Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/06—Polyethylene
• • 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
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
• • 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
  • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
• • 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
  • B32B2250/00—Layers arrangement
  • B32B2250/24—All layers being polymeric
• • 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
  • B32B2250/00—Layers arrangement
  • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
• • 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
  • B32B2270/00—Resin or rubber layer containing a blend of at least two different 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
  • B32B2272/00—Resin or rubber layer comprising scrap, waste or recycling material
• • 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
  • B32B2305/00—Condition, form or state of the layers or laminate
  • B32B2305/70—Scrap or recycled material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/30—Properties of the layers or laminate having particular thermal 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
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/558—Impact strength, toughness
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/724—Permeability to gases, adsorption
  • B32B2307/7242—Non-permeable
  • B32B2307/7244—Oxygen barrier
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/732—Dimensional 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
  • B32B2439/00—Containers; Receptacles
  • B32B2439/70—Food packaging
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2323/04—Homopolymers or copolymers of ethene
  • C08J2323/06—Polyethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2423/04—Homopolymers or copolymers of ethene
  • C08J2423/08—Copolymers of ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
  • C08J2423/30—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by oxidation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

• the present invention relates to a multilayer structure, and more particularly to a multilayer structure that has excellent transparency and impact resistance, and is easily recyclable.
• Polar group-containing resins such as ethylene-vinyl alcohol copolymers (hereinafter sometimes referred to as “EVOH”) and polyamide resins (hereinafter sometimes referred to as “PA resins”) are generally It is used by being formed into multilayer structures such as packaging films for foods and containers using a molding method.
• EVOH ethylene-vinyl alcohol copolymers
• PA resins polyamide resins
• Patent Document 1 discloses a) at least one layer containing a polyolefin component, wherein the polyolefin component is i) an ethylene homopolymer, an ethylene copolymer, a polypropylene homopolymer, a polypropylene copolymer, and combinations thereof; ii) 0 to 35 weight percent of a functional polymer component; and iii) a melt viscosity of 200,000 cP or less.
• the polyolefin component is i) an ethylene homopolymer, an ethylene copolymer, a polypropylene homopolymer, a polypropylene copolymer, and combinations thereof; ii) 0 to 35 weight percent of a functional polymer component; and iii) a melt viscosity of 200,000 cP or less.
• a compatibilizer component comprising an anhydride- and/or carboxylic acid-functionalized ethylene/alpha-olefin interpolymer having a density of 0.855 g/cc to 0.94 g/cc.
• Patent Document 1 it is stated that the recyclability of the multilayer structure can be improved because the multilayer structure contains a compatibilizing agent in advance, but the transparency and impact resistance of the multilayer structure itself may be improved. There was an issue of a decline in sexual performance.
• the present inventor speculated that the above problem was caused by the compatibilizer added to improve recyclability. Therefore, the present invention provides a multilayer structure that is easy to recycle and in which deterioration in transparency and impact resistance of the multilayer structure itself is suppressed.
• a polyolefin resin layer containing a polyolefin resin and a compatibilizer having a specific melt flow rate (MFR) can be formed into a multilayer structure including a polar group-containing resin layer. It has been discovered that the above problems can be solved by providing the device on the body.
• the melt flow rate of the compatibilizer (b2) is 600 g/10 minutes (190 ° C., load 2160 g) or less
• a multilayer structure in which the content of the compatibilizer (b2) is 10 to 200 parts by mass based on 100 parts by mass of the polar group-containing resin (a).
• the polyolefin resin (b1) is one or more polyethylenes selected from the group consisting of linear low-density polyethylene, low-density polyethylene, very low-density polyethylene, medium-density polyethylene, and high-density polyethylene, [1 ] to [7].
• the multilayer structure of the present invention includes a polar group-containing resin layer (A) containing a polar group-containing resin (a), and a polyolefin resin layer (B) containing a polyolefin resin (b1) and a compatibilizer (b2). , has an adhesive resin layer (C), the melt flow rate of the compatibilizer (b2) is 600 g/10 minutes (190 ° C., load 2160 g) or less, and the content of the compatibilizer (b2) is When the amount is 10 to 200 parts by mass based on 100 parts by mass of the polar group-containing resin (a), excellent transparency and impact resistance are achieved.
• x and/or y (x, y are arbitrary structures or components) means three combinations: x only, y only, and x and y.
• X to Y (X and Y are arbitrary numbers), unless otherwise specified, it means “more than or equal to X and less than or equal to Y", and “preferably greater than X” or “preferably It also includes the meaning of "less than Y”.
• the multilayer structure of the present invention includes a polar group-containing resin layer (A) containing a polar group-containing resin (a), and a polyolefin resin layer (B) containing a polyolefin resin (b1) and a compatibilizer (b2). , has an adhesive resin layer (C), the melt flow rate of the compatibilizer (b2) is 600 g/10 min (190°C, load 2160 g) or less, and the content of the compatibilizer (b2) is a polar group.
