JP2001079999A - Laminated packaging material - Google Patents

Abstract

(57) [Problem] To provide a laminated packaging material excellent in bending fatigue resistance, vibration fatigue resistance, drop impact resistance and gas barrier properties at low temperatures. SOLUTION: Laminated structure of surface layer (C) / adhesive resin layer (D) / resin composition layer (A) / polyamide resin layer (B) / adhesive resin layer (D) / surface layer (C) And the resin composition is a saponified ethylene-vinyl acetate copolymer 10
An olefin-vinyl carboxylate copolymer and / or 1 to 100 parts by weight of a saponified product thereof are blended with 0 part by weight.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated packaging material, and more particularly to a laminated packaging material capable of maintaining excellent gas barrier properties against severe bending fatigue, vibration fatigue and drop impact at low temperatures. An object of the present invention is to provide a laminated packaging material that is effective for preventing deterioration of a package.

[0002]

2. Description of the Related Art In general, saponified ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVOH) is excellent in transparency, antistatic property, oil resistance, solvent resistance, gas barrier property, fragrance retention property and the like. However, impact resistance, flex fatigue resistance, stretchability,
The material also has the drawback of low thermoformability, heat sealability, and low gas barrier properties when absorbing moisture or water. For this reason,
In applications intended for packaging materials, polyethylene, polypropylene, nylon, polyester layers, etc. are laminated on both sides of the EVOH layer to maintain EVOH properties such as gas barrier properties, aroma retention properties, and food discoloration prevention properties. However, the fact is that EVOH is used for various packaging applications by compensating for the drawbacks of EVOH such as bending fatigue resistance, thermoformability, heat sealability, and moisture resistance.

As one of such packaging applications, recently, a bag-in-box or bag has been used as a packaging container having a gas barrier property for transporting and storing liquids for drinking such as wine and juice and liquids such as salad oil. It is widely used for flexible laminated packaging materials represented by inner containers such as in cartons.

[0004] At this time, the performance required for the packaging material is that it can maintain excellent gas barrier properties against bending fatigue and vibration fatigue during transportation (bending fatigue resistance and vibration fatigue resistance). And the ability to maintain excellent gas barrier properties against falling and collision during handling (impact resistance). In particular, in a low-temperature distribution environment such as during winter or during low-temperature transportation or storage such as refrigeration or chilling, higher bending fatigue resistance, vibration fatigue resistance, and impact resistance are required.

As a countermeasure, a laminated structure having various layer configurations and resin compositions has been proposed. For example, the layer structure is characterized by a linear low density polyethylene layer / adhesive resin layer / EVOH layer / adhesive resin layer / linear low density polyethylene (hereinafter abbreviated as LLDPE) layer. Laminated packaging material (Japanese Patent Laid-Open No. 60-161146)
Publication), LLDPE layer / adhesive resin layer / EVOH layer /
Adhesive resin layer / Laminated packaging material consisting of ethylene-vinyl acetate copolymer resin layer or biaxially stretched nylon layer or biaxially stretched polypropylene layer (JP-A-60-168649), surface layer / adhesive resin layer / Laminated packaging material composed of EVOH layer / adhesive resin layer / EVOH layer / adhesive resin layer / surface layer (JP-A-60-168650), surface layer / carboxylic acid-modified LLDPE layer / EVOH layer / carboxylic acid-modified LLDPE Packaging material consisting of layers / surface layers (Japanese Unexamined Patent Publication
0-242054), LLDPE layer / adhesive resin layer / polyamide resin layer / EVOH layer / polyamide resin layer / adhesive resin layer / LLDPE layer or LLDPE layer / adhesive resin layer / polyamide resin layer / adhesive resin layer / EVO
A composite film composed of an H layer / adhesive resin layer / LLDPE layer (JP-A-7-101002) and the like have been proposed.
Laminated packaging materials having a resin composition layer composed of OH and an ethylene-vinyl acetate copolymer (JP-A-61-220839, JP-A-62-152847, etc.), EVOH
Having a resin composition layer composed of a partially saponified product of ethylene and an ethylene-vinyl acetate copolymer (JP-A-1-27994)
No. 9, JP-A-3-192140, etc.) and a multilayer package having a resin composition layer composed of two types of EVOH (JP-A-3-112655, JP-A-5-200865).
And the like have been proposed.

[0006]

Problems to be Solved by the Invention However, JP-A-60-161146 and JP-A-60-16864
9, JP-A-60-168650, JP-A-60-168650
In the techniques described in Japanese Patent Application Laid-Open Nos. 0-242054, JP-A-3-112655 and JP-A-5-200865,
Although improvement in flex fatigue resistance is recognized to some extent, the high gas barrier retention sufficient to withstand long-term storage and transportation is still insufficient, and is disclosed in JP-A-61-220839 and JP-A-62-152847. Gazette, JP-A-1-227
Also in the techniques described in JP-A-9949, JP-A-3-192140 and JP-A-7-101002, although excellent bending fatigue resistance, vibration fatigue resistance, impact resistance and the like are recognized at ordinary temperature, However, it has been found that there is room for further improvement under the recent severe distribution conditions at low temperatures.

[0007]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the surface layer (C) / adhesive resin layer (D) / resin composition Layer (A) / polyamide-based resin layer (B) / adhesive resin layer (D) / surface layer (C), and the resin composition is an olefin-carboxylic acid based on 100 parts by weight of EVOH. Laminated packaging material containing 1 to 100 parts by weight of acid vinyl ester copolymer and / or saponified product thereof has excellent gas barrier properties against severe bending fatigue, vibration fatigue and drop impact at low temperatures And found that the present invention was completed.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The laminated packaging material of the present invention comprises a surface layer (C) / adhesive resin layer (D) / resin composition layer (A) / polyamide resin layer (B) / adhesive resin layer (D) / surface layer (C The resin composition used in the resin composition layer (A) is obtained by blending EVOH with an olefin-vinyl carboxylate copolymer and / or a saponified product thereof. As the EVOH, those having an ethylene content of 10 to 70 mol% (more preferably 20 to 60 mol%) and a saponification degree of 90 mol% or more (more preferably 95 mol% or more) are preferably used. The amount is 10 mol%
If less, the gas barrier property at high humidity and the melt moldability are reduced,
Conversely, if it exceeds 70 mol%, sufficient gas barrier properties cannot be obtained, and if the degree of saponification is less than 90 mol%, gas barrier properties cannot be obtained.
Thermal stability, moisture resistance, etc. are undesirably reduced.

The EVOH has a melt flow rate (MFR) (210 ° C., load 2160 g) of from 0.5 to 0.5.
100 g / 10 min (more preferably 1 to 50 g / 10 min) is preferred. If the melt flow rate is smaller than the above range, the inside of the extruder will be in a high torque state at the time of molding and extrusion processing will be difficult. If it is larger than the range, the resulting laminated packaging material may be undesirably reduced in bending fatigue resistance, vibration fatigue resistance and the like.

The EVOH is obtained by saponifying an ethylene-vinyl acetate copolymer. The ethylene-vinyl acetate copolymer can be produced by any known polymerization method, for example, solution polymerization,
It is produced by suspension polymerization, emulsion polymerization, or the like, and saponification of an ethylene-vinyl acetate copolymer can also be performed by a known method.

