WO2023112929A1 - Film multicouche, structure multicouche, matériau d'emballage, composition de récupération et procédé de récupération d'un film multicouche ou d'une structure multicouche - Google Patents

Film multicouche, structure multicouche, matériau d'emballage, composition de récupération et procédé de récupération d'un film multicouche ou d'une structure multicouche Download PDF

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Publication number
WO2023112929A1
WO2023112929A1 PCT/JP2022/045916 JP2022045916W WO2023112929A1 WO 2023112929 A1 WO2023112929 A1 WO 2023112929A1 JP 2022045916 W JP2022045916 W JP 2022045916W WO 2023112929 A1 WO2023112929 A1 WO 2023112929A1
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multilayer film
resin
layer
ethylene
multilayer
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PCT/JP2022/045916
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English (en)
Japanese (ja)
Inventor
健太郎 吉田
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株式会社クラレ
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Priority to JP2023525560A priority Critical patent/JP7340125B1/ja
Publication of WO2023112929A1 publication Critical patent/WO2023112929A1/fr

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    • 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
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes

Definitions

  • the present invention relates to a multilayer film and a multilayer structure that are excellent in appearance properties, gas barrier properties, and recyclability, and also excellent in mechanical strength and stability, as well as packaging materials, recovery compositions, and recovery methods using the same.
  • Packaging materials for long-term storage of food are often required to have oxygen barrier properties and other gas barrier properties.
  • a packaging material with a high gas barrier property it is possible to suppress oxidative degradation of food and breeding of microorganisms due to infiltration of oxygen.
  • metal foils such as aluminum foils and inorganic deposition layers such as silicon oxide and aluminum oxide are widely used.
  • resin layers having gas barrier properties such as vinyl alcohol-based polymers and polyvinylidene chloride, are also widely used.
  • Vinyl alcohol-based polymers have the characteristic of exhibiting gas barrier properties by crystallizing and densifying due to hydrogen bonding between hydroxyl groups in the molecule.
  • ethylene-vinyl alcohol copolymer (hereinafter sometimes abbreviated as "EVOH”) is suitable for melt molding due to its excellent thermal stability. Therefore, with the development of coextrusion technology, multi-layer films having an EVOH layer as an intermediate layer are widely used as gas barrier packaging materials.
  • recycling post-consumer recycling
  • packaging materials are required to be composed of a single material as much as possible (mono-materialization), so that high-purity and high-quality recycled raw materials can be obtained.
  • Patent Document 1 discloses a hard layer having a puncture strength of 40 N/mm or more and 150 N/mm or less; ) a multilayer film having a resin composition layer having a modified EVOH containing a modifying group having a specific primary hydroxyl group. Patent Document 1 discloses that such a multilayer film has excellent mechanical strength and thermoformability even though it does not have a polyamide layer. ) is suppressed, and the recyclability is also excellent.
  • the multilayer film described in Patent Document 1 has a large variation in mechanical strength depending on the measurement position, and may be inferior in local mechanical strength.
  • a high temperature for example, 40° C. to 50° C.
  • a long time for example, 30 days to several years
  • local mechanical strength fluctuation tends to be particularly large. Reliability may remain a concern.
  • the present invention has been made to solve the above problems, and provides a multilayer film, a multilayer structure, and a packaging material using the same, which are excellent in appearance properties, gas barrier properties and recyclability, and are also excellent in mechanical strength and stability.
  • intended to provide Another object of the present invention is to provide a recovered composition containing such a recovered multilayer film or multilayer structure, and a method for recovering such a multilayer film or multilayer structure.
  • a state in which the mechanical strength measurement value varies little regardless of the storage environment or measurement position of the multilayer film may be expressed as excellent mechanical strength stability.
