JP3204053B2 - Food packaging materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a food packaging material having an excellent gas barrier property which is optimal for food packaging.

[0002]

2. Description of the Related Art Packaging materials have various required characteristics. For example, JIS for plastic film for food packaging
In Z 1707, various performances required as food packaging plastic films are graded and defined,
Strength, elongation, mechanical properties such as impact resistance and heat sealability, or cold resistance, heat resistance, special conditions depending on the type of food used such as oil and fat resistance, etc., as gas permeability, that is, as gas barrier properties, The moisture permeability (water vapor permeability), oxygen permeability, and carbon dioxide permeability are listed. This gas barrier property is an important property not only in food packaging but also in pharmaceutical packaging, electronic component packaging, and other various packaging materials.

When a gas barrier property is imparted to a packaging material, only a material film having an excellent gas barrier property such as an ethylene-vinyl alcohol copolymer, an aromatic nylon, or polyvinylidene chloride may be used. Since many characteristics are required for the material, a laminated material is generally used. The laminated material is formed by laminating layers having respective functions, such as a layer responsible for strength, a layer responsible for heat sealing, a layer responsible for blocking oxygen, and a layer responsible for blocking water vapor. Coating, lamination, co-extrusion, metal deposition, and the like are known.

[0004]

However, there is still room for improvement in the above-mentioned laminated material, and attempts to improve the performance of each layer have been continuously made. In particular, food packaging materials that are easily affected by external influences such as oxygen are required to have even higher gas barrier properties. Therefore, an object of the present invention is to provide a food packaging material having a gas barrier layer having excellent gas barrier properties and also having excellent heat resistance, flexibility, transparency, moisture resistance, and solvent resistance. Things.

[0005]

The food packaging material of the present invention comprises a base material, an organic compound (A) having a primary and / or secondary amino group in the molecule, represented by the following general formula (I). organometallic compound (B) and / or a hydrolysis-condensation product _{^{which, R 1 m M (oR 2}} ) n ... (I) ( wherein M represents a metal element, R ¹ is may be the same or different, a hydrogen atom Represents a lower alkyl group, an aryl group, a vinyl group or a mercapto group directly bonded to a carbon chain, or a (meth) acryloyl group, and R ² may be the same or different and represents a hydrogen atom, a lower alkyl group or an acyl group. , M is 0 or a positive integer, n is an integer of 1 or more, and m + n is equal to the valency of the metal element M) and a solvent (D). The resulting gas barrier layer The olefin-based resin film layer is laminated on the gas barrier layer or ethylene - with the gist where the vinyl acetate copolymer film layer contains. The olefin-based resin film layer is preferably a non-stretched polypropylene layer or a linear low-density polyethylene layer. Further, it is preferable that the gas barrier composition further contains a compound (C) having a functional group capable of reacting with an amino group in the molecule. In the present invention, the organic compound (A) having a primary and / or secondary amino group in the molecule is represented by the following general formula (I)
I)

[0006]

Embedded image Wherein A ¹ is an alkylene group, R ³ is a hydrogen atom, a lower alkyl group, or

[0007]

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Wherein A ² represents a direct bond or an alkylene group, and R ⁷ and R ⁸ represent a hydrogen atom or a lower alkyl group.
R ⁴ represents a hydrogen atom or a lower alkyl group, R ⁵ represents the same or different lower alkyl group, aryl group or unsaturated aliphatic residue, and R ⁶ represents a hydrogen atom, a lower alkyl group or an acyl group. (However, R ³ , R ⁴ , R ⁷ , R
⁸ is at least one hydrogen atom), w is 0,
And z represents an integer of 1, 2, or 3 (where w + z = 3)] and / or a hydrolytic condensate thereof. And the organic compound (A ″) having no Si (OR ⁶ ) group (the meaning of R ⁶ is the same as described above). When it is the compound (A ″), the compound (A ″)
Is preferably a polyethyleneimine. Also,
The compound (C) in the composition for gas barrier is a compound having an epoxy group as a functional group capable of reacting with an amino group, or the compound (C) further comprises

[0009]

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[0010] A preferred embodiment is a compound (C ') having (wherein, R ⁵ , R ⁶ , w, and z have the same meanings as described above).