In the present invention, a copolymerizable ethylenically unsaturated monomer may be copolymerized as long as the effects of the present invention are not impaired. Examples of such a monomer include propylene and 1-butene. , Olefins such as isobutene, acrylic acid, methacrylic acid, crotonic acid, (anhydrous) phthalic acid,
Unsaturated acids such as (anhydride) maleic acid and (anhydride) itaconic acid or salts thereof, mono- or dialkyl esters having 1 to 18 carbon atoms, acrylamide, 1 to 1 carbon atoms
8, acrylamides such as N-alkylacrylamide, N, N-dimethylacrylamide, 2-acrylamidopropanesulfonic acid or a salt thereof, acrylamidopropyldimethylamine or an acid salt thereof or a quaternary salt thereof, methacrylamide, having 1 to 18 carbon atoms Methacrylamides such as N-alkyl methacrylamide, N, N-dimethyl methacrylamide, 2-methacrylamidopropanesulfonic acid or a salt thereof, methacrylamidopropyldimethylamine or an acid salt thereof or a quaternary salt thereof, N-vinylpyrrolidone N-vinylamides such as, N-vinylformamide and N-vinylacetamide;
Vinyl cyanides such as acrylonitrile and methacrylonitrile; vinyl ethers such as alkyl vinyl ethers having 1 to 18 carbon atoms, hydroxyalkyl vinyl ethers and alkoxyalkyl vinyl ethers; vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and vinyl bromide And vinylsilanes such as trimethoxyvinylsilane, allyl acetate, allyl chloride, allyl alcohol, dimethylallyl alcohol, trimethyl- (3-acrylamido-3-dimethylpropyl)-
Examples thereof include ammonium chloride and acrylamide-2-methylpropanesulfonic acid.

Further, the olefin-vinyl carboxylate copolymer or the saponified product thereof mixed with the EVOH is a carboxylic acid vinyl ester containing an olefin as a main component (which is represented by the general formula CH ₂ ＣＨCH—OCOR, R represents a polymer obtained by copolymerizing a linear or branched alkyl group having 0 to 20 carbon atoms) or a carboxylic acid vinyl ester component (partially) saponified to form a hydroxyl group. Is a monster.

The olefin in the copolymer includes, for example, ethylene, propylene, butylene, styrene and the like. Of these, ethylene is most preferably used. As the vinyl carboxylate in the copolymer, R in the above general formula is a linear or branched alkyl group having 0 to 20 carbon atoms, and examples thereof include vinyl formate, vinyl acetate, and propionic acid. Examples thereof include vinyl, vinyl butyrate, vinyl octanoate, vinyl dodecanoate, and vinyl stearate. Of these, vinyl acetate is most preferably used.

The content of vinyl carboxylate in the olefin-vinyl carboxylate copolymer is from 1 to
Those having 60 mol% (more preferably 2 to 50 mol%, particularly 3 to 30 mol%) are preferably used, and when the content of the vinyl carboxylate is less than 1 mol%, the bending resistance of the obtained laminated packaging material is reduced. When the content exceeds 60 mol%, the thermal stability of the resin composition tends to decrease, which is not preferable. Melt flow rate (MFR) of the copolymer (190 ° C., load 216
0 g) is 0.1 to 100 g / 10 minutes (further 0.5 to 100 g).
EVg (50 g / 10 min, especially 1 to 30 g / 10 min)
It is preferable because it has excellent compatibility with OH.

In the case of a saponified olefin-vinyl carboxylate copolymer, the content of the vinyl carboxylate in the saponified product is also 1 to 60.
Mol% (more preferably 2 to 50 mol%, especially 3 to 30 mol%) is used. When the content of the vinyl carboxylate is less than 1 mol%, the resulting laminated packaging material has bending fatigue resistance. On the other hand, vibration fatigue resistance and the like may be insufficient. Conversely, if it exceeds 60 mol%, the thermal stability of the resin composition tends to decrease, which is not preferable.

The saponification degree of the carboxylic acid vinyl ester component of the saponified product is preferably 99 mol% or less (more preferably 20 to 98 mol%, particularly preferably 40 to 95 mol%). If it exceeds 99 mol%, the resulting laminated packaging material may be insufficient in bending fatigue resistance, vibration fatigue resistance and the like, which is not preferable. The melt flow rate (MFR) of the saponified product (190 ° C., load 2160 g)
0.5 to 100 g / 10 min (further 1 to 50 g / 10 min.
(Particularly, 2 to 30 g / 10 minutes) is preferable in terms of excellent compatibility with EVOH.

In order to further improve the compatibility with EVOH, such an olefin-carboxylic acid vinyl ester copolymer or a saponified product thereof may be chemically reacted with an unsaturated carboxylic acid or an anhydride thereof by an addition reaction or a graft reaction. May be a modified product containing a carboxyl group obtained by bonding to the compound.Examples of such unsaturated carboxylic acids or anhydrides include ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, and crotonic acid. Carboxylic acid, fumaric acid, itaconic acid, citraconic acid, maleic acid, monomethyl maleate, monoethyl maleate,
Examples thereof include an ethylenically unsaturated dicarboxylic acid such as maleic anhydride, an anhydride thereof, and a half ester, and among them, maleic anhydride is preferably used.

In the present invention, an olefin-vinyl carboxylate copolymer or a saponified product thereof and EVO
In order to improve the compatibility with H, a carboxyl group obtained by chemically bonding an unsaturated carboxylic acid or an anhydride thereof to an olefin polymer by an addition reaction, a graft reaction or the like is contained as a third component. It is also preferable to incorporate a modified olefin-based polymer in that the dispersion state of the olefin-vinyl carboxylate copolymer or the saponified product thereof in EVOH becomes good, and the effects of the present invention can be more remarkably exhibited. As the unsaturated carboxylic acid or its anhydride, maleic acid, maleic anhydride, fumaric acid,
Acrylic acid, methacrylic acid, crotonic acid, itaconic acid,
Examples thereof include citraconic acid and hexahydrophthalic anhydride. Among them, maleic anhydride is preferably used. Specifically, maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, maleic anhydride-modified ethylene-propylene copolymer, maleic anhydride-modified ethylene-
One or a mixture of two or more selected from a methyl acrylate copolymer, a maleic anhydride-modified ethylene-ethyl acrylate copolymer, a maleic anhydride-modified ethylene-vinyl acetate copolymer, and the like are mentioned as preferable ones. In this case, the amount of the unsaturated carboxylic acid or anhydride thereof contained in the modified olefin polymer is 0.001 to 3% by weight.
(Furthermore, 0.01 to 1% by weight, particularly 0.03 to 0.5%
% By weight), and if the amount of modification in the modified product is small, the effect of improving the compatibility is poor, and if it is too large, the thermal stability of the resin composition may deteriorate, which is not preferred.

When the modified olefin polymer is contained, EVOH and olefin-carboxylic acid vinyl ester copolymer and / or a saponified product thereof may be added simultaneously at the time of mixing such as melt kneading, or EVOH or olefin-carboxylic acid may be added in advance. The vinyl ester copolymer and / or the saponified product thereof can be mixed by melt kneading or the like. Although the content of the modified olefin polymer is not particularly limited, it is 1 to 100 parts by weight based on 100 parts by weight of the olefin-vinyl carboxylate copolymer and / or the saponified product thereof (further 5 to 80 parts by weight). Parts, especially 20 to 50 parts by weight). When the content is less than 1 part by weight, the effect of improving the compatibility is poor, and when it is more than 100 parts by weight, the heat stability of the resin composition is low. It is not preferable because the property may be deteriorated.

