JP6901086B2 - Resin composition, molded body, laminate, gas barrier material, coating material and adhesive - Google Patents

Description

The present invention relates to resin compositions, molded bodies, laminates, gas barrier materials, coating materials and adhesives.

Packaging materials used for packaging foods and the like are required to have functions such as protection of contents, retort resistance, heat resistance, transparency, and processability. Gas barrier properties are especially important for maintaining the quality of the contents. Recently, not only packaging materials but also materials used for electronic materials such as solar cells and semiconductors are required to have high gas barrier properties.

Patent Document 1 describes that by combining a resin having a hydroxyl group and an isocyanate compound with a plate-like inorganic compound such as a clay mineral and a light blocking agent, properties such as gas barrier properties are improved.

Further, Patent Document 2 describes a material containing modified clay as a main constituent component. By using modified clay and using additives as necessary, the modified clay crystals are oriented and densely laminated. It is said that a film material having mechanical strength, gas barrier property, water resistance, thermal stability and flexibility that can be used as a self-supporting film can be obtained.

International Publication No. 2013/027609 Japanese Unexamined Patent Publication No. 2007-277078

The plate-like inorganic compound as described in Patent Document 1 is bulky, and it is difficult to obtain a good affinity with the resin. Therefore, there is a limit to the amount of addition and dispersibility. Therefore, it is difficult to increase the addition amount in order to obtain a higher gas barrier property, and increasing the addition amount leads to a decrease in dispersibility.

Further, the clay film described in Patent Document 2 is made into a self-supporting film by heating after film formation. However, heating after film formation can only be used for resins with extremely high heat resistance, so there is a problem that the intended use is limited. Further, the self-supporting membrane described in Patent Document 2 contains a large amount of filler in order to exhibit high gas barrier properties. However, if the amount of the filler is too large, the flexibility of the composition is impaired, so that there is a problem that the flexibility is insufficient for, for example, a film for flexible packaging. Therefore, there is still a demand for a resin composition capable of exhibiting high barrier properties regardless of whether the filler is highly filled or lowly filled.

Therefore, an object of the present invention is to provide a resin composition having further excellent gas barrier properties, particularly water vapor barrier properties and oxygen barrier properties, as compared with conventional resin compositions.

The present inventors have obtained a lithium partially fixed smectite obtained by heat treatment in advance, because the dispersibility in the resin is improved, the deterioration of the resin is suppressed, and the applicable resin is wide. As a result, the resin has excellent gas barrier properties. They have found that they can be suitably used as fillers for compositions, and have completed the present invention.

That is, the present invention provides a resin composition containing a polyalkyleneimine resin and a lithium partially fixed smectite. Since the resin composition of the present invention is a combination of a polyalkyleneimine resin and a lithium partially fixed smectite, gas barrier properties such as water vapor barrier property and oxygen barrier property become excellent.

The lithium partially fixed smectite preferably has a cation exchange capacity of 1 to 50 meq / 100 g. As a result, the water vapor barrier property and the oxygen barrier property are further improved.

The content of the lithium partially fixed smectite is preferably 3 to 50% by mass with respect to the total amount of the non-volatile content of the resin composition. With such a content, the water vapor barrier property and the oxygen barrier property are excellent, and the moldability is further improved.

The present invention further provides a molded body of the above-mentioned resin composition and a laminated body having the molded body on a base material.

Since the resin composition of the present invention has excellent water vapor barrier properties and oxygen barrier properties, it can be suitably used for applications such as gas barrier materials, coating materials, and adhesives.

According to the present invention, it is possible to provide a resin composition having further excellent gas barrier property, particularly water vapor barrier property and oxygen barrier property. Regarding the water vapor barrier property, the value of the water vapor transmittance based on JIS-K7129 can be set to, for example, 50 (g / m ² · day) or less, and the oxygen barrier property is based on JIS-K7126. The value of the oxygen permeability can be set to, for example, 8 (cc / m ² · day · atm) or less at ^{0% RH and 110 (cc / m 2} · day · atm) or less at 90% RH.

Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

The resin composition of the embodiment contains a polyalkyleneimine resin and a lithium partially fixed smectite.

Smectite is a kind of phyllosilicate mineral (layered clay mineral) having a layered structure. As a specific structure of smectite, structures such as montmorillonite, biderite, saponite, hectorite, stephensite, and saponite are known. Of these, the structure of the clay material is preferably a montmorillonite and / or a stephensite structure. In these structures, the octahedral sheet is negatively charged because some of the metal elements of the octahedral sheet have isomorphic substitutions or defects with low valence metal elements. As a result, these structures have empty sites on the octahedral sheet, and ions can exist stably.

Smectite in which the cation possessed is lithium ion is called lithium type smectite. Examples of the method for exchanging the cations of smectite for lithium ions include a method of adding a lithium salt such as lithium hydroxide and lithium chloride to a dispersion of natural sodium-type smectite to exchange cations. By adjusting the amount of lithium added to the dispersion, the amount of lithium ions in the amount of leachate cations of the obtained lithium-type smectite can be appropriately adjusted. The lithium-type smectite can also be obtained by a column method or a batch method using a resin in which a cation exchange resin is ion-exchanged with lithium ions.

In the present embodiment, the lithium partially fixed smectite means a smectite in which a part of lithium ions in the lithium type smectite is immobilized on an empty site of an octahedral sheet. In the lithium partially fixed type smectite, for example, lithium ions between layers are fixed to an empty site of an octahedral sheet by heat treatment of the lithium type smectite. By immobilizing lithium ions, smectite is made water resistant.

The temperature condition of the heat treatment for partially fixing lithium is not particularly limited as long as lithium ions can be fixed. As will be described later, when the cation exchange capacity is small, the water vapor barrier property and the oxygen barrier property of the resin composition containing the lithium partially fixed smectite are improved. Therefore, from the viewpoint of efficiently immobilizing lithium ions and significantly reducing the cation exchange capacity, it is preferable to heat the lithium ions to 150 ° C. or higher. The temperature of the heat treatment is more preferably 150 to 600 ° C, still more preferably 180 to 600 ° C, particularly preferably 200 to 500 ° C, and most preferably 300 to 500 ° C. By heating to the above temperature, the cation exchange capacity can be reduced more efficiently, and at the same time, the dehydration reaction of the hydroxyl group in smectite can be suppressed. The above heat treatment is preferably carried out in an open electric furnace. In this case, the relative humidity during heating is 5% or less, and the pressure is normal pressure. The time of the heat treatment is not particularly limited as long as the lithium can be partially fixed, but from the viewpoint of production efficiency, it is preferably 0.5 to 48 hours, more preferably 1 to 24 hours. preferable.

Usually, smectite is clay having a cation exchange capacity of 60-150 meq / 100 g, but the lithium partially fixed smectite of the embodiment preferably has a cation exchange capacity of 1 to 50 meq / 100 g. The cation exchange capacity of the lithium partially fixed smectite may be 5 to 50 meq / 100 g or 10 to 50 meq / 100 g. When the cation exchange capacity is within the above range, the water vapor barrier property and the oxygen barrier property of the resin composition are further excellent.

The cation exchange capacity of smectite can be measured by a method according to the Schollenberger method (Clay Handbook, 3rd edition, edited by Japan Clay Society, May 2009, p.453-454). More specifically, it can be measured by the method described in the standard test method JBAS-106-77 of the Japan Bentonite Industry Association.
The amount of leached cations of smectite was determined by leaching the interlayer cations of smectite with 0.5 g of smectite using 100 mL of a 1 M ammonium acetate aqueous solution over 4 hours or more, and adjusting the concentration of various cations in the obtained solution. , Can be measured and calculated by ICP emission spectrometry, atomic absorption spectrometry, or the like.