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is a food packaging material including a gas barrier layer obtained by coating a specific gas barrier composition on a substrate. That is, of the above-mentioned laminated materials, the layer having gas barrier properties is characterized, and other properties may be imparted by the other layers to be laminated. In order to provide a packaging material for foods, a gas barrier composition capable of forming a coating film having excellent properties such as heat resistance, flexibility, transparency, moisture resistance, and solvent resistance as well as gas barrier properties has been found. Things. This will be described in detail below.

According to the present invention, there are provided a substrate and a primary and / or intramolecular molecule.
Or organic compounds having a secondary amino group (A), the following general formula organometallic compound represented by (I) (B) and / or its hydrolytic _{^{condensate, R 1 m M (OR 2}} ) n ... (I) (However, the meanings of M, R ¹ , R ² , m, and n are as described above) and a gas barrier composition containing a solvent (D) as an essential component; Disclosed is a food packaging material comprising an olefin-based resin film layer or an ethylene-vinyl acetate copolymer film layer laminated on a layer.

[0013] In the molecule used in the present invention, primary and / or
Or an organic compound (A) having a secondary amino group
Any compound having at least one secondary and / or secondary amino group in the molecule may be used, and may be a low molecular compound or a high molecular compound. In the present invention, when the organic compound (A) is an organic silane compound (A ′) having a hydrolyzable group together with the amino group, the organic compound (A) may be a hydrolyzable Si (OR ⁶ ) group (wherein R ⁶ Organic compounds (A ") having no meaning (as described above) are roughly classified. Of course, an organic silane compound (A ') and an organic compound (A") may be used as a mixture. The organosilane compound (A ′) is represented by the following general formula (II).

[0014]

Embedded image (In the formula, A ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , w, and z have the same meanings as described above.)

As a specific example of the above (A '), N-β-
(Aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-
Aminopropyltriisopropoxysilane, N-β-
(Aminoethyl) -γ-aminopropyltributoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β- (aminoethyl)-
γ-aminopropylmethyldiethoxysilane, N-β-
(Aminoethyl) -γ-aminopropylmethyldiisopropoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldibutoxysilane, N-β- (aminoethyl) -γ-aminopropylethyldimethoxysilane, N-β- (aminoethyl) -γ-aminopropylethyldiethoxysilane, N-β- (aminoethyl) -γ
-Aminopropylethyldiisopropoxysilane, N-
β- (aminoethyl) -γ-aminopropylethyldibutoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, N-
β- (N-vinylbenzylaminoethyl) -γ-aminopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltriisopropoxysilane, N-β- (N-vinylbenzyl Aminoethyl) -γ-aminopropyltributoxysilane, N
-Β- (N-vinylbenzylaminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropylmethyldiethoxysilane, N-β- (N-vinyl Benzylaminoethyl) -γ-aminopropylmethyldiisopropoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropylmethyldibutoxysilane, N
-Β- (N-vinylbenzylaminoethyl) -γ-aminopropylethyldimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropylethyldiethoxysilane, N-β- (N-vinyl Benzylaminoethyl) -γ-aminopropylethyldiisopropoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropylethyldibutoxysilane, γ
-Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropyltributoxysilane, γ-aminopropylmethyldimethoxysilane, γ
-Aminopropylmethyldiethoxysilane, γ-aminopropylmethyldiisopropoxysilane, γ-aminopropylmethyldibutoxysilane, γ-aminopropylethyldimethoxysilane, γ-aminopropylethyldiethoxysilane, γ-aminopropylethyldi Examples include isopropoxysilane, γ-aminopropylethyldibutoxysilane, γ-aminopropyltriacetoxysilane, and the like, and one or more of these can be used.

The organic compound (A ″) does not have a hydrolyzable Si (OR ⁶ ) group (however, the meaning of R ⁶ is as described above) and has a primary and / or secondary amino group. Specific examples thereof include organic compounds such as allylamine, diallylamine, isopropylamine, diisopropylamine, iminobispropylamine, ethylamine, diethylamine, 2-ethylhexylamine, 3-ethoxypropylamine, diisobutylamine, 3-diethylaminopropylamine, and diethylamine. -2-ethylhexylamine, dibutylaminopropylamine, propylamine, dimethylaminopropylamine, methyliminobispropylamine, 3-methoxypropylamine, ethylenediamine, 1,4-diaminobutane, 1,2-diaminopropane, 1,3 −Jami Propane, hexamethylenediamine, ethanolamine, low-molecular organic compound such as diethanolamine, polyethyleneimines, for example Nippon Shokubai Co., Ltd. Epo Min Series (Epomin SP-003, Epomin SP-006, Epomin SP-012, Epomin SP-
018, Epomin SP-103, Epomin SP-11
0, epomin SP-200, epomin SP-300, epomin SP-1000, epomin SP-1020, etc.),
Polyallylamines (for example, PAA-L manufactured by Nitto Boseki Co., Ltd.
PAA-H, etc.), homopolymers of amino group-containing (meth) acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate, and these amino group-containing (meth) acrylates and other (meth) acrylates And high molecular organic compounds such as copolymers with (meth) acrylic acid and polyoxyethylene alkylamines.