The amount of the olefin-vinyl carboxylate copolymer and / or the saponified product thereof is EV
When the amount of the olefin-vinyl carboxylate copolymer and / or the saponified product thereof is less than 1 part by weight, the obtained laminated packaging material is required to be 1 to 100 parts by weight based on 100 parts by weight of OH. Flex fatigue resistance, vibration fatigue resistance, etc. are insufficient and the object of the present invention cannot be achieved, and the blending amount of the olefin-vinyl carboxylate copolymer and / or the saponified product thereof is 100 parts by weight. If it exceeds, the gas barrier properties of the obtained laminated packaging material become insufficient, and it is more preferably 3 to 70 parts by weight, particularly preferably 5 to 50 parts by weight.

In the present invention, the olefin-carboxylate vinyl ester copolymer and / or the saponified product thereof include two or more kinds of olefin-carboxylate vinyl ester copolymers having different types, structures, compositions, molecular weights (MFR) and the like. And / or a saponified product thereof may be blended and used.

The method of mixing the EVOH with the olefin-carboxylic acid vinyl ester copolymer and / or the saponified product thereof is not particularly limited, but it is preferable to knead in a molten state from the viewpoint of mixing uniformity. Can be carried out using a known kneading apparatus such as a kneader-ruder, an extruder, a mixing roll, a Banbury mixer, a plast mill, etc., but it is usually industrially possible to use a single-screw or twin-screw extruder. Preferred, and
It is also preferable to provide a vent suction device, a gear pump device, a screen device, and the like as necessary. In particular, in order to remove moisture and by-products (such as pyrolyzed low-molecular-weight products), the extruder is provided with one or more vent holes, and suction is performed under reduced pressure.
By continuously supplying an inert gas such as nitrogen into the hopper to prevent mixing of oxygen into the extruder, a resin composition of excellent quality with reduced thermal coloring and thermal deterioration is obtained. be able to.

The feeding method is not particularly limited either. EVOH and an olefin-vinyl carboxylate copolymer and / or a saponified product thereof are previously blended before being fed to an extruder. A method in which a carboxylic acid vinyl ester copolymer and / or a saponified product thereof are dry-blended and supplied to an extruder in a lump. When EVOH is supplied to an extruder and melted, a solid olefin-carboxylate vinyl ester is obtained. Method for supplying copolymer and / or saponified product thereof, EV
When OH was supplied to the extruder and melted, the olefin / vinyl carboxylate copolymer in a molten state and / or
Alternatively, there can be mentioned a method of supplying the saponified product, and among them, the method is practical in terms of simplicity of the apparatus, cost of the blend, and the like.

In the present invention, the resin composition comprising the EVOH and the olefin-carboxylate vinyl ester copolymer and / or a saponified product thereof may contain an alkali metal, and the resulting laminated packaging material may have a bending fatigue resistance. sex,
It is preferable in that the vibration fatigue resistance and the like are further improved.As the alkali metal, sodium and potassium are preferable, and when these metals are contained, acetic acid, propionic acid, butyric acid, lauric acid, stearic acid, oleic acid, Organic acids such as behenic acid, sulfuric acid, sulfurous acid, carbonic acid,
Boric acid, preferably contained as a metal salt of an inorganic acid such as phosphoric acid, preferably acetate, borate, phosphate,
It is a hydrogen phosphate. The content of the alkali metal is 5 to 1000 ppm (more preferably 10 to 10 ppm) in terms of metal with respect to the resin composition comprising EVOH and the olefin-vinyl carboxylate copolymer and / or a saponified product thereof.
When the content is less than 5 ppm, it is difficult to obtain the effect of the content, and the obtained laminated packaging material has bending fatigue resistance, vibration fatigue resistance, and the like. May be insufficient. Conversely, if it exceeds 1000 ppm, the appearance of the obtained laminated packaging material will be deteriorated,
Vibration fatigue resistance and the like also decrease, which is not preferable.
When two or more alkali metals are contained in the resin composition, the total amount is preferably within the above range.

In the present invention, the resin composition comprising the EVOH and the olefin-vinyl carboxylate copolymer and / or a saponified product thereof may contain an alkaline earth metal, or the resin composition may have a long run moldability. It is preferable in that the appearance and the like of the obtained laminated packaging material are further improved, and as such an alkaline earth metal, calcium or magnesium is preferable, and when these metals are contained, they are contained as metal salts of the above acids. Preferably, acetate, borate, phosphate and hydrogen phosphate are preferred. The content of the alkaline earth metal is 5 to 500 ppm (more preferably 10 to 300 ppm, in terms of metal) with respect to the resin composition comprising EVOH and an olefin-vinyl carboxylate copolymer and / or a saponified product thereof. In particular, 20 to 250 ppm) is preferable, and when the content is less than 5 ppm,
It is difficult to obtain the content effect, and the effect of improving the long-run moldability of the resin composition may be poor,
On the other hand, when the content exceeds 500 ppm, the appearance of the obtained laminated packaging material is deteriorated, and the bending fatigue resistance, the vibration fatigue resistance and the like are also reduced, which is not preferable. When two or more alkaline earth metals are contained in the resin composition, the total amount is preferably within the above range.

The method for incorporating an alkali metal and / or an alkaline earth metal into the resin composition is not particularly limited, and may be previously contained in EVOH, or may be previously contained in an olefin-vinyl carboxylate copolymer and / or Or, it is contained in a saponified product thereof, or simultaneously contained when EVOH and an olefin-carboxylate vinyl ester copolymer and / or the saponified product thereof is mixed, or EVOH and an olefin-carboxylate vinyl ester copolymer and / or
Alternatively, the saponified product can be contained in the resin composition after mixing, or these methods can be combined.
In order to obtain the effect of the present invention more remarkably, EVOH
Is preferred in terms of excellent dispersibility of the alkali (earth) metal.

As a method of preliminarily containing EVOH, a) a porous precipitate of EVOH having a water content of 20 to 80% by weight is brought into contact with an aqueous solution of an alkali (earth) metal compound to contain the alkali metal compound. Method of drying after drying, b) Homogeneous EVOH solution (water / alcohol solution, etc.)
A method of extruding a strand into a coagulating liquid after adding an alkali (earth) metal compound to the coagulating liquid, cutting the obtained strand into pellets, and subjecting the strand to further drying treatment. C) EVOH and alkali (earth) ) A method in which the metal compounds are mixed together and then melt-kneaded with an extruder or the like;
During the production of VOH, the alkali (sodium hydroxide, potassium hydroxide, etc.) used in the saponification step is neutralized with acetic acid, and the amount of by-produced sodium acetate, potassium acetate, etc. is adjusted by washing with water. Methods and the like can be mentioned. In order to obtain the effects of the present invention more remarkably, the methods a), b) and d) which are excellent in dispersibility of alkali (earth) metal are preferable.