• the amount is 10 to 200 parts by mass per 100 parts by mass of the resin (a).
• the polar group-containing resin layer (A) constituting the multilayer structure of the present invention contains a polar group-containing resin (a).
• the polar group-containing resin (a) is not particularly limited as long as it is a resin containing a polar group, but is preferably a thermoplastic resin containing a polar group.
• the polar group-containing resin (a) contains EVOH and/or PA resin, more preferably EVOH and/or PA resin, and more preferably EVOH.
• the content of the polar group-containing resin (a) in the polar group-containing resin layer (A) is not particularly limited, such as 1% by mass or more, 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more. However, it is preferable that the polar group-containing resin (a) is the main component.
• the content of the polar group-containing resin (a) in the polar group-containing resin layer (A) is more preferably 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more. , more preferably 95% by mass or more and 100% by mass.
• the polar group-containing resin layer (A) contains known plasticizers, lubricants, heat stabilizers, light stabilizers, ultraviolet absorbers, antioxidants, within a range that does not impede the effects of the present invention (for example, less than 30% by mass). Additives such as crystal nucleating agents, coloring agents, antistatic agents, surfactants, antibacterial agents, desiccants, oxygen absorbers, anti-blocking agents, etc. may be blended, and polar group-containing resins may be blended. good. These can be used alone or in combination of two or more.
• EVOH used as the polar group-containing resin (a) is usually a resin obtained by saponifying an ethylene-vinyl ester copolymer, which is a copolymer of ethylene and a vinyl ester monomer, and is non-aqueous. It is a thermoplastic resin.
• vinyl ester monomer vinyl acetate is generally used from an economical point of view.
• the copolymerization method of ethylene and vinyl ester monomer can be carried out using any known polymerization method, such as solution polymerization, suspension polymerization, emulsion polymerization, etc., and generally methanol is used as a solvent. Solution polymerization is used.
• the obtained ethylene-vinyl ester copolymer can also be saponified by a known method.
• EVOH produced in this way mainly contains ethylene structural units and vinyl alcohol structural units, and if the degree of saponification is less than 100 mol%, it contains a small amount of vinyl ester structural units that remain as unsaponified parts. .
• "mainly" refers to the most abundant component in the object, and usually it is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably It may be 70% by mass or more, particularly preferably 80% by mass or more, particularly preferably 90% by mass or more, and 100% by mass.
• vinyl ester monomer vinyl acetate is typically used because of its market availability and good efficiency in treating impurities during production.
• examples of other vinyl ester monomers include vinyl formate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl versatate, etc.
• examples include aliphatic vinyl esters and aromatic vinyl esters such as vinyl benzoate, and aliphatic vinyl esters having usually 3 to 20 carbon atoms, preferably 4 to 10 carbon atoms, and particularly preferably 4 to 7 carbon atoms are used. I can do it. These can be used alone or in combination of two or more.
• EVOH is usually made from petroleum-derived raw materials such as naphtha, but it is also made from natural gas-derived raw materials such as shale gas, sugars and starches contained in sugar cane, sugar beet, corn, potatoes, etc., or rice. Plant-derived raw materials purified from components such as cellulose contained in plants such as , wheat, and millet may also be used.
• the content of ethylene structural units in EVOH can be controlled by the pressure of ethylene when copolymerizing the vinyl ester monomer and ethylene, and is preferably 20 to 60 mol%. More preferably 25 to 50 mol%, particularly preferably 25 to 35 mol%. If this content is too low, the gas barrier properties and melt moldability under high humidity tend to decrease, while if it is too high, the gas barrier properties tend to decrease.
• the content of the above-mentioned ethylene structural unit can be measured based on ISO14663, for example.
• the degree of saponification of the vinyl ester component in EVOH is determined by the amount, temperature, and time of saponification catalyst (usually an alkaline catalyst such as sodium hydroxide is used) when saponifying the ethylene-vinyl ester copolymer. It can be controlled by, for example, 90 to 100 mol%, preferably 95 to 100 mol%, particularly preferably 99 to 100 mol%. When the degree of saponification is low, gas barrier properties, thermal stability, moisture resistance, etc. tend to decrease.
• the degree of saponification of EVOH can be measured based on JIS K6726 (EVOH is used as a solution uniformly dissolved in a water/methanol solvent).
• the melt flow rate (MFR, based on JISK7210) (210°C, load 2160 g) of EVOH is usually 0.5 to 100 g/10 minutes, preferably 1 to 50 g/10 minutes, particularly preferably 3 to 35 g/10 It's a minute. If the MFR is too large, the moldability tends to become unstable, and if the MFR is too small, the viscosity tends to become too high, making melt extrusion difficult.
