JP2001270023A - Gas barrier laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier laminate useful as various packaging materials, excellent in gas barrier properties and having a gas barrier layer excellent in water resistance and coating film strength. SOLUTION: In the gas barrier laminate wherein the gas barrier layer is formed on at least the single surface of a support, the gas barrier layer contains (1) at least one silicic acid condensate selected from alkali metal silicate and colloidal silica, (2) a reaction product of at least one component selected from a hydrolysate of a metal alkoxide and a hydrolysis condensate thereof and a hydrogen bondable resin, (3) a nitrogen-containing compound reacting with the silicic acid condensate, and (4) plate pigment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gas barrier laminate which is suitable as various packaging materials, molded articles or molding materials.

[0002]

2. Description of the Related Art In the packaging of foods and the like, gas barrier properties, in particular, barrier properties of oxygen, water vapor, carbon dioxide, and aroma (aroma and flavor) are important qualities from the viewpoint of protecting the quality of contents. Packaging materials using such barrier materials include confectionery bags, skipjackets, 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 packaging of carbon dioxide beverage containers, cosmetics, agricultural chemicals and pharmaceuticals. 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, and thermoplastic resins such as polystyrene and ethylene-vinyl acetate copolymer have strength, heat resistance, transparency, etc. Is widely used as a packaging material because of its superiority. However, when a film made of the above thermoplastic resin is used as a packaging material, the gas barrier property is insufficient, so that the film is laminated with a thermoplastic resin having a gas barrier property, an aluminum foil, an aluminum vapor-deposited film, a silicon vapor-deposited film, or the like. In general, a packaging material is used.

As thermoplastic resins having high gas barrier properties, polyvinyl alcohol (PVA), ethylene vinyl alcohol (EVOH, saponified ethylene-vinyl acetate copolymer), polyalcohol (reduced polyketone), vinylidene chloride ( PVDC) and the like, but a resin exhibiting a barrier property by a hydrogen bond due to a hydroxyl group such as PVA or EVOH has a problem that the barrier property at a high humidity (for example, 20 ° C. and 80% RH or more) rapidly decreases. There is. In addition, PVDC is a chlorine compound, and the recent situation is to try to avoid using it as a packaging material as much as possible because of increasing awareness of global environmental issues such as generation of dioxin during incineration.

[0004] On the other hand, packaging materials using aluminum foil or aluminum vapor-deposited film also have the disadvantage that metal detectors cannot be used or are opaque, in addition to environmental problems such as the problem of recycling remains. It is only used for

On the other hand, as a method of developing gas barrier properties, Japanese Patent Application Laid-Open No. Hei 7-251489 discloses a gas barrier layer having a resin having a high hydrogen bonding property and an inorganic layered compound. However, in the gas barrier film obtained by such a technique, the high hydrogen bonding resin generally has a hydrophilic polar group, and the polar group easily forms a hydrogen bond with a water molecule, so that the resin itself easily swells. Also,
Since oxygen molecules easily pass through such swollen molecular chains, the gas barrier properties of the coating deteriorate, and it cannot be said that satisfactory gas barrier properties are necessarily obtained under high humidity conditions. To compensate for the lack of water resistance of such resins, when cross-linked with a cross-linking agent such as an epoxy compound,
Since the orientation of the main chain is disturbed and the overall density is reduced, a space for transmitting oxygen molecules is easily formed. As a result, gas barrier properties are reduced, and it is in principle difficult to achieve both water resistance and gas barrier properties.

Japanese Patent Application Laid-Open No. H11-129379 proposes a gas barrier laminate comprising a hydrolyzate of an inorganic layered compound, a resin and a metal alkoxide.
According to this method, a hydrolyzate of a metal alkoxide is further added to a coating mainly composed of an inorganic layered compound and a resin. However, in such a method, the hydrolyzate of the metal alkoxide added later rapidly condenses with the resin, and the reaction proceeds to form a random three-dimensional network structure. The gas barrier layer formed in this manner must be porous, and although an inorganic layered compound is added, a high barrier property cannot be expected.

There is also a method of obtaining a gas barrier laminate by applying an aqueous solution comprising an alkali metal silicate solution and a coupling agent to the surface of a polymer molded article to form a thin film (Japanese Patent Laid-Open No. Hei 8-238711). No.). This has the advantage that it can be manufactured at low cost without performing operations such as vapor deposition,
There are cases where the gas barrier properties are still insufficient, and there is a problem that the coating film strength and water resistance are weak.

Japanese Patent Application Laid-Open No. 7-18202 discloses that
There is a gas barrier laminate comprising a mixture of an aqueous solution of sodium silicate, which is an alkali metal silicate, and lithium silicate. It is difficult to say that these gas barrier films containing alkali metal silicate as a main component completely solve the problem of insufficient water resistance and cracks of the alkali metal silicate film. In particular, the occurrence of cracks is unavoidable, and if the gas barrier film thickness is increased in order to obtain gas barrier properties, cracks will occur immediately. It is difficult to say that the water resistance is perfect, and at present it is necessary to specify the environment in which the gas barrier laminate is used.

There is also a gas barrier film (JP-A-11-962) in which a gas barrier layer mainly comprising a condensate obtained by hydrolyzing a metal alkoxide which is one of silicic acid condensates is formed. Hydrolysis condensates of metal alkoxides include metal alkoxides such as tetraethoxysilane, titanium, aluminum, and zircon. Among them, a method for producing a silicic acid condensate from an alkoxysilane is generally called a sol-gel method, in which an alkoxysilane is hydrolyzed in an alcohol solvent such as ethanol in the presence of water. These alkoxysilane hydrolysis condensates can also have a structure very similar to alkali metal silicate condensates.

However, when a gas barrier layer containing a nitrogen-containing compound that undergoes a condensation reaction with a silicic acid condensate as in the present invention, the alkoxysilane hydrolyzate and the nitrogen-containing compound gel violently and become cloudy. In the worst case, the coating becomes impossible in addition to the failure. On the other hand, the property of easily condensing the hydrolyzate of the alkoxysilane becomes a disadvantage, resulting in poor dispersion of the pigment, generation of lumps (agglomerates) and an increase in paint viscosity.

[0011] Further, the hydrolysis condensate of the metal alkoxide has an amorphous structure during film formation and the condensation proceeds rapidly. Therefore, the film has many surface defects such as pinholes, and penetrates the gas barrier layer. At present, under the high-humidity condition, which is the object of the present invention, moisture tends to enter the surface of the support, causing problems such as a decrease in gas barrier properties and the gas barrier layer falling off the support. Was.

Further, Japanese Patent No. 2556940 discloses that a composition containing an alkoxysilane, a silane coupling agent and polyvinyl alcohol is polycondensed to form a gas barrier laminated film from a composite polymer whose main component is a linear polymer. Are described.
In this method, the hydroxyl group of polyvinyl alcohol is firmly bonded to the linear alkoxysilane hydrolyzate by crosslinking or hydrogen bonding by reacting the alkoxysilane and the silane coupling agent with polyvinyl alcohol under previously defined conditions. Thus, it is intended to prevent a decrease in gas barrier properties under high humidity. By this method, an attempt was made to improve the humidity dependency of a highly hydrogen-bonding resin represented by PVA and EVOH having a high humidity dependency. However, gas barrier properties under high humidity were still not sufficient.

