JP2001096682A - Laminated packaging material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated packaging material excellent in bending fatique resistance, vibration fatigue resistance, falling impact resistance and gas barrier properties at low temperature. SOLUTION: A laminated packaging material has laminated constitution of surface layer (C)/adhesive resin layer (D)/layer (A) comprising saponified ethylene/vinyl acetate copolymer or compsn. thereof/polyamide resin layer (B)/ layer (A) comprising saponified ethylene/vinyl acetate copolymer or compsn. thereof/adhesive resin layer (D)/surface layer (C).

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 has been proposed. For example, linear low density polyethylene layer / adhesive resin layer / EVOH layer / adhesive resin layer / linear low density polyethylene (hereinafter LLDP)
E), a layered packaging material (Japanese Patent Application Laid-Open No. 60-161146), an LLDPE layer / adhesive resin layer / EVOH layer / adhesive resin layer / ethylene-vinyl acetate copolymer resin layer Alternatively, a laminated packaging material comprising a biaxially stretched nylon layer or a biaxially stretched polypropylene layer (JP-A-60-1985)
168649), surface layer / adhesive resin layer / EVO
Laminated packaging material consisting of H layer / adhesive resin layer / EVOH layer / adhesive resin layer / surface layer (JP-A-60-168650), surface layer / carboxylic acid-modified LLDPE layer / EVOH
Packaging material consisting of layer / carboxylic acid-modified LLDPE layer / surface layer (JP-A-60-24205), LLDP
E layer / adhesive resin layer / polyamide resin layer / EVOH layer /
Composite film composed of polyamide resin layer / adhesive resin layer / LLDPE layer or LLDPE layer / adhesive resin layer / polyamide resin layer / adhesive resin layer / EVOH layer / adhesive resin layer / LLDPE layer (JP-A-7-101002) Gazette)
The present applicant also proposes a bag-in-box inner container comprising a surface layer / adhesive resin layer / resin composition (a blend of EVOH and thermoplastic polyester) layer / adhesive resin layer / surface layer. JP-A-6-91823) has been proposed.

[0005]

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 layer structure described in Japanese Patent Application Laid-Open No. 0-242054, although improvement in bending fatigue resistance is recognized to some extent, high gas barrier retention enough to withstand long-term storage and transportation is still insufficient. No. 91823, Japanese Unexamined Patent Publication No.
In the layer structure described in JP-A-101002, excellent bending fatigue resistance, vibration fatigue resistance, impact resistance, and the like are recognized at room temperature, but under the recent severe distribution conditions at low temperatures, further improvement is required. It turns out that there is room for improvement.

[0006]

Means for Solving the Problems Accordingly, the present inventors have:
As a result of intensive research to solve the above problems,
Surface layer (C) / adhesive resin layer (D) / EVOH or its composition layer (A) / polyamide resin layer (B) / EVO
H or its composition layer (A) / adhesive resin layer (D) / surface layer (C) has a laminated structure which is resistant to severe bending fatigue, vibration fatigue and drop impact at low temperatures. The present inventors have found that excellent gas barrier properties can be maintained, and have completed the present invention.

[0007]

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) / EVOH or its composition layer (A) / polyamide resin layer (B) / EVOH or its composition layer (A).
The EVOH used for the EVOH or its composition layer (A) is not particularly limited, and has an ethylene content of 10 to 10 / adhesive resin layer (D) / surface layer (C). 70 mol% (further 20 to 60 mol%), and the degree of saponification is 90 mol% or more (furthermore, 95 mol%
When the ethylene content is less than 10 mol%, the gas barrier property and the melt moldability at high humidity decrease, and when it exceeds 70 mol%, sufficient gas barrier property cannot be obtained. Further, when the saponification degree is less than 90 mol%, the gas barrier properties, heat stability, moisture resistance, etc. are undesirably reduced. Also, the melt flow rate (MFR) of the EVOH
(210 ° C., load 2160 g) is 0.5 to 100 g /
10 minutes (more preferably 1 to 50 g / 10 minutes) 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 too large, the resulting laminated packaging material may be undesirably deteriorated in bending fatigue resistance, vibration fatigue resistance and the like.

The EVOH is obtained by saponifying an ethylene-vinyl acetate copolymer, and 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.
Olefins such as butene and isobutene, acrylic acid, methacrylic acid, crotonic acid, (phthalic anhydride), (phthalic anhydride)
Unsaturated acids such as maleic acid, (anhydride) itaconic acid or salts thereof or mono- or dialkyl esters having 1 to 18 carbon atoms, acrylamide, N- having 1 to 18 carbon atoms
Acrylamides such as alkylacrylamide, N, N-dimethylacrylamide, 2-acrylamidopropanesulfonic acid or a salt thereof, acrylamidopropyldimethylamine or an acid salt thereof or a quaternary salt thereof;
Methacrylamide, N-alkyl methacrylamide having 1 to 18 carbon atoms, N, N-dimethyl methacrylamide, 2
Methacrylamides such as methacrylamidopropanesulfonic acid or a salt thereof, methacrylamidopropyldimethylamine or an acid salt or a quaternary salt thereof,
N-vinylpyrrolidone, N-vinylformamide, N-
N-vinylamides such as vinylacetamide, acrylonitrile, vinyl cyanides such as methacrylonitrile,
C1-C18 alkyl vinyl ether, hydroxyalkyl vinyl ether, vinyl ether such as alkoxyalkyl vinyl ether, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl halide such as vinyl bromide, trimethoxy vinyl silane, etc. Vinylsilanes, allyl acetate, allyl chloride, allyl alcohol, dimethylallyl alcohol, trimethyl- (3
-Acrylamido-3-dimethylpropyl) -ammonium chloride, acrylamido-2-methylpropanesulfonic acid and the like.

In the present invention, it is also preferable to include an alkali metal in the EVOH from the viewpoint of further improving the bending fatigue resistance, the vibration fatigue resistance and the like of the obtained laminated packaging material. Sodium and potassium are preferred, and in containing these metals, acetic acid, propionic acid, butyric acid, lauric acid, stearic acid, oleic acid, organic acids such as behenic acid, sulfuric acid,
It is preferably contained as a metal salt of an inorganic acid such as sulfurous acid, carbonic acid, boric acid, and phosphoric acid, and is preferably an acetate, borate, phosphate, or hydrogen phosphate. In addition, the content of the alkali metal is 5 to 5 in terms of metal with respect to EVOH.
1000 ppm (further 10 to 500 ppm, especially 2 ppm
When the content is less than 5 ppm, it is difficult to obtain the content effect, and the resulting laminated packaging material has insufficient flex fatigue resistance, vibration fatigue resistance, and the like. May be 1000 pp
If it exceeds m, the appearance of the obtained laminated packaging material will be deteriorated, and the bending fatigue resistance, the vibration fatigue resistance and the like will also be reduced, which is not preferable. When two or more kinds of alkali metals are contained in EVOH, it is preferable that the total amount is within the above range.

The method of adding an alkali metal to EVOH is not particularly limited.
A method in which a porous precipitate of EVOH of about 80% by weight is brought into contact with an aqueous solution of an alkali metal compound so as to contain the alkali metal compound and then dried; b) a uniform solution of EVOH (water / alcohol solution or the like) After containing the compound, extrude into a coagulating solution in the form of a strand, then cut the obtained strand into pellets, and further perform a drying treatment; c) mixing EVOH and the alkali metal compound all at once A method of melt-kneading with an extruder or the like,
D) In the production of EVOH, 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. Or the like. In order to obtain the effect of the present invention more remarkably, the method a), b) or d), which is excellent in dispersibility of alkali metal, is preferable.

For the EVOH or the composition layer (A) of the present invention, the EVOH as described above can be used, but the EVOH composition comprising a blend with a thermoplastic resin may be used. The EVOH composition is preferable in that the effect is more remarkably obtained. Examples of the EVOH composition include an EVOH composition containing a thermoplastic polyester, an EVOH composition containing an acid graft-modified polyolefin resin and a polyamide polymer, and an olefin-unsaturated carboxylic acid. EVOH compositions such as an EVOH composition containing a copolymer and / or an olefin-unsaturated carboxylic acid ester copolymer, and an EVOH composition containing an olefin-vinyl carboxylate copolymer and / or a saponified product thereof. Can be.

As the thermoplastic polyester contained in the EVOH composition, a differential scanning calorimeter (heating rate 1
The glass transition temperature (Tg) measured at 0 ° C./min) is preferably −150 to 25 ° C. (further, −100 to 0 ° C.). The composition is blocked and workability is poor, and Tg
If the temperature exceeds 25 ° C., the resulting laminated packaging material may be insufficient in bending fatigue resistance, vibration fatigue resistance and the like, which is not preferable. Further, the heat of crystal fusion (ΔHu) of the thermoplastic polyester measured by a differential scanning calorimeter (heating rate: 20 ° C./min) is preferably 30 J / g or less (more preferably 25 J / g or less). When ΔHu exceeds 30 J / g, the obtained laminated packaging material is not preferable because the bending fatigue resistance, the vibration fatigue resistance and the like may be insufficient. The thermoplastic polyester has an intrinsic viscosity of 0.3 to 2.
It is preferably 0 dl / g (more preferably 0.5 to 1.8 dl / g), and a value outside this range is not preferred because the compatibility with EVOH may be poor. Here, the intrinsic viscosity is a value measured at 25 ° C. in a mixed solvent of phenol and ethane tetrachloride (50% by weight / 50% by weight).

