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WO2013002069A1 - Film multi-couches et contenant d'emballage à base du film - Google Patents

Film multi-couches et contenant d'emballage à base du film Download PDF

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Publication number
WO2013002069A1
WO2013002069A1 PCT/JP2012/065642 JP2012065642W WO2013002069A1 WO 2013002069 A1 WO2013002069 A1 WO 2013002069A1 JP 2012065642 W JP2012065642 W JP 2012065642W WO 2013002069 A1 WO2013002069 A1 WO 2013002069A1
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WIPO (PCT)
Prior art keywords
acid
polyamide resin
mol
multilayer film
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2012/065642
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English (en)
Japanese (ja)
Inventor
尚史 小田
大滝　良二
健太郎 石井
翔太 荒川
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Mitsubishi Gas Chemical Co Inc
Original Assignee
Mitsubishi Gas Chemical Co Inc
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Priority to JP2013522772A priority Critical patent/JP5954323B2/ja
Publication of WO2013002069A1 publication Critical patent/WO2013002069A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/40—Closed containers

Definitions

  • the present invention relates to a multilayer film having oxygen barrier performance and oxygen absorption performance, and a film packaging container including the multilayer film.
  • nylon MXD6 Polyamide obtained from polycondensation reaction of xylylenediamine and aliphatic dicarboxylic acid, for example, polyamide obtained from metaxylylenediamine and adipic acid (hereinafter referred to as nylon MXD6) has high strength, high elastic modulus, oxygen, carbonic acid. Since it shows low permeability to gaseous substances such as gas, odor and flavor, it is widely used as a gas barrier material in the field of packaging materials. Nylon MXD6 has better thermal stability when melted than other gas barrier resins, so co-extrusion and co-extrusion with thermoplastic resins such as polyethylene terephthalate (hereinafter abbreviated as PET), nylon 6 and polypropylene. Injection molding or the like is possible. Therefore, nylon MXD6 is used as a gas barrier layer constituting a multilayer structure.
  • PET polyethylene terephthalate
  • nylon MXD6 is added and mixed with a small amount of transition metal compound to give nylon MXD6 an oxygen-absorbing function, and this is used as an oxygen barrier material constituting containers and packaging materials.
  • Nylon MXD6 absorbs the incoming oxygen and nylon MXD6 also absorbs oxygen remaining inside the container, so that a method for improving the storage stability of the contents over conventional containers using oxygen-barrier thermoplastic resin is practical. (See, for example, Patent Documents 1 and 2).
  • Patent Documents 3 and 4 describe an oxygen-absorbing multilayer body and an oxygen-absorbing film in which an oxygen absorbent such as iron powder is dispersed in a resin.
  • Patent Document 5 describes a product having an oxygen scavenging layer containing an ethylenically unsaturated compound such as polybutadiene and a transition metal catalyst such as cobalt, and an oxygen barrier layer such as polyamide.
  • JP 2003-341747 A Japanese Patent No. 2991437 Japanese Patent Laid-Open No. 2-72851 Japanese Patent Laid-Open No. 4-90848 Japanese Patent Laid-Open No. 5-115776
  • the oxygen-absorbing multilayer body and oxygen-absorbing film in which an oxygen absorbent such as iron powder is dispersed in the resin are opaque due to the resin being colored by the oxygen absorbent such as iron powder.
  • an oxygen absorbent such as iron powder
  • a resin composition containing a transition metal such as cobalt has an advantage that it can be applied to packaging containers that require transparency, but is not preferred because the resin composition is colored by a transition metal catalyst.
  • the resin is oxidized by absorbing oxygen by the transition metal catalyst.
  • the problem to be solved by the present invention is that oxygen barrier performance is expressed, oxygen absorption performance can be expressed without containing a transition metal, and the strength of the oxygen absorption barrier layer as oxygen absorption progresses
  • the object is to provide a multilayer film with very little reduction.
  • the present invention provides the following multilayer film and film packaging container.
  • a multilayer film comprising a layer (A) containing a polyamide resin (A) and a layer (B) containing the resin (B) as a main component
  • the polyamide resin (A) is An aromatic diamine unit represented by the following general formula (I-1), an alicyclic diamine unit represented by the following general formula (I-2), and a straight chain represented by the following general formula (I-3) 25 to 50 mol% of diamine units containing a total of 50 mol% or more of at least one diamine unit selected from the group consisting of aliphatic diamine units;
  • a dicarboxylic acid unit containing a total of 50 mol% or more of a linear aliphatic dicarboxylic acid unit represented by the following general formula (II-1) and / or an aromatic dicarboxylic acid unit represented by the following general formula (II-2) 25 to 50 mol%
  • m represents an integer of 2 to 18.
  • n represents an integer of 2 to 18.
  • Ar represents an arylene group.
  • R represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.
  • the multilayer film of the present invention exhibits oxygen barrier performance, can exhibit oxygen absorption performance without containing a transition metal, and the strength of the oxygen absorption barrier layer is extremely lowered as oxygen absorption proceeds. small. In addition, since the strength of the oxygen absorption barrier layer is maintained even in long-term use, delamination hardly occurs when the multilayer film is a laminate film.
  • the film packaging container including the multilayer film is excellent in suppressing the oxidative deterioration of the contents, hardly generating substances that cause a strange odor or a change in flavor, and excellent in flavor retention.
  • the multilayer film of the present invention comprises a layer (A) containing a polyamide resin (A) (hereinafter also referred to as “oxygen absorption barrier layer”), and a layer (B) containing the resin (B) as a main component.
  • A polyamide resin
  • B layer containing the resin (B) as a main component.
  • the layer structure in the multilayer film of the present invention is not particularly limited, and the number and type of layers (A) and layers (B) are not particularly limited.
  • an A / B configuration including one layer (A) and one layer (B) may be used, and B / A / consisting of one layer (A) and two layers (B).
  • a three-layer structure of B may be used.
  • the multilayer film of the present invention may include an arbitrary layer such as an adhesive layer (AD) as necessary, for example, a seven-layer structure of B1 / AD / B2 / A / B2 / AD / B1. Also good.
  • AD adhesive layer
  • the oxygen absorption barrier layer can exhibit oxygen absorption performance and oxygen barrier performance by containing a specific polyamide resin (hereinafter also referred to as “polyamide resin (A)”) described later.
  • the polyamide resin (A) contained in the oxygen absorption barrier layer may be one kind or a combination of two or more kinds.
  • an oxygen absorption barrier layer contains a polyamide resin (A) as a main resin component.
  • a resin other than the polyamide resin (A) may be added to the oxygen absorption barrier layer, but the ratio of the polyamide resin (A) in the total resin of the oxygen absorption barrier layer is preferably more than 95% by mass.
  • the resin contained in the oxygen absorption barrier layer may be only the polyamide resin (A), and the ratio of the polyamide resin (A) in the total resin of the oxygen absorption barrier layer is preferably 100% by mass or less.
  • a resin other than the polyamide resin (A) may be added to the oxygen-absorbing barrier layer, and as the added resin, performance that is desired to be imparted to the oxygen-absorbing barrier layer as long as the object of the present invention is not impaired.
  • various conventionally known resins may be used.
  • polyolefins such as polyethylene and polypropylene, and various modified products thereof, polyolefin elastomers, polyamide elastomers, styrene-butadiene copolymer resins And other hydrogenated products thereof, various thermoplastic elastomers typified by polyester elastomers, various polyamides such as nylon 6, 66, 12, nylon 12, and the like.
  • polybutadiene And carbon-carbon unsaturated double bond-containing resins such as modified polybutadiene.
  • the additive resin may be one kind or a combination of two or more kinds.
  • the ratio of the additive resin in the total resin of the oxygen absorption barrier layer is preferably 5% by mass or less.
  • the oxygen-absorbing barrier layer may contain an additive to be described later (hereinafter also referred to as “additive (C)”) depending on the desired performance and the like.
  • the content of the polyamide resin (A) in the oxygen absorption barrier layer is preferably 90% by mass to 100% by mass, and 95% by mass to 100% by mass from the viewpoints of moldability, oxygen absorption performance, and oxygen barrier performance. It is more preferable that
  • the thickness of the oxygen absorption barrier layer is preferably 2 to 100 ⁇ m, more preferably from the viewpoint of securing various physical properties such as flexibility required for the multilayer film while improving oxygen absorption performance and oxygen barrier performance. The thickness is 5 to 90 ⁇ m, more preferably 10 to 80 ⁇ m.
  • polyamide resin (A) ⁇ Configuration of polyamide resin (A)>
  • the polyamide resin (A) includes an aromatic diamine unit represented by the following general formula (I-1), an alicyclic diamine unit represented by the following general formula (I-2), and the following general formula: 25 to 50 mol% of diamine units containing a total of 50 mol% or more of at least one diamine unit selected from the group consisting of linear aliphatic diamine units represented by (I-3), and the following general formula (II-1) 25 to 50 mol% of dicarboxylic acid units containing a total of 50 mol% or more of linear aliphatic dicarboxylic acid units represented by formula (II-2) and aromatic dicarboxylic acid units represented by the following general formula (II-2): Tertiary hydrogen-containing carboxylic acid unit (preferably a structural unit represented by the following general formula (III)) 0.1 to 50 mol%.
  • I-1 aromatic diamine unit represented by the following general formula (I-1)
  • m represents an integer of 2 to 18.
  • n represents an integer of 2 to 18.
  • Ar represents an arylene group.
  • R represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.
  • the polyamide resin (A) may further contain structural units other than those described above as long as the effects of the present invention are not impaired.
  • the content of the tertiary hydrogen-containing carboxylic acid unit is 0.1 to 50 mol%. If the content of the tertiary hydrogen-containing carboxylic acid unit is less than 0.1 mol%, sufficient oxygen absorption performance is not exhibited. On the other hand, when the content of the tertiary hydrogen-containing carboxylic acid unit exceeds 50 mol%, the tertiary hydrogen content is too high, and the physical properties such as gas barrier properties and mechanical properties of the polyamide resin (A) are deteriorated.
  • the secondary hydrogen-containing carboxylic acid is an amino acid
  • the peptide bond is continuous, so that the heat resistance is not sufficient, and a cyclic product composed of a dimer of amino acids is formed, thereby inhibiting polymerization.
  • the content of the tertiary hydrogen-containing carboxylic acid unit is preferably 0.2 mol% or more, more preferably 1 mol% or more, and preferably from the viewpoint of the oxygen absorption performance and the properties of the polyamide resin (A). It is 40 mol% or less, More preferably, it is 30 mol% or less.
  • the diamine unit content is 25 to 50 mol%, and preferably 30 to 50 mol% from the viewpoint of oxygen absorption performance and polymer properties.
  • the content of dicarboxylic acid units is 25 to 50 mol%, preferably 30 to 50 mol%.
  • the proportion of the content of the diamine unit and the dicarboxylic acid unit is preferably substantially the same from the viewpoint of the polymerization reaction, and the content of the dicarboxylic acid unit is ⁇ 2 mol% of the content of the diamine unit. More preferred.
  • the degree of polymerization of the polyamide resin (A) becomes difficult to increase, so it takes a lot of time to increase the degree of polymerization, Deterioration is likely to occur.
  • the diamine unit in the polyamide resin (A) is an aromatic diamine unit represented by the general formula (I-1), an alicyclic diamine unit represented by the general formula (I-2), and the general formula.
  • a total of 50 mol% or more of diamine units selected from the group consisting of linear aliphatic diamine units represented by (I-3) is contained in the diamine units, and the content is preferably 70 mol% Above, more preferably 80 mol% or more, still more preferably 90 mol% or more, and preferably 100 mol% or less.
  • Examples of the compound that can constitute the aromatic diamine unit represented by the general formula (I-1) include orthoxylylenediamine, metaxylylenediamine, and paraxylylenediamine. These can be used alone or in combination of two or more.