• MFR is an index of the degree of polymerization of EVOH, and can be adjusted by the amount of polymerization initiator and the amount of solvent when copolymerizing ethylene and vinyl ester monomer.
• EVOH may further contain a structural unit derived from a comonomer shown below within a range that does not impede the effects of the present invention (for example, 10 mol% or less of EVOH).
• Comonomers include olefins such as propylene, 1-butene, and isobutene; 3-buten-1-ol, 3-buten-1,2-diol, 4-penten-1-ol, 5-hexene-1,2- Derivatives such as hydroxy group-containing ⁇ -olefins such as diols and their esterification products and acylation products; Hydroxyalkylvinylidenes such as 2-methylenepropane-1,3-diol and 3-methylenepentane-1,5-diol; 1 , 3-diacetoxy-2-methylenepropane, 1,3-dipropionyloxy-2-methylenepropane, 1,3-dibutyryloxy-2-methylenepropane and other hydroxyal
• EVOH copolymerized with hydroxy group-containing ⁇ -olefins that is, EVOH having a hydroxyl group in the side chain
• EVOH having a hydroxyl group in the side chain is preferable because it has good secondary moldability while maintaining gas barrier properties. It is an EVOH having a primary hydroxyl group, and particularly preferably an EVOH having a 1,2-diol structure in its side chain.
• the content of structural units derived from the monomer having the primary hydroxyl group is usually 0.1 to 20 mol%, more preferably 0.5 to 15 mol%, particularly is preferably 1 to 10 mol%.
• the EVOH may be one that has been "post-modified” such as urethanation, acetalization, cyanoethylation, or oxyalkylenation.
• the EVOH may be a mixture of two or more types of EVOH, such as those having different degrees of saponification, those having different degrees of polymerization, and those having different copolymerization components.
• PA resin The PA resin used as the polar group-containing resin (a) is not particularly limited, and common polyamide resins include, for example, polycapramide (nylon 6), poly- ⁇ -aminoheptanoic acid (nylon 7), and polyamide. Examples include homopolymers such as - ⁇ -aminononanoic acid (nylon 9), polyundecaneamide (nylon 11), and polylauryllactam (nylon 12). Copolymerized polyamide resins include polyethylenediamine adipamide (nylon 26), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), and polyhexamethylene sebacamide (nylon 610).
• polyhexamethylene dodecamide (nylon 612), polyoctamethylene adipamide (nylon 86), polydecamethylene adipamide (nylon 108), caprolactam/lauryllactam 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), ethylenediamine azide Pamide/hexamethylene diammonium adipate copolymer (nylon 26/66), caprolactam/hexamethylene diammonium adipate/hexamethylene diammonium sebacate copolymer (nylon 66/610), ethylene ammonium adipate/hexamethylene diammonium Aliphatic polyamides such as a
• the melting point of the PA resin is preferably 160 to 270°C, more preferably 180 to 250°C, particularly preferably 200 to 230°C. If the melting point of the PA resin is too low, the heat resistance tends to decrease. On the other hand, if the melting point of the PA resin is too high, the difference in melting point with resins used in other layers may become large, which may be unfavorable from the viewpoint of moldability. From the above viewpoint, preferred PA resins include, for example, nylon 6 (melting point: about 220°C), nylon 6/66 (melting point: about 200°C), and the like.
• the polyolefin resin layer (B) constituting the multilayer structure of the present invention contains a polyolefin resin (b1) and a compatibilizer (b2). Since the multilayer structure of the present invention has a polyolefin resin layer (B) containing a polyolefin resin (b1) and a compatibilizer (b2), it is possible to improve the compatibility of the entire multilayer structure after recycling. , the multilayer structure can be easily recycled.
• the total content of the polyolefin resin (b1) and compatibilizer (b2) in the polyolefin resin layer (B) is 1% by mass or more, 2% by mass or more, 10% by mass or more, 20% by mass or more, 30% by mass. As mentioned above, it is more preferable that the total content of the polyolefin resin (b1) and the compatibilizer (b2) in the polyolefin resin layer (B) is 50 mass% or more, although it is not particularly limited, such as 40 mass% or more, More preferably, the content is 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, and 100% by mass. Note that the polyolefin resin layer (B) preferably does not contain EVOH, and even if EVOH is contained, the content of EVOH in the polyolefin resin layer (B) is preferably 5% by mass or less.
• the content of the polyolefin resin (b1) in the polyolefin resin layer (B) is not particularly limited, but is preferably 1 to 99% by mass, more preferably 30 to 95% by mass, particularly preferably 50 to 90% by mass. . From the viewpoint of recyclability, it is preferable that the amount is within the above range.
• the content of the compatibilizer (b2) in the polyolefin resin layer (B) is not particularly limited, but is preferably 1 to 99% by mass, more preferably 5 to 50% by mass, particularly preferably 10 to 30% by mass. . From the viewpoint of moldability, it is preferable that the amount is within the above range.