  • Ethylene-vinyl alcohol copolymer (a) having an ethylene unit content of 20 to 50 mol% and a degree of saponification of 90 mol% or more (hereinafter sometimes abbreviated as "EVOH (a)") as a main component (hereinafter sometimes abbreviated as "barrier layer (A)")
  • EVOH (a) ethylene- ⁇ -olefin copolymer resin
  • barrier layer (A) an adhesive layer (B) containing an adhesive resin (b) as a main component
  • Adhesive layer (B)” an ethylene- ⁇ -olefin copolymer resin (c) having a density of 0.880 to 0.920 g/cm 3
  • the heat sealing layer (C) is a higher fatty acid amide compound (d) having a melting point of 60 to 120 ° C. (hereinafter referred to as “high A multilayer film containing 100 to 7000 ppm of a fatty acid amide compound (d)”;
  • the ethylene- ⁇ -olefin copolymer resin (c) has an MFR (190°C, under a load of 2.16 kg) measured according to JIS K7210 (2014) of 0.5 to 2.0 g/10.
  • the ethylene- ⁇ -olefin copolymer resin (c) of [1] to [4] is a linear low-density polyethylene obtained by copolymerizing ethylene and an ⁇ -olefin having 6 or more carbon atoms.
  • the higher fatty acid amide compound (d) is at least one selected from the group consisting of saturated fatty acid monoamides having 10 to 25 carbon atoms and unsaturated fatty acid monoamides having 10 to 25 carbon atoms, [1] to [5] ] any multilayer film; [7] The multilayer film of any one of [1] to [6], wherein the higher fatty acid amide compound (d) contains two or more higher fatty acid amide compounds having different melting points; [8]
  • the thermal adhesive layer (C) contains 500 to 5000 ppm of inorganic oxide particles (e) having an average particle size of 1 to 30 ⁇ m, and the inorganic oxide particles (e) are silicon oxide particles and metal oxides.
  • the barrier layer (A) contains 10 to 200 ppm of at least one polyvalent metal ion (f) selected from the group consisting of magnesium ions, calcium ions and zinc ions, [1] to [8]
  • the adhesive resin (b) is a mixture of an unmodified resin (bx) and an acid-modified resin (by), and the unmodified resin (bx) contains an ethylene- ⁇ -olefin copolymer resin (c).
  • any multilayer film of [15] [17] A multilayer structure obtained by laminating the multilayer film of any one of [1] to [16] and at least one resin layer (R) containing a thermoplastic resin (g) as a main component; [18] The multilayer structure of [17], wherein the thermoplastic resin (g) contains polyethylene resin as a main component; [19] A packaging material comprising the multilayer film of any one of [1] to [16] or the multilayer structure of [17] or [18]; [20] A recovered composition comprising a recovered multilayer film of any one of [1] to [16] or a multilayer structure of [17] or [18]; [21] A method for recovering a multilayer film or multilayer structure, comprising a step of melt molding after pulverizing the multilayer film of any one of
  • the multilayer film and multilayer structure of the present invention are excellent in appearance characteristics, gas barrier properties and recyclability, and are also excellent in mechanical strength and stability. According to the recovery composition and the method for recovering the multilayer film or multilayer structure of the present invention, such multilayer film and multilayer structure can be effectively reused.
  • the multilayer film of the present invention comprises a barrier layer (A) containing, as a main component, EVOH (a) having an ethylene unit content of 20 to 50 mol% and a degree of saponification of 90 mol% or more, and an adhesive resin (b). and an adhesive layer (B) containing as a main component an ethylene- ⁇ -olefin copolymer resin (c) having a density of 0.880 to 0.920 g/cm 3 as a main component. and does not have a layer containing a resin having a melting point of 200° C.
  • "containing as a main component” means containing more than 50% by mass, preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more. , 95% by mass or more, 97% by mass or more, or 99% by mass or more.
  • the adhesive layer (B) tends to improve mechanical strength and recyclability.