  • Examples of the compound that can constitute the alicyclic diamine unit represented by the formula (I-2) include bis (amino) such as 1,3-bis (aminomethyl) cyclohexane and 1,4-bis (aminomethyl) cyclohexane. Methyl) cyclohexanes. These can be used alone or in combination of two or more. Bis (aminomethyl) cyclohexanes have structural isomers, but by increasing the cis-isomer ratio, the crystallinity is high and good moldability can be obtained. On the other hand, if the cis-isomer ratio is lowered, a transparent material with low crystallinity can be obtained.
  • the cis-isomer content ratio in the bis (aminomethyl) cyclohexane is preferably 70 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol% or more.
  • the cis body content ratio in the bis (aminomethyl) cyclohexanes is preferably 50 mol% or less, more preferably 40 mol% or less, still more preferably 30 mol% or less.
  • m represents an integer of 2 to 18, preferably 3 to 16, more preferably 4 to 14, and still more preferably 6 to 12.
  • Examples of the compound that can constitute the linear aliphatic diamine unit represented by the general formula (I-3) include ethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and heptamethylenediamine.
  • aliphatic diamines such as octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, and dodecamethylene diamine, but are not limited thereto.
  • hexamethylenediamine is preferable. These can be used alone or in combination of two or more.
  • a diamine unit in the polyamide resin (A) in addition to imparting excellent gas barrier properties to the polyamide resin (A), the transparency and color tone are improved, and the moldability of a general-purpose thermoplastic resin is facilitated.
  • it preferably contains an aromatic diamine unit represented by the general formula (I-1) and / or an alicyclic diamine unit represented by the general formula (I-2).
  • the aromatic diamine unit represented by the general formula (I-1) is included.
  • the diamine unit in the polyamide resin (A) is a metaxylylenediamine unit from the viewpoint of facilitating the moldability of a general-purpose thermoplastic resin in addition to exhibiting excellent gas barrier properties in the polyamide resin (A).
  • the content is preferably 50 mol% or more, and the content is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and preferably 100 mol% or less.
  • Examples of the compound that can constitute a diamine unit other than the diamine unit represented by any one of the general formulas (I-1) to (I-3) include aromatic diamines such as paraphenylenediamine, and 1,3-diaminocyclohexane. Fats such as 1,4-diaminocyclohexane, alicyclic diamines, N-methylethylenediamine, 2-methyl-1,5-pentanediamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, etc. Examples include, but are not limited to, group diamines, polyether diamines having ether bonds represented by Huntsman's Jeffamine and elastamine (both are trade names), and the like. These can be used alone or in combination of two or more.
  • the dicarboxylic acid unit in the polyamide resin (A) is a linear aliphatic group represented by the general formula (II-1) from the viewpoints of reactivity during polymerization and crystallinity and moldability of the polyamide resin (A).
  • the dicarboxylic acid unit and / or the aromatic dicarboxylic acid unit represented by the general formula (II-2) is contained in the dicarboxylic acid unit in a total of 50 mol% or more, and the content is preferably 70 mol% or more, more Preferably it is 80 mol% or more, More preferably, it is 90 mol% or more, Preferably it is 100 mol% or less.
  • the linear aliphatic dicarboxylic acid unit represented by the general formula (II-1) is necessary for a packaging material and a packaging container in addition to imparting an appropriate glass transition temperature and crystallinity to the polyamide resin (A). It is preferable at the point which can provide a softness
  • n represents an integer of 2 to 18, preferably 3 to 16, more preferably 4 to 12, and still more preferably 4 to 8.
  • Examples of the compound that can constitute the linear aliphatic dicarboxylic acid unit represented by the general formula (II-1) include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1, Examples include 10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, but are not limited thereto. These can be used alone or in combination of two or more.
  • the type of the linear aliphatic dicarboxylic acid unit represented by the general formula (II-1) is appropriately determined according to the application.
  • the linear aliphatic dicarboxylic acid unit in the polyamide resin (A) gives excellent gas barrier properties to the polyamide resin (A), and from the viewpoint of maintaining heat resistance after heat sterilization of the packaging material and packaging container.
  • At least one selected from the group consisting of an adipic acid unit, a sebacic acid unit, and a 1,12-dodecanedicarboxylic acid unit is contained in a total of 50 mol% or more in the linear aliphatic dicarboxylic acid unit,
  • the content is more preferably 70 mol% or more, still more preferably 80 mol% or more, particularly preferably 90 mol% or more, and preferably 100 mol% or less.
  • the linear aliphatic dicarboxylic acid unit in the polyamide resin (A) is a linear aliphatic unit from the viewpoint of gas barrier properties of the polyamide resin (A) and thermal properties such as an appropriate glass transition temperature and melting point. It is preferable to contain 50 mol% or more in the dicarboxylic acid unit.
  • the linear aliphatic dicarboxylic acid unit in the polyamide resin (A) is converted from the sebacic acid unit to the linear aliphatic dicarboxylic acid unit from the viewpoint of imparting appropriate gas barrier properties and molding processability to the polyamide resin (A).
  • the 1,12-dodecanedicarboxylic acid unit is a linear aliphatic group. It is preferable to contain 50 mol% or more in the dicarboxylic acid unit.
  • the aromatic dicarboxylic acid unit represented by the general formula (II-2) facilitates the molding processability of packaging materials and packaging containers in addition to imparting further gas barrier properties to the polyamide resin (A). It is preferable at the point which can do.
  • Ar represents an arylene group.
  • the arylene group is preferably an arylene group having 6 to 30 carbon atoms, more preferably 6 to 15 carbon atoms, and examples thereof include a phenylene group and a naphthylene group.
  • Examples of the compound that can constitute the aromatic dicarboxylic acid unit represented by the general formula (II-2) include terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid, but are not limited thereto. is not. These can be used alone or in combination of two or more.
  • the kind of the aromatic dicarboxylic acid unit represented by the general formula (II-2) is appropriately determined according to the use.
  • the aromatic dicarboxylic acid unit in the polyamide resin (A) is a total of at least one selected from the group consisting of an isophthalic acid unit, a terephthalic acid unit, and a 2,6-naphthalenedicarboxylic acid unit in the aromatic dicarboxylic acid unit.
  • the content is preferably 70 mol% or more, more preferably 80 mol% or more, particularly preferably 90 mol% or more, and preferably 100 mol% or less. is there. Among these, it is preferable to contain isophthalic acid and / or terephthalic acid in the aromatic dicarboxylic acid unit.
  • the content ratio of the isophthalic acid unit to the terephthalic acid unit is not particularly limited and is appropriately determined according to the application.
  • the molar ratio is preferably 0/100 to 100/0, more preferably 0/100 to 60/40, More preferably, it is 0/100 to 40/60, and more preferably 0/100 to 30/70.
  • the content ratio of the linear aliphatic dicarboxylic acid unit to the aromatic dicarboxylic acid unit is particularly limited. Rather, it is determined appropriately according to the application. For example, when the purpose is to increase the glass transition temperature of the polyamide resin (A) to lower the crystallinity of the polyamide resin (A), the linear aliphatic dicarboxylic acid unit / aromatic dicarboxylic acid unit is both units.
  • the molar ratio is preferably 0/100 to 60/40, more preferably 0/100 to 40/60, still more preferably 0/100 to 30/70.
  • the linear aliphatic dicarboxylic acid unit / aromatic dicarboxylic acid unit is When the total is 100, the molar ratio is preferably 40/60 to 100/0, more preferably 60/40 to 100/0, still more preferably 70/30 to 100/0.
  • Examples of the compound that can constitute a dicarboxylic acid unit other than the dicarboxylic acid unit represented by the general formula (II-1) or (II-2) include oxalic acid, malonic acid, fumaric acid, maleic acid, 1,3- Examples thereof include, but are not limited to, dicarboxylic acids such as benzenediacetic acid and 1,4-benzenediacetic acid.
  • the tertiary hydrogen-containing carboxylic acid unit in the polyamide resin (A) has at least one amino group and one carboxyl group from the viewpoint of polymerization of the polyamide resin (A), or two or more carboxyl groups.
  • tertiary hydrogen-containing carboxylic acid unit in the polyamide resin (A) has at least one amino group and one carboxyl group from the viewpoint of polymerization of the polyamide resin (A), or two or more carboxyl groups.
  • Specific examples include structural units represented by any of the following general formulas (III), (IV), or (V).
  • R, R 1 and R 2 each represent a substituent, and A 1 to A 3 each represent a single bond or a divalent linking group. However, the case where both A 1 and A 2 in the general formula (IV) are single bonds is excluded. ]
  • the polyamide resin (A) includes a tertiary hydrogen-containing carboxylic acid unit.
  • a tertiary hydrogen-containing carboxylic acid unit By containing such a tertiary hydrogen-containing carboxylic acid unit as a copolymerization component, the polyamide resin (A) can exhibit excellent oxygen absorption performance without containing a transition metal.
  • the mechanism by which the polyamide resin (A) having a tertiary hydrogen-containing carboxylic acid unit exhibits good oxygen absorption performance has not yet been clarified, but is estimated as follows.
  • a compound that can constitute a tertiary hydrogen-containing carboxylic acid unit an electron-withdrawing group and an electron-donating group are bonded to the same carbon atom, so that unpaired electrons existing on the carbon atom are energetic. It is considered that a very stable radical is generated by a phenomenon called a captodative effect that is stabilized in a stable manner.
  • the carboxyl group is an electron withdrawing group
  • the carbon to which the adjacent tertiary hydrogen is bonded becomes electron deficient ( ⁇ + )
  • the tertiary hydrogen also becomes electron deficient ( ⁇ + ) Dissociates as a radical.
  • oxygen and water it is considered that oxygen reacts with this radical to show oxygen absorption performance. It has also been found that the higher the humidity and temperature, the higher the reactivity.
  • R, R 1 and R 2 each represent a substituent.
  • substituent represented by R, R 1 and R 2 in the present invention include a halogen atom (eg, chlorine atom, bromine atom, iodine atom), alkyl group (1 to 15, preferably 1 to 6).
  • Linear, branched or cyclic alkyl groups having the following carbon atoms for example, methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, n-octyl group, 2-ethylhexyl group, cyclopropyl group, cyclopentyl Group), an alkenyl group (a linear, branched or cyclic alkenyl group having 2 to 10, preferably 2 to 6 carbon atoms, such as a vinyl group, an allyl group), an alkynyl group (2 to 10, preferably Alkynyl groups having 2 to 6 carbon atoms, such as ethynyl groups, propargyl groups), aryl groups (aryls having 6 to 16, preferably 6 to 10 carbon atoms) 1 to 12 groups obtained by removing one hydrogen atom from a group, for example, phenyl group, naphthyl group, heterocyclic group (5-membered or 6-
  • An alkylthio group an alkylthio group having 1 to 10, preferably 1 to 6 carbon atoms, such as a methylthio group, an ethylthio group
  • an arylthio group (6 to 12, preferably 6 to 8 carbon atoms).
  • heterocyclic thio groups for example, heterocyclic thio groups having 2 to 10, preferably 2 to 6 carbon atoms, such as - benzothiazolylthio group
  • an imido group (2 to 10, preferably an imido group having 4 to 8 carbon atoms, for example, N- succinimido group, N- phthalimido group.
  • those having a hydrogen atom may be further substituted with the above groups, for example, an alkyl group substituted with a hydroxyl group (for example, hydroxyethyl group), an alkyl group substituted with an alkoxy group (Eg, methoxyethyl group), an alkyl group substituted with an aryl group (eg, benzyl group), an aryl group substituted with an alkyl group (eg, p-tolyl group), an aryloxy group substituted with an alkyl group ( Examples thereof include, but are not limited to, 2-methylphenoxy group.
  • the carbon number mentioned above shall not include the carbon number of the further substituent.
  • a benzyl group is regarded as a C 1 alkyl group substituted with a phenyl group, and is not regarded as a C 7 alkyl group substituted with a phenyl group.
  • the following description of the number of carbon atoms shall be similarly understood unless otherwise specified.
  • a 1 to A 3 each represents a single bond or a divalent linking group.
