JP6878925B2 - Gas barrier laminate and method for manufacturing gas barrier laminate - Google Patents

Description

The present invention relates to a laminated body for a gas barrier having excellent gas barrier properties and a method for producing the laminated body.
The laminate according to the present invention can be applied to products in various fields that require a high degree of barrier property. For example, it can be used for packaging products, electric / electronic products such as solar cells, organic light emitting diodes, wavelength conversion sheets, and display devices.
The laminate according to the present invention can be particularly preferably used as a packaging material. For example, it can be used for pharmaceuticals, cosmetics, chemicals, foods and drinks, and the like.

It is known that an inorganic oxide such as aluminum oxide or silicon oxide is vapor-deposited on a base film to obtain a gas-barrier laminate having a gas-barrier property against oxygen and water vapor. Further, it is known that such an inorganic oxide-deposited film is easily damaged and peeled off in a post-treatment step such as printing or laminating, and in order to prevent this, a transparent primer layer is provided on the surface of the inorganic oxide-deposited layer. (Patent Document 1).

_{A laminate having a barrier layer typified by Al 2} O ₃ formed on a base material by an atomic layer deposition method or the like, and a protective layer containing silica nanoparticles and a curable binder for protecting the barrier layer. those are known, the gas barrier properties of the principal is an Al ₂ O ₃ layer, which is an essential layer in the Al ₂ O _3, requires a complicated process for forming Al ₂ O ₃ layer is there. (Patent Document 2).

A laminate having a metal or metal oxide layer, specifically a layer obtained by vacuum-depositing Al on a substrate, and a coating layer containing a silica colloid having an average particle size of less than 15 nm is known. A layer of metal or metal oxide is essential and requires complex steps to form the layer of metal or metal oxide. (Patent Document 3).

A barrier layer formed from a resin composition containing silica nanoparticles, water-insoluble resin fine particles, and a water-soluble polymer in a base film is known, but it requires long-term drying and is also good. In order to have film-forming properties and not cause cracks, it is necessary to contain water-insoluble resin fine particles to a certain extent or more. (Patent Document 4).

Japanese Patent Application Laid-Open No. 5-269914 Special table 2016-504214 JP 2016-163994 JP-A-2009-269218

The present invention provides a gas barrier laminate that is uniform over the entire surface of the film and has excellent gas barrier properties, and a method for producing the same.

The present inventors have studied diligently to solve the above problems, and by forming a layer obtained by applying the resin composition of the present invention on a base material or the like, the obtained laminate is uniform over the entire surface. We have found a gas barrier laminate that can provide gas barrier properties.
Specifically, the resin composition of the present invention is applied to one surface of a base film made of a plastic material via an adhesive layer, if necessary, dried at a low temperature for a short time, and at a low temperature if necessary. By aging, the above-mentioned target gas barrier laminate was obtained.
The present invention is characterized by the following points.

1. 1. A gas barrier laminate having a base material layer (X) and a layer (Y) formed by using a resin composition, wherein the resin composition contains at least silica nanoparticles and a hydrolyzable metal element. A mixture containing a compound, a water-soluble organic polymer compound, and a solvent contains a component hydrolyzed and condensed by a sol-gel method, and the hydrolyzable metal element-containing compound has two or more hydroxyl groups by hydrolysis. The average primary particle size of the silica nanoparticles is 7 nm or more and 60 nm or less, and the molar ratio Si / metal of the Si atom of the silica nanoparticles and the metal atom of the hydrolyzable metal element-containing compound is , 1.2 or more, 9 or less, gas barrier laminate.
2. The gas barrier laminate according to 1 above, wherein the hydrolyzable metal element-containing compound is a hydrolyzable silicon compound.
3. 3. The gas barrier laminate according to 1 or 2 above, wherein the hydrolyzable metal element-containing compound is silicon alkoxide.
4. The gas barrier laminate according to any one of 1 to 3 above, wherein the hydrolyzable metal element-containing compound is tetraethoxysilane.
5. The gas barrier laminate according to any one of 1 to 4, wherein the content of the water-soluble organic polymer compound in the layer (Y) is 1% by mass or more and 20% by mass or less.

6. The content of the water-soluble organic polymer compound in all non-solvent components of the resin composition before hydrolysis is 0.5% by mass or more and 10% by mass or less, according to any one of 1 to 5 above. The described gas barrier laminate.
7. The gas barrier laminate according to any one of 1 to 6 above, wherein the water-soluble organic polymer compound is a water-soluble organic polymer compound having a hydroxyl group.
8. The gas barrier laminate according to any one of 1 to 7 above, wherein the water-soluble organic polymer compound is a water-soluble organic polymer compound having an alcoholic hydroxyl group.
9. The gas barrier laminate according to any one of 1 to 8 above, wherein the water-soluble organic polymer compound is a water-soluble organic polymer compound composed of an aliphatic main skeleton.
10. The gas barrier laminate according to any one of 1 to 9 above, wherein the water-soluble organic polymer compound is polyvinyl alcohol.
11. The gas barrier laminate according to any one of 1 to 10 above, wherein the thickness of the layer (Y) is 0.05 μm or more and 2 μm or less.
12. A gas barrier packaging material produced by using the laminate according to any one of 1 to 11 above.
13. A production method for producing the gas barrier laminate according to any one of 1 to 11 above, which comprises at least the steps a), b), c), d), and e) below. Production method.
a) A step of preparing a solution A containing a hydrolyzate of the hydrolyzable metal element-containing compound.
b) A step of preparing a solution C by mixing the solution B in which the silica nanoparticles are dispersed and the water-soluble organic polymer compound.
c) Solution C and solution A are mixed little by little, and the molar ratio of the Si atom of the silica nanoparticles to the metal atom of the hydrolyzable metal element-containing compound is 1.2 or more and 9 or less. A step of preparing solution D.
d) A step of applying the solution D to the base material layer (X) to obtain a coated product E.
e) A step of heating the coated product E at a temperature of 40 ° C. or higher and 120 ° C. or lower to form a layer (Y).