• the polyolefin resin layer (B) contains known plasticizers, lubricants, heat stabilizers, light stabilizers, and ultraviolet absorbers within a range that does not impede the effects of the present invention (for example, less than 30% by mass, preferably less than 5% by mass). Even if additives such as anti-oxidants, crystal nucleating agents, colorants, antistatic agents, surfactants, antibacterial agents, desiccants, oxygen absorbers, anti-blocking agents, and inorganic fillers are included as optional ingredients, Often, other polyolefin resins and compatibilizers may be blended.
• the polyolefin resin (b1) used in the polyolefin resin layer (B) is not particularly limited, but includes, for example, linear low density polyethylene (LLDPE), low density polyethylene (LDPE), very low density polyethylene (VLDPE), medium Polyethylene such as density polyethylene (MDPE) and high density polyethylene (HDPE), polypropylene (PP), ethylene-vinyl acetate copolymer (EVA), ionomer, ethylene-propylene (block or random) copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, propylene- ⁇ -olefin ( ⁇ -olefin having 4 to 20 carbon atoms) copolymer, Examples include ethylene- ⁇ -olefin ( ⁇ -olefin having 4 to 20 carbon atoms) copolymers
• EVA ethylene-vinyl acetate copolymer
• PP polypropylene
• polyethylene, polypropylene (PP) and ethylene-propylene (block or random) copolymers are particularly preferable since the effects of the present invention are particularly excellent.
• the melt flow rate (MFR) (190° C., load 2160 g) of the polyolefin resin (b1) is usually 0.1 to 50 g/10 minutes, more preferably about 0.5 to 30 g/10 minutes.
• the compatibilizing agent (b2) used in the polyolefin resin layer (B) is characterized by a melt flow rate (MFR) of 600 g/10 minutes (190° C., load 2160 g) or less.
• MFR melt flow rate
• the MFR of the compatibilizer (b2) is preferably 0.1 to 300 g/10 minutes, more preferably 1 to 100 g/10 minutes, particularly preferably 10 to 30 g/10 minutes.
• MFR is an index of the degree of polymerization of the compatibilizer (b2), and can be adjusted by adjusting the amount of polymerization initiator, the amount of solvent, the amount of modification, etc.
• the compatibilizer (b2) may have an MFR within the above range and be compatible with the polar group-containing resin (a) and the polyolefin resin (b1), and the type of resin is not particularly limited, but for example, , chemically adding an unsaturated carboxylic acid or its anhydride to an ethylene-vinyl acetate copolymer or its saponified product, a polyolefin resin, or an ethylene-vinyl acetate copolymer or a polyolefin resin by an addition reaction or a graft reaction.
• Examples include modified polyolefin polymers containing carboxy groups obtained by bonding.
• modified polyolefin polymers containing carboxyl groups include maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, maleic anhydride-modified ethylene-propylene (block and random) copolymers, and maleic anhydride-modified ethylene-propylene copolymers.
• Butene (block and random) copolymers examples include maleic anhydride-modified polymers such as resins. These may be used alone or as a mixture of two or more. In addition, when two or more types of compatibilizers (b2) having different MFRs are used, the weighted average value of these compatibilizers (b2) is taken as the MFR of the compatibilizers (b2).
• the content of the compatibilizer (b2) with respect to the polar group-containing resin (a) in the multilayer structure of the present invention is 10 to 200 parts by mass, preferably 30 to 150 parts by mass, per 100 parts by mass of the polar group-containing resin (a). Parts by weight, more preferably 50 to 100 parts by weight. It is preferable that the amount is within the above range since the compatibility between the polar group-containing resin (a) and the polyolefin resin can be further improved. If the content of the compatibilizer (b2) is less than 10 parts by mass based on 100 parts by mass of the polar group-containing resin (a), there is a tendency that no improvement in recyclability can be obtained. When the content of the compatibilizer (b2) exceeds 200 parts by mass based on 100 parts by mass of the polar group-containing resin (a), transparency and impact resistance tend to be poor.
• the MFR ratio (b1/b2) of the polyolefin resin (b1) and the compatibilizer (b2) is not particularly limited, but is preferably 0.003 to 300, more preferably 0.03 to 60, and 0.1 to 30. is particularly preferred. When the MFR ratio is within the above range, the effects of the present invention can be further enhanced.
• the thermal stability of the polyolefin resin (B) can be further improved, and gel formation of the polyolefin resin (B) can be further suppressed. I can do it.
• hydrotalcites examples include hydrotalcite-based solid solutions represented by the following general formula (1).
• M 1 2+ is at least one metal selected from Mg, Ca, Sr and Ba
• M 2 2+ is at least one metal selected from Zn, Cd, Pb
• Sn M x 3 + is a trivalent metal
• a n- is an n-valent anion
• M 1 2+ is preferably Mg or Ca, and M 2 2+ is preferably Zn or Cd.