  • the divalent linking group include linear, branched or cyclic alkylene groups (C 1-12, preferably C 1-4 alkylene groups such as methylene and ethylene groups), aralkylene groups (carbon numbers). Examples thereof include an aralkylene group having 7 to 30 carbon atoms, preferably 7 to 13 carbon atoms, such as a benzylidene group, and an arylene group (arylene group having 6 to 30 carbon atoms, preferably 6 to 15 carbon atoms such as a phenylene group).
  • substituents represented by R, R 1 and R 2 examples include the functional groups exemplified above as substituents represented by R, R 1 and R 2 .
  • substituents represented by R, R 1 and R 2 examples include, but are not limited to, an arylene group substituted with an alkyl group (for example, a xylylene group).
  • the polyamide resin (A) preferably contains at least one structural unit represented by any one of the general formulas (III), (IV), and (V).
  • a carboxylic acid unit having tertiary hydrogen on the ⁇ -carbon (carbon atom adjacent to the carboxyl group) is more preferable, and is represented by the general formula (III).
  • the structural unit is particularly preferred.
  • R in the general formula (III) is as described above.
  • a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group are more preferable, and a substituted or unsubstituted C 1-6 carbon atom is more preferable.
  • An alkyl group and a substituted or unsubstituted aryl group having 6 to 10 carbon atoms are more preferred, and a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms and a substituted or unsubstituted phenyl group are particularly preferred.
  • R examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, 1-methylpropyl group, 2-methylpropyl group, hydroxymethyl group, 1- Examples thereof include, but are not limited to, a hydroxyethyl group, a mercaptomethyl group, a methylsulfanylethyl group, a phenyl group, a naphthyl group, a benzyl group, and a 4-hydroxybenzyl group. Among these, a methyl group, an ethyl group, an isopropyl group, a 2-methylpropyl group, and a benzyl group are more preferable.
  • the compounds that can constitute the structural unit represented by the general formula (III) include alanine, 2-aminobutyric acid, valine, norvaline, leucine, norleucine, tert-leucine, isoleucine, serine, threonine, cysteine, methionine, 2 -Alpha-amino acids such as phenylglycine, phenylalanine, tyrosine, histidine, tryptophan, proline and the like can be exemplified, but are not limited thereto.
  • examples of the compound that can constitute the structural unit represented by the general formula (IV) include ⁇ -amino acids such as 3-aminobutyric acid, which constitute the structural unit represented by the general formula (V).
  • examples of the compound that can be used include, but are not limited to, dicarboxylic acids such as methylmalonic acid, methylsuccinic acid, malic acid, and tartaric acid. These may be any of D-form, L-form and racemate, or allo-form. Moreover, these can be used individually or in combination of 2 or more types.
  • ⁇ -amino acids having tertiary hydrogen in the ⁇ carbon are particularly preferable from the viewpoint of availability of raw materials and improvement of oxygen absorption.
  • alanine is most preferable from the viewpoints of ease of supply, inexpensive price, ease of polymerization, and low yellowness (YI) of the polymer. Since alanine has a relatively low molecular weight and a high copolymerization rate per 1 g of the polyamide resin (A), the oxygen absorption performance per 1 g of the polyamide resin (A) is good.
  • the purity of the compound that can constitute the tertiary hydrogen-containing carboxylic acid unit is 95% or more from the viewpoint of the influence on the polymerization such as the delay of the polymerization rate and the influence on the quality such as the yellowness of the polymer. Preferably, it is 98.5% or more, more preferably 99% or more.
  • sulfate ions and ammonium ions contained as impurities are preferably 500 ppm or less, more preferably 200 ppm or less, and still more preferably 50 ppm or less.
  • polyamide resin (A) when the polyamide resin (A) needs flexibility or the like, in addition to the diamine unit, the dicarboxylic acid unit and the tertiary hydrogen-containing carboxylic acid unit, the polyamide resin (A) An ⁇ -aminocarboxylic acid unit represented by the formula (X) may be further contained.
  • p represents an integer of 2 to 18.
  • the content of the ⁇ -aminocarboxylic acid unit is preferably from 0.1 to 49.9 mol%, more preferably from 3 to 40 mol%, still more preferably from 5 to 35, based on all constituent units of the polyamide resin (A). Mol%. However, the total of the diamine unit, dicarboxylic acid unit, tertiary hydrogen-containing carboxylic acid unit, and ⁇ -aminocarboxylic acid unit does not exceed 100 mol%.
  • p represents an integer of 2 to 18, preferably 3 to 16, more preferably 4 to 14, and still more preferably 5 to 12.
  • Examples of the compound that can constitute the ⁇ -aminocarboxylic acid unit represented by the general formula (X) include ⁇ -aminocarboxylic acid having 5 to 19 carbon atoms and lactam having 5 to 19 carbon atoms.
  • Examples of the ⁇ -aminocarboxylic acid having 5 to 19 carbon atoms include 6-aminohexanoic acid and 12-aminododecanoic acid, and examples of the lactam having 5 to 19 carbon atoms include ⁇ -caprolactam and laurolactam. However, it is not limited to these. These can be used alone or in combination of two or more.
  • the ⁇ -aminocarboxylic acid unit preferably contains 6-aminohexanoic acid units and / or 12-aminododecanoic acid units in a total of 50 mol% or more in the ⁇ -aminocarboxylic acid unit, and the content is More preferably, it is 70 mol% or more, More preferably, it is 80 mol% or more, More preferably, it is 90 mol% or more, Preferably it is 100 mol% or less.
  • the relative viscosity is used for the degree of polymerization of the polyamide resin (A).
  • the preferred relative viscosity of the polyamide resin (A) is preferably 1.8 to 4.2, more preferably 1.9 to 4.0, and still more preferably 2 from the viewpoint of the strength and appearance of the molded product and molding processability. 0.0 to 3.8.
  • the oxygen absorption rate of the polyamide resin (A) and the oxidative deterioration of the polyamide resin (A) due to oxygen absorption can be controlled by changing the terminal amino group concentration of the polyamide resin (A).
  • the terminal amino group concentration of the polyamide resin (A) is preferably in the range of 5 to 150 ⁇ eq / g, more preferably 10 to 100 ⁇ eq / g, still more preferably 15 ⁇ 80 ⁇ eq / g.
  • the polyamide resin (A) includes a diamine component that can constitute the diamine unit, a dicarboxylic acid component that can constitute the dicarboxylic acid unit, and a tertiary hydrogen-containing carboxylic acid component that can constitute the tertiary hydrogen-containing carboxylic acid unit.
  • the ⁇ -aminocarboxylic acid component that can constitute the ⁇ -aminocarboxylic acid unit if necessary, can be produced by polycondensation, and the degree of polymerization can be controlled by adjusting the polycondensation conditions and the like. it can.
  • a small amount of monoamine or monocarboxylic acid may be added as a molecular weight modifier during polycondensation. Further, in order to suppress the polycondensation reaction and obtain a desired degree of polymerization, the ratio (molar ratio) between the diamine component and the carboxylic acid component constituting the polyamide resin (A) may be adjusted from 1.
  • Examples of the polycondensation method of the polyamide resin (A) include, but are not limited to, a reactive extrusion method, a pressurized salt method, an atmospheric pressure dropping method, and a pressure dropping method. Moreover, the one where reaction temperature is as low as possible can suppress the yellowing and gelatinization of a polyamide resin (A), and the polyamide resin (A) of the stable property is obtained.
  • a polyamide composed of a diamine component and a dicarboxylic acid component (a polyamide corresponding to the precursor of the polyamide resin (A)) or a polyamide composed of a diamine component, a dicarboxylic acid component and an ⁇ -aminocarboxylic acid component (polyamide resin (A And a tertiary hydrogen-containing carboxylic acid component are melt-kneaded with an extruder and reacted.
  • a screw suitable for reactive extrusion is used, and a twin screw extruder having a large L / D is used. It is preferable to use it.
  • a polyamide resin (A) containing a small amount of a tertiary hydrogen-containing carboxylic acid unit it is a simple method and suitable.
  • the pressurized salt method is a method of performing melt polycondensation under pressure using a nylon salt as a raw material. Specifically, after preparing an aqueous nylon salt solution comprising a diamine component, a dicarboxylic acid component, a tertiary hydrogen-containing carboxylic acid component, and an ⁇ -aminocarboxylic acid component as necessary, the aqueous solution is concentrated, Next, the temperature is raised under pressure, and polycondensation is performed while removing condensed water. While the inside of the can is gradually returned to normal pressure, the temperature is raised to about the melting point of polyamide resin (A) + 10 ° C.
  • the pressurized salt method is useful when a volatile component is used as a monomer, and is a preferable polycondensation method when the copolymerization rate of the tertiary hydrogen-containing carboxylic acid component is high.
  • it is suitable for producing a polyamide resin (A) containing 15 mol% or more of tertiary hydrogen-containing carboxylic acid units in all structural units of the polyamide resin (A).
  • Normal pressure dropping method In the atmospheric pressure dropping method, a diamine component is continuously dropped into a mixture obtained by heating and melting a dicarboxylic acid component, a tertiary hydrogen-containing carboxylic acid component, and, if necessary, an ⁇ -aminocarboxylic acid component under normal pressure. Then, polycondensation is performed while removing condensed water. The polycondensation reaction is performed while raising the temperature of the reaction system so that the reaction temperature does not fall below the melting point of the produced polyamide resin (A). Compared with the pressurized salt method, the atmospheric pressure dropping method does not use water to dissolve the salt, so the yield per batch is large, and the reaction rate is not required for vaporization / condensation of raw material components. The process time can be shortened.
  • a dicarboxylic acid component, a tertiary hydrogen-containing carboxylic acid component, and, if necessary, an ⁇ -aminocarboxylic acid component are charged into a polycondensation can, and the components are agitated and melt mixed.
  • the diamine component is continuously dropped into the mixture while the inside of the can is preferably pressurized to about 0.3 to 0.4 MPaG, and polycondensation is performed while removing condensed water.
  • the polycondensation reaction is performed while raising the temperature of the reaction system so that the reaction temperature does not fall below the melting point of the produced polyamide resin (A).
  • the dropping of the diamine component is terminated, and while gradually raising the inside of the can to normal pressure, the temperature is raised to about the melting point of the polyamide resin (A) + 10 ° C. and maintained, and then ⁇ 0.02 MPaG The pressure is gradually reduced until it is maintained at the same temperature, and the polycondensation is continued.
  • the inside of the can is pressurized to about 0.3 MPaG with nitrogen to recover the polyamide resin (A).
  • the pressure dropping method is useful when a volatile component is used as a monomer, and is a preferred polycondensation method when the copolymerization rate of the tertiary hydrogen-containing carboxylic acid component is high. .
  • it is suitable for producing a polyamide resin (A) containing 15 mol% or more of tertiary hydrogen-containing carboxylic acid units in all structural units of the polyamide resin (A).
  • a polyamide resin (A) excellent in properties can be obtained. Furthermore, since the pressure drop method does not use water for dissolving the salt compared to the pressure salt method, the yield per batch is large, and the reaction time can be shortened as in the atmospheric pressure drop method. It is possible to obtain a polyamide resin (A) having a low yellowness, which can be suppressed.
  • the polyamide resin (A) produced by the polycondensation method can be used as it is, but may be subjected to a step for further increasing the degree of polymerization.
  • Further examples of the step of increasing the degree of polymerization include reactive extrusion in an extruder and solid phase polymerization.
  • a heating device used in solid phase polymerization a continuous heating drying device, a tumble dryer, a conical dryer, a rotary drum heating device called a rotary dryer, etc., and a rotary blade inside a nauta mixer are provided.
  • a conical heating device can be preferably used, but a known method and device can be used without being limited thereto.
  • the rotating drum type heating device in the above-described device can seal the inside of the system and perform polycondensation in a state where oxygen that causes coloring is removed. It is preferably used because it is easy to proceed.
  • [Phosphorus atom-containing compound, alkali metal compound] In the polycondensation of the polyamide resin (A), it is preferable to add a phosphorus atom-containing compound from the viewpoint of promoting the amidation reaction.