Particularly excellent gas barrier properties are the compounds exemplified as the organic silane compound (A '), ethanolamine in the organic compound (A "), and a high molecular weight organic compound. In order to improve the properties, the compound exemplified as the organic compound (A ′) having a hydrolyzable group may be preliminarily (co) hydrolyzed and condensed to a high molecular weight as described later, or the organic compound (A ″) may be used. It is more advantageous to use a high molecular organic compound in the above. Among the high molecular weight organic compounds, it is particularly preferable to use polyethyleneimines which have good gas barrier properties and other properties of the obtained coating film.
When a high molecular weight organic compound is used as the organic compound (A "), the preferred molecular weight is from 250 to 200,000, more preferably from 250 to 100,000. This is because flexibility is inferior, and conversely, if it is more than 200,000, transparency is inferior, which is not preferable as a food packaging material.

The organometallic compound (B) used as an essential component together with the organic compound (A) as a gas barrier composition in the present invention is represented by the following general formula (I). R ¹ _mm (OR ² ) _n (I) (where M, R ¹ , R ² , m and n have the same meanings as described above)

Specifically, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane , Ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane,
Diethyldimethoxysilane, diethyldiethoxysilane, diethyldiisopropoxysilane, diethyldibutoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, γ-mercaptopropyltrimethoxysilane, γ -Alkoxysilanes such as mercaptopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, titanium tetraethoxide,
Titanium alkoxides such as titanium tetraisopropoxide and titanium tetrabutoxide, zirconium alkoxides such as zirconium tetraethoxide, zirconium tetraisopropoxide and zirconium tetrabutoxide, aluminum triethoxide, aluminum triisopropoxide and aluminum tributoxide Aluminum alkoxides, acyloxysilanes such as tetraacetoxysilane and methyltriacetoxysilane, and silanols such as trimethylsilanol. One or more of these can be used. Among them, tetramethoxysilane and tetraethoxysilane are preferred from the viewpoint of reducing the humidity dependence of the gas barrier properties of the coating film.

The amount of the organometallic compound (B) to be used is 50 to 50 parts with respect to the organic compound (A) [including the organic compounds (A ′) and (A ″) unless otherwise specified).
Preferably it is 2000% by weight. If the amount of the organometallic compound (B) is less than 50% by weight, the moisture resistance of the gas barrier layer will be inferior, but if it exceeds 2,000% by weight, the flexibility of the coating film will deteriorate. The more preferable amount of the organometallic compound (B) used is 50 to 1500% by weight, and the most preferable range is 80 to 1500% by weight based on the organic compound (A).

In order to prevent the evaporation of the organometallic compound (B) during drying during the formation of the coating film, the organometallic compound (B) is preferably subjected to hydrolysis and condensation in advance. Co-hydrolysis condensation with the above-mentioned organic compound (A ') or the compound (C') described below may be performed. For the (co) hydrolysis condensation reaction, a known catalyst can be used, and it is advantageous to carry out the reaction in a solvent (D) described below.

In the present invention, the compound (C) having a functional group capable of reacting with the amino group of the organic compound (A) is preferably present in the composition for gas barrier. The compound (C) functions as a cross-linking agent, so that a denser coating film having excellent gas barrier properties can be obtained. The functional group capable of reacting with the amino group in the compound (C) includes an epoxy group, a carboxyl group, an isocyanate group, an oxazolinyl group, a hydroxyl group, an alkoxysilyl group and the like. This functional group
In the compound (C), it is preferable that the number is plural, and in that case, the functional groups may be the same or different. The epoxy group is the most reactive among the above functional groups. In order to further improve the water resistance of the coating film, the compound (C) preferably has an aromatic ring or a hydrogenated ring thereof. When the organic compound (A ″) is used as the organic compound (A), the compound (C) may have a hydrolyzable group together with the functional group capable of reacting with an amino group.