The gas barrier laminate of the present invention is a sol-gel containing a base material layer (X), silica nanoparticles having an average primary particle size of 7 to 60 nm, a hydrolyzable metal element-containing compound, a water-soluble organic polymer compound, and a solvent. It contains a layer (Y) which is a gas barrier layer formed by using a resin composition containing a component hydrolyzed and condensed by a method, and the layer (Y) is a special device such as vacuum vapor deposition or a complicated one. It is obtained by coating and heating at a low temperature for a short time without requiring a step, high temperature or long-time drying, and the hydrolyzable metal element-containing compound can have two or more hydroxyl groups by hydrolysis. The molar ratio Si / metal of the Si atom of the silica nanoparticles and the metal atom of the metal compound capable of having two or more hydroxyl groups by hydrolysis is 1.2 or more and 9 or less, so that the gas barrier property is excellent. It is a laminated body that exhibits a stable film-forming state.

Further, since the laminate can be obtained by heating at a low temperature for a short time, it is possible to apply a low heat resistant material to the base material layer (X).
Furthermore, the laminate according to the present invention can be applied to products in various fields that require a high degree of barrier property. For example, it can be used for packaging products, electric / electronic products such as solar cells, organic light emitting diodes, wavelength conversion sheets, and display devices, and can be particularly preferably used as a packaging material for packaging products. For example, it can be used for pharmaceuticals, cosmetics, chemicals, foods and drinks, and the like.

It is a schematic cross-sectional view which shows one aspect of the layer structure of the gas barrier laminated body which concerns on this invention. It is a schematic cross-sectional view which shows one aspect of the layer structure of the gas barrier laminated body which concerns on this invention. It is a schematic cross-sectional view which shows one aspect of the layer structure of the gas barrier laminated body which concerns on this invention.

The present invention will be described in more detail below with reference to drawings and the like. Hereinafter, the resin names used in the present specification will be those commonly used in the industry. Moreover, the present invention is not limited to the specific examples described.

<Layer structure of the gas barrier laminate of the present invention>
FIG. 1 is a schematic cross-sectional view showing an aspect of the layer structure of the gas barrier laminate of the present invention. As shown in FIG. 1, the gas barrier laminate of the present invention is formed by laminating 1 base material layer (X) and 2 gas barrier layers (Y), in some cases, via an adhesive layer. You can do it.
FIG. 2 is a schematic cross-sectional view showing an aspect of the layer structure of the gas barrier laminate of the present invention. As shown in FIG. 2, the gas barrier laminate of the present invention has 1 base material layer (X), 2a gas barrier layer (Y), and 2b gas barrier layer (Y), and in some cases, an adhesive layer. It may be laminated through.
Alternatively, as shown in FIG. 3, the two gas barrier layers (Y) may have three additional sealant layers on the opposite surface to the one base material layer (X).

<Layer with gas barrier property (Y)>
In the present invention, the layer (Y) having a gas barrier property is formed from a resin composition. The resin composition is a sol-gel process in which a mixture containing at least silica nanoparticles, a hydrolyzable metal element-containing compound capable of having two or more hydroxyl groups by hydrolysis, a water-soluble organic polymer compound, and a solvent is used. It contains components hydrolyzed and condensed by the above, and is unreacted products such as hydrolyzed condensation products, unhydrolyzed products of hydrolyzable metal element-containing compounds, uncondensed products of silica nanoparticles, etc. Things are also included.

[Silica nanoparticles]
The silica nanoparticles are generally silica particles having an average particle size of 1 nm or more and 100 nm or less, but in the present invention, those having an average primary particle size of 7 nm or more and 60 nm or less are used for the purpose. Therefore, any average primary particle size in the above range can be appropriately selected, preferably 8 nm or more and 55 nm or less, more preferably 9 nm or more and 50 nm or less, and most preferably 10 nm. Above, it is 45 nm or less.

In order to suppress the occurrence of cracks in the layer (Y), the average primary particle size is preferably 7 nm or more and 60 nm or less, and further, when the average primary particle size is smaller than 7 nm, the resin composition The tix property tends to be too high and the coatability tends to decrease, and when the average primary particle size is larger than 60 nm, the smoothness of the layer (Y) tends to decrease.