• M x 3+ include Al, Bi, In, Sb, B, Ga, Ti, etc., and these may be used alone or in combination of two or more, and among them, Al is practical.
• the compound represented by the above general formula (2) includes Mg 4.5 Al 2 (OH) 13 CO 3 ⁇ 3.5H 2 O, Mg 5 Al 2 (OH) 14 CO 3 ⁇ 4H 2 O, Mg 6 Al 2 (OH) 16 CO 3 ⁇ 4H 2 O, Mg 8 Al 2 (OH) 20 CO 3 ⁇ 5H 2 O, Mg 10 Al 2 (OH) 22 (CO 3 ) 2 ⁇ 4H 2 O, Mg 6 Al Examples include 2 (OH) 16 HPO 4 .4H 2 O, Ca 6 Al 2 (OH) 16 CO 3 .4H 2 O, Zn 6 Al 6 (OH) 16 CO 3 .4H 2 O, and the like.
• compounds in which M is Mg and E is CO 3 are preferably used because they further improve the effects obtained by hydrotalcites.
• the average particle size of hydrotalcites is usually 10 ⁇ m or less, more preferably 5 ⁇ m or less, particularly preferably 1 ⁇ m or less.
• the average particle diameter referred to here is a value measured by the LUZEX method. Note that among the above hydrotalcites, it is particularly preferable to use the hydrotalcite solid solution represented by the above general formula (1) from the viewpoint of obtaining better effects.
• higher fatty acid metal salts include alkali metal salts such as lithium, sodium, and potassium of organic acids having 8 or more carbon atoms (more preferably 12 to 30 carbon atoms, particularly preferably 12 to 20 carbon atoms), magnesium,
• metal salts such as alkaline earth metal salts such as calcium and barium, and transition metal salts such as zinc, copper, cobalt, iron, and manganese.
• metal salts with a carbon number of 12 to 20 alkaline earth metal and transition metal salts are preferred, particularly the magnesium, calcium and zinc salts of stearic acid, hydroxystearic acid, oleic acid and lauric acid.
• the thermal stability of the polyolefin resin (B) can be further improved, and gel formation of the polyolefin resin (B) can be further suppressed. can.
• antioxidants include hindered phenol compounds: dibutylhydroxytoluene, 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-p-cresol, 4,4'-thiobis- (6-t-butylphenol), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), Tetrakis-[methylene-3-(3',5'-di-t-butyl-4') -hydroxyphenyl)propionate]methane, N,N'-hexamethylene-bis(3,5-di-t-butyl-4'-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4 , 6 tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, pentaerythritol-tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], triethylene glycol
• alkylaryl phosphites such as dialkylmonophenyl phosphites such as isooctyl phosphite and phenyldiisodecyl phosphite; trialkyl phosphites such as triisooctyl phosphite and tristearylphosphite; bis(2,4-di-t- butylphenyl) pentaerythritol-di-phosphite, etc.; thioether compounds: pentaerythritol-tetrakis-( ⁇ -laurylthiopropionate), tetrakis[methylene-3-(dodecylthio)propionate]methane, bis[2-methyl- 4-(3-n-alkylthiopropionyloxy)-5-t-butylphenyl] sulfide, dilauryl-3,3'-thiodipropionate, dimist
• the antioxidant may be in any form such as powder, granules, liquid, paste, emulsion, etc.
• hindered phenolic antioxidants are preferred, particularly pentaerythritol-tetrakis-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate and octadecyl-3-(3,5-di -t-butyl-4-hydroxyphenyl)propionate is preferably used from the viewpoint of obtaining better effects.
• the multilayer structure of the present invention may further include an adhesive resin layer (C) if necessary.
• the adhesive resin layer (C) may be provided as a layer for bonding the polar group-containing resin layer (A) and the polyolefin resin layer (B).
• the adhesive resin contained in the adhesive resin layer (C) for example, a carboxyl group obtained by chemically bonding an unsaturated carboxylic acid or its anhydride to a polyolefin resin by an addition reaction, a graft reaction, etc. Examples include modified polyolefin polymers.
• modified polyolefin polymers containing carboxyl groups include maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, maleic anhydride-modified ethylene-propylene (block and random) copolymers, and maleic anhydride-modified ethylene-propylene copolymers.
• maleic anhydride-modified polymers such as ethyl acrylate copolymer, maleic anhydride-modified ethylene-vinyl acetate copolymer, maleic anhydride-modified polycyclic olefin resin, and maleic anhydride-modified polyolefin resin. These may be used alone or as a mixture of two or more.
• maleic anhydride-modified polyethylene and maleic anhydride are particularly useful because they contribute not only to the adhesiveness of the resin but also to suppressing gel formation during melting and heating and suppressing decreases in transparency.
• Maleic anhydride-modified polymers such as modified ethylene- ⁇ -olefin copolymers are preferred.