In the present invention, a saturated aliphatic amide (eg, stearic acid amide), an unsaturated fatty acid amide (eg, oleic acid amide, etc.), Fatty acid amide
(E.g., ethylene bisstearic acid amide, etc.), fatty acid metal salt (e.g., calcium stearate, etc.), low molecular weight polyolefin (e.g., low molecular weight polyethylene having a molecular weight of about 500 to 10,000, or low molecular weight polypropylene, etc.)
Lubricants, inorganic salts (such as hydrotalcite, etc.),
Plasticizers (eg, aliphatic polyhydric alcohols such as ethylene glycol, glycerin, hexanediol, etc.), oxygen absorbers (eg, reduced iron powders as inorganic oxygen absorbers, and water-absorbing substances and electrolytes added thereto) , Aluminum powder, potassium sulfite, photocatalytic titanium oxide, etc., as organic compound-based oxygen absorbers, ascorbic acid, furthermore, fatty acid esters and metal salts thereof, and polyhydric phenols such as hydroquinone, gallic acid, and hydroxyl-containing phenol aldehyde resins. , Bis-salicylaldehyde-imine cobalt, tetraethylene pentamine cobalt, cobalt-Schiff base complex, porphyrins, macrocyclic polyamine complex, coordination conjugate of a transition metal with a nitrogen-containing compound such as polyethyleneimine-cobalt complex, terpene Compounds, amino acids and hydroxyl Reactants containing reducing agent, triphenylmethyl compounds and the like, as a polymer-based oxygen absorbing agent,
Coordination conjugate of nitrogen-containing resin and transition metal (eg, combination of MXD nylon and cobalt), blend of tertiary hydrogen-containing resin and transition metal (eg, combination of polypropylene and cobalt), carbon-carbon unsaturated A blend of a bond-containing resin and a transition metal (eg, a combination of polybutadiene and cobalt), a photo-oxidatively degradable resin (eg, a polyketone), an anthraquinone polymer (eg, polyvinyl anthraquinone),
Further, a heat stabilizer, a light stabilizer, an oxidizing agent, etc., in which a photoinitiator (benzophenone, etc.), a peroxide supplement (a commercially available antioxidant, etc.) or a deodorant (activated carbon, etc.) is added to these compounds. Incorporates inhibitors, ultraviolet absorbers, colorants, antistatic agents, surfactants, antibacterial agents, antiblocking agents, slip agents, fillers (eg, inorganic fillers, etc.), and other resins (eg, polyolefins, polyamides, etc.). May be.

As the EVOH, two or more different EVOHs can be used. In this case, the ethylene content differs by 5 mol% or more and / or the saponification degree is 1%.
Use of a blend of EVOH having a mol% difference of at least 4 and / or an MFR ratio of 4 or more is useful because the flexibility, thermoformability, film forming stability, etc. are further improved while maintaining gas barrier properties. It is.

The laminated packaging material of the present invention comprises at least a surface layer (C) / adhesive resin layer (D) / resin composition layer (A) / polyamide resin layer (B) / adhesive resin layer (D) / The resin, which is composed of a six-layer laminate of the surface layer (C) and is used for each layer, will be described in detail following the resin composition layer (A) described above.

The polyamide resin used for the polyamide resin layer (B) is not particularly limited, and various resins can be used. Examples of such polyamide resins include polycapramide (nylon 6), poly-ω-aminoheptanoic acid (nylon 7), poly-ω-aminononanoic acid (nylon 9), polyundecaneamide (nylon 11), and polylauryl lactam (nylon 12). ), Polyethylene diamine adipamide (nylon 26), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (Nylon 612), polyoctamethylene adipamide (nylon 86), polydecamethylene adipamide (nylon 108), caprolactam / lauryl lactam copolymer (nylon 6/12), caprolactam / ω-aminononanoic acid copolymer (Nylon 6/9 , Caprolactam / hexamethylene diammonium adipate copolymer (nylon 6/66), lauryl lactam /
Hexamethylene diammonium adipate copolymer (nylon 12/66), ethylenediamine adipamide / hexamethylene diammonium adipate copolymer (nylon 26/66), caprolactam / hexamethylene diammonium adipate / hexamethylene diammonium sebacate copolymer Polymer (nylon 66/610), ethylene ammonium adipate / hexamethylene diammonium adipate / hexamethylene diammonium sebacate copolymer (nylon 6/66/610), polyhexamethylene isophthalamide, polyhexamethylene terephthalamide, hexa Methylene isophthalamide / terephthalamide copolymers or their polyamide resins can be converted to aromatic amines such as methylenebenzylamine and meta-xylenediamine. Modified ones and m-xylylenediamine adipate and the like, these one or more blend is used, even among these, a melting point of 240 ° C. or less, in particular melting point 160 to 230
C. Polyamide-based resin is preferable, specifically, polycapramide (nylon 6), polylauryl lactam (nylon 12), caprolactam / lauryl lactam copolymer (nylon 6/12), caprolactam / hexamethylene diammonium adipate copolymer (Nylon 6/6
6) and the like are used.

Examples of the resin used for the surface layer (C) include polyolefin resins, polyester resins, polyamide resins, copolymerized polyamides, polystyrene resins, polyvinyl chloride resins, polyvinylidene chloride, and acrylic resins. , Vinyl ester resins, polyester elastomers, polyurethane elastomers, chlorinated polyethylenes, chlorinated polypropylenes, aromatic and aliphatic polyketones, aliphatic polyalcohols, and the like. Polyolefin resins are preferably used. Specific examples of the polyolefin resin include linear low density polyethylene (LLDPE), low density polyethylene (LDPE),
Very low density polyethylene (VLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE),
Ethylene-vinyl acetate copolymer (EVA), ionomer, ethylene-propylene (block and random)
Copolymer, ethylene-acrylate copolymer, polypropylene, propylene-α-olefin (C 4
To α-olefins), homo- or copolymers of olefins such as polybutene and polypentene, or those obtained by graft-modifying homo- or copolymers of these olefins with unsaturated carboxylic acids or esters thereof, and the like. Examples include polyolefin-based resins in a broad sense such as blends, and among others, linear low-density polyethylene (L
LDPE), low-density polyethylene (LDPE), very low-density polyethylene (VLDPE), ethylene-vinyl acetate copolymer (EVA), and ionomer are excellent in bending fatigue resistance, vibration fatigue resistance, and the like of the obtained laminated packaging material. It is preferred in that respect.

In particular, a density of 0.86 to 0.95 g / cm ³
Linear low-density polyethylene comprising an ethylene-α-olefin copolymer is preferably used, and when the density is smaller than the above range, the mechanical properties of the laminated packaging material are insufficient or blocking occurs. . On the other hand, when it is large, the bending fatigue resistance, the vibration fatigue resistance and the like may be insufficient, which is not preferable. The density referred to here is 20
It is a value measured according to JIS K6760 at ℃, and ethylene-α-olefin means ethylene and 18 or less carbon atoms of butene-1, pentene-1,4-methylpentene-1, hexene-1, octene-1 and the like. Is a copolymer of Among these, an ethylene-α-olefin copolymer using an olefin having 4 to 8 carbon atoms is preferably used.

In the above-mentioned linear low-density polyethylene, the ethylene-α-olefin copolymer produced in the presence of a single-site catalyst may further exhibit the effects of the present invention. preferable. A single-site catalyst is a catalyst that has the characteristic that the active sites are uniform (single-site), whereas the current Ziegler catalysts and Phillips catalysts have non-uniform active sites and are called multi-site catalysts. A typical example is a metallocene catalyst. As a specific product name,
"Kernel" (made by Nippon Polychem), "Evolu"
(Manufactured by Mitsui Chemicals, Inc.), “Exact” (manufactured by Exxon Chemical), “Affinity” (manufactured by Dow Chemical) and the like. In the laminated packaging material of the present invention, two surface layers (C) are used, but it is not always necessary to use the same resin, and different types of resins can be used.

