-20 times as large as that of the colloidal silica (B). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a gas barrier laminate suitable as various packaging materials and molding materials.

In packaging materials used for packaging foods and the like, gas barrier properties, particularly oxygen, water vapor, carbon dioxide, and aroma (aroma, flavor) barrier properties are important qualities from the viewpoint of protecting the quality of the contents.
Packaging materials using such barrier materials include confectionery bags, bonito packs, retort pouches, meat packaging such as ham and sausage, seafood packaging, dairy packaging, miso packaging, tea and coffee packaging. It is used in many fields such as carbon dioxide beverage containers, cosmetics, agricultural chemicals and pharmaceutical packaging.
On the other hand, polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyamide resins such as nylon 6 and nylon 66, polystyrene, ethylene vinyl acetate copolymer, etc. Plastic resins are widely used as packaging materials because of their excellent strength, heat resistance, transparency, and the like.
However, when films made of these thermoplastic resins are used as packaging materials, the gas barrier properties are insufficient, so they are laminated with thermoplastic resins having gas barrier properties, aluminum foil, aluminum vapor deposited films, silicon vapor deposited films, etc. The method used as a material is common.

  Examples of the thermoplastic resin having high gas barrier properties include polyvinyl alcohol (hereinafter referred to as PVA), polyethylene vinyl alcohol (EVOH, saponified ethylene-vinyl acetate copolymer), polyalcohol (reduced product of polyketone), and polyvinylidene chloride (PVDC). However, high hydrogen bonding resins that exhibit barrier properties due to hydrogen bonding by hydroxyl groups such as PVA and EVOH have sharp barrier properties at high humidity (for example, 20 ° C. and 80% RH or more). There is a problem that decreases. PVDC is excellent in barrier properties under high humidity conditions, but has a large decrease in barrier properties at high temperatures. Moreover, since PVDC is a chlorinated compound, there is a possibility that problems such as the generation of dioxins may occur during incineration, and the recent situation is to refrain from using it as a packaging material as much as possible due to the increased awareness of global environmental problems. is there.

Further, there is a conventional technique for forming a gas barrier layer with an alkali metal silicate solution. For example, an aqueous liquid composed of an alkali metal silicate solution and a coupling agent is applied to the surface of a polymer molded article to form a thin film to obtain a gas barrier laminate (Patent Document 1), an aqueous solution of sodium silicate and silicic acid A method of mixing a lithium aqueous solution and obtaining a coating composition from this mixture (Patent Document 2), and further applying a liquid composition containing water glass and a water-soluble polymer having a plurality of acidic functional groups to form a gas barrier property (Patent Document 3).
All of these have the advantage that the gas barrier laminate can be produced at low cost without performing operations such as vapor deposition, but the gas barrier properties are still insufficient, and the problems of poor coating strength and water resistance remain. .
Patent Document 4 discloses a gas barrier coating mainly comprising an alkali metal polysilicate (silica condensate of alkali metal silicate) and a water-soluble polymer or nitrogen compound on at least one surface of a biaxially stretched polyolefin film having a multilayer structure. A technique for obtaining a gas barrier laminate by coating a metal is disclosed. However, the multi-layer structure of the base material in this method is a technique of laminating inexpensive polypropylene on one side or both sides of a highly permeable cyclic olefin copolymer layer, and the structure, physical properties and gas barrier properties of the base material are completely considered. Absent. In addition, the gas barrier properties are insufficient in terms of changes over time when exposed to a high humidity environment for a long period of time, white flower phenomenon, crack resistance, and moisture resistance adhesion. Patent Document 4 discloses a technique for providing a gas barrier layer containing an alkali metal polysilicate and a water-soluble polymer or nitrogen compound, but has insufficient moisture-resistant gas barrier properties, white flower, crack resistance, and moisture-resistant adhesion. It is. A technique for providing an anchor layer made of an acrylic resin and an isocyanate compound is also disclosed, but it does not solve the above problem.

Patent Document 5 discloses a technology relating to a gas barrier film in which a primer layer made of colloidal silica and a water-based polyurethane resin, and a gas barrier layer made of a metal polysilicate and a water-soluble polymer are sequentially laminated on a substrate surface made of a polyolefin-based resin or the like. Is disclosed. However, even in this technique, as in Patent Document 4, problems such as moisture resistance and whiteness of the gas barrier layer (condensate layer of alkali metal silicate) cannot be solved.
In Patent Document 6, an anchor coat layer made of an organic polymer having a urethane bond or urea bond and a gas barrier layer mainly composed of an alkali metal polysilicate are formed on the surface of a base material made of a polyolefin resin or the like. Sequentially laminated gas barrier films have been proposed. However, this method also cannot solve problems such as moisture resistance of the gas barrier layer (condensate layer of alkali metal silicate) and white flower as in Patent Document 4.

  In Patent Document 7, a gas barrier layer mainly composed of an alkali metal polysilicate, a nitrogen compound, and a water-soluble polymer is laminated on one side of a base material, and a metal alkoxide, a silane coupling agent, or the like is mainly contained in the gas barrier layer. A technique for providing a protective layer is disclosed. The protective layer is an attempt to prevent deterioration of gas barrier properties and decrease in adhesion strength due to exposure under high humidity conditions. As is clear from the results of oxygen permeability in Examples, the protective layer has some effect. Although recognized, there is a problem that the gas barrier property is greatly deteriorated by exposure to a high humidity environment.

  In Patent Document 8, an anchor coat layer made of an organic polymer having a urethane bond or a urea bond on the surface of the substrate, having an excellent alkali resistance, a gas barrier layer mainly composed of an alkali metal polysilicate, and an organic polymer having an excellent moisture resistance. There has been proposed a gas barrier film in which overcoat layers made of the above are sequentially laminated. However, this technique is a technique that physically protects the gas barrier layer from being damaged by an overcoat in a subsequent process such as lamination, and cannot prevent deterioration of the gas barrier layer in a high humidity environment.

  Patent Document 9 proposes an attempt to impart water resistance and crack resistance by introducing an organosilicon compound into an alkali metal polysilicate on a substrate that has been surface-modified by a method such as corona discharge or plasma treatment. Has been. In this patent document, by introducing an organic component derived from an organosilicon compound, the shrinkage of the film due to dehydration and condensation during drying that occurs during the formation of the inorganic oxide film is reduced, and a uniform film without cracks is formed. It is possible to obtain a highly flexible film that can withstand stress such as, and it has a hydrolyzable alkoxysilane terminal so that it can be uniformly dispersed and compatible without phase separation from alkali metal polysilicate. The amount of organic components introduced can be increased, and the water resistance due to adhesion between different components (strength deterioration due to moisture permeating the organic / inorganic component interface and prevention of coating cracks) There is a description that can be improved. However, as is clear from the examples, the oxygen permeability increased 20 times or more (the barrier property deteriorated) in a short period of 40 ° C. and 90% for 3 days, and the barrier property deteriorated under high humidity conditions. It has not yet been prevented.