The content of the lithium partially fixed smectite is preferably 3 to 50% by mass with respect to the total amount of the non-volatile content in the resin composition. The non-volatile content is the mass excluding the mass of the diluting solvent and the mass of the volatile components contained in the polyalkyleneimine resin, the modifier and various additives from the total mass of the resin composition.

When the content of the lithium partially fixed smectite is 3% by mass or more with respect to the total amount of the non-volatile content, the water vapor barrier property and the oxygen barrier property are further excellent. Further, when the content of the lithium partially fixed smectite is 50% by mass or less, the moldability of the resin composition is further improved, and the adhesion to the substrate is improved. The content of the lithium partially fixed smectite is more preferably 5 to 35% by mass and further preferably 7 to 20% by mass with respect to the total amount of the non-volatile content in the resin composition.

The resin composition of the embodiment contains a polyalkyleneimine resin. The polyalkyleneimine resin is a resin having a polyalkyleneimine skeleton, and is obtained by polymerizing one or more of alkyleneimines (for example, ethyleneimine and propyleneimine) by a conventional method. The polyalkyleneimine resin may have a linear polyalkyleneimine chain or a branched polyalkyleneimine chain. The polyalkyleneimine resin may be a linear polyalkyleneimine resin composed of a linear polyalkyleneimine chain or a branched polyalkyleneimine resin having a branched polyalkyleneimine chain, but may be synthesized. It is preferable to use a branched polyalkyleneimine resin because it is easy to use and the molecular weight can be adjusted. The branched polyalkyleneimine resin is preferably a branched polyethyleneimine resin. Examples of the polyalkyleneimine resin include polyethyleneimine and polypropyleneimine. The polyalkyleneimine resin may be one in which a substituent (for example, a hydroxypropyl group or a hydroxyethyl group) is introduced into at least a part of the nitrogen atoms of the polyalkyleneimine chain.

Commercially available polyalkyleneimine resins include Epomin SP-006 (trade name: Nippon Catalyst Co., Ltd., polyethyleneimine, number average molecular weight: 600, branched polyethyleneimine resin), Epomin P-1000 (trade name:). Nippon Catalyst Co., Ltd., polyethyleneimine, number average molecular weight: 70000, branched polyethyleneimine resin), Epomin PP-061 (trade name: Nippon Catalyst Co., Ltd., PO (propylene oxide) modified polyethyleneimine, N-hydroxypropylpolyethyleneimine , Number average molecular weight of about 1400, branched polyethyleneimine resin) and the like.

The number average molecular weight of the polyalkyleneimine resin of the embodiment is preferably 300 to 70,000 from the viewpoint of lower viscosity, and more preferably 1,000 to 70,000 from the viewpoint of storage stability and safety.

The number average molecular weight of the polyalkyleneimine resin can be measured by a known and commonly used measuring method, and can be measured by, for example, a boiling point elevation method or a viscosity method.

In the embodiment, one kind of polyalkyleneimine resin may be used alone, or a plurality of polyalkyleneimine resins may be used in combination.

The content of the polyalkyleneimine resin may be 50 to 97% by mass, 70 to 93% by mass, or 80 to 95% by mass with respect to the total amount of the non-volatile content in the resin composition. Good. When the content of the polyalkyleneimine resin is 50% by mass or more, the water vapor barrier property and the oxygen barrier property are further excellent. Further, when the content of the polyalkyleneimine resin is 97% by mass or less, the moldability of the resin composition becomes further excellent.

The resin composition may be obtained by synthesizing a polyalkyleneimine resin and mixing the synthesized polyalkyleneimine resin with a lithium partially fixed smectite. In this case, as the polyalkyleneimine resin, the above-mentioned commercially available one may be used as it is. Further, the resin composition may be obtained by blending alkyleneimine and lithium partially fixed smectite and then polymerizing alkyleneimine.

