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
  • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
• • 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
• • 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
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins

Definitions

• the present invention relates to a multilayer film, a vapor-deposited multilayer film, and a multilayer structure, as well as a packaging material, a recovery composition, and a recovery method using the same.
• Packaging materials for long-term storage of foods and the like are often required to have gas barrier properties, including oxygen barrier properties.
• gas barrier properties including oxygen barrier properties.
• Metal foils or metal deposition layers such as aluminum, and inorganic oxide deposition layers such as silicon oxide and aluminum oxide are widely used as layers that improve gas barrier properties.
• resin layers with gas barrier properties such as vinyl alcohol polymers and polyvinylidene chloride are also widely used.
• Vinyl alcohol polymers have the characteristic that they exhibit gas barrier properties by crystallizing and densifying due to hydrogen bonding between hydroxyl groups in the molecules.
• EVOH ethylene-vinyl alcohol copolymers
• recycling post-consumer recycling
• a process is generally adopted in which the recovered packaging materials are cut, separated and washed as necessary, and then melt-mixed using an extruder.
• Various molded products are manufactured using the pellets obtained in this way.
• the packaging material be composed of a single material as much as possible (mono-materialization), which allows for the production of high-purity, high-quality recycled resin.
• barrier films made mainly of polyolefins, which are widely used as packaging materials.
• a vapor-deposited multilayer film has been proposed in which an inorganic vapor-deposited layer is laminated on the surface of the EVOH layer of a polyolefin-based multilayer film, the outermost layer of which is an EVOH layer, in order to achieve extremely high gas barrier properties (Patent Document 2).
• the first object of the present invention is to provide a multilayer film in which die build-up during production is suppressed and which has excellent gas barrier properties and recyclability, and a method for producing the same.
• the second object of the present invention is to provide, using the multilayer film, a vapor-deposited multilayer film, which has excellent gas barrier properties and recyclability, a multilayer structure, and a packaging material containing the multilayer structure.
• the third object of the present invention is to provide a recovered composition containing a recovered material of the multilayer structure, and a method for recovering the same.
• the present inventors have intensively studied combinations of various resin compositions and laminate structures, and have found that, when a multilayer film in which a gas barrier resin layer is the outermost layer is produced, die build-up during production can be suppressed and a multilayer film excellent in gas barrier properties and recyclability can be obtained by using a gas barrier resin composition containing a specific polyolefin. Furthermore, they have found that the use of this multilayer film can produce a vapor-deposited multilayer film and a multilayer structure excellent in gas barrier properties and recyclability, and have completed the present invention.
• the above-mentioned object is to [1] A multilayer film having a layer (X) as an outermost layer and at least one layer different from the layer (X), wherein the layer (X) is a layer made only of a resin composition (A) containing at least one gas barrier resin (a) selected from the group consisting of polyamide (hereinafter sometimes abbreviated as "PA”) and vinyl alcohol-based resins, and a polyolefin (b) having a melt flow rate of 3.0 g/10 min or more at 190° C.
• PA gas barrier resin
• b having a melt flow rate of 3.0 g/10 min or more at 190° C.
• [20] The multilayer film of any one of [1] to [19], wherein the ratio of the total average thickness of layers mainly composed of a polyethylene-based resin or a polypropylene-based resin is 75% or more;
• [21] A vapor-deposited multilayer film comprising the multilayer film according to any one of [1] to [20] and an inorganic vapor-deposited layer (I) laminated on the exposed surface side of the layer (X) in the multilayer film;
• [22] The vapor-deposited multilayer film according to [21], wherein the inorganic vapor-deposited layer (I) is a vapor-deposited metal layer mainly composed of aluminum or a vapor-deposited inorganic oxide layer mainly composed of alumina or silica;
• [23] The multilayer film or vapor-deposited multilayer film according to any one of [1] to [22], which has an oxygen transmission rate of less than 60 cc/( m2 ⁇ day ⁇ atm) under conditions of 20°C and 65% RH
• a multilayer film can be provided that suppresses die build-up during production and has excellent gas barrier properties and recyclability.
• a vapor-deposited multilayer film, a multilayer structure, and a packaging material using the same that have excellent gas barrier properties and recyclability can be provided.
• the multilayer structure has good recyclability, a recovered composition containing the recovered multilayer structure and a recovery method thereof can be provided.
• recyclability in this specification means that when the recovered multilayer structure or packaging material of the present invention is melt-kneaded to produce a recovered composition, gelation of the resin is suppressed, and a recovered composition with excellent appearance can be efficiently produced, and can be evaluated by a recovery test described in the examples.
• die build-up in this specification means a polymer deposit that occurs on the gas barrier layer side of the die outlet.
• the multilayer film of the present invention has a layer (X) as the outermost layer and at least one layer different from layer (X), where layer (X) is a layer consisting of only a resin composition (A) containing at least one gas barrier resin (a) selected from the group consisting of PA and vinyl alcohol-based resins, and a polyolefin (b) having a melt flow rate of 3.0 g/10 min or more at 190°C and a load of 2.160 kg measured in accordance with JIS K7210-1 (2014), and the resin composition (A) contains 0.1 parts by mass or more and 20 parts by mass or less of polyolefin (b) per 100 parts by mass of gas barrier resin (a).
• At least one gas barrier resin (a) selected from the group consisting of PA and vinyl alcohol-based resins has excellent gas barrier properties, and the multilayer film of the present invention having layer (X) as the outermost layer can achieve high gas barrier properties.
• the gas barrier resin (a) of the outermost layer has high affinity with the inorganic vapor deposition layer (I) described below, when it is made into a vapor deposition film of the present invention, it tends to stably exhibit high gas barrier properties.
• gas barrier resin (a) is prone to die build-up during the production of the multilayer film, possibly due to its high affinity with the metal surface of an extruder, etc., and it has been difficult to simultaneously produce a multilayer film having gas barrier resin (a) in the outermost layer and stable production with suppressed die build-up.
• the present inventors conducted extensive research and found that by using a resin composition (A) containing a polyolefin (b) having a melt flow rate of 3.0 g/10 min or more in JIS K7210-1 (2014) (190°C, 2.160 kg load), the slipperiness between the metal surface of an extruder or the like and the molten resin during multilayer film production is improved, and as a result, die build-up during production is suppressed.
• die build-up occurs when the pressure of the molten resin received in the die is released at the die exit, causing volume expansion, and the molten resin adheres to the die lip surface, and is not caused by thermal degradation due to retention in the extruder, etc.
• the outermost layer (X) contains polyolefin (b), which reduces the friction between the gas barrier resin (a) having polar groups and the metal wall surface inside the die, and the stress received by the gas barrier resin (a) is reduced. As a result, the volume expansion of the molten gas barrier resin (a) is suppressed, which is thought to be effective in reducing die build-up.
• the layer (X), the layer (Y), and the layer (Z) are stacked adjacent to each other in this order means that adjacent layers are directly stacked, and specifically means that the layer (X), the layer (Y), and the layer (Z) are stacked in this order, the layer (X) and the layer (Y) are directly stacked, and the layer (Y) and the layer (Z) are directly stacked.
• major component means a component that is contained in an amount of more than 50% by mass.
• the "average thickness" of each layer, etc. refers to the average value of thicknesses measured at any five points, unless otherwise specified.
• ppm means the content based on mass (ppm by mass).
• Polyethylene refers to a homopolymer of ethylene, a copolymer of 80 mol % or more ethylene and 20 mol % or less of an ⁇ -olefin monomer, and a copolymer of 90 mol % or more ethylene and less than 10 mol % of a non-olefin monomer whose functional groups contain atoms other than carbon, oxygen, and hydrogen atoms.
• Polypropylene refers to a homopolymer of propylene, a copolymer of 80 mol % or more of propylene and 20 mol % or less of an ⁇ -olefin monomer, and a copolymer of 90 mol % or more of propylene and less than 10 mol % of a non-olefin monomer whose functional groups contain atoms other than carbon, oxygen, and hydrogen atoms.
• the term "acid-modified polyethylene” refers to a polymer obtained by modifying polyethylene with an acid.
• the acid-modified polyethylene may be a polymer in which at least one of an acid group and an acid anhydride group is introduced into polyethylene.
• the term "acid-modified polypropylene” refers to a polymer obtained by modifying polypropylene with an acid.
• the acid-modified polypropylene may be a polymer in which at least one of an acidic group and an acid anhydride group is introduced into polypropylene.
• polyethylene resin refers to polyethylene and modified polyethylene (such as acid-modified polyethylene).
• Modified polyethylene refers to a polymer obtained by modifying polyethylene.
• polypropylene resin refers to polypropylene and modified polypropylene (such as acid-modified polypropylene).
• Modified polypropylene refers to a polymer obtained by modifying polypropylene.
• a multilayer film or a multilayer structure does not mean to distinguish between the front and back, but refers to the exposed surface.
• a multilayer film or a multilayer structure has two surfaces.
• a multilayer film or a multilayer structure has two outermost layers.