  As described above, there are many attempts to produce a gas barrier laminate using an alkali metal silicate, but no technology has yet been found for the deterioration of gas barrier properties under high humidity conditions caused by the alkali metal silicate. is the current situation.

  On the other hand, the present inventors have developed a technique for producing a gas barrier laminate by applying an alkali silicate aqueous solution to a substrate and drying to form an alkali silicate condensation film.

  Patent Document 10 proposes a laminate comprising a polypropylene-based film support made of a resin and a flat pigment as the first gas barrier layer, and the second gas barrier layer made of a silicic acid condensate and an inorganic compound. Improves barrier properties. However, it is difficult to say that the barrier property in a high humidity state is sufficient.

Patent Document 11 discloses a first layer containing a nitrogen-containing compound such as polyalkyleneimine, a second layer containing a silicic acid condensate such as an alkali metal silicate and a flat pigment, and a third layer containing a high hydrogen bonding resin. The present inventors have proposed a laminate having these layers. In this technology, the silanol group contained in the second layer containing the silicic acid condensate and the functional group of the high hydrogen bonding resin contained in the third layer form ionic bonds or covalent bonds to form a strong film and resist This is a technology that greatly improves the whiteness resistance under bending and high humidity conditions. Although the technology of the present invention has made it possible to provide a gas barrier laminate that can withstand use under high humidity conditions, moisture gas barrier resistance under further high humidity conditions has been demanded.
In Patent Document 12, a first gas barrier layer layer containing a high hydrogen bonding resin and a nitrogen-containing compound, and a second gas barrier layer containing a silicic acid condensate, a flat pigment, and boron are sequentially laminated on a support. The formed laminate has been proposed by the present inventors. The technology of the present invention has succeeded in greatly improving the moisture-resistant gas barrier property and the moisture-resistant adhesion property by causing the first gas barrier layer and the second gas barrier layer to react with each other and causing the inclined structures to mutually react. However, a moisture-resistant gas barrier property under further high humidity conditions has been demanded.

In Patent Document 13, the present inventors have proposed a laminate having a gas barrier layer containing a silicic acid condensate such as an alkali metal silicate, a flat pigment, and a neutralized salt formed of an acidic substance other than silicic acid. The present invention neutralizes an excess alkali metal salt contained in a silicate alkali metal salt with an acidic substance, so that the barrier property and white resistance when the gas barrier laminate is left in a high humidity condition for a long time (72 hours). It is a technology that greatly improves the flower. However, a moisture-resistant gas barrier property under further high humidity conditions has been demanded.
Patent Document 14 discloses a laminate in which a first gas barrier layer containing a silicic acid condensate such as an alkali metal silicate and a second gas barrier layer containing a high hydrogen bonding resin and an acidic substance are sequentially laminated on a support. Proposed. Although the present invention has greatly improved the resistance to moisture gas barrier. There has been a demand for moisture gas barrier resistance under further high humidity conditions.

JP-A-8-238711 JP-A-7-18202 JP 05-295299 A JP 2001-071425 A JP 2001-096676 A JP 2001-129915 A JP 2001-162716 A JP 2002-307601 A JP 2002-316382 A JP 2001-212917 A JP 2002-036417 A JP 2002-086610 A JP 2003-071971 A JP 2003-170522 A

  The present invention provides a gas barrier laminate that is excellent as a packaging material and has excellent gas barrier properties even when left in the atmosphere for a long period of time under high humidity conditions.

In order to solve the above problems, the present invention takes the following means.
That is, according to the first aspect of the present invention, in the gas barrier laminate in which the gas barrier layer is formed on at least one surface of the support, the gas barrier layer comprises an alkali metal silicate (A), colloidal silica (B), and colloidal silica (C). The colloidal silica (B) has an average particle diameter of 1 to 50 nm, the colloidal silica (C) has an average particle diameter of 10 to 1000 nm, and the colloidal silica (C) has an average particle diameter of the average of the colloidal silica (B). It is a gas barrier laminate having a particle diameter of 2 to 20 times.

  2nd of this invention is a gas-barrier laminated body as described in 1st of this invention which has an anchor layer between a support body and a gas barrier layer.

  A third aspect of the present invention is the gas barrier laminate according to any one of the first and second aspects, wherein an overcoat layer is provided on the gas barrier layer.

  According to the present invention, it is possible to provide a gas barrier laminate that has excellent gas barrier properties even when it has passed for a long time in the atmosphere under high humidity conditions, prevents white bloom, and is suitable as a packaging material. It has become possible.

The present invention is described in detail below.
The present inventors examined the gas barrier property by forming a gas barrier layer by applying and drying a paint combining a silicate compound or a silicate condensate having different particle sizes on a substrate. In general, a dry film in which two or more types of colloidal silica (silica condensate) having different particle diameters are combined is said to have a dense structure by packing small particle diameter colloidal silica into voids having a large particle diameter (The Chemistry of Silica, Ralph K. Iler, A Wiley-Interscience Publication, P369-P372, P519-P525, 1979).
However, the present inventors have found that the gas barrier property cannot be obtained at all by the combination of colloidal silica as exemplified in the past literature.
For example, simply mixing colloidal silica having different particle diameters (for example, a combination of colloidal silica having a particle diameter of 10 nm and colloidal silica having a particle diameter of 50 nm) causes the colloidal silica to aggregate during drying of the paint, resulting in a dense film. Therefore, it is considered that gas barrier properties cannot be obtained.
In addition, a layer made of only an alkali metal silicate or a layer made of an alkali metal silicate and one kind of colloidal silica (for example, a combination of lithium silicate which is a silicic acid condensate having a particle diameter of 1 nm or less and colloidal silica having a particle diameter of 10 nm). In such a case, a certain level of gas barrier properties can be obtained, but high moisture-resistant gas barrier properties cannot be obtained.
As a result of further intensive studies, it was found that when a plurality of colloidal silicas having specific particle diameters were combined in the presence of an alkali metal silicate, extremely high moisture gas barrier properties were exhibited.
For example, it was found that a gas barrier laminate formed by a paint in which lithium silicate, which is an alkali metal silicate, colloidal silica having a particle size of 15 nm, and colloidal silica having a particle size of 65 nm was blended in a specific mixing ratio was very good. The present invention has been reached.

