WO2021261560A1 - 多層フィルム及びそれを用いた多層構造体 - Google Patents

多層フィルム及びそれを用いた多層構造体 Download PDF

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Publication number
WO2021261560A1
WO2021261560A1 PCT/JP2021/023968 JP2021023968W WO2021261560A1 WO 2021261560 A1 WO2021261560 A1 WO 2021261560A1 JP 2021023968 W JP2021023968 W JP 2021023968W WO 2021261560 A1 WO2021261560 A1 WO 2021261560A1
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WIPO (PCT)
Prior art keywords
layer
multilayer film
resin
less
vinyl alcohol
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
Application number
PCT/JP2021/023968
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
昌宏 北村
健太郎 吉田
ルイテン，ワウト
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kuraray Co Ltd
Original Assignee
Kuraray Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kuraray Co Ltd filed Critical Kuraray Co Ltd
Priority to EP21829021.1A priority Critical patent/EP4173822A4/en
Priority to US18/012,906 priority patent/US20230294380A1/en
Priority to BR112022025255A priority patent/BR112022025255A2/pt
Priority to JP2021562188A priority patent/JP7025605B1/ja
Priority to CN202180044974.8A priority patent/CN115697702A/zh
Publication of WO2021261560A1 publication Critical patent/WO2021261560A1/ja
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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
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    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
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    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/03—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers with respect to the orientation of features
    • B32B7/035—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers with respect to the orientation of features using arrangements of stretched films, e.g. of mono-axially stretched films arranged alternately
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
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    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
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    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging

Definitions

  • the present invention includes a multilayer film having a vinyl alcohol-based polymer having a melting point of less than 150 ° C. on the outermost layer, a multilayer structure using the same, a method for recovering the multilayer structure, and a recovered product of the multilayer structure. Regarding the composition.
  • Packaging materials for long-term storage of food are often required to have gas barrier properties such as oxygen barrier properties.
  • gas barrier properties such as oxygen barrier properties.
  • a packaging material having a high gas barrier property it is possible to suppress oxidative deterioration of foods and the growth of microorganisms due to oxygen infiltration.
  • a metal foil such as aluminum and an inorganic vapor deposition layer such as silicon oxide and aluminum oxide are widely used.
  • resin layers having a gas barrier property such as vinyl alcohol-based polymers and polyvinylidene chloride are also widely used.
  • Vinyl alcohol-based polymers have the characteristic of exhibiting gas barrier properties by crystallizing and increasing the density by hydrogen-bonding hydroxyl groups in the molecule.
  • ethylene-vinyl alcohol copolymer (hereinafter, may be abbreviated as "EVOH”) is suitable for melt molding because it has excellent thermal stability, and with the development of coextrusion technology, an EVOH layer is inserted in the middle.
  • EVOH ethylene-vinyl alcohol copolymer
  • the multilayer film having a layer is widely used as a gas barrier packaging material (Patent Document 1).
  • recycling post-consumer recycling
  • packaging materials consumed in the market are collected and recycled due to environmental problems and waste problems. It is increasing worldwide.
  • recycling a process is generally adopted in which the recovered packaging material is cut, separated and washed as necessary, and then melt-mixed using an extruder.
  • the EVOH layer is used as the outermost layer of the multilayer film in order to diversify the layer structure and seek the synergistic effect of improving the barrier property by laminating with the inorganic thin-film deposition layer.
  • the EVOH layer in direct contact with the die wall, and the EVOH layer discharged from the die is rapidly cooled. Peeling can be a problem.
  • the multilayer film is stretched uniaxially or biaxially in anticipation of improvement in mechanical properties and the like, such problems of appearance defects and delamination are more likely to become apparent, and improvement has been sought.
  • the first object of the present invention is to provide a multilayer film having a vinyl alcohol-based polymer on the outermost layer and having excellent appearance and interlayer adhesion.
  • a second object of the present invention is to use the multilayer film to prepare a multilayer structure having both gas barrier properties and recyclability, a packaging material containing the multilayer structure, and a recovered composition of the multilayer structure. It is to provide a thing and a method of collecting it.
  • the present inventors have obtained a result in appearance and interlayer adhesion when a vinyl alcohol-based polymer having a certain metal amount and melting point is used for the outermost layer.
  • a vinyl alcohol-based polymer having a certain metal amount and melting point is used for the outermost layer.
  • a multilayer structure having both gas barrier properties and recyclability can be obtained by specifying the material and the laminated structure used for the multilayer film and other layers to be laminated with the multilayer film, and completed the present invention.
  • the layer (X) is on the outermost layer, and at least the layer (X), the layer (Y), and the layer (Z) are laminated adjacent to each other in this order, and the layer (X) has a melting point of 150.
  • It comprises a resin composition (A) containing a vinyl alcohol-based polymer (a) having a melting point of less than ° C. (a) as a main component, and a layer (Y) containing an adhesive resin (B) having a melting point of less than 150 ° C. as a main component and a layer (Z).
  • a resin composition (A) containing a vinyl alcohol-based polymer (a) having a melting point of less than ° C. (a) as a main component
  • a polyolefin resin (C) having a melting point of less than 150 ° C.
  • the resin composition (A) contains 25 to 1500 ppm of an alkali metal ion (b);
  • the vinyl alcohol-based polymer (a) is an ethylene-vinyl alcohol copolymer having an ethylene unit content of 15 to 85 mol%;
  • [X in formula represents a group represented by hydrogen atom, methyl group, or R 2 -OH.
  • R 1 and R 2 each independently represent a single bond, an alkylene group having 1 to 9 carbon atoms or an alkylene oxy group having 1 to 9 carbon atoms, and the alkylene group and the alkylene oxy group contain a hydroxyl group, an alkoxy group or a halogen atom.
  • R 1 is a single bond in said general formula (I)
  • X is hydroxymethyl group, a multilayer film of [3]
  • [5] The multilayer film of [3] in which R 1 in the general formula (I) is hydroxymethylene and X is a hydrogen atom
  • R 1 is a methyl methylene group of the formula (I), wherein X is a hydrogen atom, a multilayer film of [3]
  • [7] The multilayer film according to any one of [3] to [6], wherein the content of the modifying group containing the primary hydroxyl group in the vinyl alcohol polymer (a) is 2 mol% or more and less than 20 mol%
  • [8] The multilayer film according to any one of [1] to [7], wherein the resin composition (A) contains less than 50% by mass of the vinyl alcohol polymer (a') having a melting point of 150 ° C.
  • the resin composition (A) contains 10 to 300 ppm of at least one polyvalent metal ion (c) selected from the group consisting of magnesium ion, calcium ion and zinc ion, [1] to [ 8] Any of the multilayer films; [10] The multilayer film according to any one of [1] to [9], wherein the resin composition (A) contains 100 to 4000 ppm of a higher aliphatic carboxylic acid (d) having 8 to 30 carbon atoms; [11] The multilayer film according to any one of [1] to [10], wherein the polyolefin resin (C) contains a polyethylene resin as a main component; [12] The thickness of the layer (X) is 0.2 ⁇ m or more and less than 20 ⁇ m, and the ratio of the thickness of the layer (X) to the total thickness of all the layers of the multilayer film is less than 25% [1] to [ 11] Any of the multilayer films; [13] The multilayer film according to any one of [1]
  • thermoplastic resin (D) contains a polyolefin resin having a melting point of less than 150 ° C. as a main component
  • thermoplastic resin (D) contains a polyolefin resin having a melting point of less than 150 ° C. as a main component
  • the multilayer film of the present invention is suitably used as a gas barrier film because it has a vinyl alcohol-based polymer on the outermost layer and is excellent in appearance and interlayer adhesion.
  • the multilayer structure of the present invention containing the multilayer film is excellent in appearance and is suitably used as a packaging material having both gas barrier properties and recyclability.
  • the multi-layer structure has good recyclability, it is possible to provide a recovery composition containing a recovered product of the multi-layer structure and a recovery method thereof.
  • the "interlayer adhesiveness” means the adhesiveness between the layer (X) and the layer (X) adjacent to the layer (X), and specifically, the adhesiveness mainly to the layer (Y) described later. Means.
  • the interlayer adhesiveness can be evaluated by the T-type peel strength as described in Examples. Further, "recyclability" means that when the recovered product of the multilayer structure or packaging material of the present invention is melt-kneaded to produce a recovered composition, coloring and gelation of the resin are suppressed, and the appearance and mechanical characteristics are excellent. It means that the recovered composition can be efficiently produced, and can be evaluated by the recovery test described in Examples.