[0013] Such thermoplastic polyesters may be 20 to 7
0% by weight of an aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid; and 80 to 30% by weight of an aliphatic dicarboxylic acid such as adipic acid or sebacic acid, as an acid component, 1,6-hexanediol, 1,4-butane It is produced by polycondensation of alkylene glycols having 2 to 6 carbon atoms such as diol, ethylene glycol and propylene glycol. The glass transition temperature (Tg) and heat of crystal fusion (△ Hu) are controlled by the above composition. can do. That is, the glass transition temperature (Tg) can be controlled by the mixing ratio of the aromatic acid and the aliphatic acid, and the glass transition temperature decreases as the ratio of the aliphatic acid increases. In addition, the heat of crystal fusion (ΔHu) is reduced by increasing the amount of a raw material that degrades crystallinity such as phthalic acid. In addition, the intrinsic viscosity can be controlled by the amount of the polymerization catalyst added and the polymerization time.

The content of the thermoplastic polyester is as follows:
It is preferable that the content is 1 to 100 parts by weight with respect to 100 parts by weight of EVOH. If the content of the thermoplastic polyester is less than 1 part by weight, the content effect is poor. Beyond the department,
The gas barrier properties of the obtained laminated packaging material become insufficient, which is not preferable.
It is preferably 0 parts by weight. In the present invention, the thermoplastic polyester may be used by blending two or more kinds of thermoplastic polyesters having different glass transition temperatures (Tg) and / or heats of crystal melting (ΔHu) and / or intrinsic viscosities.

The method of mixing the EVOH and the thermoplastic polyester is not particularly limited, but it is preferable to knead in a molten state from the viewpoint of the uniformity of the mixing. For example, a kneader-ruder, an extruder, a mixing machine, etc. Roll, Banbury mixer, can be carried out using a known kneading device such as a plast mill, but it is usually industrially preferable to use a single-screw or twin-screw extruder, and if necessary, a vent suction device , Gear pump device,
It is also preferable to provide a screen device or the like. In particular, in order to remove moisture and by-products (such as pyrolyzed low molecular weight products),
By providing one or more vent holes in the extruder and sucking under reduced pressure, or by continuously supplying an inert gas such as nitrogen into the hopper to prevent oxygen from being mixed into the extruder , EVO of excellent quality with reduced thermal coloring and thermal deterioration
H composition can be obtained. Also, the supply method is not particularly limited, and a) a method in which EVOH and a thermoplastic polyester are previously blended before being supplied to the extruder;
B) a method in which EVOH and thermoplastic polyester are dry-blended and supplied collectively to an extruder; c) a method in which EVOH is supplied to an extruder and solid thermoplastic polyester is supplied where the EVOH is melted; A method in which EVOH is supplied to an extruder and melted to supply a thermoplastic polyester in a molten state can be mentioned. Among them, the method of b) is simpler in terms of the simplicity of the apparatus and the cost of the blend. It is practical.

In the present invention, as described above, the alkali-metal is contained in the thermoplastic polyester-containing EVOH composition, which further improves the bending fatigue resistance, vibration fatigue resistance and the like of the obtained laminated packaging material. The preferable type, the compound type, and the content of the alkali metal are as described above. The method of including the alkali metal in the EVOH composition is not particularly limited. , Or previously contained in the thermoplastic polyester, or simultaneously contained when mixing the EVOH and the thermoplastic polyester,
The VOH and the thermoplastic polyester can be contained in the resin composition after mixing, or these methods can be combined.However, in order to obtain the effect more remarkably, a method in which the EVOH is previously contained in the EVOH, The method is preferable in that the alkali metal is excellent in dispersibility, and the method of preliminarily containing the alkali metal in EVOH is also the same as described above.

The acid graft-modified polyolefin resin contained in the EVOH composition may be a polyolefin resin dissolved or suspended in an appropriate solvent, or a peroxide or diazo-based initiator in a molten state. It is obtained by activating a resin chain and performing a graft reaction with an ethylenically unsaturated carboxylic acid or a derivative thereof.

Specific examples of the polyolefin resin described above include linear low-density polyethylene (LLDP)
E), low density polyethylene (LDPE), very low density polyethylene (VLDPE), medium density polyethylene (MDP)
E), high-density polyethylene (HDPE), ethylene-vinyl acetate copolymer (EVA), ionomer, ethylene-propylene (block and random) copolymer, ethylene-acrylate copolymer, polypropylene, propylene-α- Olefin (α having 4 to 20 carbon atoms)
-Olefin) homopolymers or copolymers of olefins such as copolymers, polybutenes and polypentenes, and polyolefin resins in a broad sense such as blends thereof. Among them, linear low-density polyethylene (LLD)
PE), 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.

The degree of polymerization of the polyolefin resin is 35.
Those having a melt flow rate (MFR) (230 ° C., load 2
160 g), about 0.1 to 50 g / 10 minutes
It is preferred because it has excellent compatibility with EVOH (a1).

The ethylenically unsaturated carboxylic acids and derivatives thereof include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid, and anhydrides and half esters thereof. And the like. Further, the polyamide polymer is produced by a known method such as polyaddition of a lactam, polycondensation of an aminocarboxylic acid, and polycondensation of a diamine and a dicarboxylic acid. Ε-caprolactam, enantholactam, caprylactam,
Lactams such as lauryl lactam, α-pyrrolidone, α-piperidone, ω-amino acids such as 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, adipic acid, glutaric acid , Pimelic acid, speric acid, azelaic acid, sebacic acid, undecandionic acid, dodecadionic acid, hexadecadionic acid, hexadecenedionic acid, eicosandioic acid, eicosadienedioic acid, diglycolic acid, 2,2,
4-trimethyladipic acid, xylylenedicarboxylic acid,
1,4-cyclohexanedicarboxylic acid, terephthalic acid,
Dibasic acids such as isophthalic acid, hexamethylenediamine, tetramethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4 (or 2,4,4) -trimethylhexamethylenediamine, bis Diamines such as-(4,4'-aminocyclohexyl) methane and meta-xylylenediamine; Monoamines such as laurylamine and oleylamine can also be used as appropriate for the purpose of controlling the molecular weight. The degree of polymerization of the polyamide polymer is 5 to 100.
0, more preferably about 15 to 500, is preferred because it has excellent compatibility with EVOH.

The amount of these components in the EVOH composition is 0.5 to 100 parts by weight (more preferably 1 to 70 parts by weight) based on 100 parts by weight of the EVOH, of the acid graft-modified polyolefin resin and the polyamide type polymer. Parts, in particular, 1 to 50 parts by weight), and when the total amount of the acid graft-modified polyolefin resin and the polyamide polymer is less than 0.5 part by weight, the resulting laminated packaging material has a high durability. Insufficient bending fatigue, vibration fatigue resistance, etc.
Conversely, if it exceeds 100 parts by weight, the gas barrier properties of the obtained laminated packaging material are insufficient, and the object of the present invention cannot be achieved.

The above EVOH (a1), acid graft-modified polyolefin resin (a2) and polyamide polymer (a
There is no particular limitation on the composition of 3), and a method of preliminarily blending or blending two specific kinds in advance and then blending with the other kind can be adopted, but (a2) and (a3) are blended in advance. The reaction of the carboxylic acid group of (a2) with the amino acid group of (a3) is also particularly preferred in that the compatibility with (a1) is excellent and the effects of the present invention can be more remarkably obtained. (A3)
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 usually a single-shaft or a twin-screw (Wäner type, Friedler type, etc.) ) Is industrially preferable to use an extruder, 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 oxygen from being mixed into the extruder, excellent quality (a2) with reduced thermal coloring and thermal deterioration (a2) The composition of a3) can be obtained.

The mixing ratio of (a2) and (a3) is
Although it is necessary to consider the compounding amount with 1), it is usually 100 / 0.1 to 100/30 in terms of weight ratio, and more preferably 100 / 0.1
/ 1 to 100/20 are preferred. If it is less than 100 / 0.1, the compatibility with EVOH (a1) may be insufficient, and if it is more than 100/30, the melt viscosity at the time of molding processing will increase significantly, and the resulting laminated packaging material will The appearance tends to deteriorate, which is not preferable. It is preferable that a part or all of the compound obtained from (a2) and (a3) is reacted as described above. 1 mole (and even 0.
(0.5 to 0.9 mol) of the amino group (a3) is preferably reacted. In such a reaction, if the reaction ratio is less than 0.01 mol, the compatibility with EVOH (a1) may be insufficient, and if it exceeds 1 mol, the melt viscosity at the time of molding processing will increase significantly, The appearance of the obtained laminated packaging material tends to deteriorate, which is not preferable.

In blending (a1) to (a3), of course, only these three types may be used. However, in view of the excellent balance between appearance and flexibility of the obtained molded product, other ethylene-based materials are used. It is preferable to blend with the polymer (a4), and the ethylene polymer (a4) is a homopolymer of ethylene or a copolymer with another copolymerizable monomer, and is not particularly limited. Although not typically, the above-mentioned polyolefin-based resin in a broad sense,
Among them, linear low density polyethylene (LLDPE),
Low density polyethylene (LDPE), very low density polyethylene (VLDPE), ethylene-vinyl acetate copolymer (E
VA) and an ionomer are preferable in that the obtained laminated packaging material is excellent in bending fatigue resistance, vibration fatigue resistance, and the like. In the present invention, different types (structure, composition, degree of polymerization, etc.)
It is also possible to use more than one kind of ethylene polymer.