The mechanism of the present invention is considered as follows.
When a paint in which two or more types of colloidal silica with different particle sizes are uniformly dispersed is dried in the presence of an alkali metal silicate, the alkali metal of the alkali metal silicate neutralizes the silanol on the surface of the colloidal silica, Prevent aggregation. By adding colloidal silica having different particle diameters to the alkali metal silicate, the leveling property of the gas barrier coating is improved, and it is considered that very fine cracks during film formation can be prevented.
Colloidal silica having a small particle diameter has a large surface area per unit mass, resulting in an increase in the number of silanol groups, and serves to neutralize alkali metal ions of the alkali metal silicate.
Moreover, it is thought that colloidal silica with a large particle diameter improves the leveling property at the time of film-forming, and has a role which prevents a micro crack.

In the present invention, alkali metal silicate (A) (hereinafter referred to as (A)), colloidal silica (B) (hereinafter referred to as (B)) which is colloidal silica having a smaller average particle diameter, and a larger average The combination of the average particle sizes of colloidal silica (C) (hereinafter referred to as (C)), which is colloidal silica having a particle size, is (B) 1 nm to 50 nm, (C) 10 to 1000 nm, and (C ) Is 2 to 20 times the average particle diameter of (B), and a combination of satisfying all of these conditions provides an excellent effect of improving the moisture-resistant gas barrier property.
When the average particle diameter of (B) is less than 1 nm, the physical properties very close to those of the alkali metal silicate are exhibited, so that the effect of improving the moisture gas barrier resistance is not recognized.
Further, when the average particle size of (B) is larger than 50 nm, the surface area per unit mass is reduced (the number of silanol groups is reduced), the neutralizing effect of alkali metal ions is reduced, and the moisture-resistant gas barrier property is improved. Is no longer allowed.
Further, when the average particle size of (C) is less than twice the average particle size of (B), the effect of improving the leveling property by (C) cannot be exhibited, and the effect of preventing the aggregation of (B) is obtained. Disappear.
In addition, when the average particle size of (C) exceeds 20 times the average particle size of (B), the leveling improvement effect cannot be exhibited, and the aggregation of (B) cannot be prevented. .
In the present invention, the average particle diameter of the alkali metal silicate (A) used is preferably 1 nm or less.
More preferable combinations of average particle diameters are (A) 0.2 nm to 1 nm, (B) 3 nm to 40 nm, (C) 15 to 600 nm, and 2.5 times the particle diameter of (B). ~ 15 times.
A combination satisfying this condition makes it possible to obtain an excellent moisture-resistant gas barrier layer having an oxygen permeability of 23 ° C. and 90% under 10 cc / m ² · 24 hr.
In the present invention, the most preferable combinations of average particle sizes are (A) 0.3 nm to 1 nm, (B) 5 nm to 30 nm, (C) 20 to 300 nm, and (B) 3 to 10 times.
A combination satisfying this condition makes it possible to obtain an excellent moisture-resistant gas barrier layer having an oxygen permeability of 23 ° C. and 90% under 5 cc / m ² · 24 hr.
Moreover, it is preferable that the particle diameter of (C) shall be 2 times or less of the thickness of a gas barrier layer. If the particle diameter exceeds twice the thickness of the gas barrier layer, cracks are likely to be generated starting from (C), and gas barrier properties deteriorate, which is not preferable.

The compounding ratio of the silicic acid compound is preferably (A) / (B) / (C) = 100/70 to 2/30 to 0.5, more preferably in terms of mass / solid content in the gas barrier layer. (A) / (B) / (C) = 100/50 to 3/20 to 1, most preferably (A) / (B) / (C) = 100/30 to 3/15 to 1.5. .
Further, (C) is preferably 50% or less with respect to (B).
If the colloidal silica (B) is larger than 70 parts or larger than (C) is larger than 30 parts relative to 100 parts of the alkali metal silicate (A), the gas barrier layer cannot be densely packed, and the gas barrier It is not preferable because the properties are lowered and cracks occur in the coating film.
Further, when the colloidal silica (B) is less than 2 parts or the (C) is less than 0.5 parts with respect to 100 parts of the alkali metal silicate (A), the humidity deterioration of the gas barrier becomes large, which is not preferable.

In the present invention, the alkali metal silicate (A) is a compound represented by M ₂ O.nSiO ₂ (M is an alkali metal, n> 0). Usually, it is handled as a concentrated aqueous solution, but the particle size increases when the concentration is high, and the particle size decreases when the concentration is low.
The alkali metal M is lithium, sodium, potassium or the like. In the present invention, a cationic ion such as ammonium is also included in the category of M. n is also called a molar ratio, and a range of about 0.5 to 10 is preferable. If the molar ratio is less than 0.5, the film-forming ability due to the condensation of alkali metal silicate is reduced, or the content of alkali metal salt is too high, so the water resistance and moisture resistance are often lowered, and the white flower phenomenon also occurs. Cheap. On the other hand, when the molar ratio exceeds 10, there may be a problem in the coated surface such as the occurrence of cracks. Further, the smaller the molar ratio, the smaller the particle diameter, and the larger the molar ratio, the larger the particle diameter.

  Note that alkali metal silicates having a high molar ratio exceeding 10 are generally not commercially available, but a method of adding various alkali metal hydroxides to amorphous silica or colloidal silica and dissolving them, or commercially available silicic acid It can be prepared by a method of dissolving amorphous silica or colloidal silica in an alkali metal salt, and the alkali metal silicate prepared in this way can also be used in the present invention.

Examples of the alkali metal silicate include sodium orthosilicate (Na ₂ O.1 / 2SiO ₂ or Na ₄ SiO ₄ ) having a molar ratio of 0.57 and sesquioxide having a molar ratio of 0.67 when the alkali metal is sodium silicate. sodium silicate (3Na ₂ O · 2SiO ₂ or _Na 6 _Si 2 _O 7), sodium metasilicate molar ratio 1 _{(Na 2} O · SiO 2 or _Na 2 _SiO 3), sodium disilicate molar ratio 2 _(Na 2 O・ 2SiO ₂ or Na ₂ Si ₂ O ₅ ), sodium tetrasilicate with a molar ratio of 4 (Na ₂ O.4SiO ₂ or Na ₂ Si ₄ O ₉ , also known as: sodium silicate No. 4), etc. Sodium silicate No. 1 (molar ratio 2), No. 2 (molar ratio 2.5), No. 3 (molar ratio 3), metasilicate sodium specified in JIS-K-1408 Helium one, there are sodium metasilicate two.

There are various compositions of potassium silicate in which the alkali metal is potassium, but examples include potassium metasilicate (K ₂ O · SiO ₂ ), potassium tetrasilicate (K ₂ O · 4SiO ₂ · H ₂ O, also known as Potassium dihydrogen silicate). Lithium silicate whose alkali metal is lithium is lithium orthosilicate (Li ₂ O · 1 / 2SiO ₂ ), lithium metasilicate (Li ₂ O · SiO ₂ ), 3.5 lithium silicate, 7.5 lithium silicate (Li ₂ O.7.5SiO ₂ ).