  • the ethylene- ⁇ -olefin copolymer resin (c) in which the main component of the heat sealing layer (C) is 0.880 to 0.920 g/cm 3 , excellent mechanical strength can be achieved.
  • the heat sealing layer (C) contains 100 to 7000 ppm of the higher fatty acid amide compound (d) having a melting point of 60 to 120° C., the stability of mechanical strength and good recyclability tend to be maintained. Become.
  • the multilayer film of the present invention does not have a layer containing a resin having a melting point of 200° C.
  • the recyclability in this specification can be evaluated by evaluation of lumps and coloration in the melt-molded product of the crushed multilayer film and the melt viscosity stability of the crushed multilayer film. It can be evaluated by the method.
  • the mechanical strength in this specification can be evaluated by puncture breaking strength, impact strength, and drop bag breakage resistance evaluation, and specifically can be evaluated by the method described in Examples.
  • the multilayer film of the present invention has a barrier layer (A) containing EVOH (a) as a main component. Since EVOH (a) has excellent gas barrier properties, a multilayer film having a layer containing EVOH (a) as a main component is preferably used as a packaging material with high preservability of contents. In addition, since EVOH (a) can be easily melt-mixed with polyethylene resin, a packaging material with excellent recyclability can be provided.
  • the content of EVOH (a) in the barrier layer (A) must be more than 50% by mass, preferably 70% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more.
  • EVOH (a) is usually obtained by saponifying an ethylene-vinyl ester copolymer obtained by polymerizing ethylene and vinyl ester.
  • the ethylene unit content of EVOH (a) is 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.
  • the gas barrier properties of the multilayer film of the present invention are improved.
  • the ethylene unit content is preferably 46 mol% or less, more preferably 42 mol% or less, and may be 38 mol% or less.
  • the degree of saponification of EVOH (a) is 90 mol % or more.
  • the degree of saponification means the ratio of the number of vinyl alcohol units to the total number of vinyl alcohol units and vinyl ester units in EVOH (a).
  • the degree of saponification is preferably 95 mol% or more, more preferably 99 mol% or more, even more preferably 99.9 mol% or more.
  • the ethylene unit content and saponification degree of EVOH (a) can be determined by 1 H-NMR measurement.
  • EVOH (a) may be a mixture of two or more types of EVOH having different ethylene unit contents.
  • the difference in ethylene unit content between EVOHs having the most distant ethylene unit content is preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 15 mol% or less, and 3 mol% or more.
  • EVOH (a) may be a mixture of two or more types of EVOH with different degrees of saponification.
  • the difference in saponification degree between the most distant EVOHs is preferably 7 mol % or less, more preferably 5 mol % or less, and may be 0.5 mol % or more.
  • EVOH (a-1) having an ethylene unit content of 24 mol% or more and less than 34 mol% and a degree of saponification of 99 mol% or more
  • EVOH (a-2) having an ethylene unit content of 34 mol% or more and less than 50 mol% and a saponification degree of 99 mol% or more
  • a blending mass ratio (a-1/a-2) 60/40 It is preferable to mix to 90/10 and use as EVOH (a).
  • EVOH (a) may contain monomer units other than ethylene, vinyl ester and vinyl alcohol as long as they do not impair the effects of the present invention.
  • a modifying group containing a primary hydroxyl group having a specific structure it may be possible to achieve both gas barrier properties and moldability of EVOH (a) at a high level.
  • the content of other monomer units is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less, and particularly preferably not substantially contained.
  • Examples of such other monomers include ⁇ -olefins such as propylene, n-butene, isobutylene, and 1-hexene; acrylic acid and its salts; unsaturated monomers having an acrylic acid ester group; Acids and their salts; Unsaturated monomers having a methacrylic acid ester group; Acrylamide, N-methylacrylamide, N-ethylacrylamide, N,N-dimethylacrylamide, diacetoneacrylamide, acrylamidopropanesulfonic acid and its salts, acrylamidopropyl Dimethylamine and its salts (eg quaternary salts); methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, methacrylamidopropanesulfonic acid and its salts, methacrylamidopropyldimethylamine and its salts (eg quaternary salts) ; methyl vinyl ether, ethyl vinyl ether, n-propy
  • the MFR of EVOH (a) measured according to JIS K7210 (2014) (190°C, under 2.16 kg load) is preferably 0.2 to 20 g/10 minutes.