The adhesive resin used for the adhesive resin layer (D) is not particularly limited, and various ones can be used. Generally, unsaturated carboxylic acids or anhydrides thereof are used. Examples of the modified olefin polymer containing a carboxyl group obtained by chemically bonding to an olefin polymer (the above-mentioned polyolefin resin in a broad sense) by an addition reaction, a graft reaction, or the like, include unsaturated carboxylic acids or Examples of the anhydride include maleic acid, maleic anhydride, fumaric acid, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, citraconic acid, and hexahydrophthalic anhydride, among which maleic anhydride is preferably used. . Specifically, maleic anhydride graft-modified polyethylene, maleic anhydride graft-modified polypropylene, maleic anhydride graft-modified ethylene-propylene copolymer, maleic anhydride graft-modified ethylene-ethyl acrylate copolymer, maleic anhydride graft-modified ethylene One or a mixture of two or more selected from vinyl acetate copolymers and the like are mentioned as preferable ones, and in particular, the ethylene-α-olefin copolymer having a density of 0.86 to 0.95 g / cm ³ described above. A linear low-density polyethylene composed of coalescing is preferably used. At this time, the amount of the unsaturated carboxylic acid or anhydride thereof contained in the olefin polymer is preferably 0.001 to 3% by weight, more preferably 0.01 to 1% by weight, and particularly preferably 0.1 to 1% by weight. 03
~ 0.5% by weight. If the amount of modification in the modified product is small, the effect of improving interlayer adhesion is poor, and if it is too large, a crosslinking reaction occurs, and moldability may deteriorate, which is not preferable.

The adhesive properties of these adhesive resins are improved by blending a rubber / elastomer component such as polyisobutylene or ethylene-propylene rubber, or a polyolefin resin different from the base polyolefin resin of the adhesive resin. It is useful because it can improve. In the laminated packaging material of the present invention, the adhesive resin (D)
Although two layers are used, it is not always necessary to use the same resin, and different types of resins can be used.

In the laminated packaging material of the present invention, the specific resin composition layer (A) and the polyamide resin layer (B) as described above are used as an intermediate layer [(A) / (B)]. Provided with an adhesive resin layer (D), and further provided with a surface layer (C) outside the adhesive resin layer. A method for manufacturing such a laminated packaging material will be described.

In producing the laminated packaging material of the present invention, finally, a surface layer (C) / adhesive resin layer (D) / resin composition layer (A) / polyamide resin layer (B) / adhesion It is sufficient that a laminate having a layer configuration of the conductive resin layer (D) / surface layer (C) is obtained, and the lamination method is not limited.
For example, a method of co-extrusion of each resin, a single-layer (A) film of a resin composition or a multilayer [(A) / (B)] film of a resin composition and a polyamide-based resin is prepared in advance. A method of melt-extruding another resin, such as a single-layer (A) film of a resin composition or a multilayer [(A) / (B)] film of a resin composition and a polyamide-based resin, is prepared in advance. A method of dry laminating a single-layer film or a multi-layer film made of another resin using a known adhesive such as an organic titanium compound, an isocyanate compound, a polyester-based compound, or a polyurethane compound is exemplified. The molding temperature during melt molding is often selected from the range of 150 to 300 ° C.

In the present invention, the surface layer (C) / adhesive resin layer (D) / resin composition layer (A) / polyamide resin layer (B) / adhesive resin layer (D) / surface layer ( The thickness of each layer of the laminated packaging material of (C) cannot be unconditionally determined depending on the type of thermoplastic resin of the surface layer, the use, the form of the packaging material, the required physical properties, and the like. ) / (D) / (A) / (B) / (D) / (C) = 5
２００200 μm / 1 to 50 μm / 1 to 50 μm / 1 to 50
μm / 1 to 50 μm / 5 to 200 μm, preferably = 10 to 100 μm / 2 to 20 μm
/ 2 to 30 μm / 2 to 30 μm / 2 to 20 μm / 10
100 μm.

When the thickness of the resin composition layer (A) is less than 1 μm, the gas barrier properties become insufficient, and the thickness control becomes unstable.
Conversely, if it exceeds 50 μm, bending fatigue resistance, vibration fatigue resistance and the like are inferior, and it is not economical and is not preferred. When the thickness of the polyamide resin layer (B) is less than 1 μm, the effect of improving bending fatigue resistance and vibration fatigue resistance is poor, and the thickness control becomes unstable. On the other hand, when the thickness exceeds 50 μm, bending fatigue resistance and vibration fatigue resistance are reduced. It is not economical and unfavorable. If the surface layer (C) is less than 5 μm, the mechanical strength is insufficient and the film tends to be broken. Conversely, if it exceeds 200 μm, the flexibility is lowered and the weight is increased more than necessary, which is not preferable.
When the thickness of the adhesive resin layer (D) is less than 1 μm, the interlayer adhesion strength becomes insufficient, and the thickness control becomes unstable.
If it exceeds, the flexibility is lowered, and it is not economical and is not preferable.

The greatest feature of the present invention resides in that a specific resin composition layer (A) and a polyamide resin layer (B) are employed for the intermediate layer. (D)
/ (A) / (B) / (D) / (C)
(C) A further surface layer was provided outside the surface layer.
(C) / (D) / (A) / (B) / (D) / (C),
(C) / (D) / (C) / (D) / (A) / (B) /
(D) / (C), (C) / (D) / (A) / (B) /
(D) / (C) / (C), (C) / (D) / (A) /
(B) / (D) / (C) / (D) / (C), (C) /
(C) / (D) / (A) / (B) / (D) / (C) /
(C), two or more polyamide resin layers (B) are provided,
(C) / (D) / (B) / (A) / (B) / (D) /
(C), (C) / (D) / (A) / (B) / (B) /
(C) / (D) / (A) / (B) / (A) / (D) provided with two or more (D) / (C) resin composition layers (A).
/ (C), (C) / (D) / (A) / (A) / (B) /
(D) / (C), another resin layer was provided between the resin composition layer (A) and the polyamide resin layer (B), (C) / (D)
/ (A) / (D) / (B) / (D) / (C), (C) /
(D) / (A) / (C) / (B) / (D) / (C),
(C) / (D) / (A) / (D) / (C) / (D) /
(B) / (D) / (C) or the like can be a laminated packaging material having seven or more layers. Of course, even when the symbols in the layer constitution are the same, the resins and compositions used may be the same or different.

Of these, (C) / (D) / (B)
/ (A) / (B) / (D) / (C), that is, the polyamide resin layer (B), the resin composition layer (A), and the polyamide resin layer (B) are formed into an intermediate layer [( B) / (A) /
(B)], the adhesive resin layer (D) is provided on both sides of the intermediate layer, and the surface layer (C) is further provided outside the adhesive resin layer. Is particularly preferred in that it can express more.

Further, (C) / (D) / (A) / (D)
/ (B) / (D) / (C), that is, an adhesive resin layer (D) is provided between the polyamide resin layer (B) and the resin composition layer (A) to form an intermediate layer [( A) / (D) /
(B)], the adhesive resin layer (D) is provided on both sides of the intermediate layer, and a surface layer (C) is further provided outside the adhesive resin layer. It is particularly preferable in that it has a good balance between moisture resistance and moisture resistance.

Each layer of the laminated packaging material of the present invention may be provided with the above-mentioned various additives, modifiers, fillers, other resins, etc. in order to improve the formability and various physical properties. It can also be added in a range that does not inhibit it.