  For example, ammonium salts such as ammonium silicate using tetramethylammonium ions as counter ions are also included in the category of alkali metal silicates in the present invention.

  These alkali metal silicates have different degrees of condensation and different particle sizes depending on the molar ratio. The size cannot be clearly determined because the solubility in the liquid increases as the molar ratio decreases, but most are those of several nm or less by analogy with the dynamic light scattering method. In addition, the particle diameter of the alkali metal silicate compound decreases as the concentration decreases. When the concentration is less than 10%, most of the particle diameter is considered to be 1 nm or less. These alkali metal silicates can be used as a mixture of two kinds.

The colloidal silica (B) and colloidal silica (C) that can be used in the present invention can be obtained by neutralizing sodium silicate with an inorganic acid or hydrolyzing a silicon ester or a silicon halide.
In addition, after passing an alkali metal silicate such as sodium silicate through the cation ion exchange resin layer, the pH is adjusted with an alkali, and then heated to produce a core of colloidal silica, and the cation exchange resin layer is further passed through the liquid. It can obtain by dripping the sodium silicate liquid which was made. At this time, if the dropping speed is high, the condensation proceeds rapidly, aggregation is generated, and a porous structure is obtained. By slowing the dropping speed, the monomer deposits on the silanol groups on the surface of the nucleus to grow particles. Colloidal silica can be grown to an arbitrary size of several nm to several μm by adjusting pH appropriately and slowing the dropping rate.

  The gas barrier layer in the present invention can contain a boron compound, a water-soluble polymer, an aqueous synthetic resin emulsion, and a nitrogen-containing compound in addition to the silicic acid compounds (A), (B), and (C). It is. Boron compounds and nitrogen-containing compounds improve the moisture barrier property of the gas barrier layer, and water-soluble polymers and aqueous synthetic resin emulsions improve the flexibility of the gas barrier film.

The support in the present invention is a molded body made of a synthetic resin, and the shape thereof can be appropriately selected as necessary, such as a film or a sheet.
Specific examples of the synthetic resin constituting the support include polyolefin resins such as polyethylene, polypropylene, polyisoprene, and polyolefin having an alicyclic structure, polyethylene terephthalate, polyethylene naphthalate, polysuccinic acid ester, polylactic acid ester, polybutyric acid ester. Polyester resins such as nylon 6 and nylon 66, acrylic resins such as polymethyl methacrylate, ethylene vinyl acetate copolymer, polyvinyl alcohol, ethylene vinyl alcohol, polystyrene, and polysulfane. Moreover, it is also possible to use what laminated | stacked these resin by arbitrary methods, and the support body obtained by mixing resin.
Among these resins, particularly, polypropylene, polyethylene terephthalate, and nylon 66 are preferably used.
Moreover, a uniaxially stretched or biaxially stretched film can be used as the film to be the support. In addition, as a support body used for this invention, since a biaxially stretched polypropylene film is excellent in moisture resistance, it is the most suitable.
The above support includes an antioxidant, weathering stabilizer, light stabilizer, antistatic agent, pigment, dye, plasticizer, flame retardant, inorganic filler, such as silica, alumina, calcium carbonate, talc, kaolin. Various additives such as clay, zeolite, mica, carbon black, and glass fiber may be included as necessary.

When laminating the gas barrier layer of the present invention on a support such as a film made of these synthetic resins, the gas barrier layer may be provided directly on the support, but in order to improve the adhesion between the gas barrier layer and the support. Further, it is more desirable to activate the support surface.
Examples of the method for activating the surface of the synthetic resin support include corona discharge treatment, plasma discharge treatment, black mixed acid solution treatment, fuming sulfuric acid treatment, sulfuric acid solution treatment, electron beam treatment, ultraviolet ray treatment, and flame treatment. Among these, a corona discharge treatment, a plasma discharge treatment, and a flame treatment are preferable for the reason that the effect of improving the wettability to the substrate and the productivity are excellent.
By performing these treatments, hydrophilic components such as hydroxyl groups, carbonyl groups, ester groups, carboxylic acid groups, ether bonds, amino groups, imino groups, amide groups, sulfuric acid groups, amide groups are formed on the surface of the synthetic resin support. Can be introduced.
Applying a gas barrier coating to the surface of the synthetic resin support thus treated has the effect of preventing the occurrence of repellency and irregularities and improving the adhesion between the gas barrier layer and the substrate.

When sufficient adhesion cannot be obtained only by such surface treatment of the support (when the base material is a polyolefin resin, etc.), an anchor layer is provided on the surface of the support, or anchors are further added to the surface-treated support. It is desirable to provide a layer.
The anchor layer in the present invention is preferably an anchor layer containing a nitrogen-containing compound. The reason for this is that the anionic functional group such as a carboxylic acid group, a carbonyl group or a hydroxyl group on the surface of the support subjected to the surface treatment and a nitrogen-containing compound exhibiting a cationic property form an ionic bond, thereby providing moisture resistance. Forming an anchor layer excellent in
Furthermore, the silicic acid (SiOH) contained in the silicic acid condensate in the gas barrier layer and the nitrogen-containing compound form an ion complex or promote the cross-linking of the silicic acid condensate, thereby improving the moisture gas barrier resistance of the gas barrier layer There is.

  Typical nitrogen-containing compounds are those called imine compounds and amine compounds. Among these, as the imine compound, polyalkyleneimine is representative, polyethyleneimine, alkyl or cyclopentyl modified polyethyleneimine, imine adduct of ethylene urea, poly (ethyleneimine-urea) and ethyleneimine adduct of polyamine polyamide, or There are polyimine compounds selected from the group consisting of these alkyl-modified products, alkenyl-modified products, benzyl-modified products, or aliphatic cyclic hydrocarbon-modified products, polyamideimides, and polyimide varnishes.

Examples of amine compounds include polyalkylene polyamines. For example, there are compounds such as polyethylene polyamine, ethylenediamine, diethylenetriamine, triethylenetetramine. In addition, examples of the same effect include polyamides such as polyamidoimide adducts of polyamides, hydrazine compounds, and epichlorohydrin adducts of polyamine polyamides (saturated dibasic carboxylic acids having 3 to 10 carbon atoms and polyamines). Polyamineamide compounds such as water-soluble and cationic thermosetting resins obtained by reacting polyamides with epichlorohydrin from alkylene polyamines, quaternary nitrogen-containing acrylic polymers, quaternary nitrogen-containing benzyl polymers, urethanes, carboxylate amines There are nitrogen-containing quaternary salt compounds such as compounds having a base, compounds such as methylolated melamine, and cationic polyurethane. Further, cationic resins such as cation-modified polyurethane resins, polyvinyl pyrrolidone, vinyl pyrrolidone-vinyl acetate copolymers, tertiary nitrogen-containing acrylic resins and the like can be mentioned (for cation resins, JP-A-8-90898, JP (Described in JP-A 63-162275, JP-A 62-148292, etc.).
Among the nitrogen-containing compounds, polyalkylenimine is most preferable in terms of moisture gas barrier property and moisture adhesion resistance.