  • the MFR of EVOH (a) is more preferably 0.5 g/10 minutes or more, still more preferably 0.8 g/10 minutes or more.
  • the MFR of EVOH (a) is more preferably 15 g/10 minutes or less, even more preferably 10 g/10 minutes or less, even more preferably 5 g/10 minutes or less, and particularly preferably 3 g/10 minutes or less.
  • the barrier layer (A) preferably contains 10 to 200 ppm of at least one polyvalent metal ion (f) selected from the group consisting of magnesium ions, calcium ions and zinc ions. Containing a certain amount of polyvalent metal ions (f) suppresses viscosity increase, gelation, and resin adhesion to the screw during melt molding of pulverized EVOH (a) and multi-layer films containing EVOH (a). be done.
  • the barrier layer (A) preferably contains magnesium ions or calcium ions, more preferably magnesium ions, as polyvalent metal ions (f).
  • the carboxylic acid at this time may be either an aliphatic carboxylic acid or an aromatic carboxylic acid, but an aliphatic carboxylic acid is preferred.
  • aliphatic carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, lauric acid, stearic acid, myristic acid, behenic acid, montanic acid, etc., and higher fatty acids having 10 to 25 carbon atoms are more preferred. 14-22 higher fatty acids are more preferred. From the viewpoint of suppressing coloration during melt molding, it is also preferable to contain the polyvalent metal ion (f) as a salt of a polyvalent carboxylic acid, which will be described later.
  • the content of polyvalent metal ions (f) in the barrier layer (A) is preferably 10 to 200 ppm in terms of metal atoms.
  • the lower limit of the polyvalent metal ion (f) content is more preferably 20 ppm.
  • the content of the polyvalent metal ion (f) is 200 ppm or less, excessive decomposition of the pulverized multi-layer film containing EVOH (a) is suppressed, and the hue of the recovered composition is improved.
  • the upper limit of the content of polyvalent metal ions (f) is more preferably 160 ppm, more preferably 120 ppm.
  • the barrier layer (A) may contain components other than EVOH (a) and polyvalent metal ions (f) as long as the effects of the present invention are not impaired.
  • Other components include, for example, alkali metal ions, polyvalent metal ions other than polyvalent metal ions (f), carboxylic acids, phosphoric acid compounds, boron compounds, antioxidants, antioxidants, plasticizers, heat stabilizers ( melt stabilizers), photoinitiators, deodorants, ultraviolet absorbers, antistatic agents, lubricants, coloring agents, fillers, desiccants, fillers, pigments, dyes, processing aids, flame retardants, antifogging agents, etc. mentioned.
  • the content of other components in the barrier layer (A) is usually 5% by mass or less, preferably 3% by mass or less, more preferably 1% by mass or less.
  • the barrier layer (A) preferably contains alkali metal ions.
  • the lower limit of the alkali metal ion content is preferably 100 ppm, more preferably 150 ppm.
  • the upper limit of the alkali metal ion content is preferably 400 ppm, more preferably 350 ppm. If the content of alkali metal ions is less than 100 ppm, the interlayer adhesion of a multilayer molded article containing a layer obtained by molding EVOH (a) may be insufficient. On the other hand, when the content of alkali metal ions exceeds 400 ppm, coloration due to thermal deterioration may become a problem. Further, by controlling the content ratio of the alkali metal ion and the carboxylic acid to be described later, the melt moldability and coloration resistance can be further improved.