On the other hand, the alkali metal silicate or colloidal silica, which is a silicic acid condensate, has ultra-fine particles whose primary particles are not more than nanometers or nanometers. In a solution, monomers, dimers, trimers, octomers, etc. , Which contain a large number of oligomers, etc., which are condensed.The particles have reactive functional groups on the surface, and not only can each particle be spread when forming a film, but also a condensation reaction occurs when dried, resulting in a uniform barrier film. There are advantages that can be made.

The present inventors have conducted intensive studies on a gas barrier layer using these silicic acid condensates, and have disclosed in Japanese Patent Application Nos.
Japanese Patent No. 6984 has filed an application for a gas barrier laminate in which cracks are prevented by combining a silicic acid condensate and a tabular pigment. However, the gas barrier layer composed of the silicic acid condensate and the plate-like pigment is not resistant to extreme deformation of the support, such as breakage and wrinkles, and a physical defect may be generated in the gas barrier layer. At present, it was necessary to specify use conditions.

[0015]

DISCLOSURE OF THE INVENTION The present invention provides a gas-barrier laminate which is improved in flexibility of a gas-barrier film using an alkali metal silicate or colloidal silica and a plate-like pigment, and which has excellent coating strength. Is what you do.

[0016]

For this purpose, the present invention has the following structure. 1. A gas barrier laminate having a gas barrier layer formed on at least one surface of a support, wherein the gas barrier layer contains the following components. (1) at least one kind of silicic acid condensate selected from alkali metal silicate or colloidal silica; (2) a reaction product of at least one kind selected from hydrolyzate or hydrolytic condensate of metal alkoxide with a hydrogen bonding resin (3) 1.) Nitrogen-containing compound that reacts with the silicic acid condensate (4) Tabular pigment After forming an organic layer containing a nitrogen-containing compound on the surface of a support having a polar group, on the organic layer, at least one silicic acid condensate selected from alkali metal silicate or colloidal silica, and a hydrolyzate of a metal alkoxide 2. The gas barrier according to claim 1, wherein a reaction product of at least one selected from a hydrolytic condensate and a hydrogen bonding resin and an inorganic layer containing a plate-like pigment are formed as a gas barrier layer. Laminate. 3. The metal of the metal alkoxide is Si, Al, Ti, Zr
The gas barrier laminate according to any one of claims 1 to 2, wherein the laminate is at least one kind selected from the group consisting of: 4. The gas barrier laminate according to any one of claims 1 to 3, wherein the gas barrier layer contains a water resistance improver. 5. The gas barrier laminate according to any one of claims 1 to 4, wherein the nitrogen-containing compound is at least one of polyalkylenimine and polyalkyleneamine. 6. Tabular pigments, smectite clay, phyllosilicate,
The gas barrier laminate according to any one of claims 1 to 5, wherein the laminate is at least one kind selected from synthetic mica. 7. The gas barrier laminate according to any one of claims 1 to 6, wherein a gas barrier layer is provided on the surface of the support having the metal thin film layer. 8. The gas barrier laminate according to any one of claims 1 to 7, wherein the support is made of a thermoplastic resin.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
A first aspect of the present invention relates to a gas barrier laminate having a gas barrier layer formed on at least one surface of a support. The support in the present invention is a film mainly composed of various resins, or a molded article of a plastic container having an arbitrary shape such as a bottle or a tray. Further, the gas barrier layer formed on the support is formed by hydrogen bonding with at least one kind selected from alkali metal silicates and colloidal silica, at least one kind selected from hydrolysates or hydrolysis condensates of metal alkoxides. A reactive resin, a nitrogen-containing compound that reacts with the silicic acid condensate, and a tabular pigment.

Among the silicic acid condensates, the alkali metal silicate is also called water glass, and sodium silicate,
Examples include lithium silicate, potassium silicate, and ammonium silicate. Colloidal silica is typically obtained by subjecting an alkali metal silicate to a dealkalization treatment using an ion exchange resin and then condensing the colloidal silica to form colloidal particles.

The silicic acid condensate is anionic in water, and exists as a dissolved monomer, dimer, trimer, tetramer or an oligomer obtained by condensing them. These silicic acid condensates cannot be easily condensed as a whole under low-temperature drying conditions of about 100 ° C., and have a disadvantage that gas barrier properties deteriorate with time and water resistance is insufficient because silanol groups remain. are doing. In particular, if left for a long period of time, it may fall off from the support or cracks may occur, causing a significant decrease in gas barrier properties.

When the silicic acid condensate is dried to form a film, the silanol groups condense to form siloxane bonds. For this reason, the volume of the coating shrinks, and the coating is peeled off from the support, falling off occurs frequently, and cracks occur frequently, so that only a very brittle coating is usually obtained.

As a result of intensive studies on this point, the present inventors have found that when a tabular pigment is used in combination with a silicic acid condensate, the tabular pigment exerts resistance to shrinkage of these films. That is, in the present invention, the occurrence of cracks accompanying the condensation of the silicate condensate can be prevented by mixing the plate-like pigment, and the strength of the film formed of the silicate condensate can be increased. Such an effect is not found in spherical pigments such as calcium carbonate, but is an effect peculiar to tabular pigments.

In the present invention, the tabular pigment is a two-dimensionally flat plate-like pigment having substantially flatness, and the ratio of the average particle diameter to the thickness (aspect ratio) thereof.
Means 5 or more.

Further, the flat pigment has not only the above-mentioned effects but also an effect peculiar to gas barrier properties. In the present invention, a silicate condensate and a flat pigment are blended in the gas barrier layer,
The gas is prevented from entering by laying flat pigments in the gas barrier layer like scales of fish. The plate-like pigment is an inorganic substance having crystallinity, and gas molecules do not permeate from the plane direction to the thickness direction.
In the present invention, such tabular pigments are spread. The so-called curved effect is exhibited, in which gas molecules to be permeated bypass and permeate the plate-like pigment by the plate-like pigment being piled up in the thickness direction of the layer, and a spherical shape such as calcium carbonate which is a general-purpose pigment is exhibited. The gas barrier properties expected from a gas barrier layer composed of a pigment and a silicic acid condensate close to the above can be significantly improved.

The tabular pigment used in the present invention is preferably an inorganic layered compound having a layered structure in which unit crystal layers are stacked on each other. A “layered compound” is a compound or substance having a layered structure. A “layered structure” refers to a surface in which atoms are strongly bonded by covalent bonds or the like and are densely arranged, and a weak binding force such as van der Waals force. Refers to pigments having a high flatness and a structure stacked in parallel with each other or bonded with ions.

Further, as a result of examining various substances for making the gas barrier layer containing the silicic acid condensate water resistant,
It has been found that surprisingly high water resistance and good gas barrier properties can be obtained by adding a silicic acid condensate and a nitrogen-containing compound such as polyethyleneimine. When the reason for this is examined in detail, the nitrogen-containing compound that undergoes a condensation reaction with such a silicic acid condensate not only reacts with silanol groups on the surface of the silicic acid condensate, but also forms hydroxyl ions and reacts. It has been found that it acts on non-silanol groups to promote condensation and newly expands the network of siloxane bonds, thus exhibiting surprising water resistance and high gas barrier properties. For this reason, the gas barrier layer containing the nitrogen-containing compound and the silicic acid condensate that undergoes a condensation reaction with the silicic acid condensate becomes a strong, dense, and water-resistant film.

However, the gas barrier layer made of the above-mentioned silicate condensate, tabular pigment, and nitrogen-containing compound which reacts with the silicate condensate has flexibility, especially under extreme deformation conditions such as breakage of a support and wrinkles. Problems remain with flexibility.