  As the polyalkyleneimine, polyethyleneimine and polypropyleneimine are preferable, and in particular, polyethyleneimine is most preferable in terms of moisture resistance. These polyalkyleneimines may be used alone or in the form of a salt with acetic acid, p-toluenesulfonic acid, sulfuric acid, hydrochloric acid or the like.

  The anchor layer of the present invention preferably contains a highly hydrogen-bonding water-soluble resin, colloidal silica, or a silane coupling agent. In particular, combining the three components of nitrogen-containing compounds, highly hydrogen-bonding water-soluble resins, and colloidal silica improves moisture-resistant gas barrier properties and moisture-resistant adhesion, and nitrogen-containing compounds, highly hydrogen-bonding water-soluble resins, and colloidal silica. When the four components of silane coupling agent are combined, the moisture-resistant gas barrier property and moisture-resistant adhesion are further improved.

The high hydrogen bonding resin serves to form an anchor layer uniformly, and also serves as a protective colloid of colloidal silica that prevents aggregation of the colloidal silica and the nitrogen-containing compound. Colloidal silica has the effect of imparting moisture resistance to the anchor layer. In particular, moisture resistance is enhanced by forming a complex in the anchor layer with a water-soluble resin having high hydrogen bonding properties. Furthermore, the coupling agent improves moisture resistance by reacting with the surface of the base material, reacting with a silanol group on the surface of colloidal silica, or a functional group of a high hydrogen bonding resin, and crosslinking.
Examples of the high hydrogen bonding water-soluble resin include polyvinyl alcohol, starch, ethylene-vinyl alcohol copolymer, polyacrylic acid, hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose and the like. Among these, polyvinyl alcohol can be preferably used from the viewpoint of film formability. Among polyvinyl alcohols, polyvinyl alcohol modified with a silyl group is preferable because of its excellent compatibility with colloidal silica and silane coupling agents.

  As the colloidal silica contained in the anchor layer, colloidal silica having a particle diameter of 1 to 400 nm, more preferably 2 to 200 nm, and more preferably 3 to 100 nm can be used. From the viewpoint of water resistance, colloidal silica neutralized with ammonia can be preferably used.

  Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and γ-glycidoxy. Propyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, methyltrimethoxysilanephenyltriethoxysilane, and γ-fluoropropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, and the like. Among these, amino group-containing silane coupling agents can be suitably used from the viewpoint of moisture-resistant gas barrier properties and moisture-resistant adhesion.

In the present invention, an overcoat layer can be provided on the gas barrier layer in order to improve moisture adhesion, gas barrier properties, and printability.
The overcoat layer in the present invention more preferably contains at least one selected from a hydroxyl group-containing highly hydrogen bonding resin, a boron compound, and colloidal silica.

The gas barrier laminate of the present invention, which is based on a film, is formed by laminating a polyethylene film or polypropylene film with an adhesive on the surface of the gas barrier layer or overcoat layer, or extruding a polyethylene resin or polypropylene resin. By providing a sealant layer by means of laminating or the like, a gas barrier laminate having heat sealability can be obtained.
Such a gas barrier laminate is suitably used for foods, warmers, packaging of electronic parts, and the like.

EXAMPLES Hereinafter, the Example and comparative example of this invention are shown and this invention is demonstrated concretely.
In addition, the numerical value which shows the mixing | blending, density | concentration, addition amount, etc. in a sentence is a numerical value on the mass basis of solid content or an active ingredient.
<Preparation of gas barrier paint A>
A lithium silicate salt solution having a molar ratio of 3.5 (trade name: lithium silicate 35, 23% as solid content Li ₂ O.SiO ₂ , particle size of 1 nm or less, manufactured by Nippon Chemical Industry Co., Ltd.) is used as the alkali metal silicate (A). Then, 100 parts of a lithium silicate aqueous solution having a solid content of 3% obtained by dilution with water was added to colloidal silica (trade name: SNOWTEX XS, sodium stable colloidal silica, pH 9) as colloidal silica (B). 0.01 to 10.0, solid content 20%, manufactured by Nissan Chemical Co., Ltd.) diluted with water to 3% solid content was added and stirred.
To the resulting aqueous solution, colloidal silica (trade name: Snowtex XL, Na-stable colloidal silica, pH 9-11, solid content 40%, manufactured by Nissan Chemical Co., Ltd.) is solidified with water as colloidal silica (C). 7 parts of an aqueous solution diluted to 3% was added and stirred.
A gas barrier coating material A was prepared by adding 3 parts of an aqueous solution of boron oxide having a solid content of 3% obtained by dissolving boron oxide (manufactured by Wako Pure Chemicals, first grade reagent) with water to the obtained aqueous solution and mixing them.

<Preparation of gas barrier paint B>
100 parts of a lithium silicate aqueous solution having a solid content of 3% obtained by diluting with a lithium silicate salt solution (lithium silicate 35, manufactured by Nippon Chemical Industry Co., Ltd.) having a molar ratio of 3.5 as the alkali metal silicate (A). In addition, colloidal silica (trade name: Snowtex NXS, ammonia stable colloidal silica, pH 9.0 to 10.0, solid content 20%, manufactured by Nissan Chemical Co., Ltd.) is solidified with water as colloidal silica (B). 18 parts of an aqueous solution diluted to 3% was added and stirred.
In the resulting aqueous solution, colloidal silica (C name) having an average particle diameter of 90 nm (trade name: Snowtex ZL, Na stable colloidal silica, pH 9-11, manufactured by Nissan Chemical Co., Ltd.) is diluted with water to a solid content of 3%. 7 parts of the aqueous solution was added and stirred.
A gas barrier coating material B was obtained by adding 3 parts of a 3% solid boron oxide aqueous solution obtained by dissolving boron oxide (manufactured by Wako Pure Chemicals, first grade reagent) with water to the obtained aqueous solution and mixing them.