The method of mixing (a1) to (a3) or (a1) to (a4) is not particularly limited, but it is preferable to knead in a molten state from the viewpoint of mixing uniformity. Is, for example, a kneader ruder, an extruder,
Mixing rolls, Banbury mixer, can be performed using a known kneading device such as a plast mill,
Usually, it is industrially preferable to use a single-screw or twin-screw extruder, 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, the extruder is provided with one or more vent holes to remove water and by-products (such as pyrolyzed low-molecular-weight products), and suction is performed under reduced pressure, and mixing of oxygen into the extruder is prevented. For example, by supplying an inert gas such as nitrogen continuously into the hopper, it is possible to obtain a resin composition of excellent quality with reduced thermal coloring and thermal deterioration.

The feeding method is not particularly limited either. (A1) to (a3) or (a1) to (a4) are preliminarily blended before being fed to the extruder;
(A3) or a method in which (a1) to (a4) are dry-blended and supplied to an extruder at one time, and (a1) is supplied to an extruder to be melted and solid (a2 + a3) (above Or the method of supplying (a2 + a3) and (a4). Supplying (a1) to the extruder and feeding it to the molten state ((a2 + a3) or (a2 + a3) and (a4)) In particular, the method is practical in terms of simplicity of the apparatus and cost of the blend. The method of blending the above (a2 + a3) and (a4) is not particularly limited either, and is previously melt-mixed before being blended into (a1), (a1), (a2 + a3) and (a4).
And (a1), (a2 + a3) and (a4) are sequentially melt-mixed. Among them, the method of melting and mixing the three members at once is described in the apparatus. It is practical in terms of simplicity and cost of the blend.

In the present invention, such (a1) to (a3)
Alternatively, it is also preferable to include an alkali metal (a5) in the EVOH composition comprising (a1) to (a4) in that the resulting laminated packaging material further improves bending fatigue resistance, vibration fatigue resistance, and the like, As such an alkali metal (a5), sodium and potassium are preferable, and when these metals are contained, organic acids such as acetic acid, propionic acid, butyric acid, lauric acid, stearic acid, oleic acid, behenic acid, sulfuric acid, It is preferably contained as a metal salt of an inorganic acid such as sulfurous acid, carbonic acid, boric acid or phosphoric acid, and is preferably an acetate, borate, phosphate or hydrogen phosphate. Also,
As the content of the alkali metal (a5), (a1) to (a3)
Alternatively, the resin composition comprising (a1) to (a4) has a metal content of 5 to 1000 ppm (more preferably 10 to 500 pp).
m, in particular, 20 to 300 ppm). When the content is less than 5 ppm, it is difficult to obtain the content effect, and the obtained laminated packaging material has bending fatigue resistance, vibration fatigue resistance and the like. When the content exceeds 1000 ppm, the appearance of the obtained laminated packaging material is deteriorated, and the bending fatigue resistance, the vibration fatigue resistance, etc. are also reduced, which is not preferable. When two or more alkali metals are contained in the resin composition,
It is preferable that the total is within the range of the above content.

The method for incorporating (a5) into the EVOH composition is not particularly limited, and may be previously contained in (a1) or previously contained in (a2), (a3) or (a4). (A1)-(a3) or (a1)-(a
4) at the same time when mixing, or (a1)-(a3) or (a1)-(a4) after the mixing of the composition,
These methods can be combined. In order to obtain the effect of the present invention more remarkably, a method of preliminarily containing (a1) is preferable in terms of excellent dispersibility of (a5). As a method of preliminarily containing (a1), (a) a porous precipitate of (a1) having a water content of 20 to 80% by weight is added to (a).
5) A method of contacting with an aqueous solution of the compound to contain (a5), followed by drying. (B) After allowing the compound of (a5) to be contained in a homogeneous solution (water / alcohol solution, etc.) of (a1), solidifying A method of extruding into a liquid into a strand, and then cutting the obtained strand into pellets, followed by further drying treatment. C) The compounds of (a1) and (a5) are mixed together and then extruded by an extruder or the like. Melt kneading method, d) During the production of (a1), the alkali (sodium hydroxide, potassium hydroxide, etc.) used in the saponification step is neutralized with acetic acid, and by-produced sodium acetate, potassium acetate, etc. For example, a method of adjusting the amount by a water washing treatment or the like can be mentioned. In order to obtain the effect of the present invention more remarkably, the method (a), (b) or (d) which is excellent in the dispersibility of (a5) is preferable.

The olefin-unsaturated carboxylic acid copolymer or olefin-unsaturated carboxylic acid ester copolymer blended in the EVOH composition of the present invention refers to an unsaturated carboxylic acid and / or unsaturated carboxylic acid containing olefin as a main component. It is a polymer obtained by copolymerizing an ester, and may be a so-called ionomer in which a carboxylic acid component is (partially) neutralized by a metal ion. Examples of the olefin in the copolymer include ethylene, propylene, butylene, styrene and the like, and among them, ethylene is most preferably used.

Examples of the unsaturated carboxylic acid in the olefin-unsaturated carboxylic acid copolymer include ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid and crotonic acid, fumaric acid, itaconic acid, and the like. Examples include ethylenically unsaturated dicarboxylic acids such as maleic acid, monomethyl maleate, monoethyl maleate, and maleic anhydride, and anhydrides and half esters thereof. Of these, acrylic acid or methacrylic acid is most preferably used. The content of the unsaturated carboxylic acid in the copolymer is from 1 to
Those having 30% by weight (more preferably 2 to 25% by weight, particularly 3 to 20% by weight) are preferably used, and if the unsaturated carboxylic acid content is less than 1% by weight, the obtained laminated packaging material has bending fatigue resistance. Properties, vibration fatigue resistance, etc. may be insufficient,
Conversely, if it exceeds 30% by weight, the thermal stability of the EVOH (composition) tends to decrease, which is not preferable. Melt flow rate (MFR) of the copolymer (190 ° C., load 216
0 g) is 0.5 to 100 g / 10 min (further 1 to 50 g).
g / 10 minutes, especially 2 to 25 g / 10 minutes).
It is preferable in that it has excellent compatibility with.

Further, as the ionomer, the carboxylic acid component of the olefin-unsaturated carboxylic acid copolymer is (partially) neutralized by a metal ion. Specific examples of the metal ion include zinc and sodium. , Potassium, magnesium, calcium, barium, lithium and the like, among which zinc, sodium and potassium are most preferably used. The degree of neutralization of the carboxylic acid component with metal ions is preferably from 5 to 100% (more preferably from 10 to 90%, particularly preferably from 30 to 70%). The melt flow rate (MFR) of the copolymer (210 ° C., load 2160 g)
0.5 to 100 g / 10 min (further 1 to 50 g / 10 min.
(Especially, 1.5 to 25 g / 10 minutes) is preferable in terms of excellent compatibility with EVOH.

In the present invention, an ionomer and E
In order to improve the compatibility of VOH, as a third component,
It is also preferable to mix a polyamide resin in that the dispersion state of the ionomer in EVOH becomes good and the effect of the present invention can be more remarkably exhibited. Such polyamide resins include polycapramide (nylon 6) and poly-amide.
ω-aminoheptanoic acid (nylon 7), poly-ω-aminononanoic acid (nylon 9), polyundecaneamide (nylon 11), polylauryl lactam (nylon 1
2), polyethylene diamine adipamide (nylon 2
6), polytetramethylene adipamide (nylon 4
6), polyhexamethylene adipamide (nylon 6
6), polyhexamethylene sebacamide (nylon 61
0), polyhexamethylene dodecamide (nylon 61
2), polyoctamethylene adipamide (nylon 8
6), polydecamethylene adipamide (nylon 10
8), 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 12/6
6), ethylenediamine adipamide / hexamethylenediammonium adipate copolymer (nylon 26/6
6), caprolactam / hexamethylene diammonium adipate / hexamethylene diammonium sebacate copolymer (nylon 66/610), ethylene ammonium adipate / hexamethylene diammonium adipate / hexamethylene diammonium sebacate copolymer (nylon 6 / 66/610), polyhexamethylene isophthalamide, polyhexamethylene terephthalamide, hexamethylene isophthalamide / terephthalamide copolymer or a polyamide resin modified with an aromatic amine such as methylenebenzylamine or metaxylenediamine And metaxylylenediammonium adipate. One or more of these are used, and among them, the melting point is 240 ° C. or less, and particularly, the melting point is 11 To 230 ° C. of the polyamide resin is preferably from the viewpoint of excellent balance of miscibility improvement and thermal stability, specifically polycapramide (nylon 6), polylauryllactam (nylon 12), caprolactam /
Lauryl lactam copolymer (nylon 6/12), caprolactam / hexamethylene diammonium adipate copolymer (nylon 6/66) and the like are preferably used.