The laminated packaging material of the present invention thus obtained is
Processed into forms such as tubes and bags, it is useful as various packaging materials such as food, beverages, pharmaceuticals, cosmetics, industrial chemicals, agricultural chemicals, detergents, and can be used for a wide range of applications. It is particularly preferable to use it for bag-in-box or bag-in-carton applications. Hereinafter, the inner container for bag-in-box and bag-in-carton will be described, but the application of the laminated packaging material of the present invention is not limited to this.

A bag-in-box or bag-in-carton refers to an external cardboard box (bag-in-box) or paper carton (bag) having a foldable plastic thin-walled inner container, stackability, portability, inner container protection, and printability. (Inkerton). Further, the base material of the exterior may be plastic or metal other than paperboard or corrugated cardboard, and the shape may be a drum (column) other than a box or carton (rectangular solid). Hereinafter, these are collectively referred to as a bag-in-box.

The inner container for the bag-in-box can be manufactured mainly by a heat sealing method and a blow molding method. In the heat sealing method, a laminated body formed by a coextrusion method or the like (an inflation method or a T-die casting method) is used as it is, or as a double or triple layer as required, for sealing the liquid inlet. Is punched out, and a sealing plug of a liquid injection port previously formed by injection molding is fused to the hole by a heat sealing method. At that time,
The laminated body and another laminated body which has not been subjected to the punching treatment are combined and heat-sealed in four directions to form an inner container such as a bag-in-box.

In the blow molding method, the above-mentioned cylindrical laminate (parison) extruded from a plurality of extruders by a co-extrusion method is molded by clamping with a die. The sealing stopper of the liquid inlet is previously molded by injection molding and set in a mold, and is fused to a molding container during blow molding. afterwards,
By opening the liquid inlet, an inner container such as a bag-in-box can be obtained.

The inner container for the bag-in-box thus obtained includes wine, juice, mirin, soy sauce, sauce,
Non-food items such as noodle soup, milk, mineral water, sake, shochu, coffee, tea, various edible oils and other foods, liquid fertilizers, sodium hypochlorite, developing solutions, battery solutions, and other industrial chemicals It can be used for transportation, storage, display, etc.

[0050]

The present invention will be specifically described below with reference to examples. In the examples, “parts” and “%” mean on a weight basis unless otherwise specified.

Example 1 Using a co-extrusion multilayer inflation film forming apparatus, the resin composition layer (A) was EVOH [ethylene content 38 mol%,
Saponification degree 99.5 mol%, MFR 6 g / 10 min, sodium acetate content 150 ppm, potassium acetate 90 pp
m, 275 ppm of calcium acetate, 1500 ppm of magnesium acetate] and 100 parts of ethylene-vinyl acetate copolymer [vinyl acetate content 12 mol%, MF
R2 g / 10 min (190 ° C., load 2160 g)] 40 parts of a resin composition (sodium content in the resin composition is 30 ppm, potassium content is 25 ppm, calcium content is 50 ppm, and magnesium content is 180
ppm), and the polyamide resin layer (B) is made of nylon 6 [Mitsubishi Chemical's “Novamid 1030CA4”,
Melting point 224 ° C.], and the surface layer (C) is a linear low-density polyethylene [“Kernel KF27” manufactured by Nippon Polychem Co., Ltd.]
0 ”, MFR 2.0 g / 10 min (190 ° C.), density 0.
907 g / cm ³ ], and the adhesive resin layer (D)
Is a maleic anhydride-modified LLDPE [“Modic-AP M503” manufactured by Mitsubishi Chemical Corporation, MFR 1.7 g / 10 min (190 ° C.), density 0.92 g / cm ³ ], and the laminated packaging material of the present invention [(C) / (D) / (A) / (B) /
(D) / (C) = 35 μm / 5 μm / 10 μm / 10 μ
6-layer co-extruded multilayer blown film having a layer thickness configuration of m / 5 μm / 35 μm].

The laminated packaging material obtained above was evaluated for bending fatigue resistance (gas barrier retention after bending fatigue) in the following manner. (Bending Fatigue Resistance) The obtained laminated packaging material (cut to A4 size) was treated with a gelbo flex tester (manufactured by Rigaku Corporation) at 4 ° C. and 23 ° C. in an atmosphere of 50% RH.
After repeating reciprocating motion of 40 ° twist (3.5 inches) + straight forward (2.5 inches) 200 times and 500 times, the oxygen-permeability measuring device (MO
CON OXTRAN10 / 50)
Oxygen permeability under conditions of 3 ° C and 50% RH (cc / m ²
m) was measured.

Further, the obtained laminated packaging material (500 mm ×
(Cut to 700 mm) were stacked, and a hole (diameter: 43 mm) for liquid injection was made by a punching machine. next,
Laminated packaging material without holes (500 mm x 700 mm
Is laminated on the laminated packaging material having the above holes so that the resin composition layer (A) is closer to the inner layer and the polyamide resin layer (B) is closer to the outer layer. An inner container for a bag-in-box was manufactured. At that time, a high-density polyethylene sealing stopper was attached to the hole for liquid injection and heat-sealed around and tightly fixed.

The vibration fatigue resistance (gas barrier retention after flexural fatigue) and drop impact resistance (gas barrier retention after drop impact) of the inner container for a bag-in-box obtained above were evaluated in the following manner. did. (Vibration Fatigue Resistance) The obtained inner container for a bag-in-box was put in a cardboard box, about 20 liters of water was put therein, and the cardboard box was heated at a temperature of 5 using a vibration tester.
The sample was vibrated in the horizontal direction for 1 hour at a temperature of 50 ° C., a vibration width of 50 mm, and a vibration frequency of 168 times / minute. For the inner container for the bag-in-box after the vibration test, water was drained, and then an oxygen permeability measuring device (“OXTRAN10 / 5” manufactured by MOCON) was used.
0 ”), the oxygen permeability (cc / day · atm) was measured at 23 ° C. and 50% RH.

(Drop impact resistance) The obtained inner container for a bag-in-box is put in a cardboard box, about 20 liters of water is put therein, and stored at a temperature of 5 ° C for 24 hours. The sample was allowed to fall freely onto a concrete surface five times from a height of 1 m at a temperature of ° C. The inner container for the bag-in-box after the drop test was drained, and then subjected to oxygen permeation at 23 ° C. and 50% RH using an oxygen permeability measuring device (“OXTRAN10 / 50” manufactured by MOCON). Degree (cc / day
・ Atm) was measured.

Examples 2 to 7, Comparative Examples 1 to 5 As shown in Table 1, a resin composition layer (A), a polyamide resin layer (B), a surface layer (C) and an adhesive resin layer (D) were used. Evaluation was performed in the same manner as in Example 1.

[0057]

[Table 1] Layered structure * (C) (D) (A) (B) (D) (C) Example 1 C-1 D-1 A-1 B-1 D-1 C-1 〃2 C-1 D-1 A-2 B-1 D-1 C-1 〃 3 C-3 D-2 A-3 B-1 D-2 C-1 ４ 4 C-1 D-1 A-4 B -2 D-1 C-1 〃5 C-1 D-1 A-5 B-3 D-1 C-1 ６6 C-1 D-1 A-6 B-4 D-1 C-1 ７7 C-1 D-2 A-7 B-1 D-2 C-1 ８8 C-2 D-1 A-1 B-1 D-1 C-2 Comparative example 1 C-1 D-1 A-8 B-1 D-1 C-1 〃 2 C-1 D-1 A-9 B-1 D-1 C-1 ３ 3 C-1 D-1 A-1 None D-1 C-1 * For each layer The resins used are as follows.