Although the average primary particle size of the silica nanoparticles can be measured by various general methods, it is preferable to measure the particle size of the primary particles of the silica particles in the image taken by the transmission electron microscope (TEM), and in the present invention. When the primary particles are not spherical, the average value of the longest diameter and the shortest diameter of the primary particles is regarded as the particle size of the primary particles, and further, for example, 100 particles of the primary particles selected at random. The average value of the diameter is defined as the average primary particle size.

As the shape of the silica nanoparticles, any shape such as a true spherical shape, an elliptical spherical shape, a crushed shape, and a flake shape can be used.
Similar to ordinary silica, many reactive hydroxyl groups (silanol groups) are present on the surface of silica nanoparticles, and various chemical modifications and crosslinks are possible by chemically reacting them.
Further, since silica nanoparticles are likely to cause secondary aggregation, it is preferable to disperse them in a solution for use.

[Hydrolytic metal element-containing compound]
In the present invention, hydrolysis refers to the reaction of water molecules with an alkoxy group, phenoxy, hydrogen, etc. bonded to a metal element to generate alcohols, phenols, hydrogen molecules, and a compound in which a metal atom has a hydroxyl group. On the contrary, condensation is a chemical reaction in which alcohols, phenols, hydrogen, and a compound having a hydroxyl group attached to a metal are combined to form an alkoxy group, phenoxy, etc., and water. Hydrolysis condensation refers to both reactions of hydrolysis and condensation, and a mixture containing silica nanoparticles and a metal element-containing compound capable of having two or more hydroxyl groups by hydrolysis is hydrolyzed. Decomposition and condensation means that the metal element-containing compound is hydrolyzed, then the silica nanoparticles are condensed with each other, the silica nanoparticles and the metal element-containing compound are hydrolyzed, and the metal element-containing compound is hydrolyzed with each other. It means that the condensation of

The hydrolyzable metal element-containing compound in the present invention is a metal element-containing compound capable of having two or more hydroxyl groups by the above hydrolysis, and examples of the functional group capable of generating hydroxyl groups by hydrolysis include an alkoxy group and a phenoxy group. , Hydrogen, etc., and specific examples thereof include metal alkoxides, metal phenoxides, metal hydrides, and oligomers thereof.

Specific metal elements include silicon, aluminum, titanium, zirconium, tin, lead, borane, etc., and specific desorbing groups include hydrogen, methoxy group, ethoxy group, n-propoxy group, i. -Alkoxy groups or phenoxy groups such as propoxy group, butoxy group, 3-acryloxy group, phenoxy group and the like can be mentioned.

Specific examples of the hydrolyzable silicon compound include various silanes such as silane, methylsilane, and dimethylsilane, trimethoxysilane, triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, and tetrabutoxy. Silane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, methyltriphenoxysilane, phenylphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, dimethyl Diethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxy Silane, phenyltrimethoxysilane, phenyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacry Loxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-chloropropyltriethoxysilane, trifluoromethyltrimethoxysilane, 1,6-bis (trimethoxysilyl) hexane Various alkoxysilanes such as phenoxysilane, phenoxysilane, and the like can be mentioned.

Examples of the hydrolyzable aluminum compound include aluminum hydride, various alkoxyaluminums such as acetalkoxyaluminum diisopropylate, aluminum triisopropoxide, and aluminum trisethylacetonate.

Examples of the hydrolyzable titanium compound include titanium hydride, tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetraoctyl titanate, tetraterchary butyl titanate, tetrastearyl titanate, diisopropoxytitanium bisacetylacetonate, and the like. Various types of alkoxytitanium are mentioned.

Examples of the zirconium element-containing compound include various alkoxyzirconium such as zirconium hydride, zirconium tetrabutoxide, zirconium tetrakisacetylacetonate, and the like.
Other examples include lead hydride, tin hydride, trimethoxyborane and the like.

Among these, a hydrolyzable silicon compound is preferable because of its excellent reactivity, a silicon alkoxide is more preferable among the hydrolyzable silicon compounds, and a tetraethoxysilane is particularly preferably used among the silicon alkoxides.

Here, a hydrolyzate of the silica nanoparticles and the hydrolyzable metal element-containing compound is produced by advancing the condensation reaction between the silanol group on the surface of the silica nanoparticles and the hydroxyl group generated by hydrolyzing the hydrolyzable metal element-containing compound. The hydrolyzate of the hydrolyzable metal element-containing compound has two or more hydroxyl groups, so that the hydrolyzate of the hydrolyzable metal element-containing compound is crosslinked between the silica nanoparticles. It produces a continuous matrix, the average primary particle size of the silica nanoparticles is 7 nm or more and 60 nm or less, and the molar ratio of the Si atom of the silica nanoparticles to the metal atom of the hydrolyzable metal element-containing compound is Si / metal. , 1.2 or more and 9 or less, preferably 1.3 or more and 8.5 or less, thereby obtaining a layer (Y) having excellent gas barrier properties without cracks and having an excellent balance with various characteristics. be able to.