• "consists essentially of” means that optional components may be contained within a range that does not affect the effects of the present invention, and “consists only of” means that optional components other than impurities that are inevitably contained are excluded.
• a numerical range described using “to” means that the numerical range includes the numerical values before and after "to” as the lower limit and upper limit.
• the multilayer film of the present invention has, as an outermost layer, a layer (X) consisting of only a resin composition (A) containing at least one gas barrier resin (a) selected from the group consisting of PA and vinyl alcohol-based resins, and a polyolefin (b) having a melt flow rate of 3.0 g/10 min or more according to JIS K7210-1 (2014; 190° C., 2.160 kg load).
• the resin composition (A) contains 0.1 parts by mass or more and 20 parts by mass or less of the polyolefin (b) per 100 parts by mass of the gas barrier resin (a).
• the gas barrier resin (a) is at least one selected from the group consisting of PA and vinyl alcohol resins.
• the gas barrier resin (a) improves the gas barrier property of the multilayer film.
• the multilayer film of the present invention having a layer (X) consisting only of the resin composition (A) containing the gas barrier resin (a) as the outermost layer can easily provide the inorganic vapor deposition layer (I) on the layer (X), and the vapor deposition multilayer film having the inorganic vapor deposition layer (I) tends to stably exhibit good gas barrier property.
• PA examples include polycaproamide (nylon 6), poly- ⁇ -aminoheptanoic acid (nylon 7), poly- ⁇ -aminononanoic acid (nylon 9), polyundecaneamide (nylon 11), polylauryl lactam (nylon 12), polyethylenediamineadipamide (nylon 26), polytetramethyleneadipamide (nylon 46), polyhexamethyleneadipamide (nylon 66), polyhexamethylenesebacamide (nylon 610), polyhexamethylenedodecamide (nylon 612), etc.
• polyoctamethylene adipamide (nylon 86), polydecamethylene adipamide (nylon 106), caprolactam/lauryl lactam copolymer (nylon 6/12), caprolactam/ ⁇ -aminononanoic acid copolymer (nylon 6/9), caprolactam/hexamethylene diammonium adipate copolymer (nylon 6/66), lauryl lactam/hexamethylene diammonium adipate copolymer (nylon 12/66), ethylenediammonium adipate/hexamethylene diammonium ammonium adipate copolymer (nylon 26/66), caprolactam/hexamethylenediammonium adipate/hexamethylenediammonium sebacate copolymer (nylon 6/66/610), ethylenediammonium adipate/hexamethylenediammonium adipate/hexamethylenediammonium sebac
• Meta xylylene diammonium adipate is also included.
• the PA is preferably nylon 6/66 or nylon 6 because of its excellent economical efficiency, melt moldability, and mechanical properties, and more preferably nylon 6/66 from the viewpoint of recyclability of the multilayer film.
• the vinyl alcohol resin may be a polymer in which the content (mol %) of vinyl alcohol units relative to the total monomer units exceeds 50 mol %.
• vinyl alcohol resins include polyvinyl alcohol (hereinafter sometimes abbreviated as "PVA") and ethylene-vinyl alcohol copolymer (EVOH).
• PVA polyvinyl alcohol
• EVOH ethylene-vinyl alcohol copolymer
• the vinyl alcohol resin is preferably EVOH, and in particular, from the viewpoint of being able to enhance gas barrier properties, melt moldability, and recyclability in a particularly balanced manner, EVOH with an ethylene unit content of 20 to 50 mol % and a saponification degree of 90 mol % or more is more preferable.
• PVA is a polymer obtained by saponifying polyvinyl ester, which is usually obtained by polymerizing vinyl ester.
• the viscosity average degree of polymerization of the PVA is preferably 400 or more and 2000 or less.
• the lower limit of the viscosity average degree of polymerization is more preferably 500, and even more preferably 700.
• the upper limit of the viscosity average degree of polymerization is more preferably 1500, and even more preferably 1000. When the viscosity average degree of polymerization is equal to or less than the upper limit, the melt moldability of the PVA is improved.
• the saponification degree of PVA is preferably 70 mol% or more, more preferably 75 mol% or more, and even more preferably 85 mol% or more.
• the saponification degree of PVA means the ratio of the number of vinyl alcohol units to the total number of vinyl alcohol units and vinyl ester units in the PVA.
• the saponification degree of PVA is preferably 95 mol% or less, more preferably 93 mol% or less, and even more preferably 90 mol% or less.
• the saponification degree of PVA is measured in accordance with JIS K6726 (1994).
• the total content of vinyl alcohol units and vinyl ester units in all monomer units constituting the PVA is preferably 95 mol% or more.
• the total content of vinyl alcohol units and vinyl ester units is more preferably 97 mol% or more, even more preferably 98 mol% or more, and particularly preferably 99 mol% or more.
• PVA may contain monomer units other than vinyl alcohol units and vinyl ester units, so long as the effects of the present invention are not impaired.
• monomers include ⁇ -olefins such as ethylene units, propylene, n-butene, and isobutylene; acrylic acid and its salts; acrylic acid esters; methacrylic acid and its salts; methacrylic acid esters; acrylamide; acrylamide derivatives such as N-methylacrylamide, N-ethylacrylamide, N,N-dimethylacrylamide, diacetone acrylamide, acrylamidopropanesulfonic acid and its salts, acrylamidopropyldimethylamine and its salts or its quaternary salts, and N-methylolacrylamide and its derivatives; methacrylamide; N-methylmethacrylamide, N-ethylmethacrylamide, methacrylamidepropanesulfonic acid and its salts, methacrylamidepropyldimethylamine and its salts or its
• Examples of the monomer include methacrylamide derivatives such as methylol methacrylamide and its derivatives; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, dodecyl vinyl ether, and stearyl vinyl ether; nitriles such as acrylonitrile and methacrylonitrile; vinyl halides such as vinyl chloride and vinyl fluoride; vinylidene halides such as vinylidene chloride and vinylidene fluoride; allyl compounds such as allyl acetate and allyl chloride; unsaturated dicarboxylic acids and their salts or esters such as maleic acid, itaconic acid, and fumaric acid; vinyl silyl compounds such as vinyltrimethoxysilane; and isopropenyl acetate
• the content of these monomers varies depending on the purpose and application of use, but is preferably 10 mol% or less, more preferably less than 5 mol%, even more preferably less than 1 mol%, particularly preferably less than 0.5 mol%, and may be 0 mol%.
• One type of PVA may be contained alone, or two or more types may be contained.
• EVOH is a polymer obtained by saponifying an ethylene-vinyl ester copolymer, which is usually obtained by polymerizing ethylene and a vinyl ester.
• the ethylene unit content of EVOH is preferably 20 to 50 mol%.
• the ethylene unit content is preferably 23 mol% or more, more preferably 26 mol% or more, and may be 29 mol% or more, 32 mol% or more, 35 mol% or more, or 38 mol% or more.
• the gas barrier property of the multilayer film of the present invention is improved.
• the ethylene unit content is preferably 46 mol% or less, more preferably 42 mol% or less, and may be 38 mol% or less, 34 mol% or less, or 30 mol% or less.
• the ethylene unit content is the content (mol%) of ethylene units relative to the total monomer units constituting EVOH.
• the saponification degree of EVOH is preferably 90 mol% or more.
• the saponification degree of EVOH means the ratio of the number of vinyl alcohol units to the total number of vinyl alcohol units and vinyl ester units in EVOH.
• the saponification degree is preferably 95 mol% or more, more preferably 99 mol% or more, and even more preferably 99.9 mol% or more.
• the upper limit of the saponification degree of EVOH may be 100 mol%.
• the ethylene unit content and saponification degree of EVOH are determined by 1 H-NMR measurement.
• EVOH may be a mixture of two or more types of EVOH with different ethylene unit contents.
• the difference in ethylene unit content between the EVOH with the most different ethylene unit contents is preferably 30 mol% or less, more preferably 20 mol% or less, even more preferably 15 mol% or less, and may be 3 mol% or more.
• EVOH may be a mixture of two or more types of EVOH with different saponification degrees.
• the difference in saponification degree between the EVOH with the most different ethylene unit contents is preferably 7 mol% or less, more preferably 5 mol% or less, and may be 0.5 mol% or more.
• thermoformability and gas barrier properties it is preferable to use a mixture of EVOH (less than 34 mol%) having an ethylene unit content of 24 mol% or more and less than 34 mol% and a saponification degree of 99 mol% or more, and EVOH (34 mol% or more) having an ethylene unit content of 34 mol% or more and less than 50 mol% and a saponification degree of 99 mol% or more, in a blending mass ratio (less than 34 mol%/34 mol% or more) of 60/40 to 90/10.
• the EVOH may be EVOH having a melting point of 150°C or more and less than 190°C, or may be EVOH having a melting point less than 150°C.
• the melting point of EVOH is less than 150°C, the appearance and interlayer adhesion of a multilayer film having the layer (X) as the outermost layer may be improved.