  • the phosphorus atom-containing compound include phosphinic acid compounds such as dimethylphosphinic acid and phenylmethylphosphinic acid; hypophosphorous acid, sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, magnesium hypophosphite, Diphosphite compounds such as calcium hypophosphite and ethyl hypophosphite; phosphonic acid, sodium phosphonate, potassium phosphonate, lithium phosphonate, magnesium phosphonate, calcium phosphonate, phenylphosphonic acid, ethylphosphonic acid, phenylphosphone Phosphonic acid compounds such as sodium phosphate, potassium phenylphosphonate, lithium phenylphosphonate,
  • hypophosphite metal salts such as sodium hypophosphite, potassium hypophosphite, lithium hypophosphite and the like are particularly preferable because they are highly effective in promoting amidation reaction and excellent in anti-coloring effect.
  • sodium hypophosphite is preferred.
  • the phosphorus atom containing compound which can be used by this invention is not limited to these compounds.
  • the addition amount of the phosphorus atom-containing compound is preferably 0.1 to 1000 ppm, more preferably 1 to 600 ppm, still more preferably 5 to 400 ppm in terms of the phosphorus atom concentration in the polyamide resin (A).
  • the polyamide resin (A) is difficult to be colored during the polymerization, and the transparency becomes high. If it is 1000 ppm or less, the polyamide resin (A) is hardly gelled, and it is possible to reduce the mixing of fish eyes considered to be caused by the phosphorus atom-containing compound into the molded product, so that the appearance of the molded product is improved.
  • an alkali metal compound in combination with the phosphorus atom-containing compound in the polycondensation system of the polyamide resin (A).
  • an alkali metal compound in order to prevent coloring of the polyamide resin (A) during the polycondensation, it is necessary to make a sufficient amount of the phosphorus atom-containing compound present.
  • the polyamide resin (A) may be gelled.
  • alkali metal compound alkali metal hydroxide, alkali metal acetate, alkali metal carbonate, alkali metal alkoxide, and the like are preferable.
  • Sodium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide, potassium methoxide, lithium methoxide, sodium carbonate and the like but can be used without being limited to these compounds.
  • the range of 1.0 / 1.5 is preferable, more preferably 1.0 / 0.1 to 1.0 / 1.2, and still more preferably 1.0 / 0.2 to 1.0 / 1. 1.
  • the oxygen absorption barrier layer of the present invention may further contain an additive (C) as necessary in addition to the polyamide resin (A) described above.
  • an additive (C) may be used, or a combination of two or more types may be used.
  • the content of the additive (C) in the oxygen absorption barrier layer is preferably 10% by mass or less, more preferably 5% by mass or less, although it depends on the type of additive.
  • a diamide compound and / or a diester compound to the polyamide resin (A) as a suppression of whitening after the hot water treatment or after a long period of time.
  • Diamide compounds and diester compounds are effective in suppressing whitening due to precipitation of oligomers.
  • a diamide compound and a diester compound may be used alone or in combination.
  • the diamide compound used in the present invention is preferably a diamide compound obtained from an aliphatic dicarboxylic acid having 8 to 30 carbon atoms and a diamine having 2 to 10 carbon atoms.
  • a whitening prevention effect can be expected.
  • the aliphatic dicarboxylic acid has 30 or less carbon atoms and the diamine has 10 or less carbon atoms, uniform dispersion in the oxygen-absorbing barrier layer is good.
  • the aliphatic dicarboxylic acid may have a side chain or a double bond, but a linear saturated aliphatic dicarboxylic acid is preferred.
  • One kind of diamide compound may be used, or two or more kinds may be used in combination.
  • Examples of the aliphatic dicarboxylic acid include stearic acid (C18), eicosanoic acid (C20), behenic acid (C22), montanic acid (C28), and triacontanoic acid (C30).
  • Examples of the diamine include ethylenediamine, butylenediamine, hexanediamine, xylylenediamine, and bis (aminomethyl) cyclohexane. A diamide compound obtained by combining these is preferred.
  • a diamide compound obtained from an aliphatic dicarboxylic acid mainly composed of stearic acid and a diamine mainly composed of ethylenediamine is particularly preferred.
  • the diester compound used in the present invention is preferably a diester compound obtained from an aliphatic dicarboxylic acid having 8 to 30 carbon atoms and a diol having 2 to 10 carbon atoms.
  • an effect of preventing whitening can be expected.
  • the aliphatic dicarboxylic acid has 30 or less carbon atoms and the diol has 10 or less carbon atoms, uniform dispersion in the oxygen-absorbing barrier layer is good.
  • the aliphatic dicarboxylic acid may have a side chain or a double bond, but a linear saturated aliphatic dicarboxylic acid is preferred.
  • diester compound may be used, or two or more types may be used in combination.
  • the aliphatic dicarboxylic acid include stearic acid (C18), eicosanoic acid (C20), behenic acid (C22), montanic acid (C28), and triacontanoic acid (C30).
  • the diol include ethylene glycol, propanediol, butanediol, hexanediol, xylylene glycol, and cyclohexanedimethanol.
  • a diester compound obtained by combining these is preferred.
  • Particularly preferred are diester compounds obtained from an aliphatic dicarboxylic acid mainly composed of montanic acid and a diol mainly composed of ethylene glycol and / or 1,3-butanediol.
  • the amount of the diamide compound and / or diester compound added is preferably 0.005 to 0.5% by mass, more preferably 0.05 to 0.5% by mass, and still more preferably in the oxygen absorption barrier layer. 0.12 to 0.5% by mass.
  • a synergistic effect of preventing whitening can be expected by adding 0.005% by mass or more to the oxygen absorption barrier layer and using it together with the crystallization nucleating agent.
  • the oxygen absorption barrier layer may contain a layered silicate.
  • a layered silicate By adding the layered silicate, not only oxygen gas barrier properties but also barrier properties against gas such as carbon dioxide gas can be imparted to the multilayer film.
  • the layered silicate is a 2-octahedron or 3-octahedral layered silicate having a charge density of 0.25 to 0.6.
  • Examples of the 2-octahedron type include montmorillonite, beidellite, and the like.
  • Examples of the octahedron type include hectorite and saponite. Among these, montmorillonite is preferable.
  • the layered silicate is obtained by expanding an interlayer of the layered silicate by previously bringing an organic swelling agent such as a polymer compound or an organic compound into contact with the layered silicate.
  • an organic swelling agent such as a polymer compound or an organic compound
  • a quaternary ammonium salt can be preferably used.
  • a quaternary ammonium salt having at least one alkyl group or alkenyl group having 12 or more carbon atoms is used.
  • organic swelling agents include trimethyl dodecyl ammonium salts, trimethyl tetradecyl ammonium salts, trimethyl hexadecyl ammonium salts, trimethyl octadecyl ammonium salts, trimethyl alkyl ammonium salts such as trimethyl eicosyl ammonium salts; trimethyl octadecenyl ammonium salts Trimethylalkenylammonium salts such as trimethyloctadecadienylammonium salt; triethylalkylammonium salts such as triethyldodecylammonium salt, triethyltetradecylammonium salt, triethylhexadecylammonium salt, triethyloctadecylammonium salt; tributyldodecylammonium salt, tributyltetradecyl Ammonium salt, tribut
  • hydroxyl group and / or ether group-containing ammonium salts among them, methyl dialkyl (PAG) ammonium salt, ethyl dialkyl (PAG) ammonium salt, butyl dialkyl (PAG) ammonium salt, dimethyl bis (PAG) ammonium salt, diethyl bis (PAG) ) Ammonium salt, dibutyl bis (PAG) ammonium salt, methyl alkyl bis (PAG) ammonium salt, ethyl alkyl bis (PAG) ammonium salt, butyl alkyl bis (PAG) ammonium salt, methyl tri (PAG) ammonium salt, ethyl tri (PAG) ammonium Salt, butyltri (PAG) ammonium salt, tetra (PAG) ammonium salt (wherein alkyl is carbon number such as dodecyl, tetradecyl, hexadecyl, octadec
  • Salts can also be used as organic swelling agents.
  • organic swelling agents trimethyldodecyl ammonium salt, trimethyl tetradecyl ammonium salt, trimethyl hexadecyl ammonium salt, trimethyl octadecyl ammonium salt, dimethyl didodecyl ammonium salt, dimethyl ditetradecyl ammonium salt, dimethyl dihexadecyl ammonium salt, dimethyl dioctadecyl ammonium salt, dimethyl A ditallow ammonium salt is preferred.
  • organic swelling agents can be used alone or as a mixture of a plurality of types.
  • a layered silicate treated with an organic swelling agent is preferably added in an amount of 0.5 to 8% by mass in the oxygen absorption barrier layer, more preferably 1 to 6% by mass, still more preferably 2 to 5% by mass. If the amount of layered silicate added is 0.5% by mass or more, the effect of improving the gas barrier property is sufficiently obtained, and if it is 8% by mass or less, pinholes are generated due to deterioration of the flexibility of the oxygen absorption barrier layer. Such problems are unlikely to occur.
  • the layered silicate is preferably uniformly dispersed without locally agglomerating.
  • the uniform dispersion here means that the layered silicate is separated into a flat plate in the oxygen absorption barrier layer, and 50% or more of them have an interlayer distance of 5 nm or more.
  • the interlayer distance refers to the distance between the centers of gravity of the flat objects. The larger the distance, the better the dispersion state, the better the appearance such as transparency, and the better the gas barrier properties such as oxygen and carbon dioxide.
  • Oxidation reaction accelerator In order to further enhance the oxygen absorption performance of the oxygen absorption barrier layer, a conventionally known oxidation reaction accelerator may be added as long as the effects of the present invention are not impaired.
  • the oxidation reaction accelerator can enhance the oxygen absorption performance of the oxygen absorption barrier layer by promoting the oxygen absorption performance of the polyamide resin (A).
  • the oxidation reaction accelerator examples include Group VIII metals such as iron, cobalt and nickel, Group I metals such as copper and silver, Group IV metals such as tin, titanium and zirconium, Group V of vanadium, Examples thereof include low-valent inorganic or organic acid salts of Group VI metals such as chromium and Group VII metals such as manganese, or complex salts of the above transition metals.
  • a cobalt salt excellent in an oxygen reaction promoting effect or a combination of a cobalt salt and a manganese salt is preferable.
  • the addition amount of the oxygen reaction accelerator is preferably 10 to 800 ppm, more preferably 50 to 600 ppm, and still more preferably 100 to 400 ppm as the metal atom concentration in the oxygen absorption barrier layer.
  • oxygen absorbent In order to further enhance the oxygen absorption performance of the oxygen absorption barrier layer, a conventionally known oxygen absorbent may be added within a range not impairing the effects of the present invention.
  • the oxygen absorbent can enhance the oxygen absorption performance of the oxygen absorption barrier layer by imparting oxygen absorption performance to the oxygen absorption barrier layer separately from the oxygen absorption performance of the polyamide resin (A).
  • the oxygen absorbent include oxidizable organic compounds typified by compounds having a carbon-carbon double bond in the molecule, such as vitamin C, vitamin E, butadiene and isoprene.
  • the amount of oxygen absorber added is preferably 0.01 to 5% by mass, more preferably 0.1 to 4% by mass, and still more preferably 0.5 to 3% by mass in the oxygen absorption barrier layer. is there.
  • carboxylates selected from sodium acetate, calcium acetate, magnesium acetate, calcium stearate, magnesium stearate, sodium stearate and derivatives thereof.
  • the derivatives include 12-hydroxystearic acid metal salts such as calcium 12-hydroxystearate, magnesium 12-hydroxystearate, and sodium 12-hydroxystearate.
  • the addition amount of the carboxylates is preferably 400 to 10000 ppm, more preferably 800 to 5000 ppm, still more preferably 1000 to 3000 ppm as the concentration in the oxygen absorption barrier layer. If it is 400 ppm or more, the thermal deterioration of the polyamide resin (A) can be suppressed, and gelation can be prevented. Moreover, if it is 10000 ppm or less, a polyamide resin (A) will not raise
  • carboxylates that are basic substances in the melted polyamide resin (A) delays the modification of the polyamide resin (A) by heat and suppresses the formation of a gel that is considered to be the final modified product.