<Preparation of gas barrier paint C>
100 parts of a lithium silicate aqueous solution having a solid content of 3% obtained by diluting with a lithium silicate salt solution (lithium silicate 35, manufactured by Nippon Chemical Industry Co., Ltd.) having a molar ratio of 3.5 as the alkali metal silicate (A). And colloidal silica (B) having an average particle diameter of 10 nm (trade name: Snowtex S, sodium-stable colloidal silica, pH 9.5 to 10.0, solid content 30%, manufactured by Nissan Chemical Co., Ltd.) in water. 18 parts of an aqueous solution diluted to 3% was added and stirred.
In the obtained aqueous solution, colloidal silica having an average particle size of 25 nm as colloidal silica (C) (trade name: Snowtex 50, Na-stable colloidal silica, pH 8.5 to 9.5, solid content 48%, manufactured by Nissan Chemical Co., Ltd.) 7 parts of an aqueous solution diluted to 3% solids with water was added and stirred.
A gas barrier coating material C was prepared by adding 3 parts of a 3% solid boron oxide aqueous solution obtained by dissolving boron oxide (manufactured by Wako Pure Chemicals, first grade reagent) with water to the obtained aqueous solution and mixing them.

<Preparation of gas barrier paint D>
100 parts of a lithium silicate aqueous solution having a solid content of 3% obtained by diluting with a lithium silicate salt solution (lithium silicate 35, manufactured by Nippon Chemical Industry Co., Ltd.) having a molar ratio of 3.5 as the alkali metal silicate (A). And colloidal silica (B) having an average particle diameter of 15 nm (trade name: Snowtex N, ammonium stable colloidal silica, pH 9.0 to 10.0, solid content 20%, manufactured by Nissan Chemical Co., Ltd.) in water. 18 parts of an aqueous solution diluted to 3% was added and stirred.
Colloidal silica having an average particle size of 65 nm as colloidal silica (C) is added to the obtained aqueous solution (trade name: Snowtex YL, Na-stable colloidal silica, pH 9.0 to 10.0, solid content 40%, manufactured by Nissan Chemical Co., Ltd.) 7 parts of an aqueous solution diluted to 3% solids with water was added and stirred.
A gas barrier coating material D was prepared by adding 3 parts of an aqueous solution of boron oxide having a solid content of 3% obtained by dissolving boron oxide (manufactured by Wako Pure Chemicals, first grade reagent) with water to the obtained aqueous solution and mixing them.

<Preparation of gas barrier paint E>
100 parts of a lithium silicate aqueous solution having a solid content of 3% obtained by diluting with a lithium silicate salt solution (lithium silicate 35, manufactured by Nippon Chemical Industry Co., Ltd.) having a molar ratio of 3.5 as the alkali metal silicate (A). Then, 18 parts of an aqueous solution obtained by diluting colloidal silica (Snowtex N, manufactured by Nissan Chemical Co., Ltd.) having an average particle diameter of 15 nm with water to 3% solid content as colloidal silica (B) was added and stirred.
To the obtained aqueous solution, 7 parts of an aqueous solution obtained by diluting colloidal silica (Snowtex ZL, manufactured by Nissan Chemical Co., Ltd.) having an average particle diameter of 90 nm with water to 3% solid content was added and stirred as colloidal silica (C).
A gas barrier coating material E was prepared by adding 3 parts of a 3% solid boron oxide aqueous solution obtained by dissolving boron oxide (manufactured by Wako Pure Chemicals, first grade reagent) with water to the obtained aqueous solution and mixing them.

<Preparation of gas barrier paint F>
100 parts of a lithium silicate aqueous solution having a solid content of 3% obtained by diluting with a lithium silicate salt solution (lithium silicate 35, manufactured by Nippon Chemical Industry Co., Ltd.) having a molar ratio of 3.5 as the alkali metal silicate (A). Then, 18 parts of an aqueous solution obtained by diluting colloidal silica (Snowtex 50, manufactured by Nissan Chemical Co., Ltd.) having an average particle diameter of 25 nm to 3% solid content with water as colloidal silica (B) was added and stirred.
To the obtained aqueous solution, 7 parts of an aqueous solution obtained by diluting colloidal silica (Snowtex ZL, manufactured by Nissan Chemical Co., Ltd.) having an average particle diameter of 90 nm with water to 3% solid content was added and stirred as colloidal silica (C).
A gas barrier coating material F was prepared by adding 3 parts of a 3% solid boron oxide aqueous solution obtained by dissolving boron oxide (manufactured by Wako Pure Chemicals, first grade reagent) with water to the obtained aqueous solution and mixing them.

<Preparation of gas barrier paint G>
100 parts of a lithium silicate aqueous solution having a solid content of 3% obtained by diluting with a lithium silicate salt solution (lithium silicate 35, manufactured by Nippon Chemical Industry Co., Ltd.) having a molar ratio of 3.5 as the alkali metal silicate (A). And colloidal silica (B) having an average particle diameter of 45 nm (trade name: Snowtex 20L, sodium stable colloidal silica, pH 9.5 to 11.0, solid content 20%, manufactured by Nissan Chemical Co., Ltd.) in water. 18 parts of an aqueous solution diluted to 3% was added and stirred.
Colloidal silica (trade name: Snowtex MP-2040, Na-stable colloidal silica, pH 8.0-10.0, solid content 40%, Nissan Chemical Co., Ltd.) 7 parts of an aqueous solution diluted with water to a solid content of 3% was added and stirred.
A gas barrier coating material G was prepared by adding 3 parts of an aqueous solution of boron oxide having a solid content of 3% obtained by dissolving boron oxide (manufactured by Wako Pure Chemicals, first grade reagent) with water to the obtained aqueous solution and mixing them.

<Preparation of gas barrier paint H>
100 parts of a lithium silicate aqueous solution having a solid content of 3% obtained by diluting with a lithium silicate salt solution (lithium silicate 35, manufactured by Nippon Chemical Industry Co., Ltd.) having a molar ratio of 3.5 as the alkali metal silicate (A). Then, 36 parts of an aqueous solution obtained by diluting colloidal silica (Snowtex N, manufactured by Nissan Chemical Co., Ltd.) having an average particle diameter of 15 nm with water to 3% solid content was added and stirred as colloidal silica (B). To the obtained aqueous solution, 14 parts of an aqueous solution obtained by diluting colloidal silica (Snowtex YL, manufactured by Nissan Chemical Co., Ltd.) having an average particle diameter of 65 nm with water to 3% solid content was added and stirred as colloidal silica (C).
A gas barrier coating material H was prepared by adding 3 parts of a 3% solid boron oxide aqueous solution obtained by dissolving boron oxide (manufactured by Wako Pure Chemicals, first grade reagent) with water to the obtained aqueous solution and mixing them.