When the polyamide resin is contained, it may be added at the same time as the mixing and kneading of the EVOH and the ionomer at the time of melt kneading or the like, or may be previously mixed with the EVOH or the ionomer by the melt kneading and the like. Further, the content of the polyamide resin is not particularly limited,
It is preferably from 1 to 100 parts by weight (more preferably from 5 to 80 parts by weight, especially from 20 to 50 parts by weight) based on 100 parts by weight of the ionomer. When the content is less than 1 part by weight, the compatibility is improved. If the effect is poor, and if the amount is more than 100 parts by weight, the heat stability of the EVOH composition may deteriorate, which is not preferable.

The unsaturated carboxylic acid ester in the olefin-unsaturated carboxylic acid ester copolymer includes:
For example, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate,
Examples thereof include butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, monomethyl fumarate, and monoethyl fumarate. Of these, methyl acrylate and ethyl acrylate are most preferably used. The content of unsaturated carboxylic acid ester in the copolymer is 2 to 50% by weight (further 4 to 40% by weight).
%, Especially 5 to 30% by weight). When the content of the unsaturated carboxylic acid ester is less than 2% by weight, the obtained laminated packaging material has poor bending fatigue resistance, vibration fatigue resistance and the like. If the content exceeds 50% by weight, the thermal stability of the EVOH composition tends to decrease, which is not preferable. The melt flow rate of the copolymer (M
FR) (190 ° C., load 2160 g) is 0.5 to 10
0 g / 10 min (further 1 to 50 g / 10 min, especially 2 to
(25 g / 10 min) is preferred in that it has excellent compatibility with EVOH.

In the present invention, olefin-
In order to improve the compatibility between the unsaturated carboxylic acid ester copolymer and EVOH, an unsaturated carboxylic acid or its anhydride is chemically bonded to the olefin polymer by an addition reaction, a graft reaction, or the like as a third component. The modified olefin-based polymer containing a carboxyl group obtained by blending the olefin-unsaturated carboxylic acid ester copolymer in EVOH also has a good dispersion state, and the effects of the present invention can be more remarkably exhibited. Preferred in terms of such unsaturated carboxylic acids or anhydrides, maleic acid, maleic anhydride, fumaric acid, acrylic acid, methacrylic acid,
Examples thereof include crotonic acid, itaconic acid, 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-methyl acrylate copolymer, maleic anhydride-modified ethylene- One or a mixture of two or more selected from ethyl acrylate copolymer, maleic anhydride-modified ethylene-vinyl acetate copolymer, and the like are mentioned as preferable examples, and the modified olefin polymer contains The amount of the unsaturated carboxylic acid or anhydride to be
It is preferably from 0.1 to 3% by weight (further preferably from 0.01 to 1% by weight, particularly preferably from 0.03 to 0.5% by weight). If the content is too high, the thermal stability of the EVOH composition may deteriorate, which is not preferable.

When the modified olefin polymer is contained, the EVOH and the olefin-unsaturated carboxylic acid ester copolymer may be added simultaneously at the time of mixing such as melt-kneading of the EVOH and the olefin-unsaturated carboxylic acid ester copolymer. It can also be mixed with the coalesced by melting and kneading. The content of the modified olefin-based polymer is not particularly limited, but may be 1 to 100 parts by weight based on 100 parts by weight of the olefin-unsaturated carboxylic acid ester copolymer.
It is preferably 5 to 80 parts by weight, more preferably 20 to 50 parts by weight. When the content is less than 1 part by weight, the effect of improving the compatibility is poor.
When the amount is more than 0 parts by weight, the thermal stability of the EVOH composition may be deteriorated, which is not preferable.

The amount of the olefin-unsaturated carboxylic acid copolymer and / or olefin-unsaturated carboxylic acid ester copolymer is based on 100 parts by weight of EVOH.
1 to 100 parts by weight, preferably an olefin-
If the amount of the unsaturated carboxylic acid copolymer and / or the olefin-unsaturated carboxylic acid ester copolymer is less than 1 part by weight, the effect of the content is poor, and conversely, the olefin-unsaturated carboxylic acid copolymer and / or If the amount of the olefin-unsaturated carboxylic acid ester copolymer exceeds 100 parts by weight, the resulting laminated packaging material will have insufficient gas barrier properties, which is not preferable, and is more preferably 3 to 70 parts by weight, particularly 5 to 70 parts by weight. Preferably it is 50 parts by weight. In the present invention, the type of the copolymer component, the copolymerization ratio, and the molecular weight (M
FR) and the like, two or more kinds of olefin-unsaturated carboxylic acid copolymers, olefin-unsaturated carboxylic acid ester copolymers, and olefin-unsaturated carboxylic acid-unsaturated carboxylic acid ester copolymers can be used. .

The method of mixing the EVOH with the olefin-unsaturated carboxylic acid copolymer and / or the olefin-unsaturated carboxylic acid ester copolymer is not particularly limited, but is kneaded in a molten state from the viewpoint of mixing uniformity. Preferably, the means include, for example, kneader ruder, extruder, mixing roll, Banbury mixer,
It can be carried out using a known kneading device such as a plast mill, but it is usually industrially preferable to use a single-screw or twin-screw extruder, and if necessary, a vent suction device, a gear pump device, a screen It is also preferable to provide a device or the like. 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 to suction under reduced pressure and prevent oxygen from being mixed into the extruder. By continuously supplying an inert gas such as nitrogen into the hopper, a high-quality EVOH composition with reduced thermal coloring and thermal deterioration can be obtained.

The supply method is not particularly limited, either. A) The EVOH and the olefin-unsaturated carboxylic acid copolymer and / or the olefin-unsaturated carboxylic acid ester copolymer are previously blended before being supplied to the extruder. B) a method in which EVOH and an olefin-unsaturated carboxylic acid copolymer and / or an olefin-unsaturated carboxylic acid ester copolymer are dry-blended and collectively supplied to an extruder; A method of supplying a solid olefin-unsaturated carboxylic acid copolymer and / or an olefin-unsaturated carboxylic acid ester copolymer to the extruder where it is melted; d) supplying EVOH to the extruder Olefin-unsaturated carboxylic acid copolymer and / or olefin-unsaturated carboxylic acid ester copolymer in the molten state Can be exemplified a method such as the supplying, among others, ii) method simplicity of apparatus, EVO
It is practical in terms of the cost of the H composition and the like.

In the present invention, as described above, the EVO containing the olefin-unsaturated carboxylic acid copolymer and / or the olefin-unsaturated carboxylic acid ester copolymer is used.
The addition of an alkali metal to the H composition is also preferable in that the resulting laminated packaging material has further improved bending fatigue resistance, vibration fatigue resistance, and the like. Preferred types, compound types, contents, and the like of such an alkali metal are preferable. Is the same as described above. The method for incorporating an alkali metal into the EVOH composition is not particularly limited, and the EVOH composition may be previously contained in EVOH or may be previously contained in the olefin-unsaturated carboxylic acid copolymer and / or olefin. -Unsaturated carboxylic acid ester copolymer or EVOH and olefin-
The unsaturated carboxylic acid copolymer and / or the olefin-unsaturated carboxylic acid ester copolymer may be simultaneously contained at the time of mixing, or EVOH may be mixed with the olefin-unsaturated carboxylic acid ester and / or the olefin-unsaturated carboxylic acid ester. The resin may be contained in the resin composition after mixing of the polymer, or these methods may be combined, but in order to obtain the effect more remarkably, the method of preliminarily containing the EVOH in an alkali metal is preferable. The method is preferable in that it has excellent dispersibility, and the method of preliminarily including it in EVOH is the same as described above.

In the present invention, the EVOH composition containing the olefin-unsaturated carboxylic acid copolymer and / or the olefin-unsaturated carboxylic acid ester copolymer may contain an alkaline earth metal. It is preferable in that the appearance and the like of the laminated packaging material obtained by improving the long-run moldability of the composition are further improved, and such alkaline earth metals are preferably calcium and magnesium. Is preferably contained as a metal salt of acetic acid, borate, phosphate and hydrogen phosphate. In addition, the content of the alkaline earth metal is
The EVOH composition containing the unsaturated carboxylic acid copolymer and / or the olefin-unsaturated carboxylic acid ester copolymer has a metal content of 5 to 500 ppm (more preferably 10 to 30 ppm).
0 ppm, particularly preferably 20 to 250 ppm). 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 EVOH composition may be poor. And conversely 5
If it exceeds 00 ppm, the appearance of the obtained laminated packaging material will be deteriorated, and the bending fatigue resistance, vibration fatigue resistance, etc. will also be reduced, which is not preferable. When two or more alkaline earth metals are contained in the EVOH composition, it is preferable that the total amount is within the above range. The method for incorporating the alkaline earth metal into the EVOH composition is also not particularly limited, and is preferably treated in the same manner as the alkali metal.

The olefin-vinyl carboxylate copolymer and the saponified product thereof to be blended in the EVOH composition of the present invention are carboxylic acid vinyl esters containing an olefin as a main component (represented by the general formula CH ₂ ＣＨCH—OCOR; Is 0
(A linear or branched alkyl group having up to 20 carbon atoms) or a saponified product in which such a carboxylic acid vinyl ester component is (partially) saponified to become a hydroxyl group. . As the olefin in the copolymer,
For example, ethylene, propylene, butylene, styrene and the like can be mentioned, among which 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 if the content of the vinyl carboxylate is less than 1 mol%, the obtained laminated packaging material has bending fatigue resistance. When the content exceeds 60 mol%, the thermal stability of the EVOH composition tends to decrease, which is not preferable. Melt flow rate (MFR) of the copolymer (190 ° C., load 2
160 g) is 0.1 to 100 g / 10 min (further, 0.1 g).
5 to 50 g / 10 min, especially 1 to 30 g / 10 min),
It is preferable because it has excellent compatibility with EVOH.