The content of the hydrolyzed condensate of the silica nanoparticles and the hydrolyzable metal element-containing compound in the layer (Y) is preferably 80% by mass or more and 99% by mass or less, and particularly 85% by mass or more and 95% by mass or less. Most preferably, it is 89% by mass or more and 92% by mass or less. When the content is larger than 99% by mass, the coatability when coating the layer (Y) tends to be poor, or the obtained layer (Y) tends to be brittle, and the content is 80% by mass. If it is smaller than, the gas barrier property tends to decrease.

The content of the resin composition for forming the layer (Y) of the silica nanoparticles and the hydrolyzable metal element-containing compound in the total non-solvent component before hydrolysis was 90% by mass or more and 99.5% by mass or less. It is preferably 91% by mass or more and 98% by mass or less, and most preferably 92% by mass or more and 96% by mass or less. When the content is larger than 99.5% by mass, the coatability when coating the layer (Y) tends to be poor, or the obtained layer (Y) tends to be brittle, and the content is 90% by mass. If it is less than%, the gas barrier property tends to decrease.

[Water-soluble organic polymer compound]
The water-soluble organic polymer compound in the present invention gives the layer (Y) excellent coatability, and also makes the layer (Y) less likely to crack and gives a stable gas barrier property.
The water-soluble organic polymer compound preferably has a hydroxyl group, and by having a hydroxyl group, it is excellent in water solubility, and has a hydrolyzable metal element compound, a hydrolyzate thereof, and silica nanoparticles. It has good affinity, becomes a part of the cross-linking matrix in some cases, has excellent film-forming property, and can obtain a homogeneous layer (Y).

The hydroxyl group of the water-soluble organic polymer compound may be either a phenolic hydroxyl group or an alcoholic hydroxyl group, but an alcoholic hydroxyl group is preferable. The structure of the main chain of the molecular skeleton may be either an aromatic main chain or an aliphatic main chain, but an aliphatic main chain is preferable because of its excellent flexibility.

The content of the water-soluble organic polymer compound in the layer (Y) is preferably 1% by mass or more and 20% by mass or less, more preferably 5% by mass or more and 15% by mass or less, and 8% by mass or more and 11% by mass. The following are the most preferable. When the content is less than 1% by mass, the coatability when coating the layer (Y) tends to be poor, or the obtained layer (Y) tends to be brittle, and the content is 20% by mass. If it is larger than, the gas barrier property tends to decrease.

The content of the water-soluble organic polymer compound in the total non-solvent component before hydrolysis of the resin composition for forming the layer (Y) is 0.5% by mass or more and 10% by mass or less. Preferably, 2% by mass or more and 9% by mass or less are particularly preferable, and 4% by mass or more and 8% by mass or less are most preferable. When the content is less than 0.5% by mass, the coatability when coating the layer (Y) tends to be poor, or the obtained layer (Y) tends to be brittle, and the content is 10% by mass. If it is larger than%, the gas barrier property tends to decrease.

The degree of polymerization of the water-soluble organic polymer compound is preferably 500 to 5000, more preferably 1000 to 4000, in order to obtain a good coatability of the resin composition and a flexible layer (Y). It is preferably 1500 to 3000, and particularly preferably 1500 to 3000.
The molecular weight of the water-soluble organic polymer compound is preferably 10,000 to 200,000, preferably 50,000 to 150,000, in order to obtain a good coatability and a flexible layer (Y) of the resin composition. It is more preferable, and it is particularly preferable that it is 70,000 to 120,000.
The average number of hydroxyl groups in one molecule of the water-soluble organic polymer compound is preferably 2 or more, and more preferably 3 or more.

Specific examples of the water-soluble organic polymer compound include polyacrylic acid, polyacrylamide, polyvinyl alcohol, poly2-hydroxymethylmethacrylate, poly2-hydroxyethylmethacrylate, polyethylene glycol and the like. Here, these are the names of polymers of a single monomer, but they may be copolymers in which other monomers are used in combination for modification. Further, a linear polymer in which two or more components are polymerized, such as a polymer of a bifunctional phenol compound and a bifunctional epoxy compound and an ethylene-vinyl alcohol copolymer, can be mentioned, and among these, flexibility and affinity. Polyvinyl alcohol is preferable, and the degree of saponification is preferably 95% or more, more preferably 97% or more, and most preferably 98% or more.

[solvent]
The solvent in the present invention is water-soluble and can uniformly dissolve or disperse silica nanoparticles and a hydrolyzable metal element-containing compound and its hydrolyzate, hydrolyzed condensate, and water-soluble organic polymer compound. _Any compound may be used, and water or an organic solvent may be used, and the octanol / water partitioning coefficient Log Power is preferably 0.5 or less, and one kind or a mixture of two or more kinds may be used. ..
Specific solvents include water, methanol (Log P _ow: -0.77), ethanol _{(Log P ow: -0.30),} 1- propanol _{(Log P ow: 0.25),} 2- propanol ( Log _Power : 0.05), and mixtures thereof and the like.