  • the multilayer film of the present invention has a layer (X) as the outermost layer, and has a structure in which at least a layer (X), a layer (Y), and a layer (Z) are laminated adjacent to each other in this order, and the layer (X).
  • a resin composition (A) containing a vinyl alcohol-based polymer (a) having a melting point of less than 150 ° C. hereinafter, may be referred to as “vinyl alcohol-based polymer (a)” as a main component (hereinafter, “resin composition”).
  • (A) ”) and the layer (Y) contains an adhesive resin (B) having a melting point of less than 150 ° C.
  • the layer (Z) contains a polyolefin resin (C) having a melting point of less than 150 ° C. (hereinafter, may be referred to as “polyolefin resin (C)”) as a main component, and the resin composition (A) is an alkali metal ion ( b) contains 25 to 1500 ppm.
  • the layer (X), the layer (Y), and the layer (Z) are laminated adjacent to each other in this order
  • the layer (X), the layer (Y), and the layer (Z) are laminated in this order, the layer (X) and the layer (Y) are directly laminated, and the layer (Y) and the layer (Z) are directly laminated. It means that they are laminated.
  • the "main component” means a component contained in an amount of more than 50% by mass.
  • the multilayer film of the present invention contains a layer (X) of a resin composition (A) containing a vinyl alcohol-based polymer (a) having a melting point of less than 150 ° C. as a main component and containing 25 to 1500 ppm of an alkali metal ion (b). Is on the outermost layer.
  • the resin composition (A) is a vinyl alcohol-based polymer (a') having a melting point of 150 ° C. or higher; at least one polyvalent selected from the group consisting of magnesium ion, calcium ion and zinc ion.
  • the metal ion (c); a higher aliphatic carboxylic acid (d) having 8 to 30 carbon atoms and other components described later may be contained.
  • ⁇ Vinyl alcohol polymer (a)> When the melting point of the vinyl alcohol-based polymer (a) is less than 150 ° C., the appearance and interlayer adhesiveness of the multilayer film having the layer (X) containing the vinyl alcohol-based polymer (a) as the main component on the outermost layer can be improved. Can be improved. The reason for this is that the melting point of the vinyl alcohol polymer (a) is less than 150 ° C., which improves the fluidity of the polymer chain. It is considered that the stress can be effectively relieved even at a low temperature and the adhesive reaction activity with the adjacent layer can be maintained.
  • the vinyl alcohol-based polymer (a) can usually be obtained by saponifying the vinyl ester polymer.
  • the vinyl ester polymer can be produced and saponified by a known method.
  • the vinyl alcohol unit content of the vinyl alcohol polymer (a) is preferably 15 mol% or more, more preferably 30 mol% or more, further preferably 40 mol% or more, and more preferably 50 mol% or more. There may be.
  • the vinyl alcohol unit content of the vinyl alcohol-based polymer (a) is preferably 85 mol% or less, more preferably 80 mol% or less, and particularly preferably 75 mol% or less.
  • the melting point of the vinyl alcohol polymer (a) is preferably less than 140 ° C, more preferably less than 130 ° C, and may be less than 120 ° C or less than 110 ° C. ..
  • the melting point of the vinyl alcohol-based polymer (a) is preferably 80 ° C. or higher, preferably 90 ° C. or higher, from the viewpoint of process passability during melt molding or secondary processing such as stretching and heat resistance as a packaging material. Is more preferable, and 100 ° C. or higher is even more preferable.
  • the melting point of the vinyl alcohol-based polymer (a) is controlled by combining the following items alone or in combination of two or more.
  • the ethylene unit content of the vinyl alcohol polymer (a) is preferably 15 mol% or more, more preferably 20 mol% or more, still more preferably 25 mol% or more.
  • the ethylene unit content of the vinyl alcohol polymer (a) is preferably 85 mol% or less, more preferably 75 mol% or less, still more preferably 60 mol% or less.
  • the ethylene unit content of the vinyl alcohol polymer (a) can be determined by NMR measurement.
  • the vinyl alcohol-based polymer (a) may consist of two or more types of vinyl alcohol-based polymers having different ethylene unit contents.
  • the ethylene unit content can be controlled by various methods, but can be controlled by the ethylene pressure used in the polymerization step, the ratio of the vinyl ester to the solvent, and the like.
  • the melting point can be lowered by lowering the saponification degree of the vinyl alcohol polymer (a).
  • the degree of saponification is too low, the gas barrier property and thermal stability may be insufficient, and the interlayer adhesiveness with the layer (Y) and the inorganic vapor deposition layer (I) described later may be lowered.
  • the saponification degree of the vinyl alcohol polymer (a) is preferably 60 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more.
  • the upper limit of the saponification degree is 100 mol%, but from the viewpoint of material balance and energy balance in the production process, the upper limit is preferably 99.99 mol%.
  • the degree of saponification means the ratio of the number of alcohol units to the total number of alcohol units and ester units in the vinyl alcohol-based polymer (a).
  • the degree of saponification of the vinyl alcohol polymer (a) can be determined by NMR measurement.
  • the vinyl alcohol-based polymer (a) may consist of two or more types of vinyl alcohol-based polymers having different saponification degrees.
  • the degree of saponification can be controlled by various methods, but it can be controlled by the amount of alkaline catalyst, water content, reaction temperature, reaction time, etc. in the saponification step. It can also be controlled by subjecting the hydroxyl group generated in the saponification step to an esterification reaction with a carboxylic acid such as acetic acid or an anhydride thereof in a step after the saponification.
  • the melting point of the vinyl alcohol polymer (a) can be lowered by introducing a modifying group containing a primary hydroxyl group represented by the following general formula (I).
  • the degree of decrease in melting point per introduction rate varies depending on the structure of the modifying group containing the primary hydroxyl group to be introduced, but when 1 mol% of the modifying group containing the primary hydroxyl group represented by the following general formula (I) is introduced, the melting point is generally.
  • the temperature drops by about 6 to 9 ° C.
  • the melting point can be lowered while relatively maintaining the gas barrier property and the thermal stability, and the interlayer adhesiveness with the layer (Y) and the inorganic vapor deposition layer (I) described later.
  • the reason for this is considered to be that the melting point can be lowered while maintaining the amount of hydroxyl groups, and that the primary hydroxyl group has a high adhesive reaction activity with the layer (Y) and the inorganic vapor deposition layer (I) described later.
  • the content of the modifying group containing the primary hydroxyl group of the vinyl alcohol polymer (a) may be appropriately adjusted in consideration of the balance between the melting point and various physical characteristics, but it is 2 mol% or more and less than 20 mol%. In many cases, the balance of physical properties is good.
  • the lower limit of the content of the modifying group containing the primary hydroxyl group of the vinyl alcohol polymer (a) is more preferably 4 mol%, further preferably 6 mol%.
  • the upper limit of the content of the modifying group containing the primary hydroxyl group of the vinyl alcohol polymer (a) is more preferably 15 mol%, further preferably 10 mol%.
  • the modifying group containing a primary hydroxyl group can be introduced by copolymerization or polymer reaction.
  • [X in formula represents a group represented by hydrogen atom, methyl group, or R 2 -OH.
  • R 1 and R 2 each independently represent a single bond, an alkylene group having 1 to 9 carbon atoms or an alkylene oxy group having 1 to 9 carbon atoms, and the alkylene group and the alkylene oxy group contain a hydroxyl group, an alkoxy group or a halogen atom. It may be included.
  • X is preferably a group represented by hydrogen or R 2 -OH, more preferably a group represented by R 2 -OH.
  • R 1 and R 2 are preferably a single bond, an alkylene group having 1 to 5 carbon atoms or an alkylene oxy group having 1 to 5 carbon atoms, and more preferably a single bond, an alkylene group having 1 to 3 carbon atoms or an alkylene group having 1 to 3 carbon atoms. It is a 1 to 3 alkyleneoxy group.
  • the alkylene group and the alkyleneoxy group may contain a hydroxyl group, an alkoxy group or a halogen atom.
  • modifying group (structure) containing a primary hydroxyl group represented by the general formula (I) include a structural unit represented by the following general formula (II).
  • R 3 and R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and the alkyl group may contain a hydroxyl group, an alkoxy group or a halogen atom.
  • R 1 in the general formula (I) is a single bond and X is a hydroxymethyl group (R 3 and R 4 in the general formula (II) are hydrogen atoms).
  • the vinyl alcohol-based polymer (a) having a modifying group containing a primary hydroxyl group can lower the melting point while maintaining particularly good gas barrier properties and thermal stability, and also has a layer (Y) and an inorganic vapor deposition described later. The decrease in interlayer adhesion with the layer (I) can also be remarkably suppressed.