• the reason for this is that the melting point of EVOH is less than 150°C, which improves the fluidity of the polymer chain, and therefore, during secondary processing such as melt molding and stretching, stress can be effectively relieved even at a relatively low temperature, and the adhesive reaction activity with adjacent layers can be maintained.
• the melting point of EVOH is preferably less than 140°C, more preferably less than 130°C, and may be less than 125°C or less than 120°C.
• the melting point of EVOH is preferably 80°C or more, more preferably 90°C or more, and even more preferably 100°C or more.
• the melting point of EVOH can be controlled by any one of the following methods or by a combination of two or more of them. In the present invention, the following method (3) can be preferably used.
• the primary hydroxyl group-containing modifying group used in (3) above is preferably a primary hydroxyl group-containing modifying group represented by the following general formula (I).
• the degree of melting point reduction per introduction rate of the modifying group varies depending on the structure of the primary hydroxyl group-containing modifying group to be introduced, but the melting point generally decreases by about 6 to 9°C when 1 mol% of the primary hydroxyl group-containing modifying group represented by the following general formula (I) is introduced.
• the melting point When the melting point is controlled in this way, the melting point can be reduced while relatively maintaining the gas barrier properties and thermal stability, and the decrease in interlayer adhesion with the layer (Y) and inorganic vapor deposition layer (I) described later is also suppressed, so that a multilayer film with particularly excellent quality and performance can be provided.
• the reasons for this are thought to be that the melting point can be reduced while maintaining the amount of hydroxyl groups, and that the primary hydroxyl group has high adhesive reaction activity with the layer (Y) and inorganic vapor deposition layer (I) described later.
• the content of the modifying group containing a primary hydroxyl group in EVOH may be appropriately adjusted in consideration of the balance between the melting point and various physical properties, but in many cases, a content of 2 mol% or more and less than 20 mol% will provide a good balance of physical properties.
• the lower limit of the content of the modifying group containing a primary hydroxyl group in EVOH is more preferably 3 mol%.
• the upper limit of the content of the modifying group containing a primary hydroxyl group in EVOH is more preferably 10 mol%, and even more preferably 8 mol%.
• the modifying group containing a primary hydroxyl group can be introduced by copolymerization or polymer reaction.
• the "content of the modifying group containing a primary hydroxyl group in EVOH" may be the content (mol%) of the monomer unit containing a primary hydroxyl group relative to the total monomer units constituting EVOH.
• X is preferably a hydrogen atom or a group represented by R 2 -OH, more preferably a hydrogen atom.
• R 1 is preferably a single bond, an alkylene group having 1 to 5 carbon atoms, or an alkyleneoxy group having 1 to 5 carbon atoms, more preferably a methylmethyleneoxy group (-O-C(CH 3 )H)-).
• R 1 is an alkyleneoxy group, the oxygen atom of the alkyleneoxy group is usually bonded to a carbon atom of the main chain.
• EVOH may contain other monomer units other than ethylene units, vinyl ester units, vinyl alcohol units, and the modifying group containing the primary hydroxyl group, so long as the effects of the present disclosure are not impaired.
• the content of other monomer units is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 1% by mass or less, and it is particularly preferable that they are not substantially contained.
• acyloxy-1-hexene 5-acyloxy-1-hexene, 6-acyloxy-1-hexene, 5,6-diacyloxy-1-hexene, 1,3-diacetoxy-2-methyl-1-butene, 3,4-diacyloxy-2-methyl-1-butene, 4-acyloxy-1-pentene, 5-acyloxy-1-pentene, 4,5-diacyloxy-1-pentene, 4-acyloxy-1-hexene, 5-acyloxy-1-hexene, 6-acyloxy-1-hexene, 5,6-diacyloxy-1-hexene, 1,3-diacetoxy-2-methyl alkenes having an ester group such as olefin propane or saponified products thereof; unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, or the like, or their anhydrides, salts, or mono- or dialkyl esters; nitriles such
• EVOH may be post-modified by methods such as urethane conversion, acetalization, cyanoethylation, and oxyalkylenation.
• the MFR (190°C, under a load of 2.160 kg) of EVOH measured in accordance with JIS K7210-1 (2014) is preferably 0.2 to 20 g/10 min.
• the MFR of EVOH is more preferably 0.5 g/10 min or more, and even more preferably 0.8 g/10 min or more.
• the MFR of EVOH is more preferably 15 g/10 min or less, even more preferably 10 g/10 min or less, even more preferably 5 g/10 min or less, and particularly preferably 3 g/10 min or less.
• the proportion of EVOH in the gas barrier resin (a) is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, and it is particularly preferable that the gas barrier resin (a) is EVOH.
• the gas barrier resin (a) may be used alone or in combination of two or more types.
• the gas barrier resin (a) is preferably the main component in the layer (X). By having the gas barrier resin (a) as the main component of the layer (X), the gas barrier properties of the multilayer film are further improved.
• the lower limit of the content of the gas barrier resin (a) in the layer (X) is preferably 70% by mass, more preferably 80% by mass, even more preferably 90% by mass, even more preferably 95% by mass, and particularly preferably 97% by mass.
• the upper limit of the content of the gas barrier resin (a) in the layer (X) is preferably 99.8% by mass, more preferably 99.5% by mass, and even more preferably 99.0% by mass.
• the MFR of the polyolefin (b) is preferably 5 g/10 min or more, more preferably 10 g/10 min or more, even more preferably 50 g/10 min or more, particularly preferably 100 g/10 min or more, and may be 130 g/10 min or more, 170 g/10 min or more, or 180 g/10 min or more. Since the accuracy of the MFR decreases when it exceeds 1000 g/10 min for convenience of measurement, in this specification, when the MFR exceeds 1000 g/10 min, the melt viscosity is defined by a different measurement method (BL type viscometer). When the MFR of polyolefin (b) is 1000 g/10 min or less, the MFR of polyolefin (b) may be 1000 g/10 min or less, 500 g/10 min or less, or 300 g/10 min or less.
• Polyolefin (b) may be a polymer having an olefin unit content (mol%) of more than 50 mol% relative to all monomer units.
• the lower limit of the olefin unit content relative to all monomer units in polyolefin (b) is preferably 60 mol%, more preferably 70 mol%, even more preferably 75 mol%, even more preferably 80 mol%, and may be 85 mol%, 90 mol%, or 92 mol%.
• the upper limit of the olefin unit content relative to all monomer units in polyolefin (b) may be 100 mol%, or may be 99 mol%, 98 mol%, 97 mol%, or 96 mol%.
• the ethylene unit content is preferably 75 mol% or more and 98 mol% or less from the viewpoint of suppressing die build-up.
• the ethylene unit content of EVA or a saponified product thereof is more preferably 85 mol% or more and 96 mol% or less.
• the ethylene unit content of EVA or a saponified product thereof is determined by 1 H-NMR measurement.
• the saponification degree is preferably 30 mol% or more, more preferably 50 mol% or more, even more preferably 70 mol% or more, and particularly preferably 85 mol% or more, from the viewpoint of suppressing die build-up.
• the saponification degree is preferably 99 mol% or less.
• the saponification degree of the saponified EVA is determined by 1 H-NMR measurement.
• the MFR of polyolefin (b) is greater than 1000 g/10 min. That is, when polyolefin (b) is polyethylene, the melt viscosity of polyolefin (b) measured at 140°C with a BL type viscometer is preferably 300 to 10,000 mPa ⁇ s, more preferably 1500 to 8,000 mPa ⁇ s, and even more preferably 3,000 to 6,000 mPa ⁇ s.
• the resin composition (A) contains 0.1 parts by mass or more and 20 parts by mass or less of polyolefin (b) per 100 parts by mass of gas barrier resin (a).
• the content of the polyolefin (b) is preferably 12 parts by mass or less, more preferably 8 parts by mass or less, even more preferably 5 parts by mass or less, and may be 4 parts by mass or less or 3 parts by mass or less.
• the content of the polyolefin (b) is preferably 0.5 parts by mass or more, more preferably 1.0 part by mass or more.
• the die build-up tends to be further suppressed.
• the resin composition (A) preferably contains 40 to 500 ppm of alkali metal ion (c).
• the resin composition (A) contains the alkali metal ion (c) in the above range, the interlayer adhesion with the layer (Y) described later tends to be significantly improved.
• the alkali metal ion (c) is 40 ppm or more, the recyclability tends to be improved.
• the content of the alkali metal ion (b) is 500 ppm or less, the recyclability and the hue of the recovered composition tend to be good.
• the lower limit of the content of the alkali metal ion (c) is more preferably 80 ppm, and more preferably 120 ppm.
• the upper limit of the content of the alkali metal ion (c) is more preferably 400 ppm, and more preferably 300 ppm.
• the melt moldability and coloring resistance of the obtained resin composition (A) can be further improved.
• alkali metal ion (c) examples include ions of lithium, sodium, potassium, rubidium, cesium, etc., but from the viewpoint of industrial availability, sodium or potassium ions are preferred. These ions may be used alone or in combination of two or more.