• the acid value of the maleic anhydride-modified polymer is usually 50 mgKOH/g or less, preferably 30 mgKOH/g or less, particularly preferably 20 mgKOH/g or less. If the acid value is too high, the number of reaction points with the hydroxyl groups in EVOH will increase, and a highly polymerized compound will be generated during the melt-kneading process, reducing stability during extrusion processing and making it difficult to obtain a good molded product. There is. Note that the lower limit of the acid value is usually 1 mgKOH/g, preferably 2 mgKOH/g. Moreover, the above acid value is measured based on JISK0070.
• the MFR (190°C, load 2160 g) is usually 0.01 to 150 g/10 minutes, preferably 0.1 to 50 g/10 minutes. It is more preferably 1 to 25 g/10 minutes, and even more preferably 3 to 10 g/10 minutes.
• the MFR (230°C, load 2160 g) is usually 0.1 to 150 g/10 minutes, preferably It is 0.5 to 100 g/10 minutes, more preferably 1 to 50 g/10 minutes, and still more preferably 5 to 35 g/10 minutes. If the MFR is too large or too small, there is a tendency for molding defects to occur when molding a multilayer structure, which is not preferable.
• additives can be appropriately blended into the adhesive resin layer (C) within a range (for example, less than 30% by mass) that does not impair the effects of the present invention.
• additives include heat stabilizers, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, neutralizing agents, rust preventives, and pigments.
• the multilayer structure of the present invention includes a polar group-containing resin layer (A), a polyolefin resin (b1), and a compatibilizer (b2) having a melt flow rate of 600 g/10 minutes or less (190°C, load 2160 g). It is a multilayer structure having a polyolefin resin layer (B).
• the multilayer structure of the present invention only needs to contain the polar group-containing resin layer (A) and the polyolefin resin layer (B), and the layer structure other than these is not particularly limited.
• the multilayer structure of the present invention may include an adhesive resin layer (C) as necessary, for example, a polyolefin-based resin layer (C) is added to the polar group-containing resin layer (A) via the adhesive resin layer (C).
• a laminated structure (B/C/A/C/B) can be mentioned.
• Another layer (D) may be laminated between these layers or on the surface layer.
• a known method can be used as a method for laminating the multilayer structure. For example, a method of melt-extrusion laminating an adhesive resin layer (C) and a polyolefin resin layer (B) on a film or sheet that will become the polar group-containing resin layer (A), or conversely, a method of laminating an adhesive resin layer (C) and a polyolefin resin layer (B) on a film or sheet, etc.
• a method of applying a solution of a resin composition to become a polar group-containing resin layer (A) on a polyolefin resin layer (B) provided with an adhesive resin layer (C), and then removing the solvent, etc. can be mentioned.
• coextrusion is preferred from the viewpoint of cost and environment.
• At least one other layer (D) may be laminated between the layers (A) to (B) or the layers (A) to (C) or on the surface layer.
• Other layers (D) include a base material layer (D1) for adding strength etc. to the multilayer structure, and an adhesive for joining this base material layer (D1) and layers (A) to (C). agent layer (D2), etc.
• Base material layer (D1) As the material used for the base layer (D1), various thermoplastic resins (hereinafter referred to as "base resin") are used. Furthermore, recycled resin obtained by remelting and molding end portions, defective products, etc. generated during the process of manufacturing the multilayer structure of the present invention may also be used. Such recycled resin may include a molten mixture of a polar group-containing resin layer (A), a polyolefin resin layer (B), an adhesive resin layer (C), and other layers (D).
• A polar group-containing resin layer
• B polyolefin resin layer
• C adhesive resin layer
• D other layers
• the base resin used for the base layer (D1) includes linear low density polyethylene, low density polyethylene, very low density polyethylene, medium density polyethylene, high density polyethylene, and ethylene-propylene (block and random) copolymers.
• polyethylene resins such as ethylene- ⁇ -olefin ( ⁇ -olefin having 4 to 20 carbon atoms) copolymer, polypropylene, polypropylene such as propylene- ⁇ -olefin ( ⁇ -olefin having 4 to 20 carbon atoms) copolymer
• Polyolefin resins cyclic olefin resins, ionomers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-acrylic acid ester copolymers, polyester resins, polyamide resins (including copolymerized polyamides) , polyvinyl chloride, polyvinylidene chloride, acrylic resins, polystyrene, vinyl ester resins, polyester elastomers, polyurethane elastomers, halogenated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, aromatic or aliphatic polyketones, etc. .
• the adhesive used in the adhesive layer (D2) for bonding the base layer (D1) and the layers (A) to (B) or the layers (A) to (C) includes organic titanium compounds, isocyanates, etc.
• Known adhesives such as compounds, polyester compounds, and polyurethane compounds can be used, and may be appropriately selected depending on the type of thermoplastic resin constituting the base layer (D1).