  • modifying group (structure) containing a primary hydroxyl group represented by the general formula (I) for example, a structural unit represented by the following general formula (III) can be mentioned.
  • R 5 is the same meaning as X in formula (I).
  • R 6 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and the alkyl group may contain a hydroxyl group, an alkoxy group or a halogen atom.
  • R 1 in the general formula (I) is hydroxymethylene and X is a hydrogen atom (R 5 and R 6 in the general formula (III) are hydrogen atoms).
  • the vinyl alcohol-based polymer (a) having a modifying group containing a primary hydroxyl group can lower the melting point while maintaining relatively good gas barrier properties and thermal stability, and also has a layer (Y) and an inorganic substance described later. It is also possible to relatively suppress a decrease in interlayer adhesiveness with the vapor-deposited layer (I).
  • modifying group (structure) containing a primary hydroxyl group represented by the general formula (I) include, for example, the structural unit represented by the following general formula (IV).
  • R 7 and R 8 independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a hydroxyl group. Further, the alkyl group and a part or all of the hydrogen atom contained in the cycloalkyl group may be substituted with a hydroxyl group, an alkoxy group or a halogen atom.
  • R 1 in the structural formula (I) is a methyl methyleneoxy group
  • X is a hydrogen atom ( one of R 7 and R 8 in the general formula (IV) is a hydrogen atom, and the other is methyl. Group) is preferable.
  • the vinyl alcohol-based polymer (a) having a primary hydroxyl group-modifying group can lower the melting point while maintaining better gas barrier properties and thermal stability, and also has a layer (Y) and an inorganic vapor-deposited layer (described later). The decrease in interlayer adhesion with I) can be further suppressed.
  • the vinyl alcohol-based polymer (a) contains an ethylene unit, a vinyl ester unit, a vinyl alcohol unit, and other monomer units other than the modifying group containing the primary hydroxyl group, as long as the effects of the present disclosure are not impaired. You may be doing it.
  • the content of the other monomer unit is preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 1% by mass or less, and particularly preferably not substantially contained.
  • examples of such other monomers include ⁇ -olefins such as propylene, n-butene, isobutylene, and 1-hexene; allyl acid and salts thereof; unsaturated monomers having an acrylic ester group; methacryl.
  • Vinyl ethers vinyl cyanide such as acrylonitrile and methacrylonitrile; vinyl halides such as vinyl chloride and vinyl fluoride; vinylidene halides such as vinylidene chloride and vinylidene fluoride; allyl acetate, 2,3-diacetoxy Allyl compounds such as -1-allyloxypropane and allyl chloride; unsaturated dicarboxylic acids such as maleic acid, itaconic acid and fumaric acid and salts or esters thereof; vinylsilane compounds such as vinyltrimethoxysilane; isopropenyl acetate and the like. ..
  • the resin composition (A) may contain less than 50% by mass of the vinyl alcohol-based polymer (a') having a melting point of 150 ° C. or higher. Except for the fact that the melting point is controlled to be high, the contents described for the vinyl alcohol polymer (a) can be applied to the vinyl alcohol polymer (a') as it is.
  • the vinyl alcohol-based polymer (a') an ethylene-vinyl alcohol copolymer having an ethylene unit content of 15 to 60 mol% and a saponification degree of 90 mol% or more is preferable.
  • the lower limit of the ethylene unit content is more preferably 20 mol%, still more preferably 23 mol%.
  • the upper limit of the ethylene unit content is more preferably 55 mol%, further preferably 50 mol%.
  • the lower limit of the saponification degree is preferably 95 mol%, more preferably 99 mol%.
  • the upper limit of the saponification degree is preferably 100 mol%, more preferably 99.99 mol%.
  • the lower limit of the content of the vinyl alcohol polymer (a') is preferably 5% by mass, more preferably 20% by mass, and even more preferably 35% by mass.
  • vinyl alcohol-based polymer (a') various brands of "EVAL (trademark) resin” manufactured by Kuraray Co., Ltd. can be preferably used.
  • the resin composition (A) contains 25 to 1500 ppm of an alkali metal ion (b).
  • the interlayer adhesiveness with the layer (Y) described later tends to be remarkably improved. The reason for this is not clear, but the fluidity of the polymer chain is improved because the melting point of the vinyl alcohol polymer (a), which is the main component of the resin composition (A), is less than 150 ° C.
  • the interlayer adhesiveness is significantly improved as compared with the case where the vinyl alcohol polymer having a high melting point contains the alkali metal ion (b). Be done.
  • the amount of the alkali metal ion (b) is too small, the resin composition (A) tends to thicken during melt molding, resulting in poor appearance such as gel or lumps, or with the layer (Y) described later.
  • the interlayer adhesiveness may decrease.
  • the amount of the alkali metal ion (b) is too large, the resin composition (A) may be excessively decomposed during melt molding, or coloring may become a problem.
  • the lower limit of the content of the alkali metal ion (b) is preferably 50 ppm, more preferably 70 ppm, still more preferably 90 ppm.
  • the upper limit of the content of the alkali metal ion (b) is preferably 1000 ppm, more preferably 750 ppm, still more preferably 500 ppm. Further, by controlling the content ratio of the alkali metal ion (b) and the carboxylic acid described later, the melt moldability and coloring resistance of the obtained resin composition (A) can be further improved.
  • alkali metal ion (b) examples include lithium, sodium, potassium, rubidium, and cesium ions, but sodium or potassium ions are preferable from the viewpoint of industrial availability.
  • potassium ions the hue of the resin composition (A) and the interlayer adhesiveness with the layer (Y) described later may be compatible at a high level. These may be used alone or in combination of two or more.
  • alkali metal compound that gives the alkali metal ion (b) examples include aliphatic carboxylates of alkali metals such as lithium, sodium, and potassium, aromatic carboxylates, carbonates, hydrochlorides, nitrates, sulfates, and phosphates. Examples include salts, hydroxides and metal complexes. Of these, aliphatic carboxylates and phosphates are more preferable because they are easily available and handled. As the aliphatic carboxylic acid salt, acetate, caprylate and stearate are preferable.
  • the resin composition (A) preferably contains 10 to 300 ppm of at least one polyvalent metal ion (c) selected from the group consisting of magnesium ion, calcium ion and zinc ion.
  • the polyvalent metal ion (c) is contained in an amount of 10 ppm or more, it tends to be possible to suppress appearance defects such as thickening and generation of gel or lumps during melt molding of the resin composition (A).
  • the content of the polyvalent metal ion (c) is 300 ppm or less, the resin composition (A) tends to be able to suppress excessive decomposition and coloring during melt molding.
  • the cross-linking reaction of the resin may proceed during melt molding of the pulverized product of the multi-layer structure, which may cause thickening or gelation.
  • the content of the multivalent metal ion (c) is preferably 20 to 260 ppm, more preferably 30 to 220 ppm.
  • the resin composition (A) preferably contains magnesium ions or calcium ions as the polyvalent metal ion (c), and more preferably contains calcium ions. Further, by controlling the content ratio of the multivalent metal ion (c) and the carboxylic acid described later, the melt moldability and coloring resistance of the obtained resin composition (A) can be further improved.
  • Examples of the polyvalent metal compound that gives the polyvalent metal ion (c) include aliphatic carboxylates of magnesium, calcium and zinc, aromatic carboxylates, carbonates, hydrochlorides, nitrates, sulfates and phosphates. Examples thereof include hydroxides and metal complexes. Of these, aliphatic carboxylic acid salts and hydroxides are more preferable because they are easily available and handled. As the aliphatic carboxylic acid salt, acetate, caprylate and stearate are preferable.
  • the resin composition (A) preferably contains 100 to 4000 ppm of the higher aliphatic carboxylic acid (d) having 8 to 30 carbon atoms.
  • the higher aliphatic carboxylic acid (d) may be contained in a part or all in the form of a salt, or may be contained as a salt of an alkali metal ion (b) or a polyvalent metal ion (c).
  • the higher aliphatic carboxylic acid (d) is preferably caprylic acid or stearic acid.
  • the multilayer film of the present invention has a layer (X) made of the resin composition (A) on the outermost layer, and the higher aliphatic carboxylic acid (d) acts as a lubricant with the surface of the die metal in the die, so that the multilayer film has multiple layers. It is considered that the appearance defect caused by the uneven thickness of the film and the generation of gels and lumps due to the stagnant resin can be suppressed. Therefore, the resin composition (A) preferably contains 100 ppm or more of the higher aliphatic carboxylic acid (d).