  • Alkali metal ions include, for example, lithium, sodium, potassium, rubidium and cesium ions, but sodium or potassium ions are preferred from the standpoint of industrial availability.
  • potassium ions it may be possible to achieve both high levels of color and interlayer adhesion with the adhesive layer (B). These may be used individually by 1 type, and may use 2 or more types together.
  • alkali metal salts that give alkali metal ions include aliphatic carboxylates, aromatic carboxylates, carbonates, hydrochlorides, nitrates, sulfates, phosphates, metal complexes, etc. of alkali metals such as sodium and potassium. is mentioned. Among them, sodium acetate, potassium acetate, sodium phosphate and potassium phosphate are more preferable from the viewpoint of easy availability.
  • the barrier layer (A) preferably contains carboxylic acid.
  • the lower limit of the carboxylic acid content is preferably 50 ppm, more preferably 100 ppm.
  • the upper limit of the carboxylic acid content is preferably 400 ppm, more preferably 350 ppm.
  • the content of carboxylic acid is 50 ppm or more, the coloring resistance tends to be improved.
  • the content of the carboxylic acid is 400 ppm or less, the interlayer adhesion with the adhesive layer (B) tends to increase and the odor tends to be suppressed.
  • the carboxylic acid content is obtained by extracting 10 g of the resin composition constituting the barrier layer (A) with 50 ml of pure water at 95° C. for 8 hours, and then titrating the obtained extract.
  • the content of carboxylic acid in the resin composition the carboxylic acid present as a salt in the extract is not considered.
  • the content of carboxylic acid in the resin composition can be obtained by subtracting the contribution of these acidic compounds from the measured value by titration. can.
  • the pKa of carboxylic acid is preferably 3.5 to 5.5.
  • the pH buffering capacity in the weakly acidic range is increased, the melt moldability is further improved, and the influence of coloring by acidic or basic substances can be further reduced.
  • the carboxylic acid may be a monovalent carboxylic acid. These may be used individually by 1 type, and may use 2 or more types together.
  • a monovalent carboxylic acid is a compound having one carboxyl group in the molecule.
  • These carboxylic acids may further have substituents such as hydroxyl groups, amino groups and halogen atoms. Among them, acetic acid is preferred because it is highly safe and easy to obtain and handle.
  • the carboxylic acid may be a polyvalent carboxylic acid.
  • the carboxylic acid is a polyvalent carboxylic acid, it may be possible to further improve the coloring resistance of EVOH (a) at high temperatures and the coloring resistance of melt-molded products of crushed multilayer films containing EVOH (a).
  • the polyvalent carboxylic acid compound preferably has 3 or more carboxyl groups. In this case, it may be possible to improve the coloring resistance more effectively.
  • a polyvalent carboxylic acid is a compound having two or more carboxyl groups in the molecule. In this case, the pKa of at least one carboxyl group is preferably in the range of 3.5 to 5.5.
  • the barrier layer (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 phosphate root.
  • the upper limit of the content of the phosphate compound is preferably 100 ppm in terms of phosphate root.
  • the phosphoric acid compound for example, various acids such as phosphoric acid and phosphorous acid, and salts thereof are used.
  • the phosphate may be a primary phosphate, a secondary phosphate, or a tertiary phosphate.
  • the cationic species of the phosphate is also not particularly limited, but the cationic species is preferably an alkali metal or an alkaline earth metal. Among them, sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, or dipotassium hydrogen phosphate is preferable as the phosphoric acid compound.
  • the barrier layer (A) may further contain a boron compound.
  • the lower limit of the content of the boron compound is preferably 50 ppm, more preferably 100 ppm in terms of boron element.
  • the upper limit of the content of the boron compound is preferably 400 ppm, more preferably 200 ppm, in terms of boron element.
  • Boron compounds include, for example, boric acid, borate esters, borates, and borohydride.