[Formation of layer (Y)]
The layer (Y) is formed by applying the resin composition to the base material layer (X) or the like, drying it at 40 to 120 ° C. by heating, and, if necessary, aging by heating.
In the present invention, the main purpose of drying is to remove the water solvent in the coating liquid, and the laminate of the present invention can be dried at a low temperature and in a short time. Since the drying temperature requires a temperature at which water evaporates, it is preferably 70 ° C. or higher and 120 ° C. or lower, and more preferably 80 ° C. or higher and 110 ° C. or lower. The drying time depends on the composition of the resin composition, but is preferably 5 seconds or more and 30 minutes or less, and more preferably 10 seconds or more and 10 minutes or less in the above temperature range.

In the present invention, the aging (calcination) is intended to promote the dehydration condensation reaction. The laminate of the present invention is not particularly limited in aging conditions, but can be aged at 60 ° C. or lower, and the reaction proceeds faster at higher temperatures, so that the time can be shortened. The aging temperature is preferably 40 to 80 ° C, more preferably 50 to 70 ° C. The aging time is preferably 1 to 70 days. In addition, water is produced as a by-product during aging, but there is no problem because the amount produced is small.
Therefore, the layer (Y) can be formed by heating at a low temperature of 40 to 120 ° C., and a laminate to which a low heat resistant base material is applied can be obtained by using a general coating machine and a simple heating facility. it can.

The thickness of the layer (Y) is preferably 0.01 to 2 μm, more preferably 0.1 to 1.5 μm, and particularly preferably 0.2 to 1 μm. If it is smaller than 0.01 μm, the gas barrier property tends not to be sufficiently exhibited, and if it is larger than 2 μm, the flexibility tends to be inferior.
Further, the layer (Y) can be composed of two or more layers having the same or different composition, and by sharing the desired action, the barrier property to various gases and various characteristics can be obtained. It becomes possible to balance.

<Base material layer (X)>
In the present invention, various materials can be applied to the base material layer depending on the type of contents to be packaged, mechanical strength, chemical resistance, solvent resistance, manufacturability and the like required in physical distribution. For example, polyethylene resins such as low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear (linear) low density polyethylene (LLDPE), polypropylene resins, cyclic polyolefin resins, Fluorine resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, Polycarbonate resin, polyethylene terephthalate (PET), polyester resin such as polyethylene naphthalate, polyamide resin such as various nylons, polyimide resin, polyamideimide resin, polyarylphthalate resin, silicone resin, polysulfone resin , Polyphenylene sulfide resin, polyether sulfone resin, polyurethane resin, acetal resin, cellulose resin, and films containing various resins such as mixtures of these resins can be used. Not limited. In particular, in the present invention, a film made of a polyethylene-based resin, a polypropylene-based resin, a polyester-based resin, or a polyamide-based resin is preferable, and a polyester-based resin is particularly preferable.

In the present invention, the base material layer may be a single layer or a multilayer film formed by a film forming method such as an extrusion method, a cast molding method, a T-die method, a cutting method, or an inflation method. The thickness of the base material layer can be appropriately determined by those skilled in the art depending on the packaging application, but is preferably 6 to 100 μm, more preferably 9 to 50 μm.

Further, the base material layer in the laminate of the present invention has workability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, releasability, flame retardancy, and resistance of the laminate. Various plastic compounding agents, additives and the like can be added for the purpose of improving and modifying mold properties, electrical properties, strength and the like. In this case, these additives may be arbitrarily contained in the base material layer from a very small amount to several tens of mass% depending on the purpose. In the present invention, as general additives, colorants such as lubricants, cross-linking agents, antioxidants, ultraviolet adsorbents, light stabilizers, fillers, antistatic agents, lubricants, antiblocking agents, dyes and pigments. Etc. can be arbitrarily contained.

Further, a resin for modification or the like can be added.
Furthermore, the base material layer can also have resin layers of various materials in order to impart high elasticity and pinhole resistance. For example, it can have layers of 6 nylon, 66 nylon, 6/66 nylon copolymer, low density polyethylene, EVOH, etc., and it is particularly preferable to have a layer of 6/66 nylon copolymer.

Further, in the present invention, low-density polyethylene (LDPE), linear (linear) low-density polyethylene (LLDPE), high-density polyethylene (HDPE), and medium-density polyethylene (MDPE) are the former JIS K6748: 1995 and JIS. Refers to the one defined in K6897-1: 2000.

<Laminated body>
The laminate of the present invention is a laminate having a base material layer (X) and a layer (Y) having a gas barrier property formed by using a resin composition. It can have various layers such as an adhesive layer.

Further, the laminate of the present invention may have various barrier layers other than the layer (Y), such as a known or commercially available gas barrier layer or a light-shielding layer. Specifically, a resin film such as PET, polybutylene terephthalate, polyethylene naphthalate, polyamide, polyimide, polyvinyl alcohol, ethylene / vinyl alcohol copolymer and a mixture thereof, and at least one of the above-mentioned gas barrier films. A vapor-deposited film such as a silica vapor-deposited film or an aluminum oxide vapor-deposited film, a metal foil such as an aluminum foil, or the like can be used on the surface of the surface, and two or more kinds can be used in combination, but the present invention is not limited thereto. Among the above films, it is preferable to use a silica-deposited film, an aluminum oxide-deposited film, or an aluminum foil from the viewpoint of excellent gas barrier properties. Further, in particular, by using an aluminum foil, it is possible to impart a light-shielding property and suppress deterioration of the laminate and the filler due to light irradiation, and it can be preferably used. Further, when a film having high strength is applied, the laminated body can be adjusted so as to have an appropriate piercing strength according to the purpose.