  • the content of the higher aliphatic carboxylic acid (d) is 4000 ppm or less, the thickening of the resin composition (A) during melt molding is suppressed, and the interlayer adhesiveness with the layer (Y) described later is improved. It tends to be sustainable. From these viewpoints, the content of the higher aliphatic carboxylic acid (d) is more preferably 200 to 3000 ppm, still more preferably 300 to 2500 ppm.
  • the resin composition (A) contains a vinyl alcohol-based polymer (a), a vinyl alcohol-based polymer (a'), an alkali metal ion (b), and a polyvalent metal ion (as long as the effects of the present invention are not impaired. It may contain components other than c) and the higher aliphatic carboxylic acid (d). Examples of other components include alkaline earth metal ions and transition metal ions other than the polyvalent metal ion (c), carboxylic acids other than the higher aliphatic carboxylic acid (d) (monocarboxylic acid, polyvalent carboxylic acid), and vinyl.
  • the resin composition (A) preferably contains a carboxylic acid other than the higher aliphatic carboxylic acid (d).
  • the lower limit of the carboxylic acid content is preferably 50 ppm, more preferably 100 ppm.
  • the upper limit of the carboxylic acid content is preferably 400 ppm, more preferably 350 ppm.
  • the content of the carboxylic acid is 50 ppm or more, the coloring resistance tends to be good.
  • the content of the carboxylic acid is 400 ppm or less, the interlayer adhesiveness is maintained and the generation of odor tends to be suppressed.
  • the pKa of the carboxylic acid is preferably 3.5 to 5.5.
  • the pH buffering capacity of the obtained resin composition (A) is enhanced, the melt moldability can be further improved, and the coloring by an acidic substance or a basic substance can be further improved.
  • the carboxylic acid may be a monovalent carboxylic acid. These may be used alone or in combination of two or more.
  • the monovalent carboxylic acid is a compound having one carboxyl group in the molecule.
  • These carboxylic acids may further have a substituent such as a hydroxyl group, an amino group or a halogen atom. Of these, acetic acid is preferable because it is highly safe and easy to obtain and handle.
  • the carboxylic acid may be a polyvalent carboxylic acid.
  • the carboxylic acid is a polyvalent carboxylic acid
  • the coloring resistance of the resin composition (A) at a high temperature and the coloring resistance of the melt-molded product of the obtained multilayer structure may be further improved.
  • the polyvalent carboxylic acid compound has three or more carboxyl groups. In this case, the coloring resistance may be improved more effectively.
  • a polyvalent carboxylic acid is a compound having two or more carboxyl groups in the molecule.
  • PKa2 4.44
  • pKa2 5.40
  • pKa2 5.41
  • the resin composition (A) may further contain a phosphoric acid compound.
  • the lower limit of the content of the phosphoric acid compound is preferably 5 ppm in terms of phosphoric acid root.
  • the upper limit of the content of the phosphoric acid compound is preferably 100 ppm in terms of phosphoric acid root.
  • the phosphoric acid compound for example, various acids such as phosphoric acid and phosphoric acid and salts thereof are used.
  • the phosphate may be any of a first phosphate, a second phosphate and a third phosphate.
  • the cation species of the phosphate is not particularly limited, but the cation species is preferably an alkali metal or an alkaline earth metal.
  • sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, and dipotassium hydrogen phosphate are preferable.
  • the resin composition (A) may further contain a boron compound.
  • a boron compound When a boron compound is contained, the lower limit of the content in the resin composition (A) is preferably 50 ppm, more preferably 100 ppm in terms of boron element.
  • the upper limit of the content of the boron compound in the resin composition (A) is preferably 400 ppm, more preferably 200 ppm in terms of boron element.
  • draw-down resistance and the neck-in resistance during film formation may be improved, or the mechanical properties of the obtained molded product may be improved. It is presumed that these effects are caused by the occurrence of a chelate interaction between the vinyl alcohol polymer (a) and the boron compound.
  • Examples of the boron compound include boric acid, borate ester, borate, and boron hydride.
  • boric acid such as orthoboric acid (H 3 BO 3 ), metaboric acid, and tetraboric acid; borate esters such as trimethyl borate and triethyl borate; alkali metal salts or alkaline earth metals of the boric acid.
  • borate esters such as trimethyl borate and triethyl borate
  • alkali metal salts or alkaline earth metals of the boric acid examples thereof include borates such as salt and boric acid. Of these, orthoboric acid is preferable.
  • the resin composition (A) may further contain a hindered phenolic compound.
  • the content of the hindered phenol-based compound in the resin composition (A) is preferably 1000 to 10000 ppm.
  • the content of the hindered phenolic compound is more preferably 2000 ppm or more.
  • the content of the hindered phenol-based compound is 10,000 ppm or less, coloring and bleed-out derived from the hindered phenol-based compound can be suppressed.
  • the content of the hindered phenolic compound is more preferably 8000 ppm or less.
  • the hindered phenolic compound has at least one hindered phenol group.
  • the hindered phenol group refers to a group in which a bulky substituent is bonded to at least one of the carbons adjacent to the carbon to which the hydroxyl group of the phenol is bonded.
  • a bulky substituent an alkyl group having 1 to 10 carbon atoms is preferable, and a t-butyl group is more preferable.
  • the hindered phenolic compound is preferably in a solid state near room temperature.
  • the melting point or softening temperature of the hindered phenolic compound is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 70 ° C. or higher.
  • the molecular weight of the hindered phenolic compound is preferably 200 or more, more preferably 400 or more, still more preferably 600 or more. On the other hand, the molecular weight is usually 2000 or less.
  • the melting point or softening temperature of the hindered phenol-based compound is preferably 200 ° C. or lower, more preferably 190 ° C. or lower, still more preferably 180 ° C. or lower. ..
  • the hindered phenolic compound preferably has an ester bond or an amide bond.
  • the hindered phenol compound having an ester bond include an ester of an aliphatic carboxylic acid having a hindered phenol group and an aliphatic alcohol
  • examples of the hindered phenol compound having an amide bond include a hindered phenol group.
  • examples thereof include an amide of an aliphatic carboxylic acid having an aliphatic amine and an aliphatic amine.
  • it is preferable that the hindered phenolic compound has an amide bond.
  • pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-), which is commercially available from BASF as Irganox 1010, is used.
  • irganox 1076 commercially available as stearyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, commercially available as irganox 1035, 2,2'-thio Diethylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3- (3,5-di-tert-butyl-4-hydroxyphenyl) commercially available as Irganox 1135.
  • Octadecil propanoate bis (3-tert-butyl-4-hydroxy-5-methylbenzenepropanoic acid) commercially available as irganox 245 ethylene bis (oxyethylene), commercially available as irganox 259 1,6- Hexadiol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylene bis [3- (3,5-di), commercially available as Irganox 1098. -Tert-Butyl-4-hydroxyphenyl) propanamide].
  • Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] is preferable, and the former is more preferable.
  • the resin composition (A) may further contain a thermoplastic resin other than the vinyl alcohol-based polymer (a) and the vinyl alcohol-based polymer (a').
  • thermoplastic resin other than the vinyl alcohol polymer (a) and the vinyl alcohol polymer (a') include various polyolefins (polyethylene, polypropylene, poly 1-butene, poly 4-methyl-1-pentene, ethylene-.
  • a propylene copolymer a copolymer of ethylene and ⁇ -olefin having 4 or more carbon atoms, a polymer of polyolefin and maleic anhydride, an ethylene-vinyl ester copolymer, an ethylene-acrylic acid ester copolymer, or Modified polyolefins obtained by graft-modifying these with unsaturated carboxylic acid or a derivative thereof), various polyamides (nylon 6, nylon 6.6, nylon 6/66 copolymer, nylon 11, nylon 12, polymethoxylylen adipamide, etc.) ), Various polyesters (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), polyvinyl chloride, polyvinylidene chloride, polystyrene, polyacrylonitrile, polyurethane, polycarbonate, polyacetal, polyacrylate, modified polyvinyl alcohol resin and the like.
  • the content of the thermoplastic resin in the resin composition (A) is usually less than 40% by mass, preferably less than 30% by mass, more preferably less than 20% by mass, still more preferably less than 10% by mass, and 5%. It may be less than mass% or less than 1% by mass, and it is particularly preferable that it is substantially absent.
  • the proportion of the vinyl alcohol-based polymer (a) in the resin constituting the resin composition (A) is preferably 60% by mass or more, more preferably 70% by mass or more, from the viewpoint that the effect of the present invention is more remarkably exhibited.