<Preparation of gas barrier paint I>
100 parts of a lithium silicate aqueous solution having a solid content of 3% obtained by diluting with a lithium silicate salt solution (lithium silicate 35, manufactured by Nippon Chemical Industry Co., Ltd.) having a molar ratio of 3.5 as the alkali metal silicate (A). Then, 10 parts of an aqueous solution obtained by diluting colloidal silica (Snowtex N, manufactured by Nissan Chemical Co., Ltd.) having an average particle diameter of 15 nm to 3% solid content with water as colloidal silica (B) was added and stirred.
To the obtained aqueous solution, 4 parts of an aqueous solution obtained by diluting colloidal silica (Snowtex YL, manufactured by Nissan Chemical Co., Ltd.) having an average particle diameter of 65 nm with water to a solid content of 3% was added and stirred as colloidal silica (C).
A gas barrier coating material I was obtained by adding 3 parts of a 3% solid boron oxide aqueous solution obtained by dissolving boron oxide (manufactured by Wako Pure Chemicals, first grade reagent) with water to the obtained aqueous solution and mixing them.

<Preparation of gas barrier paint J>
100 parts of a lithium silicate aqueous solution having a solid content of 3% obtained by diluting with a lithium silicate salt solution (lithium silicate 35, manufactured by Nippon Chemical Industry Co., Ltd.) having a molar ratio of 3.5 as the alkali metal silicate (A). Then, 10 parts of an aqueous solution obtained by diluting colloidal silica (Snowtex N, manufactured by Nissan Chemical Co., Ltd.) having an average particle diameter of 15 nm to 3% solid content with water as colloidal silica (B) was added and stirred.
To the obtained aqueous solution, 4 parts of an aqueous solution obtained by diluting colloidal silica (Snowtex YL, manufactured by Nissan Chemical Co., Ltd.) having an average particle diameter of 65 nm with water to a solid content of 3% was added and stirred as colloidal silica (C).
A gas barrier coating material J was prepared by adding 3 parts of a 3% solid boron oxide aqueous solution obtained by dissolving boron oxide (manufactured by Wako Pure Chemicals, first grade reagent) with water to the obtained aqueous solution, and mixing them.

<Preparation of gas barrier paint K>
100 parts of a lithium silicate aqueous solution having a solid content of 3% obtained by diluting with a lithium silicate salt solution (lithium silicate 35, manufactured by Nippon Chemical Industry Co., Ltd.) having a molar ratio of 3.5 as the alkali metal silicate (A). A gas barrier paint K was prepared by adding 3 parts of a 3% solid boron oxide aqueous solution obtained by dissolving boron oxide (manufactured by Wako Pure Chemicals, first grade reagent) with water.

<Preparation of gas barrier paint L>
100 parts of a lithium silicate aqueous solution having a solid content of 3% obtained by diluting with a lithium silicate salt solution (lithium silicate 35, manufactured by Nippon Chemical Industry Co., Ltd.) having a molar ratio of 3.5 as the alkali metal silicate (A). Then, 18 parts of an aqueous solution obtained by diluting colloidal silica (Snowtex N, manufactured by Nissan Chemical Co., Ltd.) having an average particle diameter of 15 nm with water to 3% solid content was added and stirred as colloidal silica (B).
A gas barrier coating material L was obtained by adding 3 parts of a 3% solid boron oxide aqueous solution obtained by dissolving boron oxide (manufactured by Wako Pure Chemicals, first grade reagent) with water to the obtained aqueous solution, and mixing them.

<Preparation of gas barrier paint M>
100 parts of a lithium silicate aqueous solution having a solid content of 3% obtained by diluting with a lithium silicate salt solution (lithium silicate 35, manufactured by Nippon Chemical Industry Co., Ltd.) having a molar ratio of 3.5 as the alkali metal silicate (A). 7 parts of an aqueous solution obtained by diluting colloidal silica (Snowtex YL, manufactured by Nissan Chemical Co., Ltd.) having an average particle diameter of 65 nm to 3% solid content with water was added and stirred as colloidal silica (C).
A gas barrier coating material M was obtained by adding 3 parts of an aqueous solution of boron oxide having a solid content of 3% obtained by dissolving boron oxide (manufactured by Wako Pure Chemicals, first grade reagent) with water to the obtained aqueous solution and mixing them.
Table 1 below shows the configurations of the gas barrier coatings A to M.

＜アンカー塗料（１）の調製＞
水１００質量部にＩＰＡ１２質量部を添加した溶液に、平均粒子径１５ｎｍのコロイダルシリカ（スノーテックスN、日産化学製）５質量部、水酸基含有水溶性樹脂であるポリビニルアルコール（商品名：ＰＶＡ−１１７、ケン化度９９％、クラレ製）の５％水溶液を８０質量部順次添加して１時間以上攪拌した。
その後、含窒素有機化合物であるポリエチレンイミン（商品名：エポミンＰ−１０００、固形分３０％、分子量７０，０００、比重１．０４、アミン価１８（mgeq／g・solid）、アミン比 １級／２級／３級＝２５／５０／２５、日本触媒製）の５％水溶液を１１質量部添加して攪拌し、固形分３％のアンカー塗料（１）とした（ｐＨ１０．５、動的表面張力５８dyne/cm、静的表面張力５０dyne/cm）。

<Preparation of anchor paint (1)>
To a solution obtained by adding 12 parts by mass of IPA to 100 parts by mass of water, 5 parts by mass of colloidal silica (Snowtex N, manufactured by Nissan Chemical Co., Ltd.) having an average particle diameter of 15 nm, polyvinyl alcohol which is a hydroxyl group-containing water-soluble resin (trade name: PVA-117) 80% by mass of a 5% aqueous solution of 99% saponification, manufactured by Kuraray Co., Ltd. was sequentially added and stirred for 1 hour or more.
Then, polyethyleneimine (trade name: Epomin P-1000, solid content 30%, molecular weight 70,000, specific gravity 1.04, amine value 18 (mgeq / g · solid), amine ratio 1st grade / 11 parts by mass of a 5% aqueous solution of 2nd grade / 3rd grade = 25/50/25, manufactured by Nippon Shokubai Co., Ltd. was added and stirred to obtain an anchor coating (1) having a solid content of 3% (pH 10.5, dynamic surface Tension 58dyne / cm, static surface tension 50dyne / cm).

<Preparation of anchor paint (2)>
To a solution obtained by adding 12 parts by mass of IPA to 100 parts by mass of water, 5 parts by mass of colloidal silica (Snowtex N, manufactured by Nissan Chemical Industries) having an average particle size of 15 nm, silyl-modified polyvinyl alcohol (trade name: PVA-) which is a hydroxyl group-containing water-soluble resin 80 parts by mass of a 5% aqueous solution of R1130 (degree of saponification 99%, manufactured by Kuraray Co., Ltd.) was sequentially added and stirred for 1 hour or more.
Thereafter, 11 parts by mass of a 5% aqueous solution of polyethyleneimine (Epomin P-1000, manufactured by Nippon Shokubai Co., Ltd.), which is a nitrogen-containing organic compound, is added and stirred. Further, an amino-modified silane coupling agent (trade name: KBM903, chemical name) : 3-aminopropyltrimethoxysilane, chemical formula (CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ NH ₃ , manufactured by Shin-Etsu Chemical Co., Ltd.) is made into a 5% aqueous solution, hydrolyzed by stirring for 30 minutes or more, and then 33 parts by mass are added. The mixture was stirred to give an anchor paint (2) having a solid content of 3% (pH 10.5, dynamic surface tension 58 dyne / cm, static surface tension 50 dyne / cm).