  • boric acids such as orthoboric acid (H 3 BO 3 ), metaboric acid and tetraboric acid; borate esters such as trimethyl borate and triethyl borate; alkali metal salts or alkaline earth metals of the above boric acids Examples include salts, borate salts such as borax, and the like. Among them, orthoboric acid is preferred.
  • the barrier layer (A) may further contain a hindered phenolic compound having an ester bond or an amide bond.
  • the content of the hindered phenol compound is preferably 1000-10000 ppm. When the content is 1000 ppm or more, coloration, thickening and gelation of the resin can be suppressed when the pulverized multilayer film is melt-molded. More preferably, the hindered phenolic compound content is 2000 ppm or more. On the other hand, when the content of the hindered phenol compound is 10000 ppm or less, coloring and bleeding out due to the hindered phenol compound can be suppressed. More preferably, the hindered phenolic compound content is 8000 ppm or less.
  • a hindered phenolic compound has at least one hindered phenol group.
  • a hindered phenol group is one in which a bulky substituent is attached to at least one of the carbons adjacent to the carbon to which the phenolic hydroxyl group is attached.
  • the bulky substituent is preferably an alkyl group having 1 to 10 carbon atoms, more preferably a t-butyl group.
  • the hindered phenol compound is preferably in a solid state around 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 more, more preferably 400 or more, and even more preferably 600 or more. On the other hand, the molecular weight is usually 2000 or less.
  • the melting point or softening temperature of the hindered phenol compound is preferably 200°C or lower, more preferably 190°C or lower, and even more preferably 180°C or lower.
  • Hindered phenolic compounds usually have an ester bond or an amide bond.
  • Hindered phenol compounds having an ester bond include esters of aliphatic carboxylic acids having a hindered phenol group and aliphatic alcohols, and hindered phenol compounds having an amide bond include hindered phenol groups. and amides of aliphatic carboxylic acids with aliphatic amines.
  • the hindered phenol compound preferably has an amide bond.
  • hindered phenolic compounds include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], which is commercially available from BASF as Irganox 1010, Irga Stearyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate commercially available as Nox 1076, 2,2′-thiodiethylbis[3-(3 ,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate, commercially available as Irganox 1135, Irganox 245 bis(3-tert-butyl-4-hydroxy-5-methylbenzenepropanoic acid) ethylene bis(oxyethylene), commercially available as Irganox 259, 1,6-hexane
  • Pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] is preferred, the former being more preferred.
  • the barrier layer (A) may further contain a thermoplastic resin other than EVOH (a).
  • thermoplastic resins other than EVOH (a) include various polyolefins (polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene-propylene copolymer, ethylene and ⁇ - Copolymers with olefins, copolymers of polyolefins and maleic anhydride, ethylene-vinyl ester copolymers, ethylene-acrylate copolymers, or modifications obtained by grafting these with unsaturated carboxylic acids or derivatives thereof polyolefin, etc.), various polyamides (nylon 6, nylon 6.6, nylon 6/66 copolymer, nylon 11, nylon 12, poly-metaxylylene adipamide, etc.), various polyesters (polyethylene terephthalate, polybutylene terephthalate, polyethylene phthalate, etc.), polyvinyl chloride, polyvinyliden
  • the proportion of EVOH (a) as a resin constituting the barrier layer (A) is preferably 60% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, 95% by mass or more, and 97% by mass. As described above, the content may be 99% by mass or more, and the resin constituting the barrier layer (A) may consist only of EVOH (a). Further, the proportion of EVOH (a) in the barrier layer (A) is preferably 60% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, 95% by mass or more, 97% by mass or more, It may be 99% by mass or more, and the barrier layer (A) may be substantially composed of EVOH (a) only.
  • the method for producing the resin composition constituting the barrier layer (A) is not particularly limited, but EVOH (a) and, if necessary, other additives It can be produced by melt-kneading (polyvalent metal ion (f), etc.).