  • 80% by mass is further preferable, 90% by mass or more is further preferable, 95% by mass or more is particularly preferable, and the resin constituting the resin composition (A) is substantially only the vinyl alcohol-based polymer (a).
  • the ratio of the vinyl alcohol polymer (a) to the resin composition (A) is preferably 60% by mass or more, more preferably 70% by mass or more, from the viewpoint that the effect of the present invention is more remarkably exhibited.
  • the resin composition (A) is substantially a vinyl alcohol-based polymer (a) and an alkali metal ion (b). It may consist only of.
  • the total content of the vinyl alcohol-based polymer (a) and the vinyl alcohol-based polymer (a') in the resin constituting the resin composition (A) is 70 mass by mass. % Or more is preferable, 90% by mass or more is more preferable, 95% by mass or more is further preferable, 99% by mass or more is particularly preferable, and the resin constituting the resin composition (A) is substantially a vinyl alcohol polymer (a). ) And the vinyl alcohol polymer (a') may be the only ones.
  • the total content of the vinyl alcohol-based polymer (a) and the vinyl alcohol-based polymer (a') in the resin composition (A) is 70% by mass or more. It is preferably 90% by mass or more, more preferably 95% by mass or more, particularly preferably 99% by mass or more, and the resin composition (A) is substantially a vinyl alcohol-based polymer (a) or a vinyl alcohol-based polymer (a). It may consist only of a') and the alkali metal ion (b).
  • melt flow rate (MFR) (210 ° C., under a load of 2160 g) measured according to the method described in JIS K7210 (2014) of the resin composition (A) is 0.1 to 30 g. / 10 minutes is preferable, 0.3 to 25 g / 10 minutes is more preferable, and 0.5 to 20 g / 10 minutes is further preferable.
  • the method for producing the resin composition (A) is not particularly limited, but the vinyl alcohol-based polymer (a) and the alkali metal ion (b), and if necessary, the vinyl alcohol-based polymer (a') and the polyvalent metal ion ( It can be produced by melt-kneading other components such as c) and higher aliphatic carboxylic acid (d). Each component may be blended in a solid state such as powder or as a melt, or may be blended as a solute contained in a solution or a dispersoid contained in a dispersion liquid. As the solution and the dispersion liquid, an aqueous solution and an aqueous dispersion liquid are suitable, respectively.
  • melt-kneading a known mixing device or kneading device such as a kneader ruder, an extruder, a mixing roll, and a Banbury mixer can be used.
  • the temperature range at the time of melt-kneading can be appropriately adjusted according to the vinyl alcohol-based polymer (a) to be used, the melting point of each component, and the like, and usually 150 to 250 ° C. is adopted. Further, it may be produced by adding some components to the vinyl alcohol polymer (a) in advance and then melt-kneading other necessary components as described above.
  • a method of pre-adding some components to the vinyl alcohol-based polymer (a) a method of immersing the vinyl alcohol-based polymer (a) as pellets or powder in a solution in which the added components are dissolved can be exemplified.
  • a solution an aqueous solution is suitable.
  • the multilayer film of the present invention has a layer (Y) containing an adhesive resin (B) having a melting point of less than 150 ° C. as a main component.
  • the adhesive resin (B) include a carboxylic acid-modified polyolefin resin obtained by graft-polymerizing an unsaturated carboxylic acid such as maleic anhydride or a derivative thereof with a polyolefin resin.
  • the melting point of the adhesive resin (B) mainly depends on the polyolefin resin before carboxylic acid modification.
  • the contents described for the polyolefin resin (C) described later can be applied as they are.
  • the proportion of the carboxylic acid-modified polyolefin resin in the adhesive resin (B) is preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 95% by mass or more, and substantially only from the carboxylic acid-modified polyolefin resin. It may be configured.
  • the proportion of the adhesive resin (B) in the layer (Y) is preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 95% by mass or more, and substantially the adhesive resin (B). It may be composed of only.
  • the multilayer film of the present invention has a layer (Z) containing a polyolefin resin (C) having a melting point of less than 150 ° C. as a main component.
  • the polyolefin resin (C) is not particularly limited as long as it is a polyolefin having a melting point of less than 150 ° C., and is a polyethylene resin such as linear low density polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene; vinyl ester resin; Examples thereof include ethylene-propylene copolymer; propylene- ⁇ -olefin copolymer ( ⁇ -olefin having 4 to 20 carbon atoms); olefin alone such as polybutene and polypentene, or a copolymer thereof; chlorinated polyethylene and the like.
  • the polyolefin resin (C) preferably contains a polyethylene resin as a main component, and more preferably a polyethylene resin. Since polyethylene resin is widely used as a packaging material regardless of whether it has a gas barrier property or not, its recycling infrastructure is widely developed in each country.
  • the polyethylene resin (C) contains a polyethylene resin as a main component
  • the polyethylene resin is preferably at least one selected from linear low-density polyethylene, low-density polyethylene, medium-density polyethylene, and high-density polyethylene. , At least one selected from linear low-density polyethylene and low-density polyethylene, or a mixture of at least one selected from linear low-density polyethylene and low-density polyethylene and high-density polyethylene. preferable.
  • the melting point of the polyolefin resin (C) is preferably less than 140 ° C, more preferably less than 130 ° C.
  • the melting point of the polyolefin resin (C) is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, from the viewpoint of process passability during melt molding or secondary processing such as stretching and heat resistance as a packaging material. ..
  • the melt flow rate (MFR) (210 ° C., under a load of 2160 g) measured according to the method described in JIS K7210 (2014) of the polyolefin resin (C) is 0.1 to 1. 30 g / 10 minutes is preferable, 0.3 to 25 g / 10 minutes is more preferable, and 0.5 to 20 g / 10 minutes is further preferable.
  • the polyolefin resin (C) preferably contains a polyethylene resin as a main component, and the content of the polyethylene resin in the polyolefin resin (C) is more preferably 70% by mass or more, further preferably 80% by mass or more, and 95% by mass.
  • the above is particularly preferable, and the polyolefin resin (C) may be substantially composed of only a polyethylene resin.
  • the proportion of the polyolefin resin (C) in the layer (Z) is preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 95% by mass or more, and substantially only from the polyolefin resin (C). It may be configured.
  • the layer (Y) and the layer (Z) contain the adhesive resin (B) and the polyolefin resin (C) as main components, respectively, as long as the effects of the present invention are not impaired in these layers.
  • Other components such as an agent, a flame retardant, and an antifogging agent may be contained.
  • the total amount is less than 50% by mass, preferably less than 40% by mass, more preferably less than 30% by mass, still more preferably less than 20% by mass, and particularly preferably less than 10% by mass with respect to each layer.
  • the multilayer film of the present invention has a layer (X) as the outermost layer, and has a structure in which at least a layer (X), a layer (Y), and a layer (Z) are laminated in this order.
  • a plurality of layers (X), layers (Y), and layers (Z) may be provided.
  • the layer (X) is represented by X
  • the layer (Y) is represented by Y
  • the layer (Z) is represented by Z
  • X / Examples thereof include Y / Z, X / Y / Z / Y / X, X / Y / Z / Y / X / Y / Z / Y / X, and the like.
  • the thickness of the layer (X) of the multilayer film of the present invention is preferably 0.2 ⁇ m or more and less than 20 ⁇ m. Further, it is also preferable that the ratio of the thickness of the layer (X) to the total thickness of all the layers of the multilayer film is less than 25%.
  • the thickness of the layer (X) is more preferably 0.4 ⁇ m or more and less than 16 ⁇ m, and further preferably 0.6 ⁇ m or more and less than 12 ⁇ m.
  • the ratio of the thickness of the layer (X) to the total thickness of all the layers of the multilayer film is more preferably less than 20%, further preferably less than 15%.
  • the thickness of all layers of the multilayer film is usually 10 ⁇ m or more and less than 200 ⁇ m, preferably 10 ⁇ m or more and less than 150 ⁇ m. In the case of the stretched multilayer film described later, the thickness of all layers is preferably 10 ⁇ m or more and less than 50 ⁇ m, more preferably less than 40 ⁇ m.
  • the multilayer film of the present invention may be a non-stretched multilayer film, but may be a stretched multilayer film stretched in a uniaxial direction or a biaxial direction (at least in the uniaxial direction).
  • the multilayer film is preferably a uniaxially stretched multilayer film and is anisotropic to mechanical properties.