[0023]

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It is preferable that the compound (C ') has the following formula (wherein the meanings of R ⁵ , R ⁶ , w and z are as described above).
The compound (C ′) reacts with the amino group in the organic compound (A ″) and is used alone or in an organometallic compound (B).
(A ") because (co) hydrolysis condensation polymerization reaction with
This is because a dense gas barrier layer having excellent flexibility and the like in which (B) is combined with (C ′) and (B) can be formed. When the organic compound (A) is an organic silane compound (A ′),
Since the organic compound (A ′) has the hydrolyzable group, the compound (C) does not need to be the compound (C ′),
(Co) hydrolysis-condensation reaction of the organic compound (A ') alone or with the organometallic compound (B), and (A') and the compound (C)
A high-performance gas barrier layer can be formed by a reaction like a crosslinking agent. Of course, the compound (C ′) may be used in combination.

Specific examples of the compound (C) which can be used in the present invention include ethylene glycol diglycidyl ether,
Diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6- Aliphatic diglycidyl ethers such as hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and glycerol diglycidyl ether; glycerol triglycidyl ether;
Diglycerol triglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanurate,
Polyglycidyl ethers such as trimethylolpropane triglycidyl ether and pentaerythritol tetraglycidyl ether; aliphatic and aromatic diglycidyl esters such as adipic acid diglycidyl ester and o-phthalic acid diglycidyl ester; bisphenol A diglycidyl ether; Resorcin diglycidyl ether, hydroquinone diglycidyl ether, bisphenol S diglycidyl ether, bisphenol F diglycidyl ether, and compounds represented by the following formula

[0026]

Embedded image

Glycidyls having an aromatic ring or a hydrogenated ring thereof (including a nuclear-substituted derivative); or oligomers having a glycidyl group as a functional group (for example, in the case of bisphenol A diglycidyl ether oligomer, Can be expressed);

[0028]

Embedded image

Isocyanates such as hexamethylene diisocyanate, tolylene diisocyanate, 1,4-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, tolidine diisocyanate, xylylene diisocyanate, dicyclohexyl methane diisocyanate;
Examples thereof include dicarboxylic acids such as tartaric acid and adipic acid; carboxyl-containing polymers such as polyacrylic acid; and oxazolinyl group-containing polymers. One or more of these can be used. Among the compounds (C) exemplified above, compounds having an aromatic ring or a hydrogenated ring thereof (including a nuclear-substituted derivative) have an effect of further improving the water resistance of the gas barrier layer.

Specific examples of compound (C ′) include β-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriisopropoxysilane, β-
(3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ -Glycidoxypropyltriisopropoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, etc. (hereinafter sometimes abbreviated as epoxy group-containing silane coupling agent); γ -Isocyanopropyltrimethoxysilane, γ-isocyanopropyltriethoxysilane, γ-isocyanopropylmethyldimethoxysilane, γ-isocyanopropylmethyldiethoxysilane, etc. (hereinafter abbreviated as isocyanate group-containing silane coupling agent) Ah ) And the like, of these 1
Species or two or more can be used.

Compound (C) [hereinafter, unless otherwise specified,
Compound (C ′) is also included] when the functional group equivalent (X) of the amino group in the organic compound (A) is used.
It is recommended to use the compound (C) so that the functional group equivalent (Y) in the compound (C) is 0.01 to 1.0 as Y / X. Preferably, Y / X is in the range of 0.05 to 0.7, more preferably 0.05 to 0.3. Y / X is 0.01
If it is smaller, the flexibility of the coating film tends to be insufficient, and Y /
When X exceeds 1.0, gas barrier properties and heat resistance may decrease.

The solvent (D) used in the present invention is not particularly limited, but a solvent capable of dissolving or dispersing the components of the gas barrier composition is preferable. For example, alcohols such as methanol, ethanol, 2-propanol, butanol and ethylene glycol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, aromatic hydrocarbons such as toluene, benzene and xylene, hexane, heptane, octane and the like Hydrocarbons, ethyl acetate, esters such as butyl acetate, and others,
Examples thereof include tetrahydrofuran, propyl ether, and water, and one or more of these can be used as a mixture.