<Preparation of overcoat paint>
Silyl-modified polyvinyl alcohol (trade name: PVA-R2105, saponification) which is a hydroxyl group-containing water-soluble resin having silyl groups in 8 parts by mass of colloidal silica (Snowtex N, manufactured by Nissan Chemical Co., Ltd.) having an average particle diameter of 15 nm in 120 parts by mass of water After adding 150 parts by mass of a 5% aqueous solution of 88%, manufactured by Kuraray) and stirring, 50 parts by mass of a 1% aqueous solution of boron oxide (B ₂ O ₃ , manufactured by Wako Pure Chemical Industries, Ltd.), which is a boron compound, is added and stirred. And an overcoat paint having a solid content of 1% (pH = 9.5, dynamic surface tension 63 dyne / cm, static surface tension 59 dyne / cm).

<Example 1>
Anchor paint (1) is applied to the surface of a biaxially oriented polypropylene film (trade name: PY101, 20 μm thick, coating-side surface roughness Rmax 191 nm, Rz 128 nm, non-coating side surface roughness Rmax 625 nm, Rz 331 nm, made by Oji Paper Co., Ltd.) After corona treatment, coat with a gravure coater (direct reverse gravure, 180 mesh, coating speed 100 m / min, drying temperature 95 ° C.) so that the coating amount is 0.12 g / m ² in terms of solid content. A laminate having an anchor layer was produced.
Next, the gas barrier coating A is applied on the anchor layer of the laminate having the anchor layer with a gravure coater (direct reverse gravure, 180 mesh, coating speed 100 m / min, drying temperature 90 ° C.) in solid content conversion. A gas barrier laminate was produced by coating at 0.12 g / m ² .

<Examples 2 to 10>
A gas barrier laminate was produced in the same manner as in Example 1 except that B to J were used as the gas barrier paint.

<Example 11>
After the anchor paint (1) is corona-treated on the surface of a biaxially stretched polypropylene film (PY101, manufactured by Oji Paper), a gravure coater (direct reverse gravure, 180 mesh, coating speed 100 m / min, drying temperature 95 ° C.) Coating was performed so that the coating amount was 0.12 g / m ² in terms of solid content, and a laminate having an anchor layer was manufactured.
Next, the gas barrier coating D is applied on the anchor layer of the laminate having the anchor layer with a gravure coater (direct reverse gravure, 180 mesh, coating speed 100 m / min, drying temperature 90 ° C.) in a solid content conversion. A laminate having a gas barrier layer was formed by coating at 0.12 g / m ² .
Furthermore, an overcoat paint is applied on the gas barrier layer by a gravure coater (normal gravure, 180 mesh, coating speed 100 m / min, drying temperature 95 ° C.), and the coating amount becomes 0.04 g / m ² in terms of solid content. Thus, an overcoat layer was laminated to produce a gas barrier laminate.

<Example 12>
After the anchor paint (2) is corona-treated on the surface of a biaxially stretched polypropylene film (PY101, manufactured by Oji Paper), a gravure coater (direct reverse gravure, 180 mesh, coating speed 100 m / min, drying temperature 95 ° C.) Coating was performed so that the coating amount was 0.12 g / m ² in terms of solid content, and a laminate having an anchor layer was manufactured.
Next, the gas barrier coating D is applied on the anchor layer of the laminate having the anchor layer with a gravure coater (direct reverse gravure, 180 mesh, coating speed 100 m / min, drying temperature 90 ° C.) in a solid content conversion. A laminate having a gas barrier layer was produced by coating at 0.12 g / m ² .
Furthermore, an overcoat paint is applied on the gas barrier layer with a gravure coater (forward gravure, 180 mesh, coating speed 100 m / min, drying temperature 95 ° C.) so that the coating amount becomes 0.04 g / m ² in terms of solid content. Then, an overcoat layer was laminated to produce a gas barrier laminate.

<Comparative Examples 1-3>
A laminate was produced in the same manner as in Example 1 except that the gas barrier paints K to M were used as the gas barrier paint.

<Comparative example 4>
On the gas barrier layer of Comparative Example 1, an overcoat paint was coated with a gravure coater (normal gravure, 180 mesh, coating speed 100 m / min, drying temperature 95 ° C.), and the coating amount was 0.04 g / m ^{2 in} terms of solid content. Then, an overcoat layer was laminated to produce a laminate.

The gas barrier laminates obtained in Examples and Comparative Examples were measured and evaluated by the following methods, and the results are shown in Table 2.
<Test method>
1) Average particle diameter of alkali metal silicate and colloidal silica The particle diameter of colloidal silica was measured using a dynamic light scattering particle size distribution device LB-550 (manufactured by Horiba, Ltd.), and the median diameter (volume basis). The particle diameter corresponding to 50% of the particle size distribution) was defined as the particle diameter.
In addition, when there is no clear peak of the particle size or when the particle size distribution results such that the particle size peak can be predicted to be 1 nm or less, the particle size is set to 1 nm or less.

2) Oxygen permeability The gas barrier laminates produced in Examples 1 to 5 and Comparative Examples 1 to 7 were left for 1 week in a state where the coating layer was in contact with an atmosphere of 23 ° C. and 90% RH, and then JIS-K. -7126 Measurement was carried out under the condition of 23 ° C. and 90% RH with the coated surface being the oxygen detector side by the B method (isobaric method) (oxygen permeability measuring device: OX-TRAN100 type, manufactured by MOCON).
The oxygen permeability was 72 hours after setting the sample and was taken as the oxygen permeability.
Oxygen permeability is preferably at most 20cc / ^{m 2} · 24hr, more preferably not more than 10cc / ^{m 2} · 24hr, more preferably not more than 5cc / ^{m 2} · 24hr.

Claims (3)

In the gas barrier laminate in which the gas barrier layer is formed on at least one surface of the support, the gas barrier layer contains an alkali metal silicate (A), colloidal silica (B), and colloidal silica (C), and the colloidal silica (B) The average particle diameter is 1 to 50 nm, the average particle diameter of the colloidal silica (C) is 10 to 1000 nm, and the average particle diameter of the colloidal silica (C) is 2 to 20 times the average particle diameter of the colloidal silica (B). A gas barrier laminate characterized by the above. The gas barrier laminate according to claim 1, further comprising an anchor layer between the support and the gas barrier layer. The gas barrier laminate according to claim 1, wherein an overcoat layer is provided on the gas barrier layer.