In the case of the saponified olefin-vinyl carboxylate copolymer, the content of the carboxylic acid vinyl ester in the saponified product is also 1 to 60.
Mol% (more preferably 2 to 50 mol%, particularly 3 to 30 mol%) is preferably used, and 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 EVOH composition tends to decrease, which is not preferable. The saponification degree of the carboxylic acid vinyl ester component of the saponified product is 99 mol% or less (furthermore, 20 to 98 mol%, particularly 40 to 95 mol%).
Mol%) is preferably used, and the saponification degree is 99%.
If it exceeds 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) (1
90 ° C., load 2160 g) is 0.5 to 100 g / 10
Minutes (further 1 to 50 g / 10 min, especially 2 to 30 g / 1
0 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 binding to the unsaturated carboxylic acid or an anhydride thereof, for example, ethylenically unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, etc. 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). If the amount of modification in the modified product is small, the effect of improving the compatibility is poor.

In incorporating such a modified olefin polymer, 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). (Particularly 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 the content is more than 100 parts by weight, the heat stability of the EVOH composition is low. It is not preferable because the property may be deteriorated.

The blending amount of the olefin-vinyl carboxylate copolymer and / or the saponified product thereof is EV
The amount is preferably 1 to 100 parts by weight with respect to 100 parts by weight of OH, and if the compounding amount of the olefin-vinyl carboxylate copolymer and / or the saponified product thereof is less than 1 part by weight, the effect of containing the olefin is poor. -When the compounding amount of the carboxylic acid vinyl ester copolymer and / or the saponified product thereof exceeds 100 parts by weight, the gas-barrier property of the obtained laminated packaging material becomes insufficient, and further 3 to 70 parts by weight, especially It is preferred to be 5 to 50 parts by weight. In the present invention, as the olefin-vinyl carboxylate copolymer and / or the saponified product thereof, the type, structure,
Two or more olefin-carboxylic acid vinyl ester copolymers having different 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 device such as a kneader-ruder, an extruder, a mixing roll, a Banbury mixer, a plast mill, etc. 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.
An EVOH of excellent quality with reduced thermal coloring and thermal degradation by continuously supplying an inert gas such as nitrogen into the hopper to prevent oxygen from being mixed into the extruder.
A composition can be obtained.

The supply method is not particularly limited either. A) A method in which EVOH and an olefin-vinyl carboxylate copolymer and / or a saponified product thereof are previously blended before being supplied to an extruder. A method in which EVOH and olefin-carboxylate vinyl ester copolymer and / or a saponified product thereof are dry-blended and supplied to an extruder at once. C) When EVOH is supplied to an extruder and melted, A method for supplying an olefin-vinyl carboxylate copolymer and / or a saponified product thereof,
D) A method in which EVOH is supplied to an extruder and melted to supply an olefin-vinyl carboxylate copolymer in a molten state and / or a saponified product thereof. The method is simple in equipment, E
It is practical in terms of the cost of the VOH composition and the like.

In the present invention, as described above, an alkali metal may be contained in the olefin-vinyl carboxylate copolymer and / or the EVOH composition containing a saponified product thereof, and the resulting laminated packaging material may have a resistance to alkali resistance. Flexural fatigue, vibration fatigue resistance and the like are preferred in that they are further improved. Preferred types and compound types and contents of such alkali metals are also as described above, and a method for incorporating an alkali metal into the EVOH composition is described. Is not particularly limited, but may be previously contained in EVOH, may be previously contained in an olefin-vinyl carboxylate copolymer and / or a saponified product thereof, or may be EVOH and olefin-vinyl carboxylate copolymer And / or a saponified product thereof at the same time when mixing the EVOH and the olefin-carboxylic acid. The resin composition after mixing the phenyl ester copolymer and / or the saponified product thereof can be contained in the resin composition, or a combination of these methods can be used. This method is preferred in terms of excellent dispersibility of the alkali metal, and the method of preliminarily containing the alkali metal in the EVOH is the same as described above.

In the present invention, the EVOH composition containing the olefin-vinyl carboxylate copolymer and / or the saponified product thereof may contain an alkaline earth metal, and the long run formability of the EVOH composition may be reduced. 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. Are preferred, and acetate, borate, phosphate and hydrogen phosphate are preferred. The content of the alkaline earth metal is 5 to 500 ppm (more preferably 10 to 3 ppm) in terms of metal with respect to the olefin-vinyl carboxylate copolymer and / or the EVOH composition containing the saponified product thereof.
It is preferable to set the content to less than 5 ppm. If the content is less than 5 ppm, it is difficult to obtain the effect of the content, and the effect of improving the long-run moldability of the EVOH 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 EVOH composition, it is preferable that the total amount is within the above range. The method for incorporating the alkaline earth metal into the EVOH composition is also not particularly limited, and is preferably treated in the same manner as the alkali metal.

In the present invention, the above-mentioned EVOH
Alternatively, within the range that does not inhibit the object of the present invention in the EVOH composition, saturated aliphatic amides (eg, stearic acid amide, etc.), unsaturated fatty acid amides (eg, oleic acid amide, etc.), bis fatty acid amides (eg, ethylene bisstearic acid amide, etc.) ), Higher fatty acid metal salts (eg, calcium stearate, etc.), low molecular weight polyolefins (eg,
Lubricants such as low molecular weight polyethylene of about 00 to 10,000 or low molecular weight polypropylene, etc., inorganic salts (eg, hydrotalcite), plasticizers (eg, aliphatic polyhydric alcohols such as ethylene glycol, glycerin, hexanediol, etc.) ), Oxygen absorbers (for example, reduced iron powder as an inorganic oxygen absorber, further added with a water-absorbing substance or electrolyte, aluminum powder, potassium sulfite, titanium oxide photocatalyst, etc.) As an agent, polyhydric phenols such as ascorbic acid, fatty acid esters and metal salts thereof, hydroquinone, gallic acid, hydroxyl-containing phenol aldehyde resin, bis-salicylaldehyde-imine cobalt, tetraethylene pentamine cobalt, cobalt-Schiff base Complexes, porphyrins, macrocyclic polya Down complex, polyethylene imine -
Coordination conjugates of nitrogen-containing compounds such as cobalt complexes and transition metals, terpene compounds, reactants of amino acids and hydroxyl group-containing reducing substances, triphenylmethyl compounds, etc.
As a polymer-based oxygen absorbent, a coordination bond between a nitrogen-containing resin and a transition metal (eg, a combination of MXD nylon and cobalt), and a blend of a tertiary hydrogen-containing resin with a transition metal (eg, polypropylene and cobalt) Combinations), blends of carbon-carbon unsaturated bond-containing resins and transition metals (eg:
A combination of polybutadiene and cobalt), a photo-oxidatively degradable resin (eg, polyketone), an anthraquinone polymer (eg, polyvinyl anthraquinone), and the like, and a photoinitiator (benzophenone, etc.) Heat stabilizers, light stabilizers, antioxidants, ultraviolet absorbers, colorants, antistatic agents, surfactants, antibacterial agents, etc., with the addition of commercially available antioxidants and deodorants (activated carbon, etc.) , An anti-blocking agent, a slip agent, a filler (eg, an inorganic filler) and the like.

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) / a saponified ethylene-vinyl acetate copolymer or its composition layer (A) / a polyamide resin layer (B) ) / A saponified ethylene-vinyl acetate copolymer or a composition layer thereof (A) / adhesive resin layer (D) / surface layer (C), consisting of seven layers, and a resin used for each layer Will be described in detail following the above-mentioned EVOH or EVOH composition layer (A).

The polyamide resin used for the polyamide resin layer (B) is not particularly limited, and various polyamide 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.

The resin used for the surface layer (C) includes polyolefin resin, polyester resin, polyamide resin, copolymerized polyamide, polystyrene resin, polyvinyl chloride resin, polyvinylidene chloride, acrylic resin. , Vinyl ester resins, polyester elastomers, polyurethane elastomers, chlorinated polyethylene, chlorinated polypropylene, 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 or random)
Copolymer, ethylene-acrylic acid copolymer, ethylene-
Acrylic acid ester copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer,
Polypropylene, propylene-α-olefin (α-olefin having 4 to 20 carbon atoms) copolymer, homo- or copolymer of olefin such as polybutene, polypentene, polymethylpentene, or homo- or copolymer of these olefins Examples include polyolefin resins in a broad sense, such as those graft-modified with unsaturated carboxylic acids or esters thereof, and blends thereof, among which linear low density polyethylene (LLDPE), low density polyethylene (LDPE), Ultra low density polyethylene (VLDP)
E), an ethylene-vinyl acetate copolymer (EVA), and an ionomer are preferred in that the obtained laminated packaging material is excellent in bending fatigue resistance, vibration fatigue resistance, and the like.