The gas barrier composition for imparting gas barrier properties to the packaging material of the present invention is, as described above,
Organic compound (A) and organometallic compound (B), solvent (D)
Is an essential component, and preferably contains the compound (C). When the organic compound (A) is an organic silane compound (A '), and when the compound (C) is a compound (C'), each of them has a hydrolyzable group together with the organometallic compound (B). Therefore, it is recommended to advance the (co) hydrolytic condensation reaction in advance, using each alone or using two or more of these. If these compounds are made to have a high molecular weight by hydrolysis and condensation, the film formability of the gas barrier layer is improved, and the uniformity and smoothness of the obtained coating film are further improved.

The (co) hydrolysis-condensation reaction proceeds with moisture in the air, but is preferably carried out in the solvent (D) since it can be used as it is as a gas barrier composition in the coating step. The reaction may be performed by adding a known acid or base as a reaction catalyst.

The method for preparing the gas barrier composition is not particularly limited. When the compound (C) is used, the amino group of the organic compound (A) is reacted with the functional group in the compound (C), and then the organic compound is reacted. Addition of the metal compound (B) or a hydrolysis-condensation product thereof improves the stability of the composition. When the organic compound (A) is (A ′) or the compound (C) is (C ′), after the amino group crosslinking reaction, before or after the addition of the organometallic compound (B). It is preferable to carry out a hydrolysis condensation reaction.

The above-mentioned composition for a gas barrier requires various inorganic and organic additives such as a curing catalyst, a wettability improver, a plasticizer, a defoaming agent and a thickener as long as the effects of the present invention are not impaired. May be added according to

The food packaging material of the present invention comprises a substrate coated with the composition for a gas barrier having the above constitution. As the substrate, a plastic film is generally used, but a plastic molded body (for example, a bottle or a container) having higher rigidity than the film may be used as the substrate. The type of the plastic constituting the film and the molded product is not particularly limited, and examples thereof include olefin resins such as polyethylene and polypropylene, styrene resins such as polystyrene, polyethylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalate, and polystyrene. Polyesters such as butylene terephthalate and copolymers thereof, polyamide resins, acrylic resins such as poly (meth) acrylic acid and esters thereof, polyoxymethylene, polyacrylonitrile, polyvinyl acetate,
Ethylene-vinyl acetate copolymer (EVA), polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyether ketone, polycarbonate, cellophane, polyether sulfone, polysulfone, polyphenylene sulfone, polyimide , Ionomer resin, thermoplastic resin such as fluororesin, melamine resin, polyurethane resin, epoxy resin,
Thermosetting resins such as phenol resins, unsaturated polyester resins, alkyd resins, urea resins, and silicon resins can be preferably used. Of course, two or more of these laminates may be used as the base material.

The method for applying the gas barrier composition to the above-mentioned substrate is not particularly limited.
A dip coating method, a bar coating method, a die coating method, or a combination thereof can be used. Among them, the die coating method is preferred because it increases the stability of the gas barrier composition. The gas barrier composition is applied to one side or both sides of a film substrate.
It is recommended that drying after coating be performed in a heating / humidifying step of 50 ° C. or more and RH of 5% or more, since a dense film can be formed with good drying efficiency. Prior to the application of the gas barrier composition, a known anchor coat layer such as a urethane resin may be provided on the substrate.

The thickness of the gas barrier layer is 0.1 to
A range of 10 μm is suitable. Preferably 0.3-5μ
m, more preferably 0.5 to 3 μm. If the gas barrier layer is thinner than 0.1 μm, the object of the present invention cannot be achieved because the gas barrier properties of the substrate become insufficient. Conversely 10 μm
If the thickness is larger, cracks occur in the gas barrier layer, and it is impossible to impart excellent gas barrier properties to the substrate.