  • the carboxylates described above are excellent in handling properties, and among them, metal stearate is preferable because it is inexpensive and has an effect as a lubricant, and can stabilize the molding process.
  • the shape of the carboxylate is not particularly limited, but when the powder and the smaller particle size are dry-mixed, it is easy to uniformly disperse in the oxygen absorption barrier layer. Is preferably 0.2 mm or less.
  • sodium acetate having a high metal salt concentration per gram it is preferable to use as a more effective gelling prevention, fisheye reduction, and kogation prevention formulation.
  • sodium acetate When sodium acetate is used, it may be dry mixed with the polyamide resin (A) and molded, but from the viewpoint of handling properties and reduction of acetic acid odor, a masterbatch comprising the polyamide resin (A) and sodium acetate is prepared. It is preferable to dry-mix with the polyamide resin (A) for molding. Since it is easy to disperse
  • antioxidant In the present invention, it is preferable to add an antioxidant from the viewpoint of controlling oxygen absorption performance and suppressing deterioration of mechanical properties.
  • the antioxidant include copper-based antioxidants, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and thio-based antioxidants. Antioxidants and phosphorus antioxidants are preferred.
  • hindered phenol antioxidant examples include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate, 4,4′-butylidenebis (3-methyl- 6-t-butylphenol), 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,4-bis- (n-octylthio) -6- (4-Hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- ( , 5-di-t-butyl-4
  • phosphorus antioxidants include triphenyl phosphite, trioctadecyl phosphite, tridecyl phosphite, trinonylphenyl phosphite, diphenylisodecyl phosphite, bis (2,6-di-tert-butyl- 4-methylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, distearyl pentaerythritol And organic phosphorus compounds such as diphosphite, tetra (tridecyl-4,4′-isopropylidene diphenyl diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl)
  • the content of the antioxidant can be used without particular limitation as long as it does not impair the various performances of the composition, but it is preferable in the oxygen-absorbing barrier layer from the viewpoint of controlling the oxygen-absorbing performance and suppressing deterioration of mechanical properties. Is 0.001 to 3 mass%, more preferably 0.01 to 1 mass%.
  • the oxygen-absorbing barrier layer has a lubricant, matting agent, heat stabilizer, weathering stabilizer, ultraviolet absorber, plasticizer, flame retardant, antistatic agent, anti-coloring agent, crystal
  • An additive such as a nucleating agent may be added. These additives can be added as necessary within a range not impairing the effects of the present invention.
  • the layer (B) in the present invention is a layer mainly composed of the resin (B).
  • the “main component” means that the layer (B) contains the resin (B) in an amount of 70% by mass or more, preferably 80% by mass or more, more preferably 90 to 100% by mass.
  • the layer (B) may contain the additive (C) in addition to the resin (B) depending on the desired performance and the like.
  • the multilayer film of the present invention may have a plurality of layers (B), and the structures of the plurality of layers (B) may be the same or different from each other.
  • the thickness of the layer (B) can be appropriately determined according to the use, and from the viewpoint of ensuring various physical properties such as strength and flexibility such as pinhole resistance and drop resistance required for the multilayer film,
  • the thickness is preferably 5 to 200 ⁇ m, more preferably 10 to 150 ⁇ m, still more preferably 15 to 100 ⁇ m.
  • Resin (B) in the present invention, any resin can be used as the resin (B) and is not particularly limited.
  • a thermoplastic resin can be used, and specific examples thereof include polyolefin, polyester, polyamide, ethylene-vinyl alcohol copolymer, and plant-derived resin.
  • the resin (B) preferably contains at least one selected from the group consisting of these resins.
  • polyolefin Specific examples of the polyolefin include olefins such as polyethylene (low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene), polypropylene, polybutene-1, poly-4-methylpentene-1, and the like.
  • Homopolymer ethylene-propylene random copolymer, ethylene-propylene block copolymer, ethylene-propylene-polybutene-1 copolymer, ethylene-cyclic olefin copolymer, etc., copolymer of ethylene and ⁇ -olefin Ethylene- ⁇ , ⁇ -unsaturated carboxylic acid copolymer such as ethylene- (meth) acrylic acid copolymer, ethylene- ⁇ , ⁇ -unsaturated carboxylic acid such as ethylene- (meth) acrylic acid ethyl copolymer Ester copolymer, ionic cross-linked product of ethylene- ⁇ , ⁇ -unsaturated carboxylic acid copolymer, ethylene - Other ethylene copolymers such as vinyl acetate copolymer; may be mentioned graft-modified polyolefin grafted modifying these polyolefins with an acid anhydride such as maleic anhydride.
  • the polyester is composed of one or more selected from polycarboxylic acids containing dicarboxylic acids and ester-forming derivatives thereof, and one or more selected from polyhydric alcohols containing glycol. Or a hydroxycarboxylic acid and an ester-forming derivative thereof, or a cyclic ester.
  • Dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, 3- Exemplified as cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, dimer acid, etc.
  • Saturated aliphatic dicarboxylic acids or ester-forming derivatives thereof unsaturated aliphatic dicarboxylic acids exemplified by fumaric acid, maleic acid, itaconic acid or the like, or ester-forming derivatives thereof, orthophthalic acid, isophthalic acid, terephthalic acid 1,3- Phthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4 ′ Aromatic dicarboxylic acids exemplified by biphenylsulfone dicarboxylic acid, 4,4′-biphenyl ether dicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p′-dicarboxylic acid, anthracene dicarboxylic
  • Examples of forming derivatives such as 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 5-lithium sulfoisophthalic acid, 2-lithium sulfoterephthalic acid, 5-potassium sulfoisophthalic acid, 2-potassium sulfoterephthalic acid, etc.
  • Aromatic dicarboxylic acids containing metal sulfonate groups The like lower alkyl esters thereof derivative.
  • dicarboxylic acids the use of terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid is particularly preferable in terms of the physical properties of the resulting polyester, and other dicarboxylic acids may be copolymerized as necessary. .
  • carboxylic acids other than these dicarboxylic acids ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3,4,3 ′, 4′-biphenyltetracarboxylic acid, And ester-forming derivatives thereof.
  • glycols ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,4 -Butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, 1,10-decamethylene glycol, 1,12-dodecanediol, polyethylene glycol, polyto Aliphatic glycols, such as methylene glycol and polytetramethylene glycol, hydroquinone,
  • glycols it is particularly preferable to use ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, and 1,4-cyclohexanedimethanol as main components.
  • polyhydric alcohols other than these glycols include trimethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol, and hexanetriol.
  • Hydroxycarboxylic acids include lactic acid, citric acid, malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, 4-hydroxycyclohexanecarboxylic acid, or these And ester-forming derivatives thereof.
  • cyclic ester examples include ⁇ -caprolactone, ⁇ -propiolactone, ⁇ -methyl- ⁇ -propiolactone, ⁇ -valerolactone, glycolide, lactide and the like.
  • ester-forming derivatives of polyvalent carboxylic acids and hydroxycarboxylic acids include these alkyl esters, acid chlorides, acid anhydrides, and the like.
  • the polyester used in the present invention is preferably a polyester in which the main acid component is terephthalic acid or an ester-forming derivative thereof or naphthalenedicarboxylic acid or an ester-forming derivative thereof, and the main glycol component is alkylene glycol.
  • the polyester in which the main acid component is terephthalic acid or an ester-forming derivative thereof is preferably a polyester containing 70 mol% or more of terephthalic acid or an ester-forming derivative thereof in total with respect to the total acid component.
  • a polyester containing 80 mol% or more is preferable, and a polyester containing 90 mol% or more is more preferable.
  • the polyester in which the main acid component is naphthalenedicarboxylic acid or an ester-forming derivative thereof is also preferably a polyester containing 70 mol% or more of naphthalenedicarboxylic acid or an ester-forming derivative thereof, more preferably 80 Polyesters containing at least mol%, more preferably polyesters containing at least 90 mol%.
  • naphthalenedicarboxylic acid or ester-forming derivative thereof used in the present invention examples include 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid exemplified in the above dicarboxylic acids, 6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, or ester-forming derivatives thereof are preferred.
  • the polyester whose main glycol component is an alkylene glycol is preferably a polyester containing 70 mol% or more of the total amount of alkylene glycol with respect to all glycol components, more preferably a polyester containing 80 mol% or more, More preferably, it is a polyester containing 90 mol% or more.
  • the alkylene glycol here may contain a substituent or an alicyclic structure in the molecular chain.
  • the copolymer components other than the terephthalic acid / ethylene glycol are isophthalic acid, 2,6-naphthalenedicarboxylic acid, diethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,2-propanediol, 1,3-propane. It is preferably at least one selected from the group consisting of diol and 2-methyl-1,3-propanediol from the viewpoint of achieving both transparency and moldability, and in particular, isophthalic acid, diethylene glycol, neopentyl glycol, More preferably, it is at least one selected from the group consisting of 1,4-cyclohexanedimethanol.
  • a preferred example of the polyester used in the present invention is a polyester whose main repeating unit is composed of ethylene terephthalate, more preferably a linear polyester containing 70 mol% or more of ethylene terephthalate units, and still more preferably an ethylene terephthalate unit.
  • a linear polyester containing 80 mol% or more is preferable, and a linear polyester containing 90 mol% or more of ethylene terephthalate units is particularly preferable.
  • polyester used in the present invention is a polyester in which the main repeating unit is composed of ethylene-2,6-naphthalate, and more preferably contains 70 mol% or more of ethylene-2,6-naphthalate units.
  • a linear polyester more preferably a linear polyester containing 80 mol% or more of ethylene-2,6-naphthalate units, and particularly preferably a linear polyester containing 90 mol% or more of ethylene-2,6-naphthalate units. Polyester.
  • polyesters containing 70 mol% or more of propylene terephthalate units linear polyesters containing 70 mol% or more of propylene naphthalate units, and 1,4-cyclohexanedimethylene terephthalate.
  • the composition of the entire polyester is transparent in combination of terephthalic acid / isophthalic acid // ethylene glycol, terephthalic acid // ethylene glycol / 1,4-cyclohexanedimethanol, and terephthalic acid // ethylene glycol / neopentyl glycol.
  • terephthalic acid / isophthalic acid // ethylene glycol
  • terephthalic acid // ethylene glycol / neopentyl glycol.
  • a small amount (5 mol% or less) of diethylene glycol produced by dimerization of ethylene glycol may be included in the esterification (transesterification) reaction or polycondensation reaction.
  • polyester used in the present invention include polyglycolic acid obtained by polycondensation of glycolic acid or methyl glycolate or ring-opening polycondensation of glycolide.
  • This polyglycolic acid may be copolymerized with other components such as lactide.
  • polyamide is not “polyamide resin (A)” in the present invention
  • polyamide resin (A) is a polyamide mainly composed of units derived from lactam or aminocarboxylic acid, or Aliphatic polyamides whose main constituent units are units derived from aliphatic diamines and aliphatic dicarboxylic acids, partially aromatic polyamides whose main constituent units are units derived from aliphatic diamines and aromatic dicarboxylic acids, aromatic Examples thereof include partially aromatic polyamides having a unit derived from a diamine and an aliphatic dicarboxylic acid as a main constituent unit, and monomer units other than the main constituent unit may be copolymerized as necessary.
  • lactam or aminocarboxylic acid examples include lactams such as ⁇ -caprolactam and laurolactam, aminocarboxylic acids such as aminocaproic acid and aminoundecanoic acid, and aromatic aminocarboxylic acids such as para-aminomethylbenzoic acid.
  • an aliphatic diamine having 2 to 12 carbon atoms or a functional derivative thereof can be used.
  • an alicyclic diamine may be used.
  • the aliphatic diamine may be a linear aliphatic diamine or a branched chain aliphatic diamine.
  • linear aliphatic diamines include ethylenediamine, 1-methylethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, Examples include aliphatic diamines such as nonamethylenediamine, decamethylenediamine, undecamethylenediamine, and dodecamethylenediamine.
  • alicyclic diamine include cyclohexanediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, and the like.
  • the aliphatic dicarboxylic acid is preferably a linear aliphatic dicarboxylic acid or an alicyclic dicarboxylic acid, and more preferably a linear aliphatic dicarboxylic acid having an alkylene group having 4 to 12 carbon atoms.