  • the multilayer film is preferably a biaxially stretched multilayer film.
  • the film is stretched at least 3 times or more and less than 12 times in the uniaxial direction.
  • a uniaxially stretched multilayer film it is preferably stretched 3 times or more and less than 12 times in the uniaxial direction, and more preferably 4 times or more and less than 10 times.
  • a biaxially stretched multilayer film it is preferably stretched 3 times or more and less than 12 times in each biaxial direction, and more preferably 4 times or more and less than 10 times.
  • the method for forming the multilayer film of the present invention is not particularly limited, but in general, a conventional coextrusion method in which each resin is extruded from a separate die or a common die and laminated can be used.
  • a conventional coextrusion method in which each resin is extruded from a separate die or a common die and laminated can be used.
  • the die either an annular die or a T die can be used.
  • the method of stretching in the uniaxial direction or the biaxial direction is not particularly limited, and a conventionally known stretching method such as a roll type uniaxial stretching, a tubular simultaneous biaxial stretching, a tenter continuous biaxial stretching, or a tenter simultaneous biaxial stretching is used.
  • the film can be produced by stretching in the flow direction and / or in the direction perpendicular to the flow direction, that is, in the width direction.
  • the temperature at the time of stretching is usually 40 to 150 ° C., more preferably 50 to 140 ° C., and may be 60 to 130 ° C. from the viewpoint of processability.
  • the multilayer film of the present invention has an advantage that problems such as poor appearance after stretching and deterioration of interlayer adhesiveness are less likely to occur even when the stretching temperature is relatively low such as 120 ° C. If necessary, it is preferable to perform a heat treatment at a temperature equal to or higher than the glass transition point and lower than the melting point after the stretching treatment to increase the crystallinity and to perform a so-called heat fixing operation in order to fix the orientation of the molecular chains.
  • the above problem is also solved by a thin-film vapor-deposited film having an inorganic thin-film film (I) on the exposed surface side of the layer (X) of the multilayer film of the present invention.
  • the inorganic vapor-filmed layer (I) is made of an inorganic substance such as a metal or an inorganic oxide, and means a layer having a gas barrier property against oxygen and water vapor.
  • the layer (X) has a higher affinity with metals and inorganic oxides than ordinary thermoplastic resins, and can form a dense and defect-free inorganic vapor-filmed layer (I), and the obtained vapor-filmed multilayer film can be formed.
  • the interlayer adhesion between the layer (X) and the inorganic vapor deposition layer (I) is good. Further, since the layer (X) has a gas barrier property, deterioration of the gas barrier property can be suppressed even when a defect occurs in the inorganic thin-film vapor deposition layer (I) due to bending or the like.
  • the thickness of the inorganic thin-film deposition layer (I) is generally less than 500 nm. When the thickness is less than 500 nm, the viscosity stability when melt-molding the pulverized product of the multilayer structure including the inorganic thin-film deposition layer (I) is excellent, and the generation of gels and lumps can be suppressed.
  • the inorganic vapor deposition layer (I) is preferably either a metal vapor deposition layer containing aluminum as a main component or an inorganic oxide vapor deposition layer containing alumina or silica as a main component.
  • a metal-deposited layer is preferable for imparting light-shielding properties, but inorganic oxidation is possible from the viewpoints of visibility of the contents as a packaging material, appropriate range, and suppression of gel and lumps when melt-molding the crushed material.
  • a thin-film deposition layer is preferred.
  • the metal vapor deposition layer is generally a layer containing aluminum as a main component.
  • the content of aluminum atoms in the metal vapor deposition layer is preferably 50 mol% or more, more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably 95 mol% or more.
  • the average thickness of the metal vapor deposition layer is preferably 120 nm or less, more preferably 100 nm or less, still more preferably 90 nm or less.
  • the average thickness of the metal vapor deposition layer is preferably 25 nm or more, more preferably 35 nm or more, and even more preferably 45 nm or more.
  • the average thickness of the metal-deposited layer is an average value of the thicknesses at any 10 points on the cross section of the metal-deposited layer measured by an electron microscope.
  • the light transmittance at a wavelength of 600 nm can be 10% or less, and the light-shielding property is excellent.
  • the inorganic oxide vapor deposition layer may be an inorganic oxide, for example, an oxide such as silicon, aluminum, magnesium, calcium, potassium, tin, sodium, boron, titanium, lead, zirconium, ittrium, etc., preferably an alumina or silica vapor deposition film. Can be mentioned.
  • the average thickness of the inorganic oxide-deposited layer is preferably 60 nm or less, more preferably 50 nm or less, still more preferably 40 nm or less.
  • the average thickness of the inorganic oxide-deposited layer is preferably 10 nm or more, more preferably 15 nm or more, and even more preferably 20 nm or more.
  • the average thickness of the inorganic oxide-deposited layer is an average value of the thicknesses at any 10 points on the cross section of the inorganic oxide-deposited layer measured by an electron microscope.
  • the light transmittance at a wavelength of 600 nm can be 80% or more, and the contents are excellent in visibility when used as a packaging material. From the viewpoint of further improving visibility, the light transmittance at a wavelength of 600 nm is more preferably 90% or more.
  • the light transmittance can be increased, for example, by suppressing the thickness unevenness of the multilayer film of the present invention used in the production of the vapor-deposited multilayer film.
  • the layer (X) which is the outermost layer of the multilayer film of the present invention contains a vinyl alcohol-based polymer (a) having a melting point of less than 150 ° C. as a main component, uneven thickness is suppressed, so that high light transmittance can be obtained. It tends to show.
  • a means for further suppressing the thickness unevenness of the multilayer film of the present invention for example, a means for stretching at least in the uniaxial direction can be mentioned.
  • the light transmittance of the multilayer film of the present invention at a wavelength of 600 nm is preferably 80% or more, and more preferably 90% or more.
  • the inorganic vapor deposition layer (I) can be formed by a known physical vapor deposition method or chemical vapor deposition method. Specific examples thereof include a vacuum vapor deposition method, a sputtering method, an ion plating method, an ion beam mixing method, a plasma CVD method, a laser CVD method, a MO-CVD method, a thermal CVD method, and the like, and a physical vapor deposition method is used. It is preferable, and it is particularly preferable to use the vacuum vapor deposition method.
  • a protective layer (top coat layer) may be provided on the inorganic thin-film deposition layer (I), if necessary, as long as the effects of the present invention are not impaired.
  • the upper limit of the surface temperature of the layer (X) at the time of forming the film of the inorganic thin-film layer (I) is preferably 60 ° C, more preferably 55 ° C, still more preferably 50 ° C. Further, the lower limit of the surface temperature of the layer (X) at the time of forming the film of the inorganic thin-film layer (I) is not particularly limited, but 0 ° C. is preferable, 10 ° C. is more preferable, and 20 ° C. is further preferable.
  • the exposed surface of the layer (X) may be plasma-treated before the film formation. A known method can be used for the plasma treatment, and atmospheric pressure plasma treatment is preferable.
  • nitrogen, helium, neon, argon, krypton, xenon, radon and the like are used as the discharge gas.
  • nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because the cost can be reduced.
  • the multilayer film or vapor-deposited multilayer film of the present invention has an oxygen permeation rate (20 ° C., 65% RH conditions) of 60 cc / (m) measured according to the method described in JIS K 7126-2 (isopressure method; 2006). is preferably 2 ⁇ day ⁇ atm) of less than, more preferably less than 40cc / (m 2 ⁇ day ⁇ atm), more preferably less than 20cc / (m 2 ⁇ day ⁇ atm), 5cc / more preferably more that (m 2 ⁇ day ⁇ atm) under a is, particularly preferably less than 1cc / (m 2 ⁇ day ⁇ atm).
  • the multilayer film and the vapor-deposited multilayer film having an oxygen permeation rate in the above range have excellent gas barrier properties.
  • the multilayer film of the present invention or the vapor-deposited multilayer film itself can be used as a packaging material having a gas barrier property, but the multilayer film in which at least one resin layer (R) containing the thermoplastic resin (D) as a main component is laminated is laminated.
  • the thermoplastic resin (D) is not particularly limited, and is linear low-density polyethylene, low-density polyethylene, medium-density polyethylene, high-density polyethylene, vinyl ester resin, ethylene-propylene copolymer, polypropylene, propylene- ⁇ -olefin.