The resin composition may further contain a modifier. Examples of the modifier include a coupling agent, a silane compound, an acid anhydride and the like. When the resin composition contains these modifiers, the wettability of the lithium partially fixed smectite is improved, and the dispersibility in the resin composition is improved. As the modifier, one type may be used alone, or a plurality of types may be used in combination.

Examples of the coupling agent include a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent and the like.

Examples of the silane coupling agent include an epoxy group-containing silane coupling agent, an amino group-containing silane coupling agent, a (meth) acrylic group-containing silane coupling agent, and an isocyanate group-containing silane coupling agent. Examples of the epoxy group-containing silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2- (3,4 epoxycyclohexyl). ) Ethyltrimethoxysilane and the like. Examples of the amino group-containing silane coupling agent include 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and 3-triethoxysilyl-N- (1,3-dimethyl). Butylidene) Propylamine, N-phenyl-γ-aminopropyltrimethoxysilane and the like can be mentioned. Examples of the (meth) acrylic group-containing silane coupling agent include 3-acryloyloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane. Examples of the isocyanate group-containing silane coupling agent include 3-isocyanatepropyltriethoxysilane and the like.

Examples of the titanium coupling agent include isopropyltriisostearoyl titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropylisostearoyldiacyl titanate, isopropyltris (dioctylpyrophosphate) titanate, and tetraoctylbis (ditridecyl). Examples thereof include phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, and bis (dioctylpyrophosphate) ethylene titanate.

Examples of the zirconium coupling agent include zirconium acetate, ammonium zirconium carbonate, zirconium fluoride and the like.

Examples of the aluminum coupling agent include acetalkoxyaluminum diisopropyrate, aluminum diisopropoxymonoethylacetate, aluminumtrisethylacetate, aluminumtrisacetylacetonate and the like.

Examples of the silane compound include alkoxysilane, silazane, and siloxane. Examples of alkoxysilanes include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, and hexyltri. Examples thereof include methoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis (trimethoxysilyl) hexane, trifluoropropyltrimethoxysilane and the like. Examples of the silazane include hexamethyldisilazane and the like. Examples of the siloxane include hydrolyzable group-containing siloxane.

Examples of acid anhydrides include succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methyl. Hexahydrophthalic anhydride alkenyl succinic anhydride and the like can be mentioned.

The blending amount of the modifier is preferably 0.1 to 50% by mass with respect to the total amount of the lithium partially fixed smectite. When the blending amount of the modifier is 0.1% by mass or more, the dispersibility of the lithium partially fixed smectite in the resin composition becomes better. Further, if the blending amount of the modifier is 50% by mass or less, the influence of the modifier on the mechanical properties of the resin composition can be further suppressed. The blending amount of the modifier is preferably 0.3 to 30% by mass, more preferably 0.5 to 15% by mass.

The resin composition may contain a solvent depending on the intended use. Examples of the solvent include organic solvents such as methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, toluene, dimethylformamide, acetonitrile, methyl isobutyl ketone, methanol, ethanol, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate and propylene glycol. Examples thereof include monomethyl ether acetate. The type and amount of the solvent may be appropriately selected depending on the intended use.

The resin composition may contain various additives (excluding polyalkyleneimine resins, lithium partially fixed smectites, and compounds corresponding to modifiers) as long as the effects of the present invention are not impaired. Additives include, for example, organic fillers, inorganic fillers, stabilizers (antioxidants, heat stabilizers, UV absorbers, etc.), plasticizers, antistatic agents, lubricants, antiblocking agents, colorants, crystal nucleating agents, etc. Examples thereof include oxygen scavengers (compounds having an oxygen scavenging function), antistatic agents and the like.
Among the additives, examples of the inorganic filler include inorganic substances such as metals, metal oxides, resins, and minerals, and a composite thereof may be used. Specific examples of the inorganic filler include silica, alumina, titanium, zirconia, copper, iron, silver, mica, talc, aluminum flakes, glass flakes, and clay minerals. Among these, it is preferable to add clay minerals for the purpose of improving the gas barrier property, and it is particularly preferable to use a swellable inorganic layered compound. Examples of the swellable inorganic layered compound include hydrous silicates (phylosilicate minerals, etc.), kaolinite group clay minerals (haloisite, etc.), smectite group clay minerals (montmorillonite, biderite, nontronite, saponite, hectrite, etc.). Saconite, Stephensite, etc.), vermiculite group clay minerals (vermiculite, etc.). These minerals may be natural clay minerals or synthetic clay minerals. These various additives may be used alone or in combination of two or more.