  • the other additives may be blended in a solid state such as powder or as a melt, or may be blended as a solute contained in the solution or as a dispersoid contained in the dispersion.
  • Aqueous solutions and aqueous dispersions are suitable as solutions and dispersions, respectively.
  • melt-kneading For melt-kneading, known mixing or kneading devices such as a kneader ruder, an extruder, a mixing roll, and a Banbury mixer can be used.
  • the temperature range during melt-kneading can be appropriately adjusted according to the melting point of the EVOH (a) used, and is usually 150 to 300°C.
  • a masterbatch containing other additives at a high concentration relative to EVOH (a) is produced by melt-kneading, and the masterbatch is EVOH (a) containing substantially no other additives.
  • EVOH(a) and other additives can be used to make multilayer films by dry blending.
  • Dry blending refers to mechanical mixing in the form of powders or pellets. Mixing may be performed using a mixing device such as a tumbler, ribbon mixer, or Henschel mixer, or may be performed by manually stirring, shaking, or the like in a closed vessel. The mixing temperature may be from room temperature to below the melting point of EVOH (a), and the mixing can be performed in an air atmosphere or a nitrogen atmosphere.
  • the thickness of one barrier layer (A) can be, for example, 0.5 to 100 ⁇ m, preferably 1 to 40 ⁇ m, more preferably 2 to 20 ⁇ m, and even more preferably 4 to 15 ⁇ m.
  • the thickness of one barrier layer (A) may be 10 ⁇ m or less.
  • the multilayer film of the present invention has an adhesive layer (B) containing an adhesive resin (b) as a main component.
  • the adhesive resin (b) may consist of only one resin, or may be a mixture of two or more resins.
  • the adhesive resin (b), which is a mixture of two or more resins, may contain a non-adhesive resin. It is sufficient that the entire mixture of two or more resins has adhesiveness.
  • the adhesive resin (b) is one or more resins including at least one adhesive resin.
  • the adhesive resin (b) may be, for example, a resin having an acid group and an acid value of 0.1 mgKOH/g or more.
  • the above oxidation represents an average value (acid number in the mixture).
  • the non-adhesive resin that may be contained in the adhesive resin (b) include an unmodified resin (bx) described later.
  • the adhesive layer (B) has the function of adhering the barrier layer (A) and the heat-sealable layer (C) or the thermoplastic resin layer described later. Therefore, the adhesive layer (B) is preferably provided between the barrier layer (A) and the heat-fusible layer (C) or the thermoplastic resin layer. ) or directly laminated with the thermoplastic resin layer.
  • the content of the adhesive resin (b) in the adhesive layer (B) must be more than 50% by mass, preferably 70% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more.
  • the adhesive resin (b) contains a carboxyl group obtained by chemically bonding, for example, an unsaturated carboxylic acid or its anhydride to an olefin polymer by an addition reaction, a graft reaction, or the like.
  • a modified olefin-based polymer can be mentioned.
  • unsaturated carboxylic acids or anhydrides thereof include maleic acid, maleic anhydride, fumaric acid, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, citraconic acid, hexahydrophthalic anhydride and the like. is preferably used.
  • maleic anhydride graft-modified polyethylene maleic anhydride graft-modified polypropylene, maleic anhydride graft-modified ethylene-propylene copolymer, maleic anhydride graft-modified ethylene-ethyl acrylate copolymer, maleic anhydride graft-modified ethylene
  • maleic anhydride graft-modified polyethylene One or a mixture of two or more selected from vinyl acetate copolymers and the like is preferred, and among these, maleic anhydride graft-modified polyethylene is most preferred.
  • the acid value of the adhesive resin (b) (acid value of the entire adhesive resin (b)) is usually 0.5-5 mgKOH/g, preferably 1-4 mgKOH/g.
  • the acid value of the adhesive resin (b) may be 3 mgKOH/g or less or 2 mgKOH/g or less from the viewpoint of recyclability.