  • Copolymer ( ⁇ -olefin having 4 to 20 carbon atoms), olefin such as polybutene and polypentene alone, or a copolymer thereof, polyamide such as nylon 6, nylon 6,6, polyethylene terephthalate, polybutylene terephthalate, polyethylene na
  • polyamide such as nylon 6, nylon 6,6, polyethylene terephthalate, polybutylene terephthalate, polyethylene na
  • polyesters such as phthalate, polystyrene, polyvinyl chloride, polyvinylidene chloride, acrylic resin, polycarbonate, chlorinated polyethylene, chlorinated polypropylene and the like.
  • polyolefin is preferable from the viewpoint of excellent moisture resistance, mechanical properties, economy, heat sealability and the like
  • polyamide and polyester are preferable from the viewpoint of excellent mechanical properties and heat resistance.
  • the thermoplastic resin (D) is preferably the same type as the above-mentioned polyolefin resin (C), that is, a polyolefin resin having a melting point of less than 150 ° C. It is more preferable to contain a polyethylene resin as a main component, and it is further preferable to use a polyethylene resin. Therefore, in order to obtain a multilayer structure having excellent recyclability, it is preferable that the polyolefin resin (C) and the thermoplastic resin (D) are contained as a main component of the polyethylene resin, and more preferably the polyethylene resin.
  • the resin layer (R) may be unstretched, or may be stretched or rolled in the uniaxial or biaxial direction.
  • a biaxially stretched layer is preferable from the viewpoint of improving the mechanical strength, and a non-stretched layer is preferable from the viewpoint of improving the heat sealability.
  • the film forming method of the resin layer (R) is not particularly limited, but is generally formed by melt extrusion with an extruder.
  • the die either an annular die or a T die can be used.
  • the method of stretching in the uniaxial direction or the biaxial direction is not particularly limited, and a conventionally known stretching method such as a roll type uniaxial stretching, a tubular simultaneous biaxial stretching, a tenter continuous biaxial stretching, or a tenter simultaneous biaxial stretching is used.
  • the film can be produced by stretching in the flow direction and / or in the direction perpendicular to the flow direction, that is, in the width direction.
  • the stretch ratio is preferably 8 to 60 times the area ratio from the viewpoint of the uniformity of the thickness of the obtained layer and the mechanical strength.
  • the area magnification is more preferably 55 times or less, further preferably 50 times or less. Further, the area magnification is more preferably 9 times or more. If the area magnification is less than 8 times, stretching spots may remain, and if it exceeds 60 times, the layer may be easily broken during stretching.
  • the thickness of the resin layer (R) is preferably 10 to 200 ⁇ m from the viewpoint of industrial productivity. Specifically, the thickness of the non-stretched layer is more preferably 10 to 150 ⁇ m, and the thickness of the biaxially stretched layer is more preferably 10 to 50 ⁇ m.
  • the total thickness of the multilayer structure of the present invention is preferably 300 ⁇ m or less.
  • the multilayer structure of the present invention is lightweight and flexible, and is therefore preferably used for flexible packaging.
  • the amount of resin used in the multilayer structure is small, and the environmental load is suppressed.
  • each layer in the multilayer structure of the present invention may be appropriately adjusted according to the intended use, but coloring can be suppressed during melt molding of the pulverized product, thermal stability during melt molding is improved, and lumps are generated.
  • the layer (Z) and the resin layer (R) at least one layer contains polyethylene resin as a main component, and the layer containing polyethylene resin as a main component with respect to the total thickness of the multilayer structure.
  • the ratio of the total thickness is preferably 0.75 or more, more preferably 0.85 or more.
  • the ratio is preferably 0.98 or less.
  • the multilayer structure of the present invention does not have a layer containing a resin having a melting point of 240 ° C. or higher as a main component and a metal layer having a thickness of 1 ⁇ m or higher.
  • a layer containing a resin having a melting point of 240 ° C. or higher as a main component and a metal layer having a thickness of 1 ⁇ m or more when a pulverized product of a multilayer structure is melt-molded, mixing with other components is non-uniform. Can be suppressed.
  • the metal layer is a layer made of metal such as aluminum foil and having continuous and discontinuous surfaces.
  • the multilayer structure of the present invention more preferably does not have a layer containing a resin having a melting point of 220 ° C. or higher as a main component, and does not have a layer containing a resin having a melting point of 200 ° C. or higher as a main component. Is even more preferable.
  • the method for laminating the resin layer (R) on the multilayer film of the present invention is not particularly limited, and examples thereof include extrusion laminating, coextrusion laminating, and dry laminating.
  • an adhesive layer may be provided. That is, each layer constituting the multilayer structure of the present invention may be laminated via an adhesive layer, if necessary. However, there is no adhesive layer between the layers (X) and the layer (Y) of the multilayer film and between the layers (Y) and the layer (Z).
  • the adhesive layer can be formed by applying a known adhesive and drying it.
  • the adhesive is preferably a two-component reaction type polyurethane adhesive in which a polyisocyanate component and a polyol component are mixed and reacted.
  • the thickness of the adhesive layer is not particularly limited, but is preferably 1 to 5 ⁇ m, more preferably 2 to 4 ⁇ m.
  • the multilayer structure of the present invention is not particularly limited, and for example, the following layer structure is preferable from the viewpoint of obtaining a multilayer structure having excellent recyclability.
  • the layer (X) is expressed as X
  • the layer (Y) is expressed as Y
  • the layer (Z) is expressed as Z
  • the inorganic vapor-deposited layer (I) is expressed as I
  • the layer (R) is expressed as R. Means that they are directly laminated, and "//" means that they are laminated via an adhesive layer.
  • the layer (X), the layer (Y) and the layer (Z) are preferably stretched at least in the uniaxial direction, and more preferably biaxially stretched.
  • the layer (Z) and the layer (R) are preferably polyethylene resins, and the layer (Y) is preferably maleic anhydride-modified polyethylene resin.
  • the layer (X) is preferably a layer made of a resin composition (A) containing a vinyl alcohol-based polymer (a) having a modifying group containing a primary hydroxyl group as a main component.
  • the multilayer structure of the present invention may have layers other than those described above as long as the effects of the present invention are not impaired.
  • An example of another layer is a recovery layer.
  • Another example of another layer is, for example, a print layer.
  • the printed layer may be contained in any position of the multilayer structure of the present invention.
  • the printing layer include a film obtained by applying a solution containing a pigment or dye and, if necessary, a binder resin, and drying the film.
  • Examples of the coating method of the print layer include various coating methods using a wire bar, a spin coater, a die coater, and the like, in addition to the gravure printing method.
  • the thickness of the ink layer is not particularly limited, but is preferably 0.5 to 10 ⁇ m, more preferably 1 to 4 ⁇ m.
  • a method for recovering a multilayer structure in which the multilayer structure of the present invention is crushed and then melt-molded, and a recovery composition containing a recovered product of the multilayer structure of the present invention are also preferred embodiments of the present invention.
  • the recovered product of the multilayer structure of the present invention is crushed.
  • the crushed recovered product may be melt-molded as it is to obtain a recovered composition, or may be melt-molded together with other components to obtain a recovered composition, if necessary.
  • a polyolefin resin is preferable, and a polyethylene resin is more preferable.
  • the polyolefin resin the same type as the above-mentioned polyolefin resin (C) is used as the one used for the multilayer film of the present invention.
  • the crushed recovered product may be directly used for manufacturing a molded product such as a multilayer structure, or the crushed recovered product is melt-molded to obtain pellets composed of the recovered composition, and then the pellet is used as a molded product. May be used for the production of.
  • the mass ratio [resin composition (A) / polyolefin resin] of the resin composition (A) to the polyolefin resin in the recovered composition is preferably 0.01 / 99.99 to 20/80. If the mass ratio is less than 0.01 / 99.99, the usage ratio of the recovered material may decrease. On the other hand, if the mass ratio exceeds 20/80, the melt moldability and mechanical properties of the recovered composition may deteriorate. From the viewpoint of improving the melt moldability and mechanical characteristics of the obtained recovered composition, the mass ratio is more preferably 15/85 or less, further preferably 10/90 or less, and may be 5/95 or less.
  • the multilayer structure of the present invention has excellent appearance, gas barrier property and recyclability, it can be suitably used as a material for various packaging such as food packaging, pharmaceutical packaging, industrial chemical packaging, pesticide packaging, etc., and particularly the multilayer structure of the present invention.
  • the packaging material provided with the structure can be suitably used as a packaging material having excellent recyclability.
  • MeOH was added to a modified ethylene-vinyl acetate copolymer (sometimes referred to as modified EVAc in the present specification) into which a structural unit derived from MPDAc was introduced by copolymerization. It was added to make a 20 mass% MeOH solution.