Examples of the compound having an oxygen trapping function include low molecular weight organic compounds that react with oxygen such as hindered phenols, vitamin C, vitamin E, organic phosphorus compounds, gallic acid, and pyrogallol, cobalt, manganese, nickel, iron, and the like. Examples thereof include transition metal compounds such as copper.

Examples of the tackifier include xylene resin, terpene resin, phenol resin, rosin resin and the like. By adding a tackifier, the tackiness to various film materials immediately after application can be improved. The amount of the tackifier added is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the total amount of the resin composition.

The molded product of the embodiment can be obtained by molding the above-mentioned resin composition. The molding method is arbitrary and may be selected in a timely manner depending on the intended use. The shape of the molded body is not limited, and it may be in the form of a plate, a sheet, or a film, may have a three-dimensional shape, may be coated on a base material, and may be a base material. It may be molded so as to exist between the substrates.

When producing a plate-shaped or sheet-shaped molded body, the resin composition is molded by using, for example, an extrusion molding method, a flat press, a deformed extrusion molding method, a blow molding method, a compression molding method, a vacuum molding method, an injection molding method, or the like. There is a way to do it. When producing a film-shaped molded product, for example, melt extrusion method, solution casting method, inflation film molding, cast molding, extrusion lamination molding, calendar molding, sheet molding, fiber molding, blow molding, injection molding, rotary molding, Coating molding can be mentioned. When the resin composition is cured by heat or active energy rays, the resin composition may be molded by using various curing methods using heat or active energy rays.

When the resin composition is liquid, it may be molded by coating. As a coating method, a spray method, a spin coating method, a dip method, a roll coating method, a blade coating method, a doctor roll method, a doctor blade method, a curtain coating method, a slit coating method, a screen printing method, an inkjet method, a dispense method, etc. Can be mentioned.

The laminated body of the embodiment is provided with the above-mentioned molded body on the base material. The laminated body may have a two-layer structure or may have a three-layer structure or more.

The material of the base material is not particularly limited and may be appropriately selected depending on the intended use. Examples thereof include wood, metal, plastic, paper, silicon and modified silicon, and the base material obtained by joining different materials. There may be. The shape of the base material is not particularly limited, and may be any shape depending on the purpose, such as a flat plate, a sheet shape, or a three-dimensional shape having a curvature on the entire surface or a part thereof. Further, there are no restrictions on the hardness, thickness, etc. of the base material.

The laminated body can be obtained by laminating the above-mentioned molded body on the base material. The molded product to be laminated on the base material may be formed by direct coating or direct molding on the base material, or the molded product of the resin composition may be laminated. In the case of direct coating, the coating method is not particularly limited, and the spray method, spin coating method, dip method, roll coating method, blade coating method, doctor roll method, doctor blade method, curtain coating method, slit coating method, etc. Examples include a screen printing method and an inkjet method. In the case of direct molding, in-mold molding, insert molding, vacuum forming, extrusion laminating molding, press molding and the like can be mentioned. When the molded product of the resin composition is laminated, the uncured or semi-cured resin composition layer may be laminated on the substrate and then cured, or the cured product layer in which the resin composition is completely cured may be laminated on the substrate. It may be laminated on.

Further, the laminate may be obtained by applying a substrate precursor to a cured product of the resin composition and curing it, and the substrate precursor or the resin composition is uncured or semi-cured. It may be obtained by adhering in a state and then curing. The precursor of the base material is not particularly limited, and examples thereof include various curable resin compositions. Further, a laminate may be prepared by using the resin composition of the embodiment as an adhesive.