The present inventors have conducted further intensive studies on this point. As a result, the combined use of the hydrolyzate or hydrolyzed condensate of the metal alkoxide and the reaction product of the hydrogen bonding resin allows the gas barrier layer to be made flexible. It has been found that the durability of the gas barrier layer under extreme deformation conditions of the support is remarkably improved.

Here, hydrolysis condensation of metal alkoxide
The structure of the material is improved by means such as optimizing the amount of water added.
The structure is not a three-dimensional mesh, but a straight chain (the straight chain means
A structure in which four or more main chain Si-O units are arranged without branching
U. ) Is important. this
Stoichiometrically reacts with the hydrogen bonding resin to be mixed later
In order to proceed. Hydrolytic condensation of metal alkoxides
As a means to confirm that the product is linear,
State of nuclear magnetic resonance (²⁹Si-NMR, manufactured by JEOL: JN
M-LA400) for measurement and structural analysis
There is a law.²⁹Si-NMR shows peaks depending on the bonding state of Si.
Is separated, and the number of cross-linking oxygens
In the case where Si is not bonded with bridging oxygen, Q⁰, Crosslinking oxygen
Is bonded to one Si¹, Two cross-linking oxygens combine
Q which is Si^Two, Si to which three bridging oxygens are bonded
Q^Three, Si having four cross-linking oxygens bonded to Q^FourAnd so on
And the structure is estimated from the ratio. Metal alkoki
If the hydrolyzed condensates of sides are all linear,
Q is Q¹, Q^TwoConsists only of Explain in more detail
And Q¹+ Q^TwoIs larger, the more linear molecules are, the Q^Twoof
The larger the ratio, the longer one molecular chain. In the present invention,
(Q of the hydrolyzed condensate of metal alkoxide ¹+ Q^Two) /
(Q⁰+ Q¹+ Q^Two+ Q^Three+ Q^Four) Is more than 60%
It is preferably at least 70%, more preferably at least 80%.
You. Furthermore, Q^Two/ (Q¹+ Q^Two) Is more than 50%
Generally, the length of the main chain is 4 or more as Si-O,
It is thought that they are lined up without.

Starting from a linear hydrolysis condensate or hydrolyzate of a metal alkoxide or a commercially available linear metal alkoxide, a hydrogen-bonding resin is added thereto, and the desired product is obtained by polycondensation. A reaction product having a linear or similar structure, ie, a polycondensation polymer, is obtained. By adding this polycondensation polymer to the above-mentioned silicic acid condensate, tabular pigment, and gas barrier layer composed of a nitrogen-containing compound, the flexibility and the gas barrier layer composed of the conventional silicic acid condensate could not be reached at all. The present inventors have found that coating film strength can be added, and have reached the present invention.

The alkali metal silicate described above will be described in detail below. The alkali metal silicate is M ₂ O.nSiO ₂
(M is an alkali metal salt, n> 0). The alkali metal M of the alkali metal silicate is lithium,
It is an alkali metal such as sodium or potassium or a cationic ion such as ammonium. The alkali metal silicate is usually handled as a concentrated aqueous solution. n is also called a molar ratio and usually has a value of about 0.5 to 10. If it is less than 0.5, the amount of alkali metal is too large and the water resistance is reduced. If it exceeds 10, cracks cannot be prevented.

The above-mentioned colloidal silica will be described in detail below. Colloidal silica is made by neutralizing sodium silicate with an inorganic acid at room temperature, hydrolyzing silicon esters and silicon halides, passing alkali metal silicates such as sodium silicate through a cation ion exchange resin layer, and then adjusting the pH with alkali. And then heating to produce colloidal silica nuclei, and then slowly dropping the sodium silicate solution through the cation exchange resin layer into the solution. If the dropping speed is increased rapidly, condensation rapidly proceeds, and aggregation is generated, resulting in a porous structure, which is not preferable. When the solution is slowly dropped, monomers are sequentially deposited on silanol groups on the nucleus surface, and particles grow. By adjusting the pH appropriately and slowing down the dropping rate, it is possible to grow from several nm to several μm. The colloidal silica thus grown preferably has a particle size of several nm to several hundred nm. Further, the packing ratio can be increased by combining colloidal silicas having different particle diameters.

Further, by adding various alkali metal hydroxides to amorphous silica or colloidal silica and dissolving the same, it is possible to prepare an alkali metal silicate having a higher molar ratio. Such an alkali metal silicate salt having a molar ratio as high as 100 can be used in the present invention. Cracks are likely to occur when such a high molar ratio alkali metal silicate is used. However, a very thin plate-like pigment having a specific shape is used, or a very thin film of 2 μm or less is formed. Cracks can be prevented by making the shrinkage in the thickness direction approximately equal to the shrinkage of the surface.

In selecting the alkali metal silicate and colloidal silica as the silicic acid condensate, the alkali metal silicate is more preferable from the viewpoint of gas barrier properties only. As the alkali metal silicate used in the present invention, for example, when the alkali metal is sodium such as sodium silicate, sodium orthosilicate having a molar ratio of 0.5 (Na ₂ O.1 / 2SiO ₂ or Na ₄ SiO ₂₎
4), a sodium sesquisilicate having a molar ratio of 0.67 (3Na
₂ O · 2SiO ₂ or Na ₆ Si ₂ O ₇ ), sodium metasilicate (Na ₂ O · SiO ₂ or Na ₂
SiO ₃ ), sodium disilicate with a molar ratio of 2 (Na ₂ O · 2)
SiO ₂ or Na ₂ Si ₂ O ₅ ), sodium tetrasilicate (Na ₂ O · 4SiO ₂ or Na ₂ Si) having a molar ratio of 4
₄ O ₉ (alias: sodium silicate No. 4), etc., and sodium silicate No. 1 (molar ratio 2), No. 2 (molar ratio 2.5), 3 specified in Japanese Industrial Standard JIS-K-1408 No. (molar ratio 3), one kind of sodium metasilicate and two kinds of sodium metasilicate.

Also, potassium silicate, whose alkali metal is potassium, has various compositions, but potassium metasilicate (K ₂ O.SiO ₂ ) and potassium tetrasilicate (K
_{2 O · 4SiO 2 · H 2} O, also known as disilicate potassium) and the like. Lithium silicate in which the alkali metal is lithium is lithium orthosilicate (Li ₂ O · 1 / 2Si).
2. O ₂ ), lithium metasilicate (Li ₂ O.SiO ₂ );
Lithium pentasilicate, 7.5 lithium silicate (Li ₂ O · 7.
5SiO ₂ ).

Also, for example, ammonium salts such as ammonium silicate having tetramethylammonium ion as a counter ion are included in the scope of the present invention.

The alkali metal silicate has a different degree of condensation and a different particle size depending on the molar ratio. The size cannot be clearly determined because the solubility in the liquid increases as the molar ratio decreases, but the dynamic light scattering method (photon correlation method) includes a portion estimated to be several nm and several tens of It is estimated to be on the order of nm and can be densely packed as a gas barrier layer.

The alkali metal silicate used in the present invention can be arbitrarily selected from the above alkali metal silicates. Further, two or more kinds of alkali metal silicates can be used in combination.