  • modified EVAc ethylene-vinyl acetate copolymer
  • modified EVOH modified ethylene-vinyl alcohol copolymer
  • the modified EVOH precipitated by decantation was collected and ground with a mixer.
  • the obtained modified EVOH powder was put into a 1 g / L acetic acid aqueous solution (bath ratio 20: ratio of 20 L of aqueous solution to 1 kg of powder) and washed by stirring for 2 hours.
  • the obtained dried product of modified EVAc was dissolved in dimethyl sulfoxide (DMSO) -d6 containing tetramethylsilane as an internal standard substance, and 1 H-NMR at 500 MHz (“GX-500” manufactured by JEOL Ltd. ) was measured at 80 ° C.
  • DMSO dimethyl sulfoxide
  • 1 H-NMR at 500 MHz (“GX-500” manufactured by JEOL Ltd. ) was measured at 80 ° C.
  • GX-500 manufactured by JEOL Ltd.
  • This treatment liquid was transferred to a 50 mL volumetric flask, and the volumetric flask was prepared with pure water.
  • the content of the alkali metal ion (b) and the polyvalent metal ion (c) was quantified by measuring this solution with an ICP emission spectrophotometer (“Optima 4300DV” manufactured by PerkinElmer).
  • the content of each component was 250 ppm for sodium ion and 100 ppm for calcium ion.
  • the content of the higher aliphatic carboxylic acid (d) was 1500 ppm as a result of calculation from the amount of calcium stearate added at the time of melt extrusion in (4) above.
  • the yellowness (YI) of the resin composition pellet obtained in (4) above was measured using a spectrophotometer (“LabScan XE Sensor” manufactured by HunterLab). Judgment was made based on the following criteria.
  • the YI value is an index showing the yellowness of the object, and the higher the YI value is, the stronger the yellowness is, while the lower the YI value is, the weaker the yellowness is and the less the coloring is.
  • the resin composition A18 is the same as in Production Example 1 except that the polymerization conditions of (1) above are changed and the ethylene unit content and the modified group unit content including the primary hydroxyl group are changed as shown in Table 1. -A21, AC3 pellets were obtained.
  • Example 1 Production of non-stretched multilayer film Resin composition A1 pellet obtained in Production Example 1, polyethylene resin (“Novatec (trademark) LD LJ400” manufactured by Nippon Polyethylene Co., Ltd .; low density polyethylene, melting point 108 ° C.) and polyethylene adhesion.
  • polyethylene resin (“Novatec (trademark) LD LJ400” manufactured by Nippon Polyethylene Co., Ltd .; low density polyethylene, melting point 108 ° C.) and polyethylene adhesion.
  • Judgment Criteria A: 250 g / 15 mm or more and B: 200 g / 15 mm or more and less than 250 g / 15 mm C: 150 g / 15 mm or more and less than 200 g / 15 mm D: 100 g / 15 mm or more and less than 150 g / 15 mm E: 100 g / 15 mm or less
  • Example 2 to 30 and Comparative Examples 1 to 6 Production and evaluation were carried out in the same manner as in Example 1 except that the resin compositions A2 to A30 and AC1 to AC6 were used instead of the resin composition A1. The results are shown in Table 2.
  • polyethylene resin (“Novatec (trademark) LD LJ400” manufactured by Nippon Polyethylene; low density polyethylene, melting point 108 ° C.) and polyethylene adhesive resin (Mitsui).
  • Judgment Criteria A: Light transmittance at 600 nm is 90% or more B: Light transmittance at 600 nm is 80% or more and less than 90% C: Light transmittance at 600 nm is 10% or more and less than 80% D: Light transmittance at 600 nm Rate is less than 10%
  • the oxygen transmission rate (unit: cc / (m 2 ⁇ day ⁇ atm)) under the conditions of carrier gas pressure 1 atm were measured, was determined by the following criteria.
  • As the carrier gas nitrogen gas containing 2% by volume of hydrogen gas was used. The results are shown in Table 3.
  • Judgment Criteria A: Less than 1cc / (m2 ⁇ day ⁇ atm) B: 1cc / (m2 ⁇ day ⁇ atm) or more and less than 5cc / (m2 ⁇ day ⁇ atm) C: 5cc / (m2 ⁇ day ⁇ atm) or more , Less than 20cc / (m2 ⁇ day ⁇ atm) D: 20cc / (m2 ⁇ day ⁇ atm) or more, less than 40cc / (m2 ⁇ day ⁇ atm) E: 40cc / (m2 ⁇ day ⁇ atm) or more, 60cc / ( Less than m2 ⁇ day ⁇ atm) F: 60cc / (m2 ⁇ day ⁇ atm) or more, less than 100cc / (m2 ⁇ day ⁇ atm) G: 100cc / (m2 ⁇ day ⁇ atm) or more
  • the multilayer film obtained in (1) is adjusted in humidity at 23 ° C and 50% RH, and then a gelboflex tester (manufactured by Rigaku Kogyo Co., Ltd.) is used. Then, bending treatment was performed. Specifically, first, the multilayer film is made into a cylindrical shape with a diameter of 3.5 inches, and both ends are gripped, with an initial gripping interval of 7 inches, a gripping interval of 1 inch at maximum bending, and the first 3.5 inches of the stroke. A twist of 440 degrees was added, and then the 2.5-inch reciprocating motion consisting of repeated motions, which is a straight horizontal motion, was performed 10 times at a speed of 40 times / minute. For the multilayer film after the bending treatment, the oxygen permeation rate was measured in the same manner as in (3), and the judgment was made based on the same criteria.
  • Example 35 An aluminum metal vapor deposition having a thickness of 50 nm was carried out on the surface of the resin composition layer of the three-kind three-layer biaxially stretched multilayer film produced in Example 34 by a known vacuum vapor deposition method, and the metal-deposited biaxially stretched multilayer film (Al) was carried out.
  • / Resin composition / Polyethylene adhesive resin / Polyethylene resin 50 nm / 2 ⁇ m / 2 ⁇ m / 16 ⁇ m) was produced and evaluated in the same manner as in Example 31. The results are shown in Table 3.
  • Example 36 Alumina inorganic oxide vapor deposition having a thickness of 30 nm was carried out on the surface of the resin composition layer of the three-kind, three-layer biaxially stretched multilayer film produced in Example 34 by a known vacuum vapor deposition method, and the inorganic oxide vapor deposition biaxially stretched.
  • the results are shown in Table 3.
  • Example 8 A biaxially stretched polyethylene film having a thickness of 20 ⁇ m was produced by forming a film and biaxially stretching in the same manner as in Example 34, except that the resin composition and the polyethylene adhesive resin were not used, and evaluated in the same manner as in Example 31. Was done. The results are shown in Table 3.
  • This crushed product and polyethylene resin (“Novatec (trademark) LD LJ400” manufactured by Nippon Polyethylene Co., Ltd .; low density polyethylene, melting point 108 ° C.) are blended in a mass ratio (crushed product / polyethylene resin) of 40/60 and described below.
  • a recovered composition film having a thickness of 50 ⁇ m was obtained.
  • the thickness of the film was adjusted by appropriately changing the screw rotation speed and the take-up roll speed. Further, as a control, a polyethylene film having a thickness of 50 ⁇ m was similarly obtained by using only a polyethylene resin.
  • Extrusion temperature: C1 / C2 / C3 / D 230/230/230/230 ° C.
  • Pick-up roll temperature 80 ° C
  • the extrusion processability of the recovered composition was stable and good.
  • the recovered composition film had almost the same amount of gel and lumps as the polyethylene film, and had a uniform and good appearance except that some coloring was observed.

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  • Laminated Bodies (AREA)
  • Wrappers (AREA)
PCT/JP2021/023968 2020-06-25 2021-06-24 多層フィルム及びそれを用いた多層構造体 Ceased WO2021261560A1 (ja)

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JP7340125B1 (ja) * 2021-12-13 2023-09-06 株式会社クラレ 多層フィルム、多層構造体、包装材料、回収組成物、及び多層フィルム又は多層構造体の回収方法
WO2024111621A1 (ja) * 2022-11-24 2024-05-30 株式会社クラレ 複合多層フィルム及びそれを用いた多層構造体
WO2024214755A1 (ja) * 2023-04-12 2024-10-17 株式会社クラレ 多層フィルム、蒸着多層フィルム、多層構造体、包装材料、回収組成物、多層構造体の回収方法及び多層フィルムの製造方法
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JPWO2024225423A1 (https=) * 2023-04-27 2024-10-31
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BR112022025255A2 (pt) 2023-01-03
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