  • linear aliphatic dicarboxylic acids include adipic acid, sebacic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, undecanoic acid, undecadioic acid, dodecanedioic acid, dimer Examples thereof include acids and functional derivatives thereof.
  • alicyclic dicarboxylic acid examples include alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid.
  • aromatic diamine examples include metaxylylenediamine, paraxylylenediamine, para-bis (2-aminoethyl) benzene and the like.
  • aromatic dicarboxylic acid examples include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, and functional derivatives thereof. It is done.
  • polyamides include polyamide 4, polyamide 6, polyamide 10, polyamide 11, polyamide 12, polyamide 4, 6, polyamide 6, 6, polyamide 6, 10, polyamide 6T, polyamide 9T, polyamide 6IT, polymetaxylylene azide.
  • a copolymerization component of the polyamide a polyether having at least one terminal amino group or terminal carboxyl group and a number average molecular weight of 2000 to 20000, or an organic carboxylate of the polyether having the terminal amino group, or An amino salt of a polyether having a terminal carboxyl group can also be used.
  • Specific examples include bis (aminopropyl) poly (ethylene oxide) (polyethylene glycol having a number average molecular weight of 2000 to 20000).
  • the partially aromatic polyamide may contain a structural unit derived from a polybasic carboxylic acid having three or more bases such as trimellitic acid and pyromellitic acid within a substantially linear range.
  • the polyamide is basically a conventionally known melt polycondensation method in the presence of water or a melt polycondensation method in the absence of water, or a polyamide obtained by these melt polycondensation methods. It can be manufactured by a method or the like.
  • the melt polycondensation reaction may be performed in one step or may be performed in multiple steps. These may be comprised from a batch-type reaction apparatus, and may be comprised from the continuous-type reaction apparatus.
  • the melt polycondensation step and the solid phase polymerization step may be operated continuously or may be operated separately.
  • the ethylene vinyl alcohol copolymer used in the present invention is not particularly limited, but preferably has an ethylene content of 15 to 60 mol%, more preferably 20 to 55 mol%, more preferably 29 to 44 mol%, The degree of saponification of the vinyl acetate component is preferably 90 mol% or more, more preferably 95 mol% or more.
  • the ethylene vinyl alcohol copolymer has a smaller amount of an ⁇ -olefin such as propylene, isobutene, ⁇ -octene, ⁇ -dodecene, ⁇ -octadecene, and unsaturated carboxylic acid as long as the effects of the present invention are not adversely affected.
  • a comonomer such as a salt thereof, a partial alkyl ester, a complete alkyl ester, a nitrile, an amide, an anhydride, an unsaturated sulfonic acid or a salt thereof may be contained.
  • Plant-derived resin Specific examples of the plant-derived resin include a portion overlapping with the above resin, but are not particularly limited, and examples thereof include aliphatic polyester-based biodegradable resins other than various known petroleum materials.
  • examples of the aliphatic polyester-based biodegradable resin include poly ( ⁇ -hydroxy acids) such as polyglycolic acid (PGA) and polylactic acid (PLA); polybutylene succinate (PBS), polyethylene succinate (PES) and the like. And polyalkylene alkanoates.
  • the multilayer film of the present invention may contain an optional layer depending on the desired performance and the like.
  • an arbitrary layer include an adhesive layer, a metal foil, a metal vapor-deposited layer, an easily peelable layer, and an easily tearable layer.
  • the adhesive layer preferably contains a thermoplastic resin having adhesiveness.
  • a thermoplastic resin having adhesiveness for example, an acid modification in which a polyolefin resin such as polyethylene or polypropylene is modified with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, etc. Examples include polyolefin resins.
  • the adhesive layer it is preferable to use a modified resin of the same type as the resin (B) used as the layer (B) from the viewpoint of adhesiveness.
  • the thickness of the adhesive layer is preferably 2 to 100 ⁇ m, more preferably 5 to 90 ⁇ m, and still more preferably 10 to 80 ⁇ m, from the viewpoint of ensuring molding processability while exhibiting practical adhesive strength.
  • the multilayer film of the present invention may contain a metal foil, a metal vapor deposition layer, and an organic-inorganic film from the viewpoint of gas barrier properties and light shielding properties.
  • a metal foil an aluminum foil is preferable.
  • the thickness of the metal foil is preferably 3 to 50 ⁇ m, more preferably 3 to 30 ⁇ m, still more preferably 5 to 15 ⁇ m, from the viewpoints of gas barrier properties, light shielding properties, bending resistance, and the like.
  • a resin film or the like on which a metal such as aluminum or alumina or a metal oxide film is deposited can be used as the metal deposition layer.
  • the formation method of a vapor deposition film is not specifically limited, For example, physical vapor deposition methods, such as a vacuum evaporation method, sputtering method, and an ion plating method, Chemical vapor deposition methods, such as PECVD, etc. are mentioned.
  • the thickness of the deposited film is preferably 5 to 500 nm, more preferably 5 to 200 nm, from the viewpoints of gas barrier properties, light shielding properties, bending resistance, and the like.
  • a resin film coated with a silica-polyvinyl alcohol hybrid film or the like prepared by a sol-gel method or the like can be used.
  • the thickness of the coating film is preferably 100 nm to 50 ⁇ m, more preferably 1 to 15 ⁇ m, from the viewpoints of gas barrier properties, light shielding properties, bending resistance, and the like.
  • the multilayer film of the present invention may include an easy peel layer and an easy tear layer in order to facilitate the opening of the multilayer film packaging container.
  • an easy peel layer a film in which two or more kinds of commonly used polyolefins are blended to control the seal strength and peel strength is used.
  • an easy tear film in which nylon MXD6 is blended with nylon 6 is used.
  • Manufacturing method of multilayer film It does not specifically limit about the manufacturing method of the multilayer film of this invention, It can manufacture by arbitrary methods, For example, it can manufacture by methods, such as a co-extrusion method and a lamination method.
  • Coextrusion method In the coextrusion method, the material constituting the layer (A) and the material constituting the layer (B) are respectively charged into an extruder and coextruded to obtain a multilayer film.
  • a multilayer film can be obtained by any method such as coextrusion by an inflation method or coextrusion by a T-die method.
  • the multilayer film obtained by the coextrusion method can be further stretched by uniaxial stretching or biaxial stretching to obtain a multilayer film in which the layers (A) and (B) are co-stretched. Examples of the stretching method include continuous biaxial stretching by a tenter method, simultaneous biaxial stretching by a tenter method, and simultaneous biaxial stretching by an inflation method.
  • a batch-type biaxial stretching apparatus may be used.
  • the coextrusion stretch ratio can be appropriately determined according to the use of the multilayer film, but it is preferable to biaxially stretch 1.1 to 15 times in the MD direction and 1.1 to 15 times in the TD direction.
  • a film constituting the layer (A) and a film constituting the layer (B) are each produced by an extrusion method or the like, and then these films are laminated to obtain a multilayer film.
  • the multilayer film can be obtained by an arbitrary method such as a hot melt lamination method, a wet lamination method, a dry lamination method, a solventless dry lamination method, an extrusion lamination method, or a thermal lamination method.
  • pretreatment such as corona treatment and ozone treatment can be applied to the film, etc.
  • pretreatment such as corona treatment and ozone treatment
  • ozone treatment can be applied to the film, etc.
  • anchor coating agents such as organic titanium, or known anchor coating agents such as polyurethane, polyacrylic, polyester, epoxy, polyvinyl acetate, and cellulose adhesives, adhesives, etc. be able to.
  • a printing layer can be provided as necessary.
  • general printing equipment that has been used for printing on a conventional polymer film such as a gravure printing machine, a flexographic printing machine, and an offset printing machine can be similarly applied.
  • the ink for forming the printing layer is also applied to conventional polymer films formed from pigments such as azo and phthalocyanine, resins such as rosin, polyamide resin and polyurethane, solvents such as methanol, ethyl acetate and methyl ethyl ketone.
  • the inks that have been used for the printing layer can be applied as well.
  • the film packaging container of this invention contains the multilayer film mentioned above.
  • the film packaging container using the multilayer film of the present invention as a whole or a part of the packaging container absorbs oxygen in the container in addition to oxygen that slightly enters from the outside of the container, and changes the contents of the stored contents due to oxygen. Can be prevented.
  • the shape of the film packaging container of the present invention is not particularly limited, and can be selected within an appropriate range depending on the articles to be stored and stored.
  • the multilayer film of the present invention comprises a three-sided seal flat bag, a standing pouch, a gusset packaging bag, a pillow packaging bag, a multi-chamber comprising a main chamber and a sub-chamber and an easy peeling wall provided between the main chamber and the sub-chamber.
  • Pouches, thermoformed containers, shrink film packaging, and the like can be used.
  • flange parts such as a thermoforming container
  • a deoxidation function can be provided to a packaging container by using the multilayer film of this invention as members, such as a cover material of a container and a top seal.
  • the capacity of the film packaging container of the present invention is not particularly limited, and can be selected within an appropriate range depending on the articles to be stored and stored. It does not specifically limit about the manufacturing method of the film packaging container of this invention, It can manufacture by arbitrary methods.
  • the film packaging container of the present invention is excellent in oxygen absorption performance and oxygen barrier performance and excellent in flavor retention of contents, it is suitable for packaging various articles.
  • Preserved items include milk, dairy products, juice, coffee, tea, alcoholic beverages; liquid seasonings such as sauces, soy sauce, dressings, soups, stews, curries, infant foods, nursing foods, etc.
  • Cooked foods pasty foods such as jam and mayonnaise; fishery products such as tuna and fish shellfish; dairy products such as cheese and butter; processed meat products such as meat, salami, sausage and ham; vegetables such as carrots and potatoes Eggs, noodles, cooked rice, cooked rice, processed rice products such as rice bran; powdered seasonings, powdered coffee, powdered milk for infants, powdered diet foods, dried vegetables, rice crackers, and other dried foods Chemicals such as agricultural chemicals and insecticides; pharmaceuticals; cosmetics; pet foods; miscellaneous goods such as shampoos, rinses and detergents; and various articles.
  • the film packaging container and the objects to be preserved can be sterilized in a form suitable for the objects to be preserved.
  • Sterilization methods include hot water treatment at 100 ° C. or lower, pressurized hot water treatment at 100 ° C. or higher, heat sterilization such as ultra-high temperature heat treatment at 130 ° C. or higher, electromagnetic wave sterilization of ultraviolet rays, microwaves, gamma rays, etc., ethylene oxide And gas sterilization such as hydrogen peroxide and hypochlorous acid.
  • the unit derived from metaxylylenediamine is “MXDA”
  • a unit derived from 1,3-bis (aminomethyl) cyclohexane is referred to as “1,3BAC”
  • the unit derived from hexamethylenediamine is “HMDA”
  • the unit derived from adipic acid is “AA”
  • the unit derived from isophthalic acid is “IPA”
  • the unit derived from DL-alanine is “DL-Ala”
  • the unit derived from DL-leucine is “DL-Leu”
  • a unit derived from ⁇ -caprolactam is referred to as “ ⁇ -CL”.
  • Polymetaxylylene adipamide is referred to as “N-MXD6”.
  • the ⁇ -amino acid content, relative viscosity, terminal amino group concentration, glass transition temperature and melting point of the polyamide resin obtained in Production Example were measured by the following methods. Moreover, the film was produced from the polyamide resin obtained by the manufacture example, and the oxygen absorption amount was measured with the following method.
  • the oxygen concentration in the bag was measured with an oxygen concentration meter (trade name: LC-700F, manufactured by Toray Engineering Co., Ltd.). The amount of oxygen absorbed was calculated from the oxygen concentration.
  • Production Example 1 (Production of polyamide resin 1) Weighed precisely in a pressure-resistant reaction vessel with an internal volume of 50 L equipped with a stirrer, partial condenser, full condenser, pressure regulator, thermometer, dripping tank and pump, aspirator, nitrogen inlet pipe, bottom exhaust valve, and strand die.