Although the substrate provided with the gas barrier layer may be used as it is as a packaging material, a non-toxic layer emphasizing safety, a layer responsible for strength, a layer responsible for heat sealing, a layer having good printability, It is recommended to use a laminate of layers having various functions, such as a layer responsible for chemical properties and a layer responsible for blocking water vapor, as a packaging material. As a laminating means,
As a substrate for coating the gas barrier layer, a material laminated by a coating method, an extrusion method, a dry lamination, a wet lamination, a lamination method such as a hot melt lamination, or the like, or after coating the gas barrier layer, further performing coating or vapor deposition ,
Lamination method and the like can be mentioned. Of course, a plurality of base materials provided with a gas barrier layer may be laminated. The material to be laminated is a plastic (the aforementioned
Thermoplastic resin or thermosetting resin described in [0037])
In addition, wood, cloth, nonwoven fabric, paper, synthetic paper, metal, metal foil, etc.
Known packaging materials can be used. If needed for lamination,
A known adhesive may be used.

The packaging material of the present invention has a gas barrier layer having excellent gas barrier properties, particularly excellent oxygen barrier properties, and excellent heat resistance, flexibility, transparency, moisture resistance, solvent resistance and the like.
For example, it is suitable for the food field where severe processing such as retort processing, freezing processing and subsequent heating processing is performed. For example, the main packaged goods in the food field include meat, seafood,
Uncooked or cooked foods such as fruits and vegetables, retort foods, frozen foods, processed foods such as sausages, kamaboko, ham,
Cooked foods such as mochi, pickles, raw (semi-raw) noodles, boiled in tsukudani,
Tea, dried foods such as bonito and freeze-dried foods, dried foods such as confectionery, viscous substances such as miso, jam, semi-liquid substances such as mayonnaise and ketchup, liquid substances such as oil, soy sauce, vinegar, sake and other beverages No. Further, the packaging material of the present invention can be applied to electronic components such as pharmaceuticals and LSIs that require strict oxygen barrier properties, and can be used as packaging materials in all fields.

[0042]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which do not limit the present invention.
Modifications and alterations that do not depart from the spirit described below are all included in the technical scope of the present invention. Note that the oxygen permeability is a result of a measurement using an oxygen permeability measuring device manufactured by MOCON under conditions of a temperature of 20 ° C. and a humidity of 90% Rh.

Synthesis Example 1 γ was added to a flask equipped with a stirrer, thermometer, and condenser.
-40 g of aminopropyltrimethoxysilane and 50 g of toluene were charged and heated to 70 ° C under a nitrogen atmosphere. Next, a mixed solution of 22 g of resorcinol diglycidyl ether and 10 g of toluene was added dropwise over 20 minutes, and the mixture was kept at 70 ° C. for 3 hours. Then, a mixed solution of 18 g of methanol and 1.25 g of water was added. After aging for a time, the hydrolysis reaction was allowed to proceed. Further, tetramethoxysilane 4
2 g and toluene 50 g were added to obtain a gas barrier composition 1.

Synthesis Example 2 Epomin SP-018 (polyethyleneimine manufactured by Nippon Shokubai) was placed in a flask equipped with a stirrer, thermometer, and cooler.
7.18 g, 3.25 g of γ-glycidoxypropyltrimethoxysilane, and 21.1 g of methanol were charged, and the mixture was stirred at 65 ° C. for 3 hours under a nitrogen atmosphere, cooled to room temperature, and cooled with 0.1 g of water and 5 g of methanol. The mixture was added dropwise over 15 minutes and further stirred at room temperature for 1 hour. Next, a mixed solution of 52.0 g of tetramethoxysilane and 15.4 g of methanol was added to the reaction solution, and the mixture was stirred at room temperature for 3 hours to obtain composition 2 for gas barrier.

Examples 1 to 7 The gas barrier composition 1 or 2 obtained in the above synthesis example was applied to the base material shown in Table 1 so that the thickness after drying became 3 μm. It was dried at Rh for 5 seconds and then aged at 50 ° C. for 2 days. The films shown in Table 1 were laminated on the obtained treated film by a dry lamination method. Table 1 also shows the oxygen permeability of the laminate film obtained in each example.

The obtained laminate film was formed into a bag, the packaged articles shown in Table 1 were put therein, sealed, and then sterilized under the conditions shown in Table 1. Each sample was placed at 40 ° C, 40
After being left for 3 months in an atmosphere of% RH, the samples were tasted, and changes in taste and smell were determined. The results are shown in Table 1.