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 linear low density polyethylene,
Further, an ethylene-α-olefin copolymer produced in the presence of a single-site catalyst is preferable in that the effects of the present invention can be further exhibited. 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. Specific product names include "Kernel" (manufactured by Nippon Polychem), "Evolu" (manufactured by Mitsui Chemicals), "Exact" (manufactured by Exxon Chemical), and "Affinity" (manufactured by Dow Chemical). Can be In the laminated packaging material of the present invention, two surface layers (B) 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 acid or its anhydride is 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, and among them, 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 layer (C)
Although three layers are used, it is not always necessary to use the same resin, and different types of resins can be used.

[0062] The laminated packaging material of the present invention is made of EVO as described above.
The H layer (A) and the polyamide resin layer (B) are used as an intermediate layer [(A) / (B) / (A)], and an adhesive resin layer (D) is provided on both sides of the intermediate layer. A method for producing such a laminated packaging material, in which a surface layer (C) is provided outside the conductive resin layer, will be described. In producing the laminated packaging material of the present invention, finally, a surface layer (C) / adhesive resin layer (D) / EVOH or EVOH composition layer (A) / polyamide resin layer (B) / EVOH or It is sufficient that a laminate having a layer configuration of the EVOH composition layer (A) / adhesive resin layer (D) / surface layer (C) is obtained, and the lamination method is not limited. For example, each resin is co-extruded. Method, a single layer (A) film of EVOH or an EVOH composition or a multilayer [(A) / (B) / (A)] film of an EVOH or an EVOH composition and a polyamide resin is prepared in advance. Method of melt extruding other resin into EV
Monolayer (A) film of OH or EVOH composition or E
A multi-layer [(A) / (B) / (A)] film or the like of a VOH or EVOH composition and a polyamide resin is prepared, and a monolayer film or a multi-layer film made of another resin is added to an organic titanium compound. A dry lamination method using a known adhesive such as an isocyanate compound, a polyester-based compound, or a polyurethane compound may, for example, be mentioned. Furthermore, when co-extrusion is performed by the inflation method,
[Outside] Surface layer (C) / Adhesive resin layer (D) / EVOH
Alternatively, after forming a multilayer film having a layer structure of the EVOH composition layer (A) / polyamide-based resin layer (B) [inside], the insides of the cylindrical films are fused by heat or the like and wound. By taking this, it is also possible to obtain a laminated packaging material having a layer configuration of the present invention. The molding temperature during melt molding is often selected from the range of 150 to 300 ° C.

The surface layer (C) / adhesive resin layer (D) / EVOH or EVOH composition layer (A) /
The thickness of each layer of the polyamide resin layer (B) / EVOH or EVOH composition layer (A) / adhesive resin layer (D) / surface layer (C) is determined by the type of the thermoplastic resin of the surface layer, Although it cannot be said unconditionally depending on the use, form of the packaging material, required physical properties, etc., as a flexible laminated packaging material,
Normal (C) / (D) / (A) / (B) / (A) / (D)
/ (C) = 5 to 200 μm / 1 to 50 μm / 1 to 50 μ
m / 1 to 50 μm / 1 to 50 μm / 1 to 50 μm / 5
Selected from the range of 200 μm, preferably
１００100 μm / 2 to 20 μm / 2 to 30 μm / 2 to 30
μm / 2 to 30 μm / 2 to 20 μm / 10 to 100 μm
It is.

If the thickness of the EVOH or the EVOH composition layer (A) is less than 1 μm, the gas barrier properties are insufficient, and the thickness control becomes unstable. And it is not economical and not preferable. 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 adhesive strength is insufficient, and the thickness control becomes unstable.

The most important feature of the present invention is that the intermediate layer has an EVOH
Alternatively, a multilayer packaging material of [(A) / (B) / (A)] in which the EVOH composition layer (A) and the polyamide-based resin layer (B) are laminated is adopted. C) /
Not only the layer configuration of (D) / (A) / (B) / (A) / (D) / (C) but also another surface layer provided outside the surface layer, (C) / ( C) / (D) / (A) / (B) / (A)
/ (D) / (C), (C) / (D) / (C) / (D) /
(A) / (B) / (A) / (D) / (C), (C) /
(D) / (A) / (B) / (A) / (D) / (C) /
(C), (C) / (D) / (A) / (B) / (A) /
(D) / (C) / (D) / (C), (C) / (C) /
(D) / (A) / (B) / (A) / (D) / (C) /
(C), (C) / (D) / (A) / (D) / (A) provided with three or more EVOH or EVOH composition layers (A).
/ (B) / (A) / (D) / (C), (C) / (D) /
(A) / (B) / (A) / (D) / (A) / (D) /
(C), (C) / (D) / (A) / (D) / (A) /
(B) / (A) / (D) / (A) / (D) / (C), between the two EVOH or EVOH composition layers (A) of the intermediate layer and the polyamide resin layer (B) (C) / (D) / (A) / (D) / (B) /
(A) / (D) / (C), (C) / (D) / (A) /
(B) / (D) / (A) / (D) / (C), (C) /
(D) / (A) / (D) / (B) / (D) / (A) /
(C) / (D) / (B) / (A) / (B) / (D) / (C), provided with two or more polyamide resin layers (B).
(A) / (D) / (C), (C) / (D) / (A) /
(B) / (A) / (B) / (D) / (C), (C) /
(D) / (B) / (A) / (B) / (A) / (B) /
(D) / (C) or the like can be a laminated packaging material of eight or more layers. Of course, even if the symbols in the layer configuration are the same,
The resins and compositions used may be the same or different.

Among these, (C) / (D) / (B)
/ (A) / (B) / (A) / (B) / (D) / (C), that is, an intermediate layer [(A) / (B) / (A)]
Is provided with a polyamide resin (B) on both sides thereof, an adhesive resin (D) on both sides of the polyamide resin layer, and a surface layer (C) provided outside the adhesive resin layer. It is particularly preferable that it has the effect of the present invention.

Each layer of the laminated packaging material of the present invention is provided with the above-mentioned various additives, modifiers, fillers, other resins and the like in order to improve moldability 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 a 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 exterior base material may be plastic or metal other than paperboard and cardboard, and 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 laminate formed by a co-extrusion method or the like (an inflation method or a T-die casting method) may be used as it is, or may be double- or triple-layered as necessary to form a liquid injection port. A hole for hermetically mounting is punched out, and a sealing plug for 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. Thereafter, an inner container such as a bag-in-box can be obtained by opening the liquid inlet.

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.

[0072]

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.

The following resin compositions and resins were prepared. However, as for the alkali (earth) metal compound in each EVOH, the hydrous porous precipitate of EVOH is converted to alkali (earth).
It was blended by bringing into contact with an aqueous solution of a metal compound to contain an alkali (earth) metal compound and then drying.
Regarding the alkali (earth) metal content, EVO
After the H or EVOH composition was ashed, it was dissolved in an aqueous hydrochloric acid solution and the amount of alkali (earth) metal was determined by atomic absorption spectrometry. [EVOH used for EVOH layer (A)] A-1 Ethylene content 35 mol%, degree of saponification 99.5 mol%,
MFR 4 g / 10 min, sodium acetate 535 ppm (sodium 150 ppm) -containing A-2 ethylene content 44 mol%, saponification degree 99.8 mol%,
MFR 6 g / 10 min, containing 285 ppm of sodium acetate (80 ppm of sodium), 100 ppm of potassium acetate
(Potassium 40ppm) contained

[EVO used for EVOH composition layer (A)]
H composition] Thermoplastic polyester-containing EVOH composition Regarding the alkali metal compound in each EVOH below,
It was contained in the same manner as above. For mixing EVOH and thermoplastic polyester, a twin-screw extruder (diameter 3)
0mmΦ, L / D = 30), molding temperature 220 ° C
Then, the vent hole was suctioned under reduced pressure, and the inside of the hopper was supplied with nitrogen gas. A-1 Acid components (terephthalic acid 55
(Mol%, adipic acid 25 mol%, sebacic acid 25 mol%) 45 parts, 1,4-butanediol 55 parts and tetraisopropyl titanate 0.015 part as a catalyst are charged and reacted at 140 to 220 ° C. for 4 to 5 hours. After that, the reaction was further performed at 220 ° C. for 2 hours, and finally 250 ° C. or less, 0.2 mm until the intrinsic viscosity became 1.5 dl / g.
The reaction is carried out under the condition of Hg, and the glass transition temperature (Tg) -2
A thermoplastic polyester (P-1) having a heat of crystal fusion (ΔHu) of 13 J / g at 5 ° C. was obtained.

The glass transition temperature and the heat of crystal fusion of the thermoplastic polyester were measured using a differential scanning calorimeter (DSC-7, manufactured by PerkinElmer, Inc.) at a heating rate of 10 ° C. /
Min (glass transition temperature) or 20 ° C / min (heat of crystal fusion)
Was measured. The intrinsic viscosity was measured in a mixed solvent of phenol and ethane tetrachloride (50% / 50%) at 25 ° C. using an Ostwald viscometer. (The same applies hereinafter) Ethylene content 35 mol%, degree of saponification 99.5 mol%, MF
An EVOH composition (EV) in which 11 parts of the above-mentioned thermoplastic polyester (P-1) is blended with 100 parts of EVOH having R4 g / 10 minutes and sodium acetate content of 535 ppm.
The sodium content in the OH composition is 135 ppm).