The phyllosilicate mineral can be mentioned first as a tabular pigment used in the present invention. Those belonging to phyllosilicate minerals are plate-like or flaky and have distinct cleavage properties, mica, pyrophyllite, talc, chlorite, septe chlorite, serpentine, stilp-nomelane, There are clay minerals and the like. Among these, minerals having a large particle size and a large amount of output, such as mica and talc, are preferred. Mica includes muscovite (muscovite), sericite (sericite), biotite (flokopite), biotite (biotite), fluorophlogopite (artificial mica), red mica, soda mica, vanadin mica, illite, Chin mica, paragonite, brittle mica and the like. Synthetic products such as synthetic mica that are similar in composition to talc are also included in the scope of the present invention.

Kaolin, which is one of the commonly used pigments, is generally referred to as tabular crystals. However, if one crystal is taken, there is a flat part, but the whole is granular. However, among kaolins, delamikaolin, which is intentionally peeled off from the crystal layer and cut into flat plates, can be used as the flat pigment in the present invention. In the case of such kaolin, the particle diameter of the pigment used for the gas barrier layer may need to be reduced in accordance with the film thickness, and these pigments may be crushed by a pulverizer such as a ball mill, a sand grinder, a cobol mill, and a jet mill. It is necessary to classify by pulverization with a desired size.

As the second of the tabular pigments used in the present invention,
A so-called inorganic layered compound having a stacked structure and high tabularity bonded by ions can be given. Specific examples of the inorganic layered compound include graphite, a phosphate derivative-type compound (zirconium phosphate-based compound), and a chalcogen compound [a dichalcogen compound represented by the formula MX2. Here, M is a group IV (Ti, Zr, H
f), Group V (V, Nb, Ta) or Group VI (Mo,
W) represents an element, and X represents a chalcogen (S, Se, Te). ].

As a third of the tabular pigments used in the present invention,
Examples include clay minerals such as smectites and vermiculites. More specifically, dickite,
Nacryte, smectite, halloysite, antigorite, chrysotile, pyrophyllite, tetrasilyl mica, sodium teniolite, margarite,
Vermiculite, zansophyllite, chlorite and the like can be mentioned.

Of these, smectite clay (smectite) is particularly preferred. Smectite clay consists of three-layered crystals, montmorillonite, beidellite,
Nontrolite, saponite, iron saponite, hectorite, sauconite, stippnsite, hectite and the like are known.

These smectite clays are fine powders of pale yellow or white and have a size of several nm to several μm.
It swells in water to create a unique colloidal structure. For example,
Montmorillonite has a three-layer structure in which an alumina layer is sandwiched between two silicas as one unit, and the flakes are connected via water. In an aqueous solution, the flakes are separated because of the water between the flakes.

In general, smectite clay easily forms a colloidal dispersion, that is, a sol, when dispersed in water. However, as the concentration increases, it becomes easier to form a gel and exhibits remarkable thixotropic properties. For this reason, it is difficult to prepare a smectite clay dispersion having a high concentration. However, by adding a deflocculant, a stable fluid dispersion (sol)
And the viscosity can be reduced. Examples of the deflocculant to be added include polyvalent phosphates such as hexametaphosphate and polyphosphate (such as sodium pyrophosphate). In particular, sodium pyrophosphate is preferable because of its excellent performance / price ratio.

The particle size of the tabular pigment used in the present invention is preferably between 10 nm and 5 μm, and more preferably between about 20 nm and 1 μm. When the thickness is less than 10 nm, the particle diameter is too small with respect to the thickness of the formed gas barrier layer, and the flat pigments are randomly aligned in the gas barrier layer without being arranged parallel to the support. Does not work effectively and it is difficult to show a curved road effect. On the other hand, when the thickness exceeds 5 μm, the pigment is protruded from the surface of the coating layer to cause poor appearance, and the film formability is deteriorated and gas molecules are easily passed, which is not preferable.

When the gas barrier laminate requires transparency, it is more preferable that the tabular pigment has a particle size of 1 μm or less. When the support is a film and is used for applications where transparency is extremely important (for example, food applications), the particle size is particularly preferably 0.5 μm or less. In this case, the transparency is 80% or more in total light transmittance at a wavelength of 500 nm, more preferably 85% or more,
The haze is in the range of 1 to 10%, more preferably 2 to 5%. The transparency can be suitably measured by a commercially available spectrophotometer (manufactured by Shimadzu Corporation: Shimadzu UV-3100PC type spectrophotometer).

More specifically, from the viewpoint of gas barrier properties, the tabular pigment preferably has an aspect ratio, which is a value obtained by dividing the average particle diameter by the thickness, of 5 or more.
Furthermore, it is particularly preferable that it is 20 or more. If the aspect ratio is less than 5, the curved path effect is small and the gas barrier property is insufficiently exhibited. On the other hand, it is technically difficult to obtain an inorganic layered compound having an aspect ratio exceeding 1000, and it is economically expensive, which is not preferable. This aspect ratio is preferably 1,000 or less from the viewpoint of easy production of the pigment. The particle size of the plate-like pigment can be measured by a light scattering method, but in the present invention, the mica group is directly dispersed using a transmission electron microscope or a scanning electron microscope, and the swellable pigment is dispersed in water. The swollen product was observed as a dried sample, and the average particle size and thickness were determined.

The ratio of the silicic acid condensate to the tabular pigment is in the range of 95/5 to 5/95 by mass. When a tabular pigment is used alone, for example, smectite clay such as montmorillonite can form a film due to its tabularity and surface charge. However, the strength of the film is low and the water resistance is low, so that the film is not practical as a gas barrier laminate. Therefore, it is necessary to reinforce with a silicic acid condensate. On the other hand, when a silicic acid condensate is used alone, the coating tends to crack with the condensation. However, the generation of cracks can be greatly reduced by adding a flat pigment. As described above, the silicic acid condensate and the tabular pigment work to compensate for each other. The mixing ratio between the silicic acid condensate and the tabular pigment can be in a wide range as described above depending on the situation. From a comprehensive viewpoint of film strength and prevention of cracks, the ratio of the silicic acid condensate to the tabular pigment is preferably about 80/20 to 40/60 by mass.

Examples of the nitrogen-containing compound that undergoes a condensation reaction with the alkali metal silicate or colloidal silica used in the present invention include cationic organic compounds. Silicic acid condensates such as alkali metal silicates have both silanol groups and dissociated silanol ions in the alkaline region, and these functional groups condense to form siloxane bonds. A cationic organic compound is one that promotes these condensation reactions. The present inventors have found a specific reaction between these cationic organic compounds and silicic acid condensates. For example, in the case of polyamines, by those compounds containing a nitrogen atom therein, the silicate condensate with a nitrogen-containing compound ~Si-O ^- H ⁺ and an amine group _{(R-NH 2, R-} NH-R ' , R-NR'-R ", wherein R, R ', R": an alkyl group) and the like react directly,
It gels in the form of -O-NH-R ~. Silicic acid condensate is O
^{H - ... H: N + H} 2 -R OH resulting dissociated by an amine in the form of ^- is urged condensation acts to silanol bonds silicate condensate, network of the siloxane bond to generate a new siloxane bond It seems to form

Representative of these nitrogen-containing compounds are those referred to as imine compounds and amine compounds. Among these, polyalkylene imines are typical examples of the imine compound, such as polyethylene imine, alkyl or cyclopentyl-modified polyethylene imine, imine adduct of ethylene urea, ethylene imine adduct of poly (ethylene imine-urea) and polyamine polyamide, or
There is a polyimine-based compound selected from the group consisting of these alkyl-modified, alkenyl-modified, benzyl-modified or aliphatic cyclic hydrocarbon-modified, polyamideimide, and polyimide varnish.