Since the resin composition of the embodiment is excellent in water vapor barrier property and oxygen barrier property, it can be suitably used as a gas barrier material.

The resin composition can be suitably used as a coating material. The coating material may be any one containing the above-mentioned resin composition. The coating method of the coating material is not particularly limited. As a specific method, various coating methods such as roll coating and gravure coating can be exemplified. Further, the coating device is not particularly limited.

Since the resin composition has excellent adhesiveness, it can be suitably used as an adhesive. The form of the adhesive is not particularly limited, and it may be a liquid or paste-like adhesive, or it may be a solid adhesive. Since the resin composition has a high gas barrier property, this adhesive can be suitably used as an adhesive for a gas barrier.

In the case of a liquid or paste-like adhesive, the method of use is not particularly limited, but the adhesive may be adhered and cured after being applied to the adhesive surface or injected into the interface of the adhesive surface.

In the case of a solid adhesive, an adhesive formed into a powder, a chip, or a sheet may be placed at the interface of the adhesive surface and thermally melted to adhere and cure.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

As the filler contained in the resin composition, lithium partially fixed smectite or non-lithium partially fixed smectite was used. As the lithium partially fixed smectite, a montmorillonite dispersion slurry (RCEC-W, cation exchange capacity 39.0 meq / 100 g) manufactured by Kunimine Kogyo Co., Ltd. was used. The content (w / w%) of the lithium partially fixed smectite in this dispersed slurry was 20 w / w%. As smectite not partially fixed with lithium, natural montmorillonite (Kunipia F, cation exchange capacity 108 meq / 100 g, manufactured by Kunimine Kogyo Co., Ltd.) was used.

(Example 1)
The lithium partially fixed smectite slurry was modified with 33.2 parts by mass, acetone with 64 parts by mass, and isopropanol with 25.6 parts by mass with respect to 100 parts by mass of polyethyleneimine (Epomin P-1000, manufactured by Nippon Catalyst Co., Ltd.). As an agent, 0.33 parts by mass of hexamethyldisilazane (trade name: LS-7150, manufactured by Shinetsu Chemical Industry Co., Ltd.) was added, and the mixture was stirred and held for 8 hours to obtain the resin composition of Example 1. This was designated as the coating liquid 1.

The obtained coating liquid 1 is dried on the corona-treated surface of a corona-treated 12 μm polyethylene terephthalate (PET) film (“E-5100” manufactured by Toyobo Co., Ltd.) using a bar coater, and the coating thickness is 2 μm. I painted it so that it would be. Immediately after coating, the PET film after coating was heat-treated in a dryer at 120 ° C. for 1 minute, and then heat-treated in a dryer at 130 ° C. for 2 hours. As a result, a molded product of the resin composition of Example 1 was formed on the PET film, and a laminated film of Example 1 was obtained.

In the resin composition and molded article of Example 1, the content (filler amount) of the lithium partially fixed smectite is 18% by mass with respect to the total amount of the non-volatile content, and the compounding amount of the modifier (modifier amount) is It was 5% by mass based on the total amount of lithium partially fixed smectite.

( Reference example 2)
For 100 parts by mass of polyethyleneimine (Epomin P-1000), 350 parts by mass of the lithium partially fixed smectite slurry, 700 parts by mass of acetone, 277 parts by mass of isopropanol, and 3.5 parts by mass of LS-7150 as a modifier. The resin composition of Reference Example 2 was obtained by adding a portion and holding the mixture for 8 hours with stirring. This was used as the coating liquid 2.

Except for using a coating liquid 2 instead of the coating liquid 1 in the same manner as in Example 1 to form a molded article of the resin composition in Reference Example 2, to obtain a laminated film of Reference Example 2.