Using 40 parts of the A-2 acid component (40 mol% of terephthalic acid, 60 mol% of adipic acid) and 60 parts of 1,4 butanediol, a thermoplastic polyester was produced in the same manner as above,
-30 ° C, Hu17J / g, intrinsic viscosity 1.0dl / g
(P-2) was obtained. Ethylene content 44 mol%, degree of saponification 99.8 mol%, MFR 6 g
/ 10 minutes, an EVOH composition in which 5.5 parts of the above-mentioned thermoplastic polyester (P-2) is blended with 100 parts of EVOH having a sodium acetate content of 285 ppm and a potassium acetate content of 100 ppm (sodium content in the EVOH composition) 75 ppm, potassium content 38 pp
m).

Acid-Modified Polyolefin Resin and Polya
Regarding the alkali metal compound in each EVOH below the amide polymer-containing EVOH composition ,
It was contained in the same manner as above. Further, regarding the blending of EVOH, acid-modified polyolefin resin, polyamide polymer, and ethylene polymer, a molding temperature of 220 mm was obtained using a twin screw extruder (diameter 30 mmΦ, L / D = 30).
At ℃, the vent hole was suctioned under reduced pressure, and nitrogen gas was supplied into the hopper. A-1 ethylene content 35 mol%, degree of saponification 99.5 mol%,
MFR 4 g / 10 min, sodium acetate content 535 pp
m of EVOH, 3 parts of the following compound and ultra-low density polyethylene [density 0.87 g / cm ³ , MFR
8.1 g / 10 min (at 230 ° C. under a load of 2160 g)] 7
EVOH composition (parts of sodium in the EVOH composition is 135 ppm). (Compound) Ultra low density polyethylene [density 0.88g / c
m ³ , MFR 6.7 g / 10 min (230 ° C., 2160 g
Ethylene-α-olefin copolymer under load)] 100 parts of maleic anhydride and 2,5-dimethyl- as a catalyst
2,5 (t-butylperoxy) hexane 500ppm
And a twin screw extruder (diameter 30 mmΦ, L / D = 30,
After a melt reaction at a temperature of 200 ° C.) to obtain an acid graft-modified polyolefin resin, a hexamethylenediamine-adipic acid polymer (nylon 6/66, average degree of polymerization 5
00) 10 parts and a twin screw extruder (diameter 30 mmΦ, L
/ D = 30, temperature 195 ° C.).

A-2 Ethylene content 44 mol%, degree of saponification 99.8 mol%,
MFR 6 g / 10 min, sodium acetate content 285 pp
m, EVOH100 with potassium acetate content of 100 ppm
Parts, the following compound 3 parts and a linear low-density polyethylene [density 0.92 g / cm ³ , MFR 2.1 g / 10
Min (at 190 ° C. under a load of 2160 g)] (a4) EVOH composition (3 ppm of sodium content and 38 ppm of potassium content in the EVOH composition). (Blend) 100 parts of a linear low-density polyethylene [ethylene-α-olefin copolymer having a density of 0.92 g / cm ³ and an MFR of 2.1 g / 10 minutes (at 190 ° C. under a load of 2160 g)] in the same manner as described above. A mixture obtained by subjecting 2 parts of maleic anhydride to a melt reaction to obtain an acid graft-modified polyolefin resin, further adding 15 parts of ε-caprolactam polymer (nylon 6, average degree of polymerization 250) and melt-kneading.

Olefin-unsaturated carboxylic acid copolymer
And / or olefin-unsaturated carboxylic acid ester copolymer
Combined EVOH composition The alkali metal compounds and alkaline earth metal compounds in each EVOH below were incorporated in the same manner as described above. Further, regarding the blending of the olefin-unsaturated carboxylic acid copolymer and / or the olefin-unsaturated carboxylic acid ester copolymer with EVOH, a twin-screw extruder (diameter 30) is used.
mmΦ, L / D = 30), molding temperature 220 ° C.
Then, the vent hole was suctioned under reduced pressure, and the inside of the hopper was supplied with nitrogen gas.

A-1 Ethylene content 44 mol%, degree of saponification 99.5 mol%,
MFR 4 g / 10 min, sodium acetate content 535 pp
m, EVOH1 with a magnesium acetate content of 295 ppm
Of the ethylene-methacrylic acid copolymer [methacrylic acid content 8 mol%, ionic species Z
n ²⁺ , neutralization degree 40%, MFR 1.5 g / 10 min (210
EVOH composition blended with 11 parts (sodium content in the EVOH composition is 135 pp.
m, magnesium content is 45 ppm).

A-2 Ethylene content 34 mol%, degree of saponification 99.7 mol%,
MFR 6 g / 10 min, sodium acetate content 285 pp
m, an ionomer of an ethylene-methacrylic acid copolymer [methacrylic acid content 8 mol%, ion species Zn ²⁺ , neutralization degree 40, relative to 100 parts of EVOH having a potassium acetate content of 100 ppm and a magnesium acetate content of 295 ppm.
%, MFR 1.5 g / 10 min (210 ° C., load 2160
g)] 16 parts and nylon 6 [melting point 225 ° C] 5 parts were blended (EVOH composition has a sodium content of 65 ppm, a potassium content of 33 ppm, and a magnesium content of 41 ppm).

A-3 Ethylene content 44 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, an ethylene-acrylic acid copolymer [acrylic acid content 7% by weight, density 0.94 g / cm ³ , MFR 5 g / 10 min (1
90 ° C., load 2160 g)] EVOH containing 13 parts
Composition (sodium content in EVOH composition is 70p
pm, potassium content 35 ppm, magnesium content 44 ppm).

A-4 Ethylene content 44 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, an ethylene-ethyl acrylate copolymer [ethyl acrylate content 25% by weight, density 0.94 g / cm ³ , MFR 5
g / 10 minutes (190 ° C., load 2160 g)] and 8 parts of a maleic anhydride-modified ethylene-ethyl acrylate copolymer [ethyl acrylate content 13% by weight, maleic anhydride-modified 2% by weight, density 0. 94 g / cm ³ , MFR ³ g
/ 10 min (190 ° C., load 2160 g)] 3 parts of an EVOH composition (sodium content in the EVOH composition is 72 ppm, potassium content is 36 ppm, and magnesium content is 43 ppm).

Olefin-carboxylate vinyl ester
EVOH composition containing copolymer and / or saponified product thereof Alkali metal compounds and alkaline earth metal compounds in each EVOH below were contained in the same manner as described above. In addition, the blending of the olefin-vinyl carboxylate copolymer and / or the saponified product thereof into the EVOH was carried out using a twin-screw extruder (diameter 30 mmΦ, L / D = 30) at a molding temperature of 220 ° C. The holes were suctioned under reduced pressure, and nitrogen gas was supplied into 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
EV blended with 40 parts of an ethylene-vinyl acetate copolymer [vinyl acetate content 12 mol%, MFR 2 g / 10 min (190 ° C., load 2160 g)] based on 100 parts of H.
OH composition (sodium content in EVOH composition is 3
0 ppm, potassium content 25 ppm, calcium content 50 ppm, magnesium content 180 pp
m).

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 an EVOH composition (5 parts by weight) (sodium content in the EVOH composition is 62 ppm, potassium content is 30 ppm, and magnesium content is 98 ppm).

A-3: ethylene content 47 mol%, degree of saponification 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
E (0 min (190 ° C., load 2160 g))
VOH composition (sodium content in EVOH composition is 40 ppm, potassium content is 30 ppm, calcium content is 70 ppm).

[Polyamide 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.
B. Nylon 12: UBE Nylon 303 manufactured by Ube Industries, Ltd.
5U ", melting point 180 ° C

[Resin for 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

[Resin for 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 Examples 1 to 18, Comparative Examples 1 to 3 Using a resin composition or resin shown in Table 1 using a coextrusion multilayer inflation film forming apparatus, (C) / ( D) /
(A) / (B) / (A) / (D) / (C) = 35 μm /
A laminated packaging material (co-extruded multilayer blown film) of the present invention having a layer constitution of 5 μm / 5 μm / 5 μm / 5 μm / 5 μm / 35 μm was obtained. In Comparative Example 1, the thickness of the layer (A) was 10 μm, and in Comparative Example 2, the thickness of the layer (A) was 15 μm. In Comparative Example 3, the thickness of the layer (B) was 15 μm.

The bending fatigue resistance (gas barrier retention after bending fatigue) of the laminated packaging material obtained above was evaluated in the following manner.

(Bending Fatigue Resistance) The obtained laminated packaging material (A
Using a gelbo flex tester (manufactured by Rigaku Kogyo Co., Ltd.), the sample was cut into 440 ° twist (3.5 inches) + straight (2.degree.) In an atmosphere of 5 ° C. and 23 ° C. and 50% RH.
5 inches) of reciprocating motion 200 times and 60 times
After performing the test 0 times, the oxygen permeability (cc) of the laminated packaging material was measured at 23 ° C. and 50% RH using an oxygen permeability measuring device (“OXTRAN10 / 50” manufactured by MOCON).
/ m ² · day · atm).

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
Was laminated with the above-described laminated packaging material having holes, and heat-sealed in four directions to produce an inner container for a bag-in-box. At that time, a high-density polyethylene sealing stopper was attached to the hole for liquid injection and heat-sealed around and tightly fixed. Vibration fatigue resistance (gas barrier retention after flexural vibration fatigue) and drop impact resistance (gas barrier retention after drop impact) of the inner container for bag-in-box obtained above were evaluated in the following manner.