• alkali metal compounds that provide the alkali metal ion (c) include aliphatic carboxylates, aromatic carboxylates, carbonates, hydrochlorides, nitrates, sulfates, phosphates, hydroxides, metal complexes, etc., of alkali metals such as lithium, sodium, and potassium.
• alkali metals such as lithium, sodium, and potassium.
• aliphatic carboxylates and phosphates are more preferred because they are easy to obtain and handle.
• aliphatic carboxylates acetates, caprylates, and stearates are preferred.
• the resin composition (A) preferably contains 20 ppm or more and 2000 ppm or less of at least one polyvalent metal ion (d) selected from the group consisting of magnesium ions, calcium ions, and zinc ions.
• d polyvalent metal ion
• the lower limit of the polyvalent metal ion (d) is more preferably 40 ppm, more preferably 100 ppm, and particularly preferably 150 ppm.
• the upper limit of the polyvalent metal ion (d) is more preferably 1500 ppm, more preferably 1000 ppm, particularly preferably 500 ppm, and may be 300 ppm.
• the resin composition (A) preferably contains magnesium ions or calcium ions as the polyvalent metal ions (d), and more preferably contains calcium ions from the viewpoint of easily maintaining the quality of the resin composition (A) and from the viewpoint of coloring of the recovered composition.
• the melt moldability and coloring resistance of the obtained resin composition (A) can be further improved.
• polyvalent metal compounds that provide the polyvalent metal ion (d) include aliphatic carboxylates, aromatic carboxylates, carbonates, hydrochlorides, nitrates, sulfates, phosphates, hydroxides, metal complexes, etc. of magnesium, calcium, and zinc.
• aliphatic carboxylates and hydroxides are more preferred because they are easy to obtain and handle.
• aliphatic carboxylates acetates, caprylates, and stearates are preferred.
• the resin composition (A) preferably contains 100 to 25,000 ppm of a higher aliphatic carboxylic acid (e) having 8 to 30 carbon atoms.
• the higher aliphatic carboxylic acid (e) may be contained in part or in whole in the form of a salt, or may be contained as a salt of an alkali metal ion (c) or a polyvalent metal ion (d).
• the higher aliphatic carboxylic acid (e) is preferably caprylic acid or stearic acid.
• the multilayer film of the present invention has a layer (X) made of the resin composition (A) as the outermost layer, and it is considered that the higher aliphatic carboxylic acid (e) acts as a lubricant with the die metal surface in the die, thereby suppressing the occurrence of poor appearance due to uneven thickness of the multilayer film and gels and bumps due to retained resin.
• the resin composition (A) preferably contains 100 ppm or more of the higher aliphatic carboxylic acid (e).
• the content of the higher aliphatic carboxylic acid (e) is 25,000 ppm or less, thickening during melt molding of the resin composition (A) tends to be suppressed, and interlayer adhesion with the layer (Y) described below tends to be maintained. From these viewpoints, the content of the higher aliphatic carboxylic acid (e) is more preferably 200 to 20,000 ppm, and even more preferably 300 to 15,000 ppm.
• the resin composition (A) may contain other components other than the gas barrier resin (a), polyolefin (b), alkali metal ion (c), polyvalent metal ion (d) and higher aliphatic carboxylic acid (e) as long as the effect of the present invention is not impaired.
• alkaline earth metal ions and transition metal ions other than polyvalent metal ions include alkaline earth metal ions and transition metal ions other than polyvalent metal ions (d), carboxylic acids (monocarboxylic acids, polyvalent carboxylic acids) other than higher aliphatic carboxylic acids (e), thermoplastic resins other than the gas barrier resin (a) and polyolefin (b), phosphoric acid compounds, boron compounds, oxidation promoters, antioxidants (hindered phenol compounds, etc.), plasticizers, heat stabilizers (melt stabilizers), photoinitiators, deodorants, ultraviolet absorbers, antistatic agents, lubricants, colorants, fillers, drying agents, bulking agents, pigments, dyes, processing aids, flame retardants, antifogging agents, surfactants, crosslinking agents, fiber reinforcements, etc.
• d alkaline earth metal ions and transition metal ions other than polyvalent metal ions
• carboxylic acids monocarboxylic acids, polyvalent
• the melt viscosity of the resin composition (A) and the pulverized product of the multilayer film or multilayer structure containing the resin composition (A) can be controlled.
• the resin composition (A) preferably contains a carboxylic acid other than the higher aliphatic carboxylic acid (e).
• 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 carboxylic acid content is 50 ppm or more, the coloring resistance tends to be good.
• the carboxylic acid content is 400 ppm or less, the interlayer adhesion tends to be 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 ability of the resulting resin composition (A) is increased, further improving the melt moldability and further improving the coloring caused by acidic or basic substances.
• the carboxylic acid may be a monocarboxylic acid. These may be used alone or in combination of two or more.
• These carboxylic acids may further have a substituent such as a hydroxyl group, an amino group, or a halogen atom. Among these, acetic acid is preferred because of its high safety and ease of availability and handling.
• the carboxylic acid may be a polycarboxylic acid.
• the carboxylic acid is a polycarboxylic acid
• the color resistance of the resin composition (A) at high temperatures and the color resistance of the melt-molded product of the crushed product of the resulting multilayer structure may be further improved.
• the polycarboxylic acid compound has three or more carboxyl groups. In this case, color resistance may be more effectively improved.
• a polycarboxylic acid is a compound having two or more carboxyl groups in the molecule.
• the pKa of at least one carboxyl group is in the range of 3.5 to 5.5
• 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 radicals.
• the upper limit of the content of the phosphoric acid compound is preferably 100 ppm in terms of phosphoric acid radicals.
• the phosphate compound various acids such as phosphoric acid and phosphorous acid and their salts can be used.
• the phosphate may be any of primary phosphate, secondary phosphate, and tertiary phosphate.
• the cationic species of the phosphate is not particularly limited, but the cationic species is preferably an alkali metal or an alkaline earth metal.
• the phosphate compound is preferably sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, and dipotassium hydrogen phosphate.
• the resin composition (A) may further contain a boron compound.
• 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.
• the drawdown resistance and neck-in resistance during film formation may be improved, and the mechanical properties of the resulting molded product may be improved. It is speculated that these effects are due to the occurrence of a chelate interaction between the gas barrier resin (a) such as EVOH and the boron compound.
• boron compounds include boric acid, boric acid esters, borate salts, and boron hydrides.
• Specific examples include boric acids such as orthoboric acid ( H3BO3 ), metaboric acid, and tetraboric acid; boric acid esters such as trimethyl borate and triethyl borate; alkali metal salts or alkaline earth metal salts of the boric acid, and borate salts such as borax.Of these, orthoboric acid is preferred.
• the resin composition (A) may further contain a hindered phenol-based compound as an antioxidant.
• a hindered phenol-based 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 phenol-based compound is more preferably 2000 ppm or more.
• the content of the hindered phenol-based compound is 10000 ppm or less, coloring and bleed-out derived from the hindered phenol-based compound can be suppressed.
• the content of the hindered phenol-based compound is more preferably 8000 ppm or less.
• Hindered phenol compounds have at least one hindered phenol group.
• a hindered phenol group is one in which a bulky substituent is bonded to at least one of the carbons adjacent to the carbon to which the phenol hydroxyl group is bonded.
• the bulky substituent an alkyl group having 1 to 10 carbon atoms is preferred, and a t-butyl group is more preferred.
• the hindered phenol compound is preferably in a solid state at about room temperature.
• the melting point or softening temperature of the hindered phenol compound is preferably 50°C or higher, more preferably 60°C or higher, and even more preferably 70°C or higher.
• the molecular weight of the hindered phenol compound is preferably 200 or higher, more preferably 400 or higher, and even more preferably 600 or higher. Meanwhile, the molecular weight is usually 2000 or lower.
• the melting point or softening temperature of the hindered phenol compound is preferably 200°C or lower, more preferably 190°C or lower, and even more preferably 180°C or lower.
• hindered phenol compounds having an ester bond or an amide bond include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] available commercially as Irganox 1010 from BASF, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)stearyl propionate available commercially as Irganox 1076, 2,2'-thiodiethylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] available commercially as Irganox 1035, and 2,2'-thiodiethylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] available commercially as Irganox 1135.
• tertiary esters examples include octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate, available commercially under the trade name Irganox 245; ethylene bis(oxyethylene)bis(3-tert-butyl-4-hydroxy-5-methylbenzenepropanoate), available commercially under the trade name Irganox 245; 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], available commercially under the trade name Irganox 259; and N,N'-hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanamide], available commercially under the trade name Irganox 1098.
• 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, even more preferably less than 10% by mass, and may be less than 5% by mass or less than 1% by mass, and is particularly preferably substantially absent.
• the total mass ratio of the gas barrier resin (a) and polyolefin (b) in the resin constituting the resin composition (A) is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more, from the viewpoint of suppressing die build-up.