As the amine compound, there is a polyalkylene polyamine. For example, polyethylene polyamine,
Compounds such as ethylenediamine, diethylenetriamine, and triethylenetetramine. Polyamides such as compounds such as polyethylene imide adducts of polyamides exhibit similar effects. Hydrazine compounds.
Epichlorohydrin adduct of polyamine polyamide (a water-soluble, cationic thermosetting resin obtained by reacting a polyamide with epichlorohydrin from a saturated dibasic carboxylic acid having 3 to 10 carbon atoms and a polyalkylene polyamine), etc. A polyamine amide compound. There are quaternary nitrogen-containing acrylic polymers, quaternary nitrogen-containing benzyl polymers, urethanes, compounds having an amine carboxylate group, nitrogen-containing quaternary salt compounds such as compounds such as melamine and cationic polyurethane. Further, cationic resins such as a cation-modified polyurethane resin, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymer, and a tertiary nitrogen-containing acrylic resin can be used (for the cationic resin, JP-A-8-90898, 63-1
62275 and JP-A-62-148292). Further, urea compounds such as urea, thiourea, guanylurea, methylurea, and dimethylurea, and dicyandiamide derivatives are also included in the scope of the present invention.

More specifically, the polyalkyleneimine used in the present invention is preferably polyethyleneimine or polypropyleneimine, and particularly preferably polyethyleneimine. These polyalkyleneimines may be used alone, or may be used after forming a salt with acetic acid, p-toluenesulfonic acid, sulfuric acid, hydrochloric acid or the like.

The organic amine compound may be any of a primary amine compound, a secondary amine compound, a tertiary amine compound, and a quaternary ammonium salt compound, and may be any of an organic monoamine and an organic polyamine. It may be. Further, the organic amine compound includes those having a different functional group other than the amino group, for example, an epoxy group, a hydroxyl group, a carboxylic acid group, a nitrile group and the like.

Examples of the modified organic amine compounds include adducts of compounds having an epoxy group such as monoepoxy compounds and diepoxy compounds with amine compounds, adducts of compounds having a hydroxyl group such as ethylene oxide and propylene oxide with amine compounds, and acrylic compounds. Examples include a Michael adduct of a nitrile and an amine compound, and an adduct obtained by a Mannich reaction of a phenol compound, an aldehyde compound, and an amine compound.

The above-mentioned modifications include 1) reducing the toxicity of the amine compound such as irritating odor and skin irritation, 2) reducing the viscosity of the amine compound, and 3) increasing the molecular weight and weighing. There are effects such as reducing the error. The degree of modification of the amine compound is not particularly limited.

The following are examples of the organic amine compound used in the present invention. 1) Aliphatic polyamine (polyalkylene polyamine) or monoamine: ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, iminobis-propylamine, bis (hexamethylene) triamine, dimethylaminopropylamine, Diethylaminopropylamine, aminoethylethanolamine, methyliminobispropylamine, menthanediamine-3, N-aminoethylpiperazine, 1,3-diaminocyclohexane, isophoronediamine, triethylenediamine, polyvinylamine, stearylamine, laurylamine and the like. 2) Aromatic polyamine or monoamine: m-phenylenediamine, 4,4'-methylenedianiline, benzidine, diaminodiphenyl ether, 4,4'-thiodianiline, dianisidine, 2,4-toluenediamine, diaminodiphenylsulfone, 4,4 '-(O-toluidine), o-phenylenediamine, methylenebis (o-chloroaniline), m-aminobenzylamine, aniline and the like. 3) Aliphatic polyamine or monoamine having an aromatic ring group: metaxylylenediamine, tetrachloroxylenediamine, trimethylaminomethylphenol, benzyldimethylamine, α-methylbenzyldimethylamine and the like. 4) Secondary amine: N-methylpiperazine, piperidine, hydroxyethylpiperazine, pyrrolidine, morpholine and the like. 5) Tertiary amines: tetramethylguanidine, triethanolamine, N, N'-dimethylpiperazine, N-methylmorpholine, hexamethylenetetramine, triethylenediamine, 1-hydroxyethyl-2-heptadecylglyoxalidine, pyridine, Pyrazine, quinoline, etc. 6) Quaternary ammonium salts: diallyldimethylammonium chloride, hexyltrimethylammonium chloride, cyclohexyltrimethylammonium chloride, octyltrimethylammonium bromide, 2
-Ethylhexyltrimethylammonium bromide,
1,3-bis (trimethylammoniomethyl) cyclohexane dichloride, lauryldimethylbenzylammonium chloride, stearyldimethylbenzylammonium chloride, tetradecyldimethylbenzylammonium chloride and the like. Examples of the amines include amines described in JP-A-10-226989.

The nitrogen-containing compound that undergoes a condensation reaction with the silicic acid condensate used in the present invention is preferably water-soluble. However, even if it is insoluble in water, it can be used by emulsification or dispersion treatment. The nitrogen-containing compounds may be used as a mixture of two or more kinds.

The nitrogen-containing compound in the gas barrier layer is preferably in the range of 0.01 to 50 parts, more preferably 0.1 to 2 parts, per 100 parts by mass of the total of the silicic acid condensate and the tabular pigment.
0 parts is more preferable, and 0.5 to 10 parts is further preferable. When the amount is less than 0.01 part, the degree of the condensation reaction with respect to the silicic acid condensate is insufficient, so that the water resistance may be insufficient. When the amount exceeds 50 parts, the condensation reaction proceeds too much and the gelling layer is too large. Gas barrier properties decrease.

In the present invention, the reaction product of the hydrolyzate or hydrolyzed condensate of the metal alkoxide and the hydrogen bonding resin in the gas barrier layer is obtained by combining the silicate condensate, the plate-like pigment and the nitrogen-containing compound. On the other hand, the mass ratio is preferably about 30/70 to 70/30.

The concentration of the coating liquid for forming the gas barrier layer is 1
It is about 20%, preferably about 3% to 10%, and can be appropriately selected depending on the coating method. The thickness of the gas barrier layer is preferably 0.1 to 5 μm, and 0.2 to 3 μm.
Is more preferable, and 0.6 to 2 μm is more preferable. When the film thickness is less than 0.1 μm, pinholes are easily generated in the gas barrier film due to unevenness of the surface of the support. Also, 5
If the thickness exceeds μm, not only cracks are easily generated, but also the gas barrier film is likely to fall off, which is economically disadvantageous, which is not preferable.

The second aspect of the present invention is a method for forming the gas barrier layer according to the first aspect. In the present application, as described below,
After forming a polar group on the surface of the support, a layer comprising a nitrogen-containing compound which reacts with the polar group is formed, and a gas barrier layer is formed thereon. Conventionally, when a functional layer is formed thereon using a thermoplastic resin as a support, in order to improve the adhesion with the support, a treatment with a chlorinated acid solution, a corona discharge treatment, a flame treatment, a silane coupling agent treatment. A method of imparting a polar group to the surface of a support by a physical treatment such as a titanium coupling agent treatment, an ionomer layer forming treatment, a polycation treatment, or a chemical treatment is known.