In the present invention, the method for laminating these layers is not particularly limited, and a known or conventional film forming method can be applied, and the layers can be formed by coextrusion by an extrusion coating, an inflation method or a casting method.

In the extrusion coating, first, the resin composition forming the layer is heated and melted, expanded and stretched in the required width direction with a T-die, extruded into a curtain shape, and the molten resin flows down onto the surface to be laminated. By sandwiching it between a rubber roll and a cooled metal roll, adhesion to the surface to be laminated and lamination are performed at the same time. When laminated by extrusion coating, the melt flow rate (MFR) of the resin composition is preferably 0.2 to 50 g / 10 minutes, more preferably 0.5 to 30 g / 10 minutes. If the MFR is less than 0.2 g / min or 50 g / min or more, it is not effective in terms of processing suitability.

For example, when the inflation method is used, the melt flow rate (MFR) of the resin composition is preferably 0.2 to 4.0 g / 10 min, more preferably 0.2 to 3.0 g / 10 min. If the MFR is less than 0.2 g / 10 min or 4.0 g / 10 min or more, it tends to be inferior in terms of processing suitability. In this specification, MFR is a value measured by a method based on JIS K7210 and JIS K 6922-2. Alternatively, the film formed in advance may be laminated via the adhesive layer by dry lamination, non-solvent lamination, sand lamination or the like.

<Adhesive layer>
In the present invention, the layers in the base material layer (X), the layers in the layer (Y), the other layers, and the layers of the base material layer (X), the layer (Y), and the other layers are adhered to each other. It is also possible to provide layers and stack them.
In one aspect of the present invention, the adhesive layer may be a layer composed of an extraction coat layer (EC coat layer), an adhesive for dry laminating, an adhesive for non-solvent laminating, and the like.

When an extension coat layer (EC coat layer) is used as the adhesive layer, the adhesive is heated and melted, expanded and stretched in the required width direction with a T-die, extruded into a curtain shape, and the molten adhesive is adhered. By flowing down onto the target film and sandwiching it between a rubber roll and a cooled metal roll, an adhesive layer is formed, adhered and laminated at the same time.
When a dry laminating adhesive is used as the adhesive layer, an adhesive dispersed or dissolved in a solvent is applied onto one film, dried, and the other film is laminated and then laminated at 30 to 120 ° C. By aging for hours to several days, the adhesive is cured and laminated.

When using a non-solvent laminating adhesive, the adhesive itself is applied onto a film without being dispersed or dissolved in a solvent, dried, and the other film is laminated and then laminated at 30 to 120 ° C. for several hours. By aging for several days, the adhesive is cured and laminated.

These adhesives may be a thermosetting type, an ultraviolet curing type, an electron beam curing type, or the like. Examples of such an adhesive include a polyvinyl acetate-based adhesive such as polyvinyl acetate and a vinyl acetate-ethylene copolymer, and a polyacrylic acid composed of a copolymer of polyacrylic acid and polystyrene, polyester, polyvinyl acetate and the like. Ethylene copolymer adhesives, cyanoacrylate adhesives, ethylene copolymer adhesives consisting of copolymers of ethylene and monomers such as vinyl acetate, ethyl acrylate, acrylic acid, and methacrylic acid, cellulose adhesives, and polyurethane adhesives. , Polyester adhesive, Polyamide adhesive, Polygon adhesive, Polyethylene adhesive, Amino resin adhesive composed of urea resin, melamine resin, etc., Phenolic resin adhesive, Epoxy adhesive, Reactive type (meta) ) Examples thereof include an acrylic adhesive, an elastomer adhesive made of chloroprene rubber, nitrile rubber, styrene-butadiene rubber, etc., a silicone adhesive, an alkali metal silicate, an inorganic adhesive made of low melting point glass, and the like.

Further, the adhesive may be in any form such as an aqueous type, a solution type, an emulsion type and a dispersed type, and the properties thereof may be any form such as a film / sheet form, a powder form and a solid form. Further, the bonding mechanism may be in any form such as a chemical reaction type, a solvent volatilization type, a heat melting type, and a hot pressure type.

The adhesive layer is formed by applying the above adhesive with, for example, a roll coat, a gravure roll coat, a kiss coat, or the like, and the coating amount thereof ^{is preferably about 0.05 to 10 g / m 2} (dry state). Good adhesiveness can be obtained by setting the coating amount of the adhesive within the above range.

In another aspect of the present invention, with the above-mentioned layers in the base material layer (X), layers in the layer (Y), other layers, and the base material layer (X), layer (Y), and other layers. Each layer of the above may be laminated by sand lamination. In this case, any resin that can be melted by heating and applied in an extruder can be used as the adhesive layer. Specifically, the resins listed as the above-mentioned thermoplastic resins having heat-sealing properties can be preferably used.