• the resin constituting the resin composition (A) may be substantially only the gas barrier resin (a) and polyolefin (b), or the resin constituting the resin composition (A) may be only the gas barrier resin (a) and polyolefin (b).
• the total mass ratio of the gas barrier resin (a) and polyolefin (b) in the resin composition (A) is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass, even more preferably 90% by mass or more, particularly preferably 95% by mass or more, and may be 98% by mass or more, or 99% by mass or more, from the viewpoint of suppressing die build-up.
• the resin composition (A) preferably has a weight loss W of 0.01 to 0.3% when held at 200°C for 30 minutes in a nitrogen atmosphere. This reflects the low molecular weight components contained in the resin composition (A) and the decomposition characteristics of the gas barrier resin (a) and polyolefin (b) due to heat, and since the layer (X) is made of the resin composition (A) that satisfies the specific TG conditions, a multilayer film with excellent appearance characteristics can be stably produced over a long period of time.
• the weight loss W when held at 200°C for 30 minutes in a nitrogen atmosphere is preferably 0.02 to 0.15%, more preferably 0.03 to 0.10%, and even more preferably 0.04 to 0.08%.
• W can be controlled by the ethylene unit content and saponification degree when the gas barrier resin (a) is EVOH, the type and content of polyolefin (b), alkali metal ion (c), polyvalent metal ion (d), higher aliphatic carboxylic acid (e) and other components contained in the resin composition (A), and the manufacturing conditions (particularly thermal history such as temperature and time) when manufacturing the resin composition (A).
• the weight loss W tends to be small by performing melt kneading while removing gas components using a vent device or the like.
• the multilayer film of the present invention has at least one layer different from the layer (X). Among them, it is preferable to have a layer (Y) containing an adhesive resin (B) having a melting point of less than 170° C. as a main component.
• a layer (Y) containing an adhesive resin (B) having a melting point of less than 170° C. as a main component.
• the multilayer film of the present invention contains the layer (Y)
• the compatibility between the layer (X) and the layer (Z) described later is improved during recycling, so that the recyclability tends to be improved.
• the adhesive resin (B) examples include an acid-modified polyolefin resin obtained by graft-polymerizing an unsaturated carboxylic acid or its derivative, such as maleic anhydride, to a polyolefin resin.
• the melting point of the adhesive resin (B) mainly depends on the polyolefin resin before acid modification.
• the contents described for the unmodified polyolefin resin (C) described later can be applied as is to the polyolefin resin, but the adhesive resin (B) is preferably an acid-modified polyethylene or an acid-modified polypropylene.
• the acid-modified polyolefin resin may be a carboxylic acid-modified polyolefin resin.
• the acid-modified polyethylene may be a carboxylic acid-modified polyethylene
• the acid-modified polypropylene may be a carboxylic acid-modified polypropylene.
• the multilayer film of the present invention preferably has a layer (Z) containing as a main component a polyolefin resin (C) having a melting point of less than 170° C.
• the polyolefin resin (C) is not particularly limited as long as it is a polyolefin having a melting point of less than 170° C., and examples thereof include polyethylene-based resins such as linear low-density polyethylene, low-density polyethylene, medium-density polyethylene, and high-density polyethylene; polypropylene-based resins such as homopolypropylene, random polypropylene, and block polypropylene; vinyl ester resins; ethylene-propylene copolymers; propylene- ⁇ -olefin copolymers ( ⁇ -olefins having 4 to 20 carbon atoms); olefins such as polybutene and polypentene, or copolymers thereof; and chlorinated polyethylene.
• the lower limit of the content of olefin units relative to all monomer units in polyolefin resin (C) is preferably 60 mol%, more preferably 70 mol%, even more preferably 80 mol%, even more preferably 90 mol%, and may be 95 mol%, 98 mol%, 99 mol% or 99.9 mol%.
• the upper limit of the content of olefin units relative to all monomer units in polyolefin resin (C) may be 100 mol%.
• Polyolefin resin (C) may be modified, such as by acid modification, or may be unmodified, but is preferably unmodified.
• polyolefin resin (C) preferably contains a polyethylene-based resin or a polypropylene-based resin as a main component, more preferably polyethylene or polypropylene, and even more preferably polyethylene.
• Polyethylene-based resins and polypropylene-based resins are widely used in packaging materials regardless of whether they have gas barrier properties, and therefore recycling infrastructures for them are widely established in various countries.
• polyethylene is preferably at least one selected from linear low-density polyethylene, low-density polyethylene, medium-density polyethylene, and high-density polyethylene, and more preferably 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.
• the melting point of the polyolefin resin (C) is preferably less than 160°C, more preferably less than 150°C, and may be less than 140°C or less than 130°C.
• the melting point of the polyolefin resin (C) is preferably 80°C or higher, more preferably 90°C or higher.
• melt flow rate (MFR) (190°C, under a load of 2.160 kg) of the polyolefin resin (C) measured in accordance with the method described in JIS K7210-1 (2014) is preferably 0.1 to 30 g/10 min, more preferably 0.3 to 25 g/10 min, and even more preferably 0.5 to 20 g/10 min.
• 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, and even more preferably 95% by mass or more, and the layer (Z) may be substantially composed of only the polyolefin resin (C), or the layer (Z) may be substantially composed of only the polyolefin resin (C).
• the total amount of these components is less than 50% by mass for each layer, preferably less than 40% by mass, more preferably less than 30% by mass, even more preferably less than 20% by mass, and particularly preferably less than 10% by mass, and may be less than 5% by mass, less than 3% by mass, or less than 1% by mass.
• the multilayer film of the present invention has a layer (X) as the outermost layer and at least one layer different from the layer (X).
• the layer different from the layer (X) is not particularly limited, but is preferably at least one type selected from the group consisting of layers (Y) and layers (Z).
• the multilayer film more preferably has a structure in which layers (X), (Y) and (Z) are laminated adjacent to each other in this order.
• the multilayer film may have a plurality of layers (X), (Y) and (Z). When there are a plurality of layers (X), it is sufficient that there is at least one layer (X) located at the outermost layer. That is, when there are a plurality of layers (X), there may be a layer (X) that is not located at the outermost layer.
• the multilayer film of the present invention may have layers other than the layer (X), the layer (Y) and the layer (Z). However, as one embodiment of the present invention, the multilayer film of the present invention may not have layers other than the layer (X), the layer (Y) and the layer (Z).
• the layer structure of the multilayer film of the present invention may be X/Y/Z, X/Y/Z/Y/X, X/Y/Z/Y/X/Y/Z, X/Y/Z/Y/X/Y/Z, X/Y/Z/Y/X/Y/Z/Y/X, etc., where X represents layer (X), Y represents layer (Y), and Z represents layer (Z), with "/" indicating that the layers are directly laminated.
• the average thickness of layer (Y) in the multilayer film is preferably 0.2 ⁇ m or more and less than 20 ⁇ m. It is also preferable that the ratio of the average thickness of layer (Y) to the average thickness of the multilayer film is less than 25%.
• the average thickness of layer (Y) is more preferably 0.4 ⁇ m or more and less than 16 ⁇ m, and even more preferably 0.6 ⁇ m or more and less than 12 ⁇ m.
• the ratio of the average thickness of layer (Y) to the average thickness of the multilayer film is more preferably less than 20%, and even more preferably less than 15%.
• the ratio of the average thickness of layer (Y) to the average thickness of the multilayer film may be 1% or more. When multiple layers (Y) are present, the average thickness of layer (Y) is the sum of the average thicknesses of the layers (Y).
• the average thickness of the layer (Z) in the multilayer film is preferably 1 ⁇ m or more and less than 200 ⁇ m. It is also preferable that the ratio of the average thickness of the layer (Z) to the average thickness of the multilayer film is more than 55%.
• the average thickness of the layer (Z) is more preferably 5 ⁇ m or more, even more preferably 10 ⁇ m or more, and may be 20 ⁇ m or more.
• the average thickness of the layer (Z) is more preferably 100 ⁇ m or less, and may be 50 ⁇ m or less.
• the ratio of the average thickness of the layer (Z) to the average thickness of the multilayer film is more preferably more than 60%, and even more preferably more than 70%.
• the ratio of the average thickness of the layer (Z) to the average thickness of the multilayer film may be 98% or less.
• the average thickness of the layer (Z) is the sum of the average thicknesses of the layers (Y).
• the average thickness of the multilayer film is preferably 10 ⁇ m or more and less than 200 ⁇ m, and more preferably 10 ⁇ m or more and less than 150 ⁇ m.
• the average thickness of the stretched multilayer film is preferably 10 ⁇ m or more and less than 50 ⁇ m, and more preferably 10 ⁇ m or more and less than 40 ⁇ m.
• the multilayer film may be an unstretched multilayer film, or may be a stretched multilayer film stretched uniaxially or biaxially (at least uniaxially).
• An unstretched multilayer film means a multilayer film that is not stretched, but some orientation during film formation (for example, orientation as if stretched 1.01 times) is considered to be unstretched.