[Resin Composition Layer (A)] Each of the following EVOHs
For the alkaline (earth) metal compounds in
Was contacted with an aqueous solution of an alkali (earth) metal compound to contain the alkali (earth) metal compound, followed by drying. Further, the content of the alkali (earth) metal, after incineration of the resin composition,
After dissolving in an aqueous hydrochloric acid solution, the amount of alkali (earth) metal was determined by atomic absorption spectrometry. Furthermore, alkali (earth) metal-containing E
As for the mixing of VOH and the olefin-carboxylic acid vinyl ester copolymer and / or the saponified product thereof, the vent hole was depressurized at a molding temperature of 230 ° C. using a twin-screw extruder (diameter 30 mmφ, L / D = 30). Suction was performed by supplying nitrogen gas to the inside of the hopper.

A-1 Ethylene content 38 mol%, degree of saponification 99.5 mol%,
MFR 6g / 10min, sodium acetate content 150pp
m, potassium acetate 90ppm, calcium acetate 275p
pm, EVO with 1500 ppm magnesium acetate content
A resin composition in which 40 parts of an ethylene-vinyl acetate copolymer [vinyl acetate content: 12 mol%, MFR: 2 g / 10 min (190 ° C., load: 2160 g)] is mixed with 100 parts of H. The quantity is 30pp
m, potassium content 25 ppm, calcium content 50 ppm, magnesium content 180 ppm).

A-2 Ethylene content 34 mol%, degree of saponification 99.7 mol%,
MFR 4 g / 10 min, sodium acetate content 285 pp
m, 100 parts of EVOH having a potassium acetate content of 100 ppm and a magnesium acetate content of 750 ppm, an ethylene-vinyl acetate copolymer [vinyl acetate content 7 mol%, MFR 2 g / 10 min (190 ° C., load 2160
g)] and 25 parts of a maleic anhydride-modified ethylene-vinyl acetate copolymer [vinyl acetate content 4 mol%, MFR 10
g / 10 minutes (190 ° C., load 2160 g)] and a resin composition containing 5 parts (sodium content in the resin composition is 6
2 ppm, potassium content 30 ppm, magnesium content 98 ppm).

A-3 ethylene content 44 mol%, saponification degree 99.6 mol%,
MFR 6 g / 10 min, sodium acetate content 355 pp
m, 100 parts of sodium dihydrogen phosphate, 100 parts of EVOH having a calcium acetate content of 450 ppm,
Ethylene-vinyl acetate copolymer [vinyl acetate content 12
Mol%, MFR 2 g / 10 min (190 ° C., load 2160
g)] 15 parts of a maleic anhydride-modified ethylene-vinyl acetate copolymer [vinyl acetate content 4 mol%, MFR 4 g
/ 10 min (190 ° C., load 2160 g)] and a resin composition containing 5 parts (sodium content in the resin composition is 10
0 ppm, calcium content 95 ppm).

A-4 ethylene content 47 mol%, saponification degree 99.6 mol%,
MFR 14g / 10min, sodium acetate content 155p
pm, 100 parts of EVOH having a potassium acetate content of 80 ppm and a calcium acetate content of 300 ppm, a saponified ethylene-vinyl acetate copolymer [vinyl acetate content 11 mol%, saponification degree 40 mol%, MFR 16 g / 1
0 minutes (190 ° C., load 2160 g)] and a resin composition containing 8 parts (sodium content in the resin composition is 40 pp.
m, potassium content 30 ppm, calcium content 70 ppm).

A-5 Ethylene content 38 mol%, degree of saponification 99.5 mol%,
MFR 6 g / 10 min, sodium acetate content 285 pp
m, 100 parts of EVOH having a potassium acetate content of 100 ppm and a magnesium acetate content of 295 ppm, and a saponified ethylene-vinyl acetate copolymer [vinyl acetate content 11 mol%, saponification degree 80 mol%, MFR 18 g /
10 minutes (190 ° C., load 2160 g)] 11 parts of a resin composition (sodium content in the resin composition is 72
ppm, potassium content 35 ppm, magnesium content 45 ppm).

A-6 ethylene content 34 mol%, degree of saponification 99.7 mol%,
MFR 4 g / 10 min, sodium acetate content 285 pp
m, a saponified product of a maleic anhydride-modified ethylene-vinyl acetate copolymer [vinyl acetate content: 14 mol%, saponification degree: 70 mol%, relative to 100 parts of EVOH having a potassium acetate content of 100 ppm and a magnesium acetate content of 295 ppm. MFR 20 g / 10 min (190 ° C., load 2160
g)] A resin composition containing 15 parts (sodium content in the resin composition is 70 ppm, potassium content is 35 p
pm, magnesium content 43 ppm).

A-7 ethylene content 38 mol%, saponification degree 99.5 mol%,
MFR 6 g / 10 min, sodium acetate content 355 pp
m, 100 parts of sodium dihydrogen phosphate, 100 parts of EVOH having a calcium acetate content of 250 ppm,
Saponified ethylene-vinyl acetate copolymer [vinyl acetate content 51 mol%, saponification degree 97 mol%, MFR 7 g /
10 minutes (190 ° C., load 2160 g)] and a resin composition containing 25 parts (sodium content in the resin composition is 95%).
ppm, calcium content is 50 ppm).

A-8 Ethylene content 38 mol%, degree of saponification 99.5 mol%,
MFR 6g / 10min, sodium acetate content 150pp
m, potassium acetate 90ppm, calcium acetate 275p
pm, EVO with 1500 ppm magnesium acetate content
A resin composition containing 0.5 part of an ethylene-vinyl acetate copolymer [vinyl acetate content: 12 mol%, MFR: 2 g / 10 min (190 ° C., load: 2160 g)] with respect to 100 parts of H. 42 pp sodium content
m, potassium content 36 ppm, calcium content 70 ppm, magnesium content 250 ppm).

A-9 ethylene content 38 mol%, saponification degree 99.5 mol%,
MFR 6g / 10min, sodium acetate content 150pp
m, potassium acetate 90ppm, calcium acetate 275p
pm, EVO with 1500 ppm magnesium acetate content
A resin composition in which 120 parts of an ethylene-vinyl acetate copolymer [vinyl acetate content: 12 mol%, MFR: 2 g / 10 min (190 ° C., load: 2160 g)] is mixed with 100 parts of H. The amount is 20pp
m, potassium content 16 ppm, calcium content 32 ppm, magnesium content 115 ppm).