Among these methods for treating the surface of the support, corona discharge treatment is known as a method for producing a carboxyl group or a carbonyl group. Further, a sulfone group can be generated by a method of treating the support surface with fuming sulfuric acid or the like, and a plasma treatment in a nitrogen gas atmosphere is performed to form a nitrogen-containing group. These are all hydrophilization treatments of the support surface, and can improve the adhesion of a coating solution using an aqueous solvent as in the present invention. In particular, when an organic layer containing a nitrogen-containing compound such as polyalkyleneimine or polyalkyleneamine is formed on the surface of the support, adhesion to the surface of the support is particularly increased if a polar group is provided to the support by such treatment. Good and preferred.

The present inventors have also diligently studied a method for greatly improving the adhesion between the support and the gas barrier layer. As a result, a method in which an organic layer is formed on the surface of a support with a nitrogen-containing compound represented by polyethyleneimine or polyamine to form an anchor layer, and then an inorganic layer is sequentially formed thereon to form a gas barrier layer, is a method of forming an organic layer. Reacts with the polar group on the surface of the support due to the ionicity of the nitrogen-containing compound, and not only strongly adheres to the support, but also forms a hydrolyzate or hydrolyzed condensate of the metal alkoxide contained in the inorganic layer formed thereon. It has been found that it is possible to form a gas barrier layer having high adhesion to the support by interacting with the anionic property of the support and firmly fixing the inorganic layer. As described above, the support and the gas barrier layer can be firmly linked by the two reactions of the reaction between the polar group on the support and the nitrogen-containing compound and the reaction between the nitrogen-containing compound and the metal alkoxide. In particular, without completely causing the reaction between the polar group on the support surface and the layer containing the nitrogen-containing compound, the amount of the polar group on the support surface was controlled so as to leave a part of the nitrogen-containing compound, and thus obtained. The gas barrier property in the present invention is further improved by adopting a structure in which a part of the nitrogen-containing compound is partially dissolved in the aqueous solution of the inorganic layer.

The third aspect of the present invention is that the metal of the metal alkoxide is
At least one of Si, Al, Ti, and Zr
Is Rukoto. These metal alkoxides include Al
Coxysilane (Si (OR)_Four), Aluminum arco
Oxide (Al (OR)_Three), Titanium alkoxide
(Ti (OR)_Four), Zirconium alkoxide (Zr
(OR)_Four). More specifically,
Alkoxysilane, tetramethoxysilane (Si (OC
H_Three)_Four), Tetraethoxysilane (Si (OC
_TwoH_Five)_Four). Specific examples of aluminum alkoxide
As aluminum triisopropoxide (Al (O
-2'-C _ThreeH₇)_Three). Titanium Arco
The oxide is (Ti (OCH_Three)_Four), (Ti (OC
_TwoH_Five)_Four), (Ti (OC)_ThreeH₇)_Four), (Ti (OC)
_FourH₉)_Four), Zirconium alkoxide is (Zr (OC
H_Three)_Four), (Zr (OC_TwoH_Five)_Four), (Zr (O-is
oC_ThreeH₇)_Four), (Zr (OC)_FourH₉)_Four)
It is. These metal alkoxides are obtained by mixing two or more kinds.
You can use it.

In the gas barrier laminate of the present invention, when used under particularly severe temperature and humidity conditions, the gas barrier layer, particularly the organic layer containing the nitrogen-containing compound, melts out at high humidity, resulting in a gas barrier layer. In some cases, the barrier layer may be peeled off from the support. In order to further improve the water resistance of the gas barrier layer, as a fourth aspect of the present invention, a water resistance improver is added to the gas barrier layer. The water resistance improver may be added by any means as long as it is present in the gas barrier layer, but it is particularly desirable to add it to the organic layer. By adding a water-proofing agent, the water resistance of the organic layer itself is improved, and even under severe high-humidity conditions, the gas barrier layer can be prevented from peeling off from the support without eluting the organic layer. . Also,
Since the organic layer containing the water resistance improver itself is crosslinked to increase the strength, a strong heat seal strength can be obtained when the organic layer is applied to a heat sealable film requiring strength between layers. It is a particularly preferred embodiment that the organic layer contains a water resistance improver.

In the present invention, the water resistance improver is primarily an epoxy compound. Epoxy compounds are mono,
It is an epoxy compound containing several epoxy groups such as di and tri. This epoxy compound includes an aliphatic epoxy compound and an aromatic epoxy compound, for example, butylene oxide, octylene oxide, butyl glycidyl ether, styrene oxide, phenyl glycidyl ether, glycidyl methacrylate, allyl glycidyl ether, phenol polyethylene glycol glycidyl ether, Lauryl alcohol polyethylene glycol glycidyl ether and the like.

Also, polyamidoamine-epihalohydrin or formaldehyde condensation reaction product, polyamine-epihalohydrin or formaldehyde condensation reaction product, polyamide polyurea-epihalohydrin or formaldehyde condensation reaction product, polyamine polyurea
An epihalohydrin or formaldehyde condensation reaction product and a polyamidoamine polyurea-epihalohydrin or formaldehyde condensation reaction product can be used alone or in combination.

The above condensation reaction product has an amino group in its molecular skeleton and has an epoxy ring or a methylol group in a side chain thereof. Generally, the following components: (i) polyalkylene polyamine, (ii) urea , (Iii) dibasic carboxylic acids, (iv) epihalohydrins or formaldehyde to react (for example, Japanese Patent Publication No. 52-22982, Japanese Patent Publication No. 60-3194).
No. 8, JP-B-61-39435, JP-A-55-127
423).

The compounding ratio of the nitrogen-containing compound to the water resistance improver is 99.9 / 0.1 to 5/95, preferably about 99/1 to 20/80, by mass. Since the preferred ratio greatly varies depending on the reactivity of each nitrogen-containing compound and the molar ratio of the nitrogen atom when copolymerized, it is most preferable to use the ratio appropriately ascertained.

Examples of the water-resistant agent added to make the organic layer water-resistant include acids (eg, hydrochloric acid, sulfuric acid, borofluoric acid, acetic acid, glycolic acid, maleic acid, lactic acid, citric acid, tartaric acid, oxalic acid) And the like, metal salts (eg, magnesium chloride, magnesium nitrate, magnesium borofluoride, zinc borofluoride, zinc chloride, zinc nitrate, sodium bisulfate), ammonium chloride, and the like, and these are used alone or in combination.

A fifth aspect of the present invention is to use at least one of polyalkyleneimine and polyalkyleneamine as the nitrogen-containing compound that undergoes a condensation reaction with the silicic acid condensate. Polyalkylenimine is a basic compound containing a nitrogen atom in the main chain skeleton or in the branched chain skeleton of a molecule and having a high nitrogen content, and a molecular weight of about 10,000 is known. The polyalkyleneamine is an amine having a primary amine, a secondary amine, or a tertiary amine in a side chain, and has a molecular weight of about 300 to about 50,000. When these have a molecular weight of tens of thousands, they do not readily dissolve themselves, but oligomers are easily dissolved in water, and thus are preferably used in combination with a water resistance improver.

A sixth aspect of the present invention is that the pigment used in the present invention is at least one selected from smectite clay, phyllosilicate, and synthetic mica. All of these pigments have high flatness and not only prevent shrinkage of the film due to the condensation reaction of the silicic acid condensate, but also have the effect of increasing the permeation distance of oxygen molecules and increasing the effective film thickness due to the curving effect. Particularly preferred.