• the adhesive resin layer (C ) may be used.
• thermoplastic resin used for the base material layer (D1) and the adhesive used for the adhesive layer (D2) may contain a content within a range that does not impede the spirit of the present invention (for example, 30% by mass or less, preferably 10% by mass or less). % or less), conventionally known plasticizers, fillers, clays (montmorillonite, etc.), colorants, antioxidants, antistatic agents, lubricants, core materials, antiblocking agents, ultraviolet absorbers, waxes, etc. Can be blended.
• the multilayer structure of the present invention includes at least one other layer (D) such as a base material layer (D1) and an adhesive layer (D2)
• the following manufacturing method may be used, for example. can be mentioned.
• the method (i) of co-extruding the resin that will become the layers (A) to (B) or the layers (A) to (C) and the resin that will become the other layer (D) is preferred.
• a polyolefin resin layer (B) is laminated on both sides of a polar group-containing resin layer (A) via an adhesive resin layer (C).
• a polyolefin resin layer (B) is laminated on both sides of a polar group-containing resin layer (A) via an adhesive resin layer (C).
• the extrusion molding temperature (barrel temperature of the extruder) of the resin composition is normally set appropriately in the range of 150 to 300°C, preferably 160 to 250°C.
• the extruder barrel temperature means the surface temperature of the extruder barrel. If the extruder barrel has multiple sections and the individual sections are set at different temperatures, the highest temperature of these is the barrel temperature.
• the obtained multilayer structure may be subjected to (heating) stretching treatment if necessary.
• the stretching treatment may be either uniaxial stretching or biaxial stretching, and in the case of biaxial stretching, simultaneous stretching or sequential stretching may be performed.
• the stretching method a method with a high stretching ratio among roll stretching methods, tenter stretching methods, tubular stretching methods, stretch blowing methods, vacuum-pressure forming, etc. can be adopted.
• the stretching temperature is selected from the range of usually 40 to 170°C, preferably about 60 to 160°C, which is the temperature near the multilayer structure. If the stretching temperature is too low, the stretching properties tend to be poor, and if the stretching temperature is too high, it tends to be difficult to maintain a stable stretched state.
• heat setting may be further performed for the purpose of imparting dimensional stability after stretching.
• Heat setting can be carried out by well-known means, for example, the multilayer structure (in the form of a stretched film) is usually heated at 80 to 180°C, preferably 100 to 165°C, for about 2 to 600 seconds while maintaining a tensioned state. Perform heat treatment.
• the thickness of the multilayer structure (including the stretched one) and the thickness of the polar group-containing resin layer (A) and the polyolefin resin layer (B) that constitute the multilayer structure depend on the layer structure and the resin content of each layer.
• the thickness of the entire multilayer structure is usually 10 to 5,000 ⁇ m, preferably 30 to 3,000 ⁇ m, and particularly preferably 50 to 2,000 ⁇ m, although it cannot be stated unconditionally depending on the type, use, packaging form, required physical properties, etc.
• the thickness of the polar group-containing resin layer (A) is usually 1 to 500 ⁇ m, preferably 3 to 300 ⁇ m, particularly preferably 5 to 200 ⁇ m.
• the thickness of the polyolefin resin layer (B) is usually 1 to 300 ⁇ m, preferably 5 to 200 ⁇ m, particularly preferably 10 to 100 ⁇ m.
• the thickness of the adhesive resin layer (C) is usually 0.5 to 250 ⁇ m, preferably 1 to 150 ⁇ m, particularly preferably 3 to 100 ⁇ m.
• the thickness of the base layer (D1) is usually 1 to 500 ⁇ m, preferably 3 to 300 ⁇ m, particularly preferably 5 to 200 ⁇ m.
• the thickness of the adhesive layer (D2) is usually 0.5 to 250 ⁇ m, preferably 1 to 150 ⁇ m, particularly preferably 3 to 100 ⁇ m.
• the ratio A/B between the thickness of the polar group-containing resin layer (A) and the thickness of the polyolefin resin layer (B) is usually 1/50 to 10/1, preferably 1/30. ⁇ 5/1, particularly preferably 1/10 ⁇ 3/1.
• A/B is within the above range, the effects of the present invention can be obtained more effectively.
• the image clarity of the multilayer structure of the present invention is preferably 70.5% or more, more preferably 75% or more, particularly preferably 80% or more, and most preferably 100%.
• the image sharpness of the multilayer structure can be measured, for example, by the method described in Examples below.
• the impact strength of the multilayer structure of the present invention is preferably 170 g or more, more preferably 200 g or more, even more preferably 230 g or more, particularly preferably 250 g or more, particularly preferably 260 g or more.
• the impact strength of the multilayer structure can be measured, for example, by the method described in Examples below.
• the multilayer structure of the present invention contains a specific compatibilizing agent (b2) in a specific proportion, so it is a multilayer structure that is easy to recycle and has excellent transparency and impact resistance.