• a uniaxially stretched multilayer film that is stretched only in a uniaxial direction is considered to be uniaxially stretched, ignoring some orientation in the other axial direction during film formation (for example, orientation as if stretched 1.01 times).
• an unstretched multilayer film it has excellent impact resistance and can be suitably used as a heat-sealed film.
• the multilayer film is preferably a uniaxially stretched multilayer film, and from the viewpoint of obtaining a film with little anisotropy in mechanical properties and a strong film, the multilayer film is preferably a biaxially stretched multilayer film. From the viewpoint of uniformity of thickness and mechanical strength of the obtained multilayer film, it is preferable that the multilayer film is stretched at least 3 times and less than 12 times in one axial direction.
• total average thickness of layers mainly composed of polyethylene resin or polypropylene resin refers to the average thickness of the total of layers mainly composed of polyethylene resin and layers mainly composed of polypropylene resin.
• layers mainly composed of polyethylene-based resin or polypropylene-based resin include layer (Y) when adhesive resin (B) is, for example, acid-modified polyethylene or acid-modified polypropylene, and layer (Z) when polyolefin resin (C) is polyethylene or polypropylene. It is preferable that adhesive resin (B) and polyolefin resin (C) are the same type of resin.
• the multilayer film of the present invention preferably does not have a layer containing as its main component a resin having a melting point of 200°C or higher, and a metal layer having an average thickness of 1 ⁇ m or higher.
• a layer containing as its main component a resin having a melting point of 200°C or higher, and a metal layer having an average thickness of 1 ⁇ m or higher it is possible to prevent uneven mixing with other components when the pulverized product of the multilayer film or multilayer structure is melt-molded.
• the metal layer here refers to a layer having continuous and discontinuous surfaces made of metal, such as aluminum foil.
• the method for stretching in the uniaxial or biaxial direction is also not particularly limited, and the film can be produced by stretching in the flow direction and/or the direction perpendicular to the flow direction, i.e., in the width direction, using a conventionally known stretching method such as roll-type uniaxial stretching, tenter-type uniaxial stretching, tubular-type simultaneous biaxial stretching, tenter-type sequential biaxial stretching, and tenter-type simultaneous biaxial stretching.
• the tenter-type sequential biaxial stretching may use a tenter type for both axes, or may be a combination of roll-type stretching and tenter-type stretching.
• the effect of the present invention is particularly remarkable in the case of a multilayer film produced by tenter-type sequential biaxial stretching, which is a combination of roll-type stretching and tenter-type stretching.
• the temperature during stretching is usually 40 to 170° C., and more preferably 50 to 160° C. If necessary, it is preferable to carry out a so-called heat setting operation by heating the film after stretching at a temperature equal to or higher than the glass transition point and lower than the melting point to increase the crystallinity and fix the orientation of the molecular chains.
• the method for producing a multilayer film preferably includes a step of melt-kneading the gas barrier resin (a) and the polyolefin (b) to obtain pellets of the resin composition (A), and a step of melt-molding the pellets of the resin composition (A) to form the layer (X).
• the specific method for obtaining the pellets of the resin composition (A) is as described above.
• the vapor-deposited multilayer film of the present invention includes the multilayer film of the present invention and an inorganic vapor-deposited layer (I) laminated on the surface of the layer (X) of the multilayer film. That is, the multilayer film of the present invention may be used by laminating the inorganic vapor-deposited layer (I) on the surface of the layer (X).
• the inorganic vapor-deposited layer (I) is preferably laminated on the surface of the layer (X) of the multilayer film directly or via another layer such as an adhesive layer, and is preferably laminated directly on the surface of the layer (X).
• the inorganic vapor-deposited layer (I) is made of an inorganic substance such as a metal or an inorganic oxide, and is a layer having gas barrier properties 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-deposited layer (I), and the interlayer adhesion between the layer (X) and the inorganic vapor-deposited layer (I) in the obtained vapor-deposited multilayer film is good.
• the layer (X) since the layer (X) has gas barrier properties, even when defects occur in the inorganic vapor-deposited layer (I) due to bending or the like, the deterioration of the gas barrier properties can be suppressed.
• the inorganic vapor deposition layer (I) generally has an average thickness of less than 500 nm.
• the average thickness is less than 500 nm, the viscosity stability is excellent when the pulverized product of the vapor deposition multilayer film or multilayer structure containing the inorganic vapor deposition layer (I) is melt-molded, and the generation of gels and lumps can be suppressed.
• the inorganic oxide deposition layer may be an inorganic oxide, such as an oxide of silicon, aluminum, magnesium, calcium, potassium, tin, sodium, boron, titanium, lead, zirconium, yttrium, or the like, preferably an alumina or silica deposition film.
• the average thickness of the inorganic oxide deposition layer is preferably 60 nm or less, more preferably 50 nm or less, and even more preferably 40 nm or less.
• the average thickness of the inorganic oxide deposition layer is preferably 10 nm or more, more preferably 15 nm or more, and even more preferably 20 nm or more.
• One way to further suppress uneven thickness of the multilayer film is, for example, to stretch it in at least one axial direction.
• the light transmittance of the vapor-deposited multilayer film 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 include vacuum vapor deposition, sputtering, ion plating, ion beam mixing, plasma CVD, laser CVD, MO-CVD, and thermal CVD. Physical vapor deposition is preferred, and vacuum vapor deposition is particularly preferred.
• the upper limit of the surface temperature of layer (X) during the formation of inorganic vapor deposition layer (I) is preferably 60°C, more preferably 55°C, and even more preferably 50°C.
• the lower limit of the surface temperature of layer (X) during the formation of inorganic vapor deposition layer (I) is not particularly limited, but is preferably 0°C, more preferably 10°C, and even more preferably 20°C.
• the exposed surface of layer (X) may be plasma-treated.
• the plasma treatment can be performed by a known method, and atmospheric pressure plasma treatment is preferred.
• nitrogen, helium, neon, argon, krypton, xenon, radon, etc. are used as discharge gas.
• nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferred because it can reduce costs.
• the flex resistance may be improved by providing a known protective layer or the like on the inorganic vapor deposition layer (I).
• the multilayer film or vapor-deposited multilayer film of the present invention preferably has an oxygen transmission rate (under conditions of 20°C and 65% RH) measured in accordance with JIS K7126-2 (isobaric method; 2006) of less than 60 cc/( m2 day atm), more preferably less than 10 cc/( m2 day atm), even more preferably less than 3 cc/( m2 day atm), and particularly preferably less than 0.5 cc/( m2 day atm).
• a multilayer film or vapor-deposited multilayer film having an oxygen transmission rate in the above range has excellent gas barrier properties.
• the multilayer film or vapor-deposited multilayer film of the present invention can itself be used as a packaging material having gas barrier properties, but by laminating at least one resin layer (R) containing a thermoplastic resin (D) as a main component to form a multilayer structure, it is possible to impart various functions as a packaging material, such as designability and heat sealability. That is, the multilayer structure of the present invention is formed by laminating the multilayer film or vapor-deposited multilayer film of the present invention and at least one resin layer (R) containing a thermoplastic resin (D) as a main component.
• Thermoplastic resin (D) is not particularly limited, and examples thereof include 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), polybutene, polypentene, and other olefins alone or copolymers thereof, PA such as nylon 6 and nylon 6,6, polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polystyrene, polyvinyl chloride, polyvinylidene chloride, acrylic resin, polycarbonate, chlorinated polyethylene, chlorinated polypropylene, etc.
• the thermoplastic resin (D) is preferably the same as the polyolefin resin (C) described above, i.e., a polyolefin resin having a melting point of less than 170°C, more preferably a polyethylene-based resin or a polypropylene-based resin as the main component, even more preferably polyethylene or polypropylene, and particularly preferably polyethylene.
• the polyolefin resin (C) and the thermoplastic resin (D) preferably contain a polyethylene-based resin or a polypropylene-based resin as the main component, more preferably polyethylene or polypropylene, and even more preferably polyethylene.
• a resin layer (R) may be unstretched, or may be stretched or rolled in a uniaxial or biaxial direction. From the viewpoint of improving mechanical strength, it is preferable to use a biaxially stretched layer, and from the viewpoint of improving heat sealability, it is preferable to use a non-stretched layer.
• the method for producing the resin layer (R) is not particularly limited, but it is generally produced by melt extrusion using an extruder. Either a circular die or a T-die can be used as the die.
• the method for stretching in the uniaxial or biaxial direction is also not particularly limited, and the film can be produced by stretching in the flow direction of the film and/or the direction perpendicular to the flow direction, i.e., the width direction, using a conventionally known stretching method such as roll-type uniaxial stretching, tubular-type simultaneous biaxial stretching, tenter-type sequential biaxial stretching, and tenter-type simultaneous biaxial stretching. From the viewpoint of the uniformity of the thickness of the obtained layer and the mechanical strength, the area ratio is preferably 8 to 60 times.