A seventh aspect of the present invention is to form a gas barrier layer of the present invention after forming a metal or metal oxide thin film on the surface of a support. The metal forming the metal thin film is not particularly limited, but is preferably a metal that is stable in air, and aluminum or the like whose film surface is oxidized and stabilized after the thin film is formed is preferably used. As the metal oxide, aluminum oxide, silicon oxide, titanium oxide, zinc oxide and the like are preferable, and their oxidation states may be various. The film thickness of these metal or metal oxide thin films is 1 nm to 1000 nm.
The range of nm is preferred. The range of 10 nm to 300 nm is more preferable.

The method for forming the metal or metal oxide thin film on the surface of the support is not particularly limited, and a CVD method, a sputtering method, or the like may be used in addition to a general vacuum deposition method. The support on which the metal or metal oxide thin film is formed is not particularly limited, but biaxially oriented polyethylene terephthalate, biaxially oriented nylon, biaxially oriented polypropylene and the like are preferably used. To laminate a layer containing a plate-like pigment on a metal or metal oxide thin film layer,
A coating containing a nitrogen-containing compound is applied and dried as an anchor layer to form an organic layer, and then a coating comprising a silicic acid condensate and a flat pigment is applied and dried in the same manner to form a gas barrier layer. At this time, a heat treatment or the like may be performed if necessary.

The eighth aspect of the present invention is that the support of the gas barrier laminate is made of polyolefin such as polyethylene or polypropylene, polyester, polyamide, polycarbonate, or the like.
It is a thermoplastic resin such as polynaphthalene.
The support is a film or a molded body. The molded article includes a bottle, a container, a tray, a can, and the like. In addition, it is preferable that the surface of these supports is treated so as to have at least one functional group selected from a carboxyl group, a carbonyl group, a sulfone group and oxygen nitride, and then the gas barrier layer of the present invention is formed.

The gas barrier laminate of the present invention has a temperature of 23 ° C.
Oxygen permeability at 90% RH is 30 cc / m ² · da
It is preferably not more than y · atm, more preferably 10 cc / m ² · day · atm, and if it is not more than this value, the oxygen permeability is low enough to be practically usable as a gas barrier laminate. It is. The oxygen permeability was measured using OX-TRAN / 100 model of MOCON.

In the present invention, in the gas barrier layer, a color adjusting agent, a viscosity adjusting agent, an inorganic pigment, an organic pigment (plastic pigment), and various hardeners of alkali metal silicates (carbonate, sulfate, hydrochloric acid). Inorganic salts such as salts, nitrates, phosphates and silicates; mineral acids such as nitric acid, phosphoric acid, hydrochloric acid and sulfuric acid; organic acids such as lactic acid, humic acid and oxalic acid; polyaluminum chloride and polyphosphoric acid Phosphoric acid compounds such as aluminum hydrogen and sodium hexametaphosphate, metal oxides such as zinc oxide and titanium oxide, and metal hydroxides such as aluminum hydroxide and magnesium hydroxide) can be added as necessary. . Further, for example, a compound such as a titanium coupling agent, a silane coupling agent, a melamine coupling agent, an epoxy coupling agent, an isocyanate coupling agent, a copper compound, and a zirconia compound may be added as a crosslinking agent. it can.

Further, a resin may be added to the gas barrier layer of the present invention as long as its properties are not impaired. Although the resin used in the present invention is not particularly limited, for example, polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), polyvinylidene chloride (PVDC), polyacrylonitrile (PAN), polysaccharide, polyacryl Acids and esters thereof.

Further, the support of the present invention includes an antioxidant, a weather resistance stabilizer, a light stabilizer, an antistatic agent, a pigment, a dye, a plasticizer, a flame retardant, an inorganic filler such as silica, alumina, calcium carbonate, It may contain talc, kaolin, clay, zeolite, mica, carbon black, glass fiber and the like.

The application of the gas barrier laminate of the present invention is mainly used for packaging, and the food applications include miso, pickles, side dishes, baby food, boiled tsukudani,
Konjac, Chikuwa, Kamaboko, processed fishery products, meatballs, hamburgers, seasoned meat for Genghis Khan, ham, sausage, other processed meat products, green tea, coffee, tea, bonito flakes, oily confectionery such as toro kombu, potato chips, butter peanuts, rice It can be widely used in confectionery, biscuits, cookies, cakes, buns, castella, cheese, butter, cut rice cakes, soups, sauces, ramen, and the like. In addition, pet food, pesticides, fertilizers, infusion packs, semiconductor packaging, oxidizing chemical packaging, precision material packaging, medical, electronic,
It is used for a wide range of applications such as packaging of industrial materials such as chemicals and machinery.

The gas-barrier laminate of the present invention comprises a support, on the surface of which a silicic acid condensate, a hydrolyzate of a metal alkoxide or a reaction product of a hydrolytic condensate and a hydrogen bonding resin, a nitrogen-containing compound, It is obtained by applying and drying a paint containing a pigment. Examples of the coating method include a direct gravure method, a reverse gravure method, a microgravure method, a roll coating method such as a two-roll beat coating method, a bottom feed three-reverse coating method, a doctor knife method, a die coating method, a dip coating method, and a bar coating method. Coating methods include kiss coating, lip coating, blade coating, air knife coating, dipping, and brush coating. In addition, a method such as a coating method in which these are combined may be mentioned, but it is not limited to these methods.

Examples of the drying method include drying with hot air, drying with dry air, drying with infrared rays, drying with microwaves, drying with a gas burner, and drying with a combination of two or more of these methods. It is not limited. Further, the paint may be applied twice or more. The drying temperature is not particularly limited, but is preferably 50 ° C to 300 ° C, more preferably 70 ° C.
C. to 200C, more preferably 90C to 150C. When a thermoplastic resin is used for the support, it is necessary to dry at a temperature lower than its melting point, so that low-temperature drying is desirable. For a polyester resin, 70 to 200 ° C is preferable, and for a polypropylene film, 40 to 150 ° C is preferable. If the drying temperature is less than 50 ° C., condensation of silicate ions is insufficient, and water resistance and barrier properties are insufficient. When a thermoplastic resin is used as a support, drying at a temperature higher than its melting point is not preferable because the strength of the support deteriorates and the color tone changes.

[0083]

The present invention will be specifically described below with reference to examples. The blending, concentration, addition amount, and the like are numerical values based on mass.