In the resin composition and the molded product of Reference Example 2, the content (filler amount) of the lithium partially fixed smectite is 70% by mass with respect to the total amount of the non-volatile content, and the compounding amount of the modifier (modifier amount) is It was 5% by mass based on the total amount of lithium partially fixed smectite.

(Comparative Example 1)
To 100 parts by mass of polyethyleneimine (Epomin P-1000), 70 parts by mass of Kunipia F, 700 parts by mass of acetone, 277 parts by mass of isopropanol, and 3.5 parts by mass of LS-7150 as a modifier were added for 8 hours. The mixture was kept with stirring to obtain the resin composition of Comparative Example 1. This was designated as the comparative coating liquid 1.

A molded body of the resin composition of Comparative Example 1 was formed in the same manner as in Example 1 except that the comparative coating liquid 1 was used instead of the coating liquid 1, to obtain a laminated film of Comparative Example 1.

In the resin composition and molded article of Comparative Example 1, the content (filler amount) of natural montmorillonite is 70% by mass with respect to the total amount of non-volatile content, and the blending amount (modifier amount) of the modifier is the total amount of natural montmorillonite. It was 5% by mass with respect to.

(Comparative Example 2)
50 parts by mass of water was added to 100 parts by mass of polyethyleneimine (Epomin P-1000), and the mixture was stirred and held for 20 minutes to obtain the resin composition of Comparative Example 2. This was designated as the comparative coating liquid 2.
A molded body of the resin composition of Comparative Example 2 was formed in the same manner as in Example 1 except that the comparative coating liquid 2 was used instead of the coating liquid 1, to obtain a laminated film of Comparative Example 2. The resin composition and the molded product of Comparative Example 2 do not contain a filler.

<Evaluation>
The film-forming property, oxygen permeability, and water vapor permeability of the laminated films of Examples, Comparative Examples, and Reference Examples were evaluated. The evaluation results are shown in Table 1. The film forming property, oxygen permeability and water vapor permeability were evaluated by the following methods.

(Film film property)
When the coated surface of the laminated film was smooth, it was evaluated as "◯", and when the coated surface was not smooth, it was evaluated as "x".

(Oxygen permeability)
The oxygen transmission rate is measured according to JIS-K7126 (isopressure method) using the oxygen transmission rate measuring device OX-TRAN1 / 50 manufactured by Mocon Co., Ltd. in an atmosphere of temperature 23 ° C. and humidity 0% RH, and temperature 23. It was carried out in an atmosphere of ° C. and humidity of 90% RH. In addition, RH represents relative humidity.

(Water vapor permeability)
The water vapor transmittance was measured according to JIS-K7129 using a water vapor transmittance measuring device 7001 manufactured by Irinoi Co., Ltd. in an atmosphere of a temperature of 40 ° C. and a humidity of 90% RH.

Since the resin composition of the present invention is excellent in gas barrier property, particularly water vapor barrier property and oxygen barrier property, it can be suitably used in various fields such as packaging materials, electronic materials, and building materials.

Claims (9)

A resin composition containing a polyalkyleneimine resin and a lithium partially fixed smectite .
The content of the polyalkyleneimine resin is 70 to 93% by mass with respect to the total amount of the non-volatile content in the resin composition . The resin composition according to claim 1, wherein the polyalkyleneimine resin is a branched polyalkyleneimine resin. The resin composition according to claim 1 or 2, wherein the lithium partially fixed smectite has a cation exchange capacity of 1 to 50 meq / 100 g. The resin composition according to any one of claims 1 to 3, wherein the content of the lithium partially fixed smectite is 3 to 20% by mass with respect to the total amount of the non-volatile content of the resin composition. A molded product of the resin composition according to any one of claims 1 to 4. A laminate comprising the molded product according to claim 5 on a base material. A gas barrier material containing the resin composition according to any one of claims 1 to 4. A coating material containing the resin composition according to any one of claims 1 to 4. An adhesive containing the resin composition according to any one of claims 1 to 4.