• the area ratio is more preferably 55 times or less, and even more preferably 50 times or less. In addition, the area ratio is more preferably 9 times or more. If the area ratio is less than 8 times, stretching unevenness may remain, and if it exceeds 60 times, the layer may easily break during stretching.
• the average thickness of the resin layer (R) is preferably 10 to 200 ⁇ m.
• the average thickness of a non-oriented layer is more preferably 10 to 150 ⁇ m
• the average thickness of a biaxially oriented layer is more preferably 10 to 50 ⁇ m.
• the average thickness of the multilayer structure of the present invention is preferably 300 ⁇ m or less. With an average thickness in this range, the multilayer structure of the present invention is lightweight and flexible, and is therefore preferably used for flexible packaging applications. In addition, the amount of resin used in the multilayer structure is small, which reduces the environmental impact.
• the average thickness of each layer in the multilayer structure of the present invention may be adjusted as appropriate depending on the application, but from the viewpoints of suppressing coloration during melt molding of the pulverized material, improving thermal stability during melt molding, and suppressing the occurrence of bumps, it is preferable that at least one of the layer (Z) and the resin layer (R) contains a polyethylene-based resin or a polypropylene-based resin as a main component.
• the ratio of the total average thickness of the layers containing a polyethylene-based resin or a polypropylene-based resin as a main component to the average thickness of the multilayer structure is preferably 80% or more, and more preferably 85% or more. On the other hand, from the viewpoint of improving gas barrier properties, the ratio is preferably 99.7% or less, more preferably 99.5% or less, and may be 99.3% or less.
• the lower limit of the ratio of the total average thickness of the layers mainly composed of a polyethylene resin in the multilayer structure of the present invention is preferably 80%, more preferably 85%.
• the upper limit of the ratio of the total average thickness of the layers mainly composed of a polyethylene resin in the multilayer structure is preferably 99.7%, more preferably 99.5%, and may be 99.3%.
• the lower limit of the ratio of the total average thickness of the layers mainly composed of a polypropylene resin in the multilayer structure of the present invention is preferably 80%, more preferably 85%.
• the upper limit of the ratio of the total average thickness of the layers mainly composed of a polypropylene resin in the multilayer structure is preferably 99.7%, more preferably 99.5%, and may be 99.3%.
• the method of laminating the resin layer (R) on the multilayer film or vapor-deposited multilayer film of the present invention is not particularly limited, and examples thereof include extrusion lamination, coextrusion lamination, dry lamination, etc.
• an adhesive layer may be provided.
• each layer constituting the multilayer structure of the present invention may be laminated via an adhesive layer as necessary.
• the adhesive layer can be formed by applying a known adhesive and drying it.
• the adhesive is preferably a two-component reactive polyurethane adhesive in which a polyisocyanate component and a polyol component are mixed and reacted.
• the average 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 from the viewpoint of obtaining a multilayer structure excellent in recyclability, for example, a layer structure as shown below is preferable.
• layer (X) is expressed as X
• layer (Y) as Y
• layer (Z) as Z
• inorganic vapor deposition layer (I) as I
• layer (R) as R
• "/" means that they are directly laminated
• "//” means that they are laminated via an adhesive layer or directly laminated, but it is a preferred embodiment that they are laminated via an adhesive layer.
• the layer (X), the layer (Y) and the layer (Z) are preferably stretched at least uniaxially, and more preferably biaxially.
• the layer (Z) and the layer (R) are preferably polyethylene-based resin or polypropylene-based resin, and the layer (Y) is preferably maleic anhydride-modified polyethylene or maleic anhydride-modified polypropylene.
• the outermost layers of the multilayer structure of the present invention have a layer containing a polyethylene-based resin or a polypropylene-based resin as a main component so that the pulverized product obtained by pulverizing the packaging material can be recovered as a composition mainly containing a polyethylene-based resin or a polypropylene-based resin.
• the resin layer (R) when the resin layer (R) is arranged on both outermost layers, the resin layer (R) is preferably a layer mainly containing a polyethylene-based resin or a polypropylene-based resin, and when the layer (Z) and the resin layer (R) are arranged on both outermost layers, the layer (Z) and the resin layer (R) are preferably a layer mainly containing a polyethylene-based resin or a polypropylene-based resin.
• the layers disposed as the outermost layers it is preferable that one is a non-stretched layer, and in some cases it is preferable that the other is a layer that is stretched at least in one direction, from the viewpoint of obtaining a multilayer structure that achieves both heat sealability and mechanical properties.
• a method for recovering a multilayer structure of the present invention which includes a step of crushing the multilayer structure of the present invention and then melt-molding it, and a recovered composition containing the recovered multilayer structure of the present invention are also preferred embodiments of the present invention.
• the recovered multilayer structure of the present invention is first pulverized.
• the pulverized recovered material may be melt-molded as it is to obtain a recovered composition, or may be melt-molded together with other components as necessary to obtain a recovered composition.
• a preferred component to be added to the recovered material is a polyolefin resin, and a polyethylene-based resin or a polypropylene-based resin is more preferred.
• the polyolefin resin the same type of polyolefin resin (C) as described above for use in the multilayer film of the present invention is used.
• the pulverized recovered material may be directly used to manufacture a molded product such as a multilayer structure, or the pulverized recovered material may be melt-molded to obtain pellets of the recovered composition, and the pellets may then be used to manufacture a molded product.
• the mass ratio of the resin composition (A) to the polyolefin resin is preferably 0.01/99.99 to 20/80.
• the mass ratio is 0.01/99.99 or more, the proportion of recovered material used increases.
• the mass ratio is 20/80 or less, the melt moldability and mechanical properties of the recovered composition are improved.
• the mass ratio is more preferably 15/85 or less, even more preferably 10/90 or less, and may be 5/95 or less.
• the multilayer structure of the present invention has gas barrier properties and recyclability, and therefore can be suitably used as a material for various types of packaging, such as food packaging, pharmaceutical packaging, industrial chemical packaging, and agricultural chemical packaging.
• packaging materials having the multilayer structure of the present invention can be suitably used as packaging materials with excellent recyclability.
• the multilayer film and vapor-deposited multilayer film of the present invention can also be suitably used as packaging materials.
• EVOH (a-1) EVOH (ethylene (Et) unit content 32 mol%, saponification degree 99.99 mol%, MFR (190°C, 2.160 kg load) 1.6 g/10 min, melting point 183°C, volatile content 0.8%, contains 180 ppm of sodium acetate calculated as sodium ions, 30 ppm of phosphate ions calculated as phosphate radicals, and 150 ppm of boric acid calculated as boron element, but does not contain polyvalent metal ions.
• Et ethylene
• MFR 190°C, 2.160 kg load
• EVOH (a-1C) EVOH (ethylene unit content 32 mol%, saponification degree 99.99 mol%, MFR (190°C, 2.160 kg load) 1.6 g/10 min, melting point 183°C, volatile content 0.8%, contains 250 ppm of sodium acetate calculated as sodium ions, 30 ppm of phosphate ions calculated as phosphate radicals, and 150 ppm of boric acid calculated as boron element, but does not contain polyvalent metal ions.
• EVOH (a-2) EVOH (ethylene unit content 27 mol%, saponification degree 99.99 mol%, MFR (210°C, 2.160 kg load) 4.0 g/10 min, melting point 191°C, volatile content 0.8%, contains 180 ppm of sodium acetate calculated as sodium ions, 30 ppm of phosphate ions calculated as phosphate radicals, and 150 ppm of boric acid calculated as boron element, but does not contain polyvalent metal ions.
• EVOH (a-3) EVOH (ethylene unit content 44 mol%, saponification degree 99.99 mol%, MFR (190°C, 2.160 kg load) 5.7 g/10 min, melting point 165°C, volatile content 0.8%, contains 180 ppm of sodium acetate calculated as sodium ions, 30 ppm of phosphate ions calculated as phosphate radicals, and does not contain polyvalent metal ions.
• the epoxypropane modification degree refers to the content of monomer units modified with epoxypropane relative to the total monomer units.
• (Production method of EVOH (a-5)) 28 parts by mass of zinc acetylacetonate monohydrate was mixed with 957 parts by mass of 1,2-dimethoxyethane to obtain a mixed solution. 15 parts by mass of trifluoromethanesulfonic acid was added to the obtained mixed solution while stirring to obtain a catalyst solution.
• EVOH having an ethylene unit content of 44 mol% and a saponification degree of 99.99 mol% or more was charged into a Toshiba Machine Co., Ltd.
• the extruder was operated under the following conditions: barrel C1 was water-cooled, barrels C2 to C3 were at 200°C, barrels C4 to C15 were at 240°C, and the screw rotation speed was 250 rpm.
• Epoxypropane (1.5 kg/hr) and the catalyst solution were added from the pressure inlet 1 of C8.
• an aqueous sodium acetate solution was added from the pressure inlet 2 of C13.
• the discharged strands were cooled and solidified in a cooling tank, cut, and then dried to obtain EVOH (a-5).