The following paints and paints and supports (a) and (b) were prepared as gas barrier laminate materials. Paint: 64 g of aqueous solution of lithium silicate (molar ratio: 3.5)
Product name: Lithium silicate 35, Li ₂ O component 2.91%,
20.74% of SiO ₂ component, pH 10.89, specific gravity 1.
209, 11.7 cps (25 ° C., manufactured by Nippon Chemical Industry Co., Ltd.), 36 g of water and 15 g of bentonite
(Trade name: Kunipia F; manufactured by Kunimine Industries Co., Ltd., average particle diameter: 520 nm, main component montmorillonite, water content: 7%) dispersed in 485 g of water and mixed with a homomixer to form an aqueous solution of an alkali silicate and a flat pigment dispersion. Prepared paint. Paint: 64 g of aqueous solution of lithium silicate (molar ratio: 3.5)
Product name: Lithium silicate 35, Li ₂ O component 2.91%,
20.74% of SiO ₂ component, pH 10.89, specific gravity 1.
209, a viscosity of 11.7 cps (25 ° C .; manufactured by Nippon Chemical Industry Co., Ltd.) and 36 g of water were added to the aqueous solution, and synthetic mica 300
g (NTS-5, swellable fluorotetrasilicic mica, solid content 5%,
pH 9.2, viscosity 80 cps (25 ° C.), aspect ratio 500-1000, true specific gravity 2.65 g / cc, Mohs hardness 3.0, particle size 2.2 μm; Paint prepared as a tabular pigment dispersion. Paint: 30 g of tetraethoxysilane (Wako Pure Chemical Industries)
30 g of ethanol, 2.21 g of 2N hydrochloric acid and 1.75 g of water were mixed and stirred at 80 ° C. for 1 hour to prepare a linear hydrolyzed condensate ( ²⁹ SiNMR).
From (Q ₁ + Q ₂ ) / (Q ₀ + Q ₁ + Q ₂ + Q ₃ ) = 75%,
Q ₂ / (Q ₁ + Q ₂ ) = 80%, which was confirmed to be linear), and 168 g of 10% PVA aqueous solution (Poval PVA-117, saponification degree 98.0 to 99.0%,
Polymerization degree 1700; manufactured by Kuraray Co., Ltd.) and stirred for 1 to 2 hours to obtain a reaction product of a metal alkoxide condensate and PVA. (A reaction product of the hydrolysis condensate of metal alkoxide and PVA was analyzed by FT-IR, and it was confirmed that the absorption of hydroxyl groups of PVA was reduced to 50% in peak area ratio, and that a condensation reaction occurred between the two. Support (a): Biaxially stretched polypropylene film (OP
P) Corona treatment on one side of 25 μm (test machine: output 0.
8 kw, 10 m / min), and 10 g of polyethylene imine (trade name; Epomin P-1000, 30) as an anchor layer
% Polyethyleneimine resin aqueous solution, molecular weight 70,00
0, specific gravity 1.04, amine value 18 (mgeq / g · so
lid), amine ratio primary / secondary / tertiary = 25/50 /
25; manufactured by Nippon Shokubai Co., Ltd.) and prepared by adding 140 g of IPA, hand-coated with a Meyer bar so as to have a dried film thickness of 0.1 μm, and then dried with a hot-air drier at 100 ° C. for 1 minute and taken out. And what. Support (b): Biaxially oriented polypropylene film (OP
P) Corona treatment on one side of 25 μm (test machine: output 0.
8 kw, 10 m / min), and 270 g of methanol was added to 10 g of a polyamine as an anchor layer (trade name: Polyment NK-200PM, aminoethylated resin, molecular weight 20,000, manufactured by Nippon Shokubai Co., Ltd.), and dried to a film thickness of 0.1 μm. Hand-painted with a Mayer bar, then
One that was dried for 1 minute with a hot-air dryer at 00 ° C and was taken out as a support.

<Example 1> A gas barrier paint (A) was prepared by mixing and dispersing 180 g of paint and 7 g of paint. The gas barrier paint (A) is applied as a solid to the anchor layer of the support so as to have a thickness of 1 μm, and dried at 120 ° C. for 1 minute using a hot air drier to produce a gas barrier laminate. did.

<Example 2> 180 g of a paint and 7 g of a paint were mixed and dispersed to obtain a gas barrier paint (B). A gas barrier laminate was produced in the same manner as in Example 1 except that the gas barrier paint (B) was used.

<Example 3> The gas barrier coating (A)
Was coated on a support so as to have a film thickness of 1 μm as a solid content, and dried at 120 ° C. for 1 minute using a hot air drier to produce a gas barrier laminate.

Example 4 The gas barrier coating (B)
A gas-barrier laminate was produced in the same manner as in Example 3 except that was used.

<Comparative Example 1> A coating material was applied as a gas barrier coating material (C) on a support (a) so as to have a thickness of 1 μm after drying, and was heated at 120 ° C. for 1 minute using a hot air drier. After drying, the desired gas barrier laminate was produced.

<Comparative Example 2> The coating material was applied as a gas barrier coating material (D) on the support (a) so that the film thickness after drying was 1 μm, and the coating was dried at 120 ° C. for 1 minute using a hot air drier. After drying, the desired gas barrier laminate was produced.

Comparative Example 3 The gas barrier paint (C)
Was coated on the support (b) so that the film thickness after drying was 1 μm, and dried at 120 ° C. for 1 minute using a hot-air drier to produce a gas barrier laminate.

Comparative Example 4 The gas barrier coating (D)
Was coated on the support (b) so that the film thickness after drying was 1 μm, and dried at 120 ° C. for 1 minute using a hot-air drier to produce a gas barrier laminate.

<Test Method> Blank: The oxygen permeability of each sample was measured. Wrinkling under constant conditions: Oxygen permeability was measured after each sample was subjected to gelbo flex tester (manufactured by Tester Sangyo Co., Ltd.) 10 times with a torsion angle of 440 ° and a linear stroke of 63.5 mm. Oxygen permeability: 20 ° C., 0% RH (Dr.)
y) Measured under the conditions (oxygen permeability measuring device: OX-TR)
AN100 type, manufactured by MOCON). Oxygen permeability is 100
cc / m ² · 24 hr or less is preferable.

[0094]

[Table 1]

[0095]

The gas barrier laminate according to the present invention comprises:
It has excellent gas barrier properties and is useful as various packaging materials.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08K 7/00 C08K 7/00 7/18 7/18 C08L 85/00 C08L 85/00 F-term (Reference) 4F100 AA19A AA20A AA21A AC03A AC03H AC05A AC05H AC10A AC10H AH03A AH03H AK01B AK07B AK31C AK52A AL05A AR00C AT00B BA02 BA03 BA10A BA10B CA13A CA30A CC00A EJ38B EJ55B01J16B1J16B1J16B1J16B1J16B1

Claims (8)

[Claims] 1. A gas barrier laminate having a gas barrier layer formed on at least one surface of a support, wherein the gas barrier layer comprises the following components. (1) at least one kind of silicic acid condensate selected from alkali metal silicate or colloidal silica; (2) a reaction product of at least one kind selected from hydrolyzate or hydrolytic condensate of metal alkoxide with a hydrogen bonding resin (3) ) Nitrogen-containing compounds which react with the silicic acid condensate (4) Tabular pigment 2. After forming an organic layer containing a nitrogen-containing compound on the surface of a support having a polar group, at least one silicic acid condensate selected from alkali metal silicate or colloidal silica is formed on the organic layer. A gas barrier layer comprising a reaction product of at least one selected from a hydrolyzate or a hydrolyzed condensate of an alkoxide and a hydrogen bonding resin, and an inorganic layer containing a plate-like pigment formed as a gas barrier layer. 2. The gas barrier laminate according to item 1. 3. The metal of the metal alkoxide is Si, Al, T
The gas barrier laminate according to any one of claims 1 to 2, wherein the laminate is at least one selected from i and Zr. 4. The gas barrier laminate according to claim 1, wherein the gas barrier layer contains a water resistance improver. 5. The method according to claim 1, wherein the nitrogen-containing compound is a polyalkyleneimine.
Alternatively, the gas barrier laminate according to any one of claims 1 to 4, which is at least one kind of a polyalkyleneamine. 6. The gas barrier laminate according to claim 1, wherein the tabular pigment is at least one selected from smectite clay, phyllosilicate, and synthetic mica. 7. The gas barrier laminate according to claim 1, wherein a gas barrier layer is provided on the surface of the support having the metal thin film layer. 8. The gas barrier laminate according to claim 1, wherein the support comprises a thermoplastic resin.