  • Adipic acid (Asahi Kasei Chemicals Co., Ltd.) 13000 g (88.96 mol), DL-alanine (Musashino Chemical Laboratory Co., Ltd.) 880.56 g (9.88 mol), sodium hypophosphite 11.7 g (0.
  • the inside of the reaction vessel was gradually returned to normal pressure, and then the inside of the reaction vessel was reduced to 80 kPa using an aspirator to remove condensed water.
  • the stirring torque of the stirrer After observing the stirring torque of the stirrer during decompression, stop stirring when the specified torque is reached, pressurize the inside of the reaction tank with nitrogen, open the bottom drain valve, extract the polymer from the strand die and form a strand Cooled and pelletized with a pelletizer. Next, this pellet was charged into a stainless steel drum-type heating device and rotated at 5 rpm. The atmosphere in the reaction system was raised from room temperature to 140 ° C. under a small nitrogen flow.
  • Production Example 5 (Production of polyamide resin 5)
  • An MXDA / AA / DL-Leu copolymer (polyamide resin 5) was obtained in the same manner as in Production Example 1 except that the amount was (mol%).
  • Production Example 6 (Production of polyamide resin 6)
  • Production Example 8 (Production of polyamide resin 8)
  • Production Example 9 (Production of polyamide resin 9)
  • Table 1 shows the charged monomer compositions of polyamide resins 1 to 10 and the measurement results of the ⁇ -amino acid content, relative viscosity, terminal amino group concentration, glass transition temperature, melting point, and oxygen absorption amount of the obtained polyamide resin.
  • Examples 1 to 41 and Comparative Examples 1 to 18 a multilayer film was produced using the polyamide resins 1 to 10, and a film packaging container (standing pouch, thermoforming container or casing container) was formed from the multilayer film.
  • a film packaging container standing pouch, thermoforming container or casing container
  • the measurement of the oxygen permeability of the coextruded multilayer film obtained in Examples and Comparative Examples, the food preservation test of the packaging container, and the measurement of odor and taste at the time of opening the packaging container were performed by the following methods.
  • Oxygen permeability of co-extruded multilayer film The oxygen permeability of the co-extruded multilayer film was measured according to ASTM D3985 using an oxygen permeability measuring device (manufactured by MOCON, model: OX-TRAN 2/21). The measurement was performed in an atmosphere of ° C and a relative humidity of 60%.
  • Example 1 Using a multilayer film manufacturing apparatus equipped with three extruders, feed block, T die, cooling roll, winder, etc., nylon 6 (N6) (Ube Industries, Ltd.) from the first and third extruders ), Product name: UBE nylon 6, grade: 1022B) are extruded at 250 ° C. from a second extruder at 250 ° C., respectively, through a feed block, nylon 6 layer / polyamide resin 1 layer / A multilayer film (A1) of two types and three layers of nylon 6 layers was produced. The thickness of each layer was 80/80/80 ( ⁇ m).
  • the obtained biaxially stretched film was converted to a 12 ⁇ m biaxially stretched polyethylene terephthalate (OPET) film (manufactured by Toray Film Processing Co., Ltd., trade name: ZK93FM), and 60 ⁇ m unstretched polypropylene (CPP) to a urethane adhesive (Mitsui Chemicals).
  • OPET polyethylene terephthalate
  • CPP polypropylene
  • main component Takelac A505
  • curing agent Takenate A20, both trade names
  • a dry laminator was used for dry lamination in a configuration of (outer layer) OPET // OA1 // CPP (inner layer). After dry lamination, it was stored in a constant temperature bath at 60 ° C. for 3 days.
  • the obtained multilayer film produced a standing pouch having a length of 200 mm, a width of 120 mm, and a set depth of 40 mm using a heat sealing machine.
  • Examples 2-5 A multilayer film and a standing pouch were prepared in the same manner as in Example 1 except that polyamide resins 2 to 5 were used.
  • Comparative Example 1 A multilayer film and a standing pouch were prepared in the same manner as in Example 1 except that the polyamide resin 10 was used.
  • Example 6 Nylon MXD6 (manufactured by Mitsubishi Gas Chemical Co., Ltd.) from the first and third extruders using a multilayer film production apparatus equipped with three extruders, feed block, T-die, cooling roll, winder, etc. , Product name: MX nylon, grade: S6011) at 260 ° C., polyamide resin 1 is extruded from the second extruder at 250 ° C., respectively, and nylon MXD6 layer / polyamide resin 1 layer / nylon MXD6 layer is fed through the feed block.
  • a multilayer film (A2) having a two-layer / three-layer structure was produced. The thickness of each layer was 80/80/80 ( ⁇ m).
  • Examples 7 and 8 A multilayer film and a standing pouch were prepared in the same manner as in Example 6 except that the polyamide resin 2 or 3 was used.
  • Comparative Example 2 A multilayer film and a standing pouch were prepared in the same manner as in Example 6 except that the polyamide resin 10 was used.
  • Table 2 shows the oxygen permeability of the coextruded multilayer film, the food storage test of the packaging container, and the odor and taste results at the time of opening.
  • the coextruded multilayer films and standing pouches of Examples 1 to 5 and 6 to 8 improved the oxygen permeability without impairing the food storage stability and the odor and taste at the time of opening compared to Comparative Example 1 or 2 of the same form. We were able to.
  • Example 9 Using a multilayer film manufacturing apparatus equipped with four extruders, feed blocks, T-die, cooling roll, winder, etc., polyamide resin 1 is fed from the first extruder at 250 ° C., and the second extruder Nylon 6 (Ube Industries, Ltd., trade name: UBE nylon 6, grade: 1022B) at 240 ° C.
  • Nylon 6 Ube Industries, Ltd., trade name: UBE nylon 6, grade: 1022B
  • polypropylene (Nihon Polypro Corporation, trade name: Novatec) , Grade: FY6) at 230 ° C
  • adhesive resin (AD) (made by Mitsui Chemicals, trade name: Admer, grade: QB515) was extruded at 220 ° C from the fourth extruder, and the feed block was 4 types and 7 layers of (outer layer) polypropylene layer / adhesive resin layer / nylon 6 layer / polyamide resin 1 layer / nylon 6 layer / adhesive resin layer / polypropylene layer (inner layer)
  • the thickness of each layer was 60/5/10/15/10/5/60 ( ⁇ m).
  • thermoforming was performed when the film surface temperature reached 170 ° C. using a pressure-air vacuum forming machine (manufactured by Asano Laboratory Co., Ltd.) equipped with plug assist, and the opening 100 mm square ⁇ bottom 90 mm ⁇ depth
  • a thermoformed container having a thickness of 10 mm, a surface area of 119 cm 2 and a volume of 90 ml was prepared.
  • Examples 10 and 11 A coextruded multilayer film and a thermoformed container were prepared in the same manner as in Example 9 except that the polyamide resin 2 or 3 was used.
  • Comparative Example 3 A coextruded multilayer film and a thermoformed container were prepared in the same manner as in Example 9 except that the polyamide resin 10 was used.
  • Comparative Example 4 A coextruded multilayer film and a thermoformed container were prepared in the same manner as in Example 9 except that polyamide resin 10 was used and cobalt stearate was added to polyamide resin 10 so that the cobalt content was 400 ppm. did.
  • Comparative Example 5 Polyamide resin 10 was used, cobalt stearate was added to polyamide resin 10 so that the cobalt content was 100 ppm, and maleic acid-modified polybutadiene (manufactured by Nippon Petrochemical Co., Ltd., trade name: M-) A coextruded multilayer film and a thermoformed container were prepared in the same manner as in Example 9, except that 3 parts by mass of 2000-20) was added to the polyamide resin 10.
  • Example 12 Using a multilayer film manufacturing apparatus equipped with four extruders, feed blocks, T-die, cooling roll, winder, etc., polyamide resin 1 is fed from the first extruder at 250 ° C., and the second extruder Nylon MXD6 (Mitsubishi Gas Chemical Co., Ltd., trade name: MX Nylon, grade: K7007C) from 250 ° C. from the third extruder to polypropylene (Nihon Polypro Co., Ltd., trade name: Novatec, Grade: FY6) was extruded at 230 ° C.
  • Nylon MXD6 Mitsubishi Gas Chemical Co., Ltd., trade name: MX Nylon, grade: K7007C
  • polypropylene Nihon Polypro Co., Ltd., trade name: Novatec, Grade: FY6
  • Examples 13 to 16 A coextruded multilayer film and a thermoformed container were prepared in the same manner as in Example 12 except that polyamide resins 2 to 5 were used.
  • Comparative Example 6 A coextruded multilayer film and a thermoformed container were prepared in the same manner as in Example 12 except that the polyamide resin 10 was used.
  • Comparative Example 7 A coextruded multilayer film and a thermoformed container were prepared in the same manner as in Example 12 except that polyamide resin 10 was used and cobalt stearate was added to polyamide resin 10 so that the cobalt content was 400 ppm. did.
  • Comparative Example 8 Polyamide resin 10 was used, cobalt stearate was added to polyamide resin 10 so that the cobalt content was 100 ppm, and maleic acid-modified polybutadiene (manufactured by Nippon Petrochemical Co., Ltd., trade name: M- A co-extruded multilayer film and a thermoformed container were prepared in the same manner as in Example 12 except that 3 parts by mass of 2000-20) was added to the polyamide resin 10.
  • maleic acid-modified polybutadiene manufactured by Nippon Petrochemical Co., Ltd., trade name: M- A co-extruded multilayer film and a thermoformed container were prepared in the same manner as in Example 12 except that 3 parts by mass of 2000-20
  • Table 3 shows the oxygen permeability of the co-extruded multilayer film, the food storage test of the packaging container, and the odor and taste results when opened.
  • the coextruded multilayer films and thermoformed containers of Examples 9 to 11 and 12 to 16 have oxygen permeability without impairing food storage stability and odor and taste at the time of opening compared to Comparative Example 3 or 6 of the same form. It was possible to improve.
  • Comparative Examples 4, 5, 7 and 8 using cobalt stearate or maleic acid-modified polybutadiene to improve oxygen permeability the oxygen permeability of the coextruded multilayer film was excellent, but over time, the cobalt catalyst The resin was oxidized and decomposed, and the food storage stability of the thermoformed container and the odor and taste at the time of opening deteriorated.
  • Example 17 Using a multilayer film manufacturing apparatus equipped with three extruders, feed block, T die, cooling roll, winder, etc., the second extruder is polyamide resin 1 at 250 ° C. from the first extruder Nylon MXD6 (Mitsubishi Gas Chemical Co., Ltd., trade name: MX nylon, grade: S6011) at 260 ° C.
  • Nylon MXD6 Mitsubishi Gas Chemical Co., Ltd., trade name: MX nylon, grade: S6011
  • nylon 6 Ube Industries, trade name: UBE nylon 6) , Grade: 1022B
  • nylon 6 Ube Industries, trade name: UBE nylon 6
  • Grade: 1022B a multilayer film
  • A3 of three types and five layers of nylon 6 layer / nylon MXD 6 layer / polyamide resin 1 layer / nylon MXD 6 layer / nylon 6 layer is fed through a feed block.
  • the thickness of each layer was 80/80/80/80/80 ( ⁇ m).
  • Examples 18-25 A multilayer film and a standing pouch were prepared in the same manner as in Example 17 except that polyamide resins 2 to 9 were used.
  • Comparative Example 9 A coextruded multilayer film and a standing pouch were prepared in the same manner as in Example 17 except that the polyamide resin 10 was used.
  • Table 4 shows the oxygen permeability of the coextruded multilayer film, the food preservation test of the packaging container, and the results of odor and taste at the time of opening.
  • Example 26 Using a simultaneous biaxially stretched multilayer film production system consisting of four extruders, feed blocks, and cylindrical dies, polyamide resin 1 was fed from the first extruder at 250 ° C. and polypropylene from the second extruder (Nippon Polypropylene). Co., Ltd., trade name: Novatec, grade: FY6) at 230 ° C. From the third extruder, 80 parts by mass of polypropylene (Nihon Polypro Co., Ltd., trade name: Novatec, grade: FY6) and others Polypropylene (trade name: Adsyl, grade: 5C37F) of 20 parts by mass of dry polypropylene and blended polypropylene at 230 ° C.