• Polyolefin (b-6) EVA (Ultrathene (trademark) 636, manufactured by Tosoh Corporation, ethylene unit content 89 mol%, MFR (190° C., 2.16 kg load) 2.5 g/10 min, number average molecular weight (Mn) unknown)
• the MFR of the gas barrier resin (a) and the polyolefin (b) was measured in accordance with JIS K7210-1 (2014).
• Example 1 (1) Preparation of resin composition (A) containing gas barrier resin (a) for layer (X) 100 parts by mass of EVOH (a-1) pellets, 2 parts by mass of polyolefin (b-1) pellets, and calcium stearate were dry blended so that the calcium ion content in the resulting resin composition was 250 ppm, and then melt-kneaded to obtain resin composition (A) pellets for layer (X).
• a mixing zone with a continuous feed type kneading disc, neutral type kneading disc, and return type kneading disc was arranged in one place in the middle of the screw, and a vacuum vent was arranged downstream of the zone.
• the resin temperature was set to 230 ° C.
• Adhesive resin (B)-containing resin composition for layer (Y) A maleic anhydride-modified polyethylene "Admer (trademark) NF518" manufactured by Mitsui Chemicals, Inc. (MFR (190°C, 2.160 kg load) 3.1 g/10 min, melting point 121°C, density 0.91 g/ cm3 , acid value 1.8 mgKOH/g) was used as adhesive resin (B) as resin composition pellets for layer (Y).
• MFR 190°C, 2.160 kg load
• a substance consisting essentially of only one component is also referred to as a composition.
• Resin Composition Containing Polyolefin Resin (C) for Layer (Z) A low-density polyethylene "INNATE (trademark) TF80" manufactured by DOW (MFR (190°C, 2.160 kg load) 1.6 g/10 min, melting point 124°C, density 0.926 g/ cm3 ) was used as polyolefin resin (C) as resin composition pellets for layer (Z).
• the ratio of the total average thickness of the layers mainly composed of polyethylene-based resin in the multilayer film was 90%.
• Extrusion temperature of resin composition (A): feeding section/compression section/metering section/adapter 175/220/220/220° C.
• Extrusion temperature of adhesive resin (B)-containing resin composition: feeding section/compression section/metering section/adapter 175/220/220/220° C.
• the oxygen transmission rate of the multilayer film obtained in (5) was measured in accordance with the method described in JIS K7126-2 (isobaric method; 2006) with the layer (Z) as the oxygen supply side. Specifically, the oxygen transmission rate (unit: cc/(m2 ⁇ day ⁇ atm)) was measured using an oxygen transmission amount measuring device ("MOCON OX-TRAN2/21" manufactured by Modern Control) under the conditions of temperature 20 °C, humidity 65% RH on the oxygen supply side, humidity 65% RH on the carrier gas side, oxygen pressure 1 atm, and carrier gas pressure 1 atm, and was judged according to the following criteria. Nitrogen gas containing 2% by volume of hydrogen gas was used as the carrier gas.
• control a monolayer film having an average thickness of 100 ⁇ m was obtained similarly using only the low-density polyethylene (hereinafter, sometimes simply referred to as "control").
• the die used was a T-die with a width of 300 mm.
• the average thickness of the single-layer film was adjusted by appropriately changing the screw rotation speed and the take-up roll speed. The temperature conditions at this time are shown below.
• the coloration and defects of the obtained monolayer film (recycled material) were visually compared with the control and judged according to the following criteria.
• the defect rating was E, it was judged that the recyclability was insufficient.
• the results are shown in Table 2.
• Defects (recyclability) evaluation Criterion A: The amount of debris was almost the same as the control. B: The amount of small particles was slightly more than in the control. C: Compared to the control, there was a greater amount of small particles. D: Compared to the control, there was a greater amount of large bumps. E: There was a significantly greater amount of large bumps compared to the control.
• Examples 2 to 23, 35, and 36, Comparative Examples 3 and 4 Resin composition pellets, multilayer films, and multilayer structures were prepared and evaluated in the same manner as in Example 1, except that the type of gas barrier resin (a), the type and content of polyolefin (b), the content of alkali metal ions (c), and the type and content of polyvalent metal ions (d) were as shown in Table 1 or Table 3.
• the contents of alkali metal ions (c) and polyvalent metal ions (d) in Tables 1 and 3 are based on the mass of the entire resin composition (A). The results are shown in Tables 1 to 4.
• magnesium stearate was used instead of calcium stearate
• Examples 16 and 17 zinc stearate was used instead of calcium stearate.
• calcium stearate was not added during melt-kneading in the preparation of the gas barrier resin (a)-containing resin composition (A) for the (1) layer (X) in Example 1.
• Example 24 Except for not adding polyolefin (b-1), gas barrier resin-containing resin composition pellets were prepared in the same manner as in Example 1. Thereafter, except for using a dry blend obtained by dry blending 100 parts by mass of the obtained resin composition and 2 parts by mass of polyolefin (b-1) pellets as the resin composition for layer (X), a multilayer film and a multilayer structure were prepared and evaluated in the same manner as in Example 1. The results are shown in Tables 3 and 4.
• Example 25 In preparing the resin composition (A) pellets for the layer (X), except that an open vent was used instead of a vacuum vent, a resin composition pellet and a multilayer film were prepared in the same manner as in Example 1, and various measurements and evaluations were carried out. The results are shown in Tables 3 and 4.
• Example 26 Resin composition pellets and a multilayer film were prepared in the same manner as in Example 1, except that a vacuum vent was not used when preparing the resin composition (A) pellets for the layer (X), and various measurements and evaluations were carried out. The results are shown in Tables 3 and 4.
• Example 27 An alumina (AlOx) vapor-deposited layer (inorganic vapor-deposited layer (I)) having an average thickness of 30 nm was laminated by a known vacuum deposition method on the surface of layer (X) of the multilayer film obtained in (5) above to prepare a vapor-deposited multilayer film, and resin composition pellets, multilayer films, vapor-deposited multilayer films, and multilayer structures were prepared and evaluated in the same manner as in Example 1, except that the vapor-deposited multilayer film was used instead of the multilayer film to prepare the multilayer structure. The results are shown in Tables 3 and 4. The oxygen transmission rate was measured for the vapor-deposited multilayer film.
• Example 28 Except for changing the alumina deposition layer to a silica (SiOx) deposition layer, a resin composition pellet, a multilayer film, a deposition multilayer film, and a multilayer structure were produced and evaluated in the same manner as in Example 27. The results are shown in Tables 3 and 4.
• Example 29 Except for changing the alumina vapor-deposited layer to an aluminum (Al) vapor-deposited layer having an average thickness of 50 nm, resin composition pellets, a multilayer film, a vapor-deposited multilayer film, and a multilayer structure were produced and evaluated in the same manner as in Example 27. The results are shown in Tables 3 and 4.
• Example 30 Resin composition pellets, multilayer films and multilayer structures were prepared in the same manner as in Example 1, except that the average thickness of each layer of the multilayer film was changed as shown in Table 4, and various measurements and evaluations were carried out. The results are shown in Tables 3 and 4.
• Example 33 As the adhesive resin (B), Mitsui Chemicals' maleic anhydride modified polypropylene "Admer (trademark) QF551" (MFR (230 ° C, 2.160 kg load) 5.7 g / 10 min, melting point 144 ° C, density 0.89 g / cm 3 ) was used, and as the polyolefin resin (C), Japan Polypropylene's polypropylene “Novatec (trademark) PP EA7AD” (MFR (230 ° C, 2.160 kg load) 1.4 g / 10 min, melting point 161 ° C, density 0.90 g / cm 3 ) was used.
• Comparative Example 1 A multilayer film and a multilayer structure were produced and evaluated in the same manner as in Example 1, except that a layer (Z) (single layer film) having an average thickness of 40 ⁇ m was used instead of the multilayer film.
• the layer (Z) having an average thickness of 40 ⁇ m was produced by extruding only a polyolefin resin (C)-containing resin composition (low density polyethylene "INNATE (trademark) TF80" manufactured by DOW) without simultaneously extruding the resin composition (A) and the adhesive resin (B) when producing the multilayer film in Example 1, and adjusting the average thickness.
• C polyolefin resin
• Comparative Example 2 Except for not adding the polyolefin (b-1), resin composition pellets, a multilayer film and a multilayer structure were prepared in the same manner as in Example 1, and various measurements and evaluations were carried out. The results are shown in Tables 3 and 4.
• Example 34 100 parts by mass of PA (a-6) pellets and 2 parts by mass of polyolefin (b-1) pellets were dry blended and then melt-kneaded to obtain resin composition (A) pellets for layer (X).
• a multilayer film and a multilayer structure were produced in the same manner as in Example 1, except that the resin composition (A) pellets obtained in this example were used as the resin composition (A) pellets, and various performances were evaluated. The results are shown in Tables 3 and 4.
• Comparative Example 5 Except for not using the polyolefin (b-1), a resin composition, a multilayer film, and a multilayer structure were prepared and evaluated in the same manner as in Example 34. The results are shown in Tables 3 and 4.

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