In yet another aspect of the invention, the seal layer is laminated by extrusion coating on the laminate. In this case, the adhesive layer provided between the laminate-seal layer may be made of any anchor coating agent, for example, an anchor coating agent such as organic titanium-based, isocyanate-based, polyethyleneimine-based, acid-modified polyethylene-based, or polybutadiene-based. Can be used.

<Packaging material>
The laminate according to the present invention can be particularly preferably used as a packaging material. For example, it can be used for pharmaceuticals, cosmetics, chemicals, foods and drinks, and the like.

<Packaging body>
The packaging body of the present invention is made by making a bag of the packaging material of the present invention, and the laminated film is bent or two sheets are overlapped so that the heat-sealing surfaces face each other, and the peripheral end thereof is, for example, Side seal type, two-way seal type, three-way seal type, four-way seal type, envelope-attached seal type, gassho-attached seal type (pillow seal type), fold-attached seal type, flat-bottom seal type, square-bottom seal type, gusset type, etc. It can be produced by heat-sealing according to the heat-sealing form.
In the present invention, as the heat sealing method, known methods such as bar sealing, rotary roll sealing, belt sealing, impulse sealing, high frequency sealing, and ultrasonic sealing can be applied.

<Products for other uses>
The laminate according to the present invention can be applied to products in various fields other than packaged products, which require a high degree of barrier property. For example, it can be used for electric / electronic products such as solar cells, organic light emitting diodes, wavelength conversion sheets, and display devices.

Details of the main raw materials used in the examples and comparative examples are as follows.
Silica nanoparticle dispersion liquid A: Snowtex ST-O-40 (manufactured by Nissan Chemical Industry Co., Ltd., solid content concentration 40% by mass, average primary particle size 23 nm)
Silica nanoparticle dispersion liquid B: Snowtex ST-OS (manufactured by Nissan Chemical Industry Co., Ltd., solid content concentration 20% by mass, average primary particle size 10 nm)
Silica nanoparticle dispersion C: Snowtex ST-OL (manufactured by Nissan Chemical Industry Co., Ltd., solid content concentration 20% by mass, average primary particle size 45 nm)
Silica nanoparticle dispersion D: Snowtex ST-OXS (manufactured by Nissan Chemical Industries, Ltd., solid content concentration 10% by mass, average primary particle size 5 nm)
Silica nanoparticle dispersion E: Snowtex ST-OYL (manufactured by Nissan Chemical Industry Co., Ltd., solid content concentration 20% by mass, average primary particle size 65 nm)
Water-soluble organic polymer compound solution A: Polyvinyl alcohol having a saponification degree of 98.5% and a degree of polymerization of about 2500 was mixed with distilled water to prepare a 4 mass% polyvinyl alcohol aqueous solution.
PET film A: Emblet manufactured by Unitika Ltd. 12 μm thick, single-sided corona treated.

(Preparation of hydrolyzed solution A of hydrolyzable metal element-containing compound)
The following raw materials were mixed and cooled so that the liquid temperature became 10 ° C.
Distilled water 129.20 parts by mass Isopropyl alcohol 22.33 parts by mass 0.5N hydrochloric acid 3.05 parts by mass Next, while cooling so that the liquid temperature becomes 10 ° C., the following is mixed to obtain hydrolyzed liquid A. It was.
Tetraethoxysilane 95.42 parts by mass

(Example 1)
Distilled water was added to the silica nanoparticle dispersion liquid A at the following blending ratio, and the water-soluble organic polymer compound solution A was further mixed and stirred so as to be uniform.
Silica nanoparticle dispersion liquid A 2.28 parts by weight Distilled water 9.76 parts by weight Water-soluble organic polymer compound solution A 3.38 parts by weight Further, while stirring the obtained mixture, add the following amount of hydrolysis liquid A. The mixture was added dropwise, and the mixture was stirred for 1 hour after the completion of the dropping to obtain a coating solution.
Hydrolyzed solution A 4.58 parts by mass

The coating liquid obtained above is applied to the corona-treated surface of the PET film A which is the base material layer (X), and the obtained coated product is heated at 110 ° C. for 5 minutes to be dried and dried to form a gas barrier layer. The precursor layer of No. 1 was formed and further aged at 60 ° C. for 10 days to form a layer (Y) which is a gas barrier layer having a thickness of 0.3 μm to obtain a laminated body.
The presence or absence of cracks on the surface of the layer (Y) of the obtained laminate was observed, and the oxygen permeability was measured. The results are shown in Table 1.

In addition, the molar ratio of the Si atom of the silica nanoparticles to the metal atom of the hydrolyzable metal element-containing compound Si / metal and the content of the water-soluble organic polymer compound in the resin composition before hydrolysis are determined from the blending ratio. Calculated. Further, the content of the water-soluble organic polymer compound in the layer (Y) was calculated on the assumption that all the hydroxyl groups of the hydrolyzable metal element-containing compound were eliminated and condensed to complete the hydrolysis condensation. ..