  • Polypropylene trade name: Adsyl, grade: 5C37F
  • adhesive resin Mitsubishi Chemicals, product
  • Admer Mitsubishi Chemicals, product
  • Grade: QB545 adhesive resin
  • (outer layer) polypropylene layer / adhesive resin layer It was produced multilayered parison of the four five-layer structure in the order of the polyamide resin 1 layer / adhesive resin layer / blend polypropylene layer (inner layer).
  • the diameter of the multilayer parison was 130 mm, and the composition ratio of each layer was 4/1/3/1/4. Subsequently, the parison is cooled at 60 ° C. and heated to 120 ° C.
  • the film was biaxially stretched 4 times in the transverse direction and heat-fixed at 200 ° C. to obtain a coextruded multilayer stretched film (B).
  • stretching became 20/5/15/5/20 (micrometer).
  • the film having a width of 100 mm was formed into a cylindrical shape at a film speed of 5 m / min, and then a hot air was blown after placing a notch on the outside of the overlapping portion of the film, Heat-sealed on the envelope.
  • the temperature of the hot air was about 400 ° C., and a casing container was prepared.
  • Examples 27-29 A coextruded multilayer film and a casing container were prepared in the same manner as in Example 26 except that the polyamide resin 2, 3 or 6 was used.
  • Comparative Example 10 A coextruded multilayer film and a casing container were prepared in the same manner as in Example 26 except that the polyamide resin 10 was used.
  • Comparative Example 11 A coextruded multilayer film and a casing container were prepared in the same manner as in Example 26 except that polyamide resin 10 was used and cobalt stearate was added to polyamide resin 10 so that the cobalt content was 400 ppm. .
  • Comparative Example 12 Polyamide resin 10 was used, cobalt stearate was added to polyamide resin 10 so that the cobalt content was 100 ppm, and maleic acid-modified polybutadiene (manufactured by Nippon Petrochemical Co., Ltd., trade name: M-) A coextruded multilayer film and a casing container were prepared in the same manner as in Example 26 except that 3 parts by mass of 2000-20) was added to the polyamide resin 10.
  • Table 5 shows the oxygen permeability of the coextruded multilayer film, the food preservation test of the packaging container, and the results of odor and taste at the time of opening.
  • the coextruded multilayer films and casing containers of Examples 26 to 29 were able to improve the oxygen permeability without impairing the food storage stability and the odor and taste at the time of opening as compared with Comparative Example 10 of the same form.
  • Comparative Examples 11 and 12 using cobalt stearate or maleic acid-modified polybutadiene to improve oxygen permeability, the oxygen permeability of the coextruded multilayer film is excellent, but the resin is oxidatively decomposed by the cobalt catalyst over time.
  • the food storage stability of the casing container and the odor and taste at the time of opening deteriorated.
  • Example 30 Using a multilayer film manufacturing apparatus equipped with four extruders, feed blocks, T-die, cooling roll, winder, etc., polyamide resin 1 is fed from the first extruder at 250 ° C., and the second extruder To ethylene-vinyl alcohol copolymer (EVOH) (manufactured by Kuraray Co., Ltd., trade name: EVAL, grade: F101B) at 230 ° C.
  • EVOH ethylene-vinyl alcohol copolymer
  • Adhesive resin Mitsubishi Chemicals, trade name: Admer, Grade: QB515
  • the thickness of each layer was 60/5/5/15/5/5/60 ( ⁇ m).
  • thermoforming was performed when the film surface temperature reached 170 ° C. using a pressure-air vacuum forming machine (manufactured by Asano Laboratory Co., Ltd.) equipped with plug assist, and the opening 100 mm square ⁇ bottom 90 mm ⁇ depth
  • a thermoformed container having a thickness of 10 mm, a surface area of 119 cm 2 and a volume of 90 ml was prepared.
  • Examples 31-38 A coextruded multilayer film and a thermoformed container were prepared in the same manner as in Example 30 except that polyamide resins 2 to 9 were used.
  • Comparative Example 13 A coextruded multilayer film and a thermoformed container were prepared in the same manner as in Example 30 except that the polyamide resin 10 was used.
  • Comparative Example 14 A coextruded multilayer film and a thermoformed container were prepared in the same manner as in Example 30, except that polyamide resin 10 was used and cobalt stearate was added to polyamide resin 10 so that the cobalt content was 400 ppm. did.
  • Comparative Example 15 Polyamide resin 10 was used, cobalt stearate was added to polyamide resin 10 so that the cobalt content was 100 ppm, and maleic acid-modified polybutadiene (manufactured by Nippon Petrochemical Co., Ltd., trade name: M-) A coextruded multilayer film and a thermoformed container were prepared in the same manner as in Example 30 except that 3 parts by mass of 2000-20) was added to the polyamide resin 10.
  • Table 6 shows the oxygen permeability of the co-extruded multilayer film, the food storage test of the packaging container, and the results of odor and taste at the time of opening.
  • the coextruded multilayer films and thermoformed containers of Examples 30 to 38 were able to improve oxygen permeability without impairing food storage stability and odor and taste at the time of opening compared to Comparative Example 13 of the same form. .
  • Comparative Examples 14 and 15 using cobalt stearate or maleic acid-modified polybutadiene to improve oxygen permeability, the oxygen permeability of the coextruded multilayer film is excellent, but the resin is oxidatively decomposed by the cobalt catalyst over time.
  • the food storage stability of the thermoformed container and the odor and taste at the time of opening deteriorated.
  • Example 39 Using a multilayer film manufacturing apparatus equipped with three extruders, feed block, T die, cooling roll, winder, etc., the second extruder is polyamide resin 1 at 250 ° C. from the first extruder To polyethylene terephthalate (PET) (trade name: POLYCLEAR, grade: 1101E manufactured by INVISTA) at 260 ° C. and adhesive resin (trade name: Modic-AP, manufactured by Mitsubishi Chemical Corporation) from the third extruder.
  • PET polyethylene terephthalate
  • adhesive resin trade name: Modic-AP, manufactured by Mitsubishi Chemical Corporation
  • Grade: F534A is extruded at 220 ° C., and through a feed block, (outer layer) PET layer / adhesive resin layer / polyamide resin 1 layer / adhesive resin layer / PET layer (inner layer), having three types and five layers.
  • a multilayer film (C4) was produced. The thickness of each layer was 60/5/10/5/60 ( ⁇ m). Next, thermoforming was performed when the film surface temperature reached 170 ° C.
  • thermoformed container having a thickness of 10 mm, a surface area of 119 cm 2 and a volume of 90 ml was prepared.
  • Examples 40 and 41 A coextruded multilayer film and a thermoformed container were prepared in the same manner as in Example 39 except that the polyamide resin 2 or 3 was used.
  • Comparative Example 16 A coextruded multilayer film and a thermoformed container were prepared in the same manner as in Example 39 except that the polyamide resin 10 was used.
  • Comparative Example 17 A coextruded multilayer film and a thermoformed container were prepared in the same manner as in Example 39 except that polyamide resin 10 was used and cobalt stearate was added to polyamide resin 10 so that the cobalt content was 400 ppm. did.
  • Comparative Example 18 Polyamide resin 10 was used, cobalt stearate was added to polyamide resin 10 so that the cobalt content was 100 ppm, and maleic acid-modified polybutadiene (manufactured by Nippon Petrochemical Co., Ltd., trade name: M- A coextruded multilayer film and a thermoformed container were prepared in the same manner as in Example 39 except that 3 parts by mass of 2000-20) was added to the polyamide resin 10.
  • maleic acid-modified polybutadiene manufactured by Nippon Petrochemical Co., Ltd., trade name: M- A coextruded multilayer film and a thermoformed container were prepared in the same manner as in Example 39 except that 3 parts by mass of 2000-20
  • Table 7 shows the oxygen permeability of the coextruded multilayer film, the food preservation test of the packaging container, and the results of odor and taste at the time of opening.
  • the co-extruded multilayer films and thermoformed containers of Examples 39 to 41 have not only excellent oxygen permeability of the co-extruded multilayer film but also excellent food preservability in the thermoformed containers as compared with Comparative Example 16 of the same form. It was. In particular, in Comparative Example 17 using cobalt stearate, delamination occurred between the polyamide resin layer and the PET layer when miso was hot-packed, and the food storage stability of the thermoformed container deteriorated. In Comparative Example 18 using maleic acid-modified polybutadiene, the odor and taste at the time of opening deteriorated due to decomposition of maleic acid-modified polybutadiene after oxygen absorption.
  • the multilayer film of the present invention can be suitably used as a packaging material.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • Polyamides (AREA)
  • Wrappers (AREA)
  • Laminated Bodies (AREA)
  • Packages (AREA)

Abstract

L'invention concerne un film multi-couches comprenant une couche (A) qui comprend une résine de polyamide (A) et une couche (B) qui comporte une résine (B) comme composant principal, la résine de polyamide (A) comprenant : 25-50 % en moles d'unités diamine, ne comprenant pas moins de 50 % en moles d'une unité diamine spécifique ; 25-50 % en moles d'unités acide dicarboxylique, ne comprenant pas moins de 50 % en moles d'une unité acide dicarboxylique spécifique ; et 0,1-50 % en moles d'une unité constitutive spécifique.
PCT/JP2012/065642 2011-06-27 2012-06-19 Film multi-couches et contenant d'emballage à base du film Ceased WO2013002069A1 (fr)

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JP2016198918A (ja) * 2015-04-08 2016-12-01 住友ベークライト株式会社 シーラントフィルム、多層フィルム、および包装体
WO2019026500A1 (fr) * 2017-07-31 2019-02-07 三菱瓦斯化学株式会社 Film facilement déchiré, film multicouche, matériau d'emballage et récipient
WO2019044882A1 (fr) * 2017-08-31 2019-03-07 宇部興産株式会社 Résine polyamide et film formé à partir de celle-ci
US20240424772A1 (en) * 2021-08-23 2024-12-26 Mitsubishi Gas Chemical Company, Inc. Stretched film, multilayer film, and packaging material

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RU2671332C1 (ru) * 2013-12-05 2018-10-30 Мицубиси Гэс Кемикал Компани, Инк. Многослойный контейнер
CN111869951B (zh) * 2020-06-23 2022-09-27 山西洁康惠医疗器械有限公司 一种口罩过滤层的制备方法

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JP2016198918A (ja) * 2015-04-08 2016-12-01 住友ベークライト株式会社 シーラントフィルム、多層フィルム、および包装体
WO2019026500A1 (fr) * 2017-07-31 2019-02-07 三菱瓦斯化学株式会社 Film facilement déchiré, film multicouche, matériau d'emballage et récipient
CN110997766A (zh) * 2017-07-31 2020-04-10 三菱瓦斯化学株式会社 易撕裂性薄膜、多层薄膜、包装材料和容器
JPWO2019026500A1 (ja) * 2017-07-31 2020-08-20 三菱瓦斯化学株式会社 易裂性フィルム、多層フィルム、包装材料および容器
JP7218724B2 (ja) 2017-07-31 2023-02-07 三菱瓦斯化学株式会社 易裂性フィルム、多層フィルム、包装材料および容器
US11873401B2 (en) 2017-07-31 2024-01-16 Mitsubishi Gas Chemical Company, Inc. Easily tearable film, multilayer film, packaging material, and container
WO2019044882A1 (fr) * 2017-08-31 2019-03-07 宇部興産株式会社 Résine polyamide et film formé à partir de celle-ci
JPWO2019044882A1 (ja) * 2017-08-31 2020-10-15 宇部興産株式会社 ポリアミド樹脂及びそれからなるフィルム
JP7180604B2 (ja) 2017-08-31 2022-11-30 Ｕｂｅ株式会社 ポリアミド樹脂及びそれからなるフィルム
US20240424772A1 (en) * 2021-08-23 2024-12-26 Mitsubishi Gas Chemical Company, Inc. Stretched film, multilayer film, and packaging material

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