(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 ° C. The sample was vibrated horizontally for 2 hours under the conditions of a vibration width of 50 mm and a vibration frequency of 168 times / minute. With respect to the inner container for the bag-in-box after the vibration test, after draining water, an oxygen permeability measuring device (“OXTR” manufactured by MOCON)
AN10 / 50 ”), the oxygen permeability (cc / day · atm) was measured under the conditions of 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, stored at a temperature of 5 ° C. for 24 hours, The sample was freely dropped eight times from a height of 1 m onto a concrete surface 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.

[0096]

[Table 1] Stacked structure * (C) (D) (A) (B) (A) (D) (C) Example 1 C-1 D-1 A-1 B-1 A-1 D- 1 C-1 〃 2 C-1 D-1 A-2 B-1 A-2 D-1 C-1 ３ 3 C-2 D-1 A-1 B-1 A-1 D-1 C-2 〃 4 C-3 D-2 A-1 B-2 A-2 D-2 C-1 ５ 5 C-1 D-1 A-1 B-1 A-1 D-1 C-1 ６ 6 C- 1 D-1 A-2 B-2 A-2 D-1 C-1 ７ 7 C-2 D-2 A-1 B-1 A-1 D-2 C-2 〃 8 C-1 D-1 A-1 B-1 A-1 D-1 C-1 ９ 9 C-1 D-1 A-2 B-3 A-2 D-1 C-1 〃 10 C-1 D-1 A-1 B -4 A-2 D-1 C-1 〃 11 C-1 D-1 A-1 B-1 A-1 D-1 C-1 〃 12 C-1 D-1 A-2 B 2 A-2 D-1 C-1 〃 13 C-1 D-1 A-3 B-3 A-3 D-1 C-1 〃 14 C-2 D-2 A-4 B-4 A-4 D-2 C-2 〃 15 C-1 D-1 A-2 B-1 A-2 D-2 C-1 〃 16 C-1 D-1 A-1 B-1 A-1 D-1 C -1 〃 17 C-1 D-1 A-2 B-2 A-2 D-1 C-1 〃 18 C-3 D-2 A-3 B-1 A-3 D-2 C-1 Comparative Example 1 C-1 D-1 A-1 B-1 None D-1 C-1 〃 2 C-1 D-1 A-1 None None D-1 C-1 ３ 3 C-1 D-1 None B- 1 None D-1 C-1

Example 19 In Example 1, the layer thickness was changed to (C) / (D) /
(A) / (B) / (A) / (D) / (C) = 30 μm /
5 μm / 7 μm / 10 μm / 7 μm / 5 μm / 20 μm
Was repeated in the same manner as above, to obtain a laminated packaging material, which was similarly evaluated.

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

Example 21 In Example 2, the layer structure was changed and (C) / (D)
/ (B) / (A) / (B) / (A) / (B) / (D) /
(C) = 30 μm / 5 μm / 5 μm / 7 μm / 5 μm /
A laminated packaging material was obtained in the same manner except that the thickness was changed to 7 μm / 5 μm / 5 μm / 20 μm, and the same evaluation was performed.

Example 22 In Example 4, the layer structure was changed to obtain (C) / (D)
/ (B) / (A) / (B) / (A) / (B) / (D) /
(C) = 30 μm / 5 μm / 5 μm / 5 μm / 5 μm /
A laminated packaging material was obtained in the same manner except that the thickness was changed to 5 μm / 5 μm / 5 μm / 30 μm, and the same evaluation was performed.

Example 23 In Example 10, the layer constitution was changed to obtain (C) /
(D) / (B) / (A) / (B) / (A) / (B) /
(D) / (C) = 30 μm / 5 μm / 5 μm / 5 μm /
A laminated packaging material was obtained in the same manner except that the thickness was changed to 5 μm / 5 μm / 5 μm / 5 μm / 30 μm, and the same evaluation was performed.

Example 24 In Example 12, the layer structure was changed to obtain (C) /
(D) / (B) / (A) / (B) / (A) / (B) /
(D) / (C) = 30 μm / 5 μm / 5 μm / 5 μm /
A laminated packaging material was obtained in the same manner except that the thickness was changed to 5 μm / 5 μm / 5 μm / 5 μm / 30 μm, and the same evaluation was performed.

Example 25 In Example 17, the layer structure was changed to obtain (C) /
(D) / (B) / (A) / (B) / (A) / (B) /
(D) / (C) = 30 μm / 5 μm / 5 μm / 7 μm /
A laminated packaging material was obtained in the same manner except that the thickness was changed to 10 μm / 7 μm / 5 μm / 5 μm / 20 μm, and evaluation was similarly performed.

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 600 times 5 ° C 23 ° C 5 ° C 23 ° C 5 ° C 23 ° C 5 ° C 23 ° C Example 1 1.7 1.2 2.4 1.3 0.7 0.5 1.5 0.7 〃 2 3.2 3.0 3.5 2.0 1.3 1.2 1.6 1.2 ３ 3 1.9 1.2 2.8 1.4 0.7 0.5 1.7 0.7 ４ 4 1.9 1.7 2.4 1.8 0.8 0.7 1.3 0.7 ５ 5 1.5 1.3 1.7 1.3 0.6 0.5 0.7 0.5 〃 6 3.3 3.3 3.5 3.3 1.2 1.2 1.3 1.2 〃 7 1.5 1.3 1.9 1.3 0.7 0.5 0.8 0.5 〃 8 1.7 1.5 1.8 1.5 0.6 0.6 0.8 0.6 ９ 9 3.3 3.3 3.4 3.3 1.2 1.2 1.3 1.2 〃 10 2.2 2.1 2.3 2.1 0.8 0.8 0.9 0.8 〃 11 3.6 3.6 3.8 3.6 1.3 1.3 1.4 1.3 〃 12 1.4 1.3 1.6 1.3 0.5 0.5 0.7 0.5 〃 13 3.7 3.7 3.9 3.7 1.3 1.3 1.5 1.3 〃 14 3.7 3.6 4.0 3.6 1.3 1.3 1.6 1.3 〃 15 1.9 1.8 2.2 1.8 0.7 0.7 0.9 0.7 〃 16 2.8 2.8 2.9 2.8 1.0 1.0 1.2 1.0 〃 17 2.0 1.9 2.1 1.9 0.7 0.7 0.9 0.7 〃 18 6.4 6.4 6.5 6.4 2.2 2.2 2.4 2.2 〃 19 1.9 1.9 2.8 1.2 0.7 0.5 1.7 0.8 〃 20 1.4 1.2 1.8 1.2 0.6 0.5 0.9 0.5 〃 21 2.3 2.1 2.5 2.1 0.9 0.9 1.1 0.9 22 1.8 1.7 2.1 1.7 0.7 0.7 1.0 0.7 〃 23 2.1 2.1 2.1 2.1 0.8 0.8 0.8 0.8 〃 24 1.3 1.3 1.4 1.3 0.5 0.5 0.5 0.5 〃 25 1.5 1.4 1.6 1.4 0.5 0.5 0.6 0.5 Comparative Example 1 * 1.2 * 1.8 2.2 0.5 * * 〃 2 * 1.1 * 2.1 2.5 0.5 * * ３ 3 * * * * * * * * 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.

[0105]

The laminated packaging material of the present invention has a
EVOH or EVOH composition layer (A) / polyamide resin layer (B) / EVOH or EVOH composition layer (A)
With the three-layer structure, it is possible to maintain excellent gas barrier properties against severe bending fatigue, vibration fatigue and drop impact at low temperatures, and is effective for preventing deterioration of packaged items It is extremely useful as a simple laminated packaging material.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F100 AK24 AK41 AK46C AK46E AK63A AK63E AK63G AK68G AK69B AK69D AL05B AL05D AL07G AL09 AT00A AT00E BA05 BA06 BA10A BA10E BA15 CB00 EH20 GB15 GB16 JD02 J10

Claims (5)

[Claims] 1. A surface layer (C) / adhesive resin layer (D) / saponified ethylene-vinyl acetate copolymer or its composition layer (A) / polyamide resin layer (B) / ethylene-vinyl acetate copolymer A laminated packaging material having a laminated structure of a saponified polymer or its composition layer (A) / adhesive resin layer (D) / surface layer (C). 2. A polyamide resin layer (B) is provided between a saponified ethylene-vinyl acetate copolymer or its composition layer (A) and an adhesive resin layer (D) to form a surface layer (C) / Adhesive resin layer (D) / polyamide resin layer (B) / saponified ethylene-vinyl acetate copolymer layer or composition (A) / polyamide resin layer (B) / ethylene-vinyl acetate copolymer ken The laminated packaging material according to claim 1, wherein the laminated packaging material has a laminated structure of a compound layer or its composition (A) / polyamide resin layer (B) / adhesive resin layer (D) / surface layer (C). 3. The method according to claim 1, wherein at least one of the surface layers (C) is a linear low-density polyethylene.
A laminated packaging material as described. 4. The laminated packaging material according to claim 2, wherein the linear low-density polyethylene is polymerized using a single-site catalyst. 5. A bag-in-box or a bag-in-carton inner container.
The laminated packaging material according to any one of the above.