[Examples 2 to 6, Comparative Examples 1 to 6]
Using each raw material according to the formulation shown in Table 1, the same operation as in Example 1 was carried out to obtain a coating liquid, and further, a laminate was obtained and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Various evaluation methods>
[Paintability]
The appearance of the coated product when the coating liquid was applied to the base material layer (X) was visually judged.
[Presence / absence of crack]
Using a scanning electron microscope (SEM. S-4800 manufactured by Hitachi High-Tech Co., Ltd.), the surface of the layer (Y) of the laminate obtained by the aging treatment was randomly placed at 20 points on one test piece. The presence or absence of cracks was detected by observing at a magnification of 5,000 times. Table 1 shows the following procedure.
Yes: With crack No: No crack

[Oxygen permeability]
JIS using an oxygen permeability measuring device (OX-TRAN 2/22 manufactured by MOCON)
The oxygen permeability of the obtained laminate was measured according to K-7126-2. The measurement conditions are as follows.
Temperature: 23 ° C
Relative humidity: 90%

[Measurement of particle size of silica nanoparticles]
For the average primary particle size of silica nanoparticles, the primary particle image is measured by a transmission electron micrograph (TEM) (H-7650 manufactured by Hitachi High-Tech), and the average value of the longest diameter and the shortest diameter of each primary particle is calculated. Then, the particle size of each primary particle was used, and the average value of the particle size of 100 randomly selected primary particles was used as the average primary particle size.

<Summary of results>
In Examples 1 to 6, there were no cracks in the layer (Y) and good oxygen barrier properties were exhibited, but the molar ratio of the Si atom of the silica nanoparticles to the metal atom of the hydrolyzable metal element-containing compound Si / metal was high. Comparative Example 1 which is too low, Comparative Example 2 which is too high, Comparative Example 3 in which the average primary particle size of the silica nanoparticles is too small, Comparative Example 4 which is too large, and Comparative Example 5 which does not contain silica nanoparticles have oxygen barrier properties. In particular, in Comparative Examples 1, 3 and 5, the oxygen permeability could not be accurately measured because the layer (Y) was cracked. Further, in Comparative Example 6 containing no water-soluble organic polymer compound, a coated product could not be obtained due to poor coatability, and subsequent evaluation could not be performed.

1. 1. Base material layer (X)
2, 2a, 2b. Gas barrier layer (Y)
3. 3. Sealant layer

Claims (12)

A gas barrier laminate having a base material layer (X) and a layer (Y) formed by using a resin composition.
The resin composition contains at least a component in which a mixture containing silica nanoparticles, a hydrolyzable metal element-containing compound, a water-soluble organic polymer compound, and a solvent is hydrolyzed and condensed by a sol-gel method.
The content of the water-soluble organic polymer compound in the layer (Y) is 1% by mass or more and 20% by mass or less.
The hydrolyzable metal element-containing compound can have two or more hydroxyl groups by hydrolysis.
The average primary particle size of the silica nanoparticles is 7 nm or more and 60 nm or less.
A gas barrier laminate in which the molar ratio Si / metal of the Si atom of the silica nanoparticles and the metal atom of the hydrolyzable metal element-containing compound is 1.2 or more and 9 or less. The gas barrier laminate according to claim 1, wherein the hydrolyzable metal element-containing compound is a hydrolyzable silicon compound. The gas barrier laminate according to claim 1 or 2, wherein the hydrolyzable metal element-containing compound is a silicon alkoxide. The gas barrier laminate according to any one of claims 1 to 3, wherein the hydrolyzable metal element-containing compound is tetraethoxysilane. Any of claims 1 to 4 , wherein the content of the water-soluble organic polymer compound in the total non-solvent component of the resin composition before hydrolysis is 0.5% by mass or more and 10% by mass or less. The gas barrier laminate according to item 1. The gas barrier laminate according to any one of claims 1 to 5 , wherein the water-soluble organic polymer compound is a water-soluble organic polymer compound having a hydroxyl group. The gas barrier laminate according to any one of claims 1 to 6 , wherein the water-soluble organic polymer compound is a water-soluble organic polymer compound having an alcoholic hydroxyl group. The gas barrier laminate according to any one of claims 1 to 7 , wherein the water-soluble organic polymer compound is a water-soluble organic polymer compound composed of an aliphatic main skeleton. The gas barrier laminate according to any one of claims 1 to 8 , wherein the water-soluble organic polymer compound is polyvinyl alcohol. The gas barrier laminate according to any one of claims 1 to 9 , wherein the thickness of the layer (Y) is 0.05 μm or more and 2 μm or less. A gas barrier packaging material produced by using the laminate according to any one of claims 1 to 10. A production method for producing the gas barrier laminate according to any one of claims 1 to 10 , which comprises at least the steps a), b), c), d), and e) below. A method for manufacturing a laminate.
a) A step of preparing a solution A containing a hydrolyzate of the hydrolyzable metal element-containing compound.
b) A step of preparing a solution C by mixing the solution B in which the silica nanoparticles are dispersed and the water-soluble organic polymer compound.
c) Solution C and solution A are mixed little by little, and the molar ratio of the Si atom of the silica nanoparticles to the metal atom of the hydrolyzable metal element-containing compound is 1.2 or more and 9 or less. A step of preparing solution D.
d) A step of applying the solution D to the base material layer (X) to obtain a coated product E.
e) A step of heating the coated product E at a temperature of 40 ° C. or higher and 120 ° C. or lower to form a layer (Y).

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