[Polyamide-based resin layer (B)] B-1 nylon 6: "Novamid 1030CA" manufactured by Mitsubishi Chemical Corporation
4, melting point 224 ° C. B-2 nylon 6/66: “Novamid 203 manufactured by Mitsubishi Chemical Corporation”
0CA ", melting point 200 [deg.] C. B-3 nylon 6/12:" UBE nylon 7 "manufactured by Ube Industries, Ltd.
024B ", melting point 203 ° C B-4 nylon 12:" UBE nylon 303 manufactured by Ube Industries, Ltd. "
5U ", melting point 180 ° C

[Surface layer (C)] C-1 linear low-density polyethylene (LLDPE): "Kernel KF270" manufactured by Nippon Polychem, MFR 2.0 g / 10
Min (190 ° C.), density 0.907 g / cm ³ C-2 linear low density polyethylene (LLDPE): “Novatech LL UF331” manufactured by Nippon Polychem, MFR 1.0
g / 10 min (190 ° C.), density 0.923 g / cm ³ C-3 low density polyethylene (LDPE): “Novatech LD LF440HB” manufactured by Nippon Polychem, MFR 2.8 g
/ 10 min (190 ° C.), density 0.925 g / cm ³

[Adhesive Resin Layer (D)] D-1 Maleic anhydride-modified LLDPE: “Modic-AP M503” manufactured by Mitsubishi Chemical Corporation, MFR 1.7 g / 10 min (1
90 ° C.), density 0.92 g / cm ³ D-2 maleic anhydride-modified EVA: “Modic-AP A503” manufactured by Mitsubishi Chemical Corporation, MFR 1.5 g / 10 min (190
° C), density 0.92 g / cm ³

Example 9 In Example 1, the layer thickness constitution was changed to (C) / (D) /
(A) / (B) / (D) / (C) = 30 μm / 5 μm /
A laminated packaging material was obtained in the same manner except that the thickness was changed to 8 μm / 7 μm / 5 μm / 20 μm, and evaluation was similarly performed.

Example 10 In Example 2, the thickness of the layers was changed to (C) / (D) using a coextrusion multilayer inflation film forming apparatus having four layers and seven layers.
/ (B) / (A) / (B) / (D) / (C) = 30 μm
/ 5μm / 5μm / 8μm / 5μm / 5μm / 30μm
Was repeated in the same manner as above, to obtain a laminated packaging material, which was similarly evaluated.

Example 11 In Example 4, the layer thickness constitution was changed to (C) / (D) using a coextrusion multilayer inflation film forming apparatus having four layers and seven layers.
/ (B) / (A) / (B) / (D) / (C) = 25 μm
/ 5μm / 7μm / 7μm / 7μm / 5μm / 25μm
Was repeated in the same manner as above, to obtain a laminated packaging material, which was similarly evaluated.

Example 12 In Example 3, the layer thickness was changed to (C) / (D) using a co-extrusion multilayer inflation film forming apparatus having four layers and seven layers.
/ (A) / (D) / (B) / (D) / (C) = 30 μm
/ 5 μm / 10 μm / 5 μm / 10 μm / 5 μm / 30
except that it was changed to μm to obtain a laminated packaging material,
Evaluation was performed similarly.

Example 13 In Example 5, the layer thickness was changed to (C) / (D) using a co-extrusion multilayer inflation film forming apparatus having four layers and seven layers.
/ (A) / (D) / (B) / (D) / (C) = 30 μm
/ 5 μm / 10 μm / 5 μm / 10 μm / 5 μm / 30
except that it was changed to μm to obtain a laminated packaging material,
Evaluation was performed similarly.

Table 2 shows the evaluation results of the examples and comparative examples.

[Table 2] Flexural fatigue resistance ¹⁾ Vibration fatigue resistance ^{2 )} Drop impact resistance ^{2 )} 200 times 500 times 5 ° C 23 ° C 5 ° C 23 ° C 5 ° C 23 ° C 5 ° C 23 ° C Example 1 2.8 2.8 3.0 2.8 1.0 1.0 1.2 1.0 〃 2 2.2 1.9 2.4 1.9 0.9 0.7 0.9 0.7 ３ 3 4.0 4.0 4.2 4.0 1.7 1.7 1.9 1.7 〃 4 6.4 6.4 6.6 6.4 2.2 2.2 2.3 2.2 〃 5 2.2 2.0 2.5 2.0 0.8 0.7 0.9 0.7 ６ 6 2.0 1.7 2.2 1.7 0.7 0.6 0.9 0.6 ７ 7 2.1 1.6 3.5 1.8 0.8 0.6 1.5 0.8 ８ 8 3.0 2.8 3.4 2.8 1.1 1.0 1.4 1.0 ９ 9 3.5 3.5 3.7 3.5 1.3 1.3 1.5 1.3 〃 10 1.9 1.9 2.1 1.9 0.7 0.7 0.7 0.7 〃 11 9.0 9.0 9.0 9.0 3.1 3.1 3.1 3.1 〃 12 4.0 4.0 4.2 4.0 1.7 1.7 1.8 1.7 〃 13 2.2 2.0 2.4 2.0 0.8 0.7 0.9 0.7 Comparative Example 1 * 1.8 * 2.4 1.2 0.7 * * 〃 2 * * * * * * * * 〃 3 4.0 2.8 * 2.8 2.0 1.0 * 1.0 1) Unit: cc / m ²・ day ・ atm 2) Unit: cc / day ・ atm *: Oxygen permeability is 50cc / m ²・ day ・ atm (or cc / day ・ atm) or more Represents that.

[0077]

The laminated packaging material of the present invention has a specific thermoplastic resin layer (A) and a polyamide resin layer (B) as intermediate layers.
It has excellent gas barrier properties against severe bending fatigue, vibration fatigue and drop impact at low temperatures, and is effective for preventing deterioration of the packaged goods. It is extremely useful as a laminated packaging material.

Continued on the front page F-term (reference) 3E086 AD01 AD30 BA15 BB01 BB22 BB42 BB51 BB74 CA11 4F100 AB09A AB40A AK04A AK21A AK24G AK46B AK48 AK63C AK63G AK68A AK69A AK70A AK70G J01 GB10

Claims (9)

[Claims] 1. Lamination of surface layer (C) / adhesive resin layer (D) / resin composition layer (A) / polyamide resin layer (B) / adhesive resin layer (D) / surface layer (C) Having a structure, and wherein the resin composition comprises 1 to 100 parts by weight of an olefin-vinyl carboxylate copolymer and / or 1 to 100 parts by weight of a saponified product thereof per 100 parts by weight of a saponified ethylene-vinyl acetate copolymer. A laminated packaging material comprising: 2. The laminated packaging material according to claim 1, wherein the olefin-vinyl carboxylate copolymer is an ethylene-vinyl acetate copolymer having a vinyl acetate content of 3 to 30 mol%. 3. The saponified olefin-vinyl carboxylate copolymer is a partially saponified ethylene-vinyl acetate copolymer having a vinyl acetate content of 3 to 30 mol% and a saponification degree of 20 to 98 mol%. 2. The laminated packaging material according to claim 1, wherein: 4. An alkali metal content in the resin composition of 5
4 to 1000 ppm.
The laminated packaging material according to any one of the above. 5. The alkaline earth metal content in the resin composition is from 5 to 500 ppm.
3. The laminated packaging material according to any one of 3. 6. A polyamide resin layer (B) is provided between the adhesive resin layer (D) and the resin composition layer (A), and the surface layer (C) / adhesive resin layer (D) / polyamide The laminated structure of a system resin layer (B) / resin composition layer (A) / polyamide system resin layer (B) / adhesive resin layer (D) / surface layer (C). 5. The laminated packaging material according to any one of 5. 7. The method according to claim 1, wherein at least one of the surface layers (C) is a linear low-density polyethylene.
7. The laminated packaging material according to any one of items 6 to 6. 8. The laminated packaging material according to claim 7, wherein the linear low-density polyethylene is polymerized using a single-site catalyst. 9. The laminated packaging material according to claim 1, which is used for an inner container of a bag-in-box or a bag-in-carton.