• the multilayer structure of the present invention can be used for various packaging materials containers and packaging for seasonings such as mayonnaise and dressings, fermented foods such as miso, oil and fat foods such as salad oil, beverages, cosmetics, pharmaceuticals, etc. It can be suitably used as a gas barrier layer of packaging materials such as films. Additionally, the multilayer structure of the present invention is suitable for recycling.
• the multilayer structure of the present invention has excellent recyclability without adding a separate compatibilizing agent when recycling offcuts and molded products of the multilayer structure.
• a resin composition or the like obtained by crushing and repelletizing the offcuts or molded products of the multilayer structure of the present invention is used.
• the resin composition includes a polar group-containing resin (a) containing an ethylene-vinyl alcohol copolymer and/or polyamide, a polyolefin resin (b1), a compatibilizer (b2), and an adhesive resin (c),
• the melt flow rate of the compatibilizer (b2) is 600 g/10 minutes (190°C, load 2160 g) or less, and the content of the compatibilizer (b2) is based on 100 parts by mass of the polar group-containing resin (a). The amount is 10 to 200 parts by mass.
• Polar group-containing resin (a): EVOH (ethylene structural unit content 32 mol%, MFR 3.5 g/10 min (210°C, load 2160 g), saponification degree 99.6 mol%)
• Polyolefin resin (b1-2): Linear low density polyethylene (LLDPE) (“UF641” manufactured by Japan Polyethylene Co., Ltd., MFR: 2.1 g/10 minutes (190°C, load 2160 g))
• Compatibilizer (b2-2): 88 parts of ethylene-vin
• a resin composition for the polyolefin resin layer (B) was prepared by mixing 63 parts of polyolefin resin (b1) and 37 parts of compatibilizer (b2-1).
• the amount of the compatibilizer (b2-1) is equivalent to the amount of EVOH contained in the multilayer structure (100 parts of the compatibilizer (b2-1) per 100 parts of EVOH).
• the resin composition prepared above, the polar group-containing resin (a), the adhesive resin (c), and the base resin (d1) were supplied to a 5-type, 7-layer, multilayer coextrusion cast film forming apparatus, and the following conditions were applied.
• base material layer (D1) / polyolefin resin layer (B) / adhesive resin layer (C) / polar group-containing resin layer (A) / adhesive resin layer (C) / polyolefin resin A multilayer structure (film) having a structure of 4 types and 7 layers of layer (B)/base material layer (D1) was obtained.
• the thickness ( ⁇ m) of each layer of the multilayer structure was 20/20/5/10/5/20/20.
• Example 1 ⁇ Examples 2 to 8, Comparative Examples 1 to 3>
• Example 1 a multilayer structure was manufactured in the same manner as in Example 1 except for the changes shown in Table 1, and various evaluations were performed according to the methods shown below.
• Examples 1 to 8 and Comparative Examples 1 to 8 were tested using aluminum darts with a diameter of 38 mm and a mass of 32 g according to Method A in accordance with JIS K 7124-1 "Plastic films and sheets - impact test method using free-fall dart method".
• the impact strength of the multilayer structure No. 3 was measured using No. 3 manufactured by Toyo Seiki Seisakusho in an atmosphere of 23° C. and 50% RH. Evaluation was made using a 613 Dart Impact Tester.
• a recycled composition was prepared by melt-kneading. The obtained recycled composition was molded into a film with a thickness of 0.1 mm using a single-layer T-die film molding machine (manufactured by GM Engineering, 40 mm ⁇ , lip opening: 0.3 mm) at a set temperature of 220°C and a screw rotation speed of 60 rpm. A film was produced. The impact resistance of the produced film was measured by the same method as above. A film (reference example) that was the same as in Example 1 except that it did not contain a compatibilizer was produced, and its impact resistance was measured in the same manner.
• Examples 1 to 8 are comparative examples containing a compatibilizer having an MFR outside the range specified by the present invention by making the polyolefin resin layer (B) contain a specific amount of a compatibilizer having a specific MFR. 1 and 3 and Comparative Example 2 in which the content of the compatibilizer is outside the range specified by the present invention, the multilayer structure has excellent image clarity (transparency) and dart impact (impact resistance). I understand. Furthermore, from Table 2, it can be seen that by containing a specific amount of a compatibilizer having a specific MFR in the polyolefin resin layer (B), the recyclability is improved compared to the case where no compatibilizer is included. Recognize.
• the multilayer structure of the present invention can be used for various packaging materials containers and packaging for seasonings such as mayonnaise and dressings, fermented foods such as miso, oil and fat foods such as salad oil, beverages, cosmetics, pharmaceuticals, etc. It can be suitably used as a gas barrier layer of packaging materials such as films. Additionally, the multilayer structure of the present invention is suitable for recycling.

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