Comparative Examples 1 to 5 Laminate films having the structure shown in Table 2 were prepared without providing a gas barrier layer, and the same tests as those of the examples were performed. The results are shown in Table 2. The abbreviations of the films in the following table are as follows. PET: polyethylene terephthalate CPP: unstretched polypropylene OPP: biaxially stretched polypropylene EVA: ethylene-vinyl acetate copolymer LLDP: linear low density polyethylene

[0048]

[Table 1]

[0049]

[Table 2]

As is clear from the table, the embodiment of the present invention
Oxygen permeability was low, it could withstand retort treatment, and various foods could be stored in good condition. On the other hand, the comparative example
Since there was no gas barrier layer and the oxygen barrier properties were poor, changes were observed in all foods.

[0051]

The present invention is constituted as described above, and is a gas barrier layer having excellent gas barrier properties, particularly excellent oxygen barrier properties, and excellent heat resistance, flexibility, transparency, moisture resistance, solvent resistance and the like. It was possible to provide a packaging material having: The packaging material of the present invention is required to have a high gas barrier property, and are subjected to severe treatments such as retort treatment, freezing treatment, and heat treatment, and pharmaceuticals and the like which require strict oxygen barrier properties. It can also be applied to electronic components such as LSIs, and can be used as packaging materials in all fields.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-7-18221 (JP, A) JP-A 5-331417 (JP, A) JP-A-63-48363 (JP, A) (58) Survey Field (Int.Cl. ⁷ , DB name) C08J ^7/ 04-7/06 B32B 9/00 B32B 27/00-27/42

Claims (8)

(57) [Claims] 1. A base material and a primary and / or secondary compound in a molecule.
Organic compounds having a grade amino group (A), the organometallic compound represented by the following general formula (I) (B) and / or its hydrolytic _{^{condensate, R 1 m M (OR 2}} ) n ... (I) ( wherein medium M represents a metal element, R ¹ may be identical or different, represent a hydrogen atom, a lower alkyl group, an aryl group, a mercapto group directly bonded to a vinyl group or a carbon chain, or a (meth) acryloyl group, R ² is Which may be the same or different and represent a hydrogen atom, a lower alkyl group or an acyl group, m is 0 or a positive integer, n is an integer of 1 or more, and m + n is equal to the valence of the metal element M) and a solvent A gas barrier layer obtained by coating the substrate with a gas barrier composition containing (D); and an olefin resin film layer or ethylene-vinyl acetate layer laminated on the gas barrier layer. A packaging material for food, comprising: a polymer film layer. 2. The food packaging material according to claim 1, wherein the olefin-based resin film layer is an unstretched polypropylene layer or a linear low-density polyethylene layer. 3. The food packaging material according to claim 1, wherein the gas barrier composition further comprises a compound (C) having a functional group capable of reacting with an amino group in the molecule. 4. An organic compound (A) having a primary and / or secondary amino group in a molecule in a composition for gas barrier.
Is an organic silane compound (A ′) represented by the following general formula (II) and / or a hydrolyzed condensate thereof: the packaging material for food according to any one of claims 1 to 3. Embedded image Wherein A ¹ is an alkylene group, R ³ is a hydrogen atom, a lower alkyl group, or Wherein A ² represents a direct bond or an alkylene group, R ⁷ and R ^{8 each} represent a hydrogen atom or a lower alkyl group, R ⁴ represents a hydrogen atom or a lower alkyl group, and R ⁵ represents the same or different lower alkyl groups. An alkyl group, an aryl group or an unsaturated aliphatic residue, R ⁶ represents a hydrogen atom, a lower alkyl group or an acyl group (provided that at least one of R ³ , R ⁴ , R ⁷ and R ⁸ is a hydrogen atom) ), W represents any one of 0, 1, and 2, and z represents an integer of 1, 2, or 3 (where w + z = 3)]. 5. An organic compound (A) having a primary and / or secondary amino group in a molecule in a composition for gas barrier.
Is a Si (OR ⁶ ) group (however, the meaning of R ⁶ is the same as above)
The food packaging material according to any one of claims 1 to 3, which is an organic compound (A ") having no compound. 6. The food packaging material according to claim 5, wherein the organic compound (A ″) is a polyethylene imine. 7. The compound (C) in the composition for gas barrier.
Is a compound having an epoxy group as a functional group capable of reacting with an amino group. The food packaging material according to any one of claims 3 to 6, wherein 8. The compound (C) in the composition for gas barrier.
But also (Provided that R ^5, R ^6, w, meaning the z are as defined above) food packaging material according to any one of claims 3 to 7 is a compound having a (C ').