  • the adhesive resin (b) may be a mixture of an unmodified resin (bx) and an acid-modified resin (by).
  • the unmodified resin (bx) preferably contains an ethylene- ⁇ -olefin copolymer resin (c) described later, and the ethylene- ⁇ -olefin copolymer resin (c ) is more preferred.
  • the unmodified resin (bx) contains the ethylene- ⁇ -olefin copolymer resin (c)
  • the ethylene- ⁇ -olefin copolymer resin (c) contained in the adhesive layer (B) and heat-sealing may be the same or different, but is preferably the same.
  • the ratio (bx/by) of the unmodified resin (bx) and the acid-modified resin (by) in the adhesive resin (b) is preferably 55/45 to 95/5, preferably 65/35 to 90/10. .
  • the acid-modified resin (by) a resin having a relatively high degree of acid modification can be preferably used, and its acid value is preferably 5 to 30 mgKOH/g, more preferably 8 to 20 mgKOH/g. By doing so, it may be possible to further improve the mechanical strength of the obtained multilayer film while maintaining the required interlayer adhesive strength.
  • the adhesive resin (b) of the present invention is a mixture of the unmodified resin (bx) and the acid-modified resin (by), the unmodified resin (bx) and the acid-modified resin (by) are melt-kneaded in advance. It may be used, or a dry blend of the unmodified resin (bx) and the acid-modified resin (by) may be used.
  • melt-kneading known mixing or kneading devices such as a kneader ruder, an extruder, a mixing roll, and a Banbury mixer can be used.
  • the temperature range during melt-kneading can be appropriately adjusted according to the melting points of the unmodified resin (bx) and the acid-modified resin (by) used, and is usually 150 to 300°C.
  • Dry blending refers to mechanical mixing in the form of powders or pellets. Mixing may be performed using a mixing device such as a tumbler, ribbon mixer, or Henschel mixer, or may be performed by manually stirring, shaking, or the like in a closed vessel.
  • the mixing temperature may be from room temperature to below the melting point of the unmodified resin (bx) and the acid-modified resin (by), and the mixing can be performed in an air atmosphere or a nitrogen atmosphere.
  • the adhesive layer (B) may contain components other than the adhesive resin (b) as long as the effects of the present invention are not impaired.
  • Other components include, for example, alkali metal ions, polyvalent metal ions, carboxylic acids, phosphoric acid compounds, boron compounds, antioxidants, antioxidants, plasticizers, heat stabilizers (melt stabilizers), photoinitiators, Deodorants, ultraviolet absorbers, antistatic agents, lubricants, colorants, fillers, desiccants, fillers, pigments, dyes, processing aids, flame retardants, antifog agents, and the like.
  • the content of other components in the adhesive layer (B) is usually 5% by mass or less, preferably 3% by mass or less, more preferably 1% by mass or less.
  • the proportion of the adhesive resin (b) as the resin constituting the adhesive layer (B) is preferably 60% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, 95% by mass or more, 97 It may be at least 99% by mass, and the resin constituting the adhesive layer (B) may consist of only the adhesive resin (b).
  • the proportion of the adhesive resin (b) in the adhesive layer (B) is preferably 60% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, 95% by mass or more, and 97% by mass. As described above, the content may be 99% by mass or more, and the adhesive layer (B) may be substantially composed only of the adhesive resin (b).
  • the thickness of one adhesive layer (B) can be, for example, 0.5 to 100 ⁇ m, preferably 1 to 40 ⁇ m, more preferably 2 to 20 ⁇ m, and even more preferably 4 to 15 ⁇ m.
  • the thickness of one adhesive layer (B) may be 10 ⁇ m or less.
  • the multilayer film of the present invention has a heat-sealable layer (C) containing, as a main component, an ethylene- ⁇ -olefin copolymer resin (c) having a density of 0.880 to 0.920 g/cm 3 .
  • the heat-sealable layer (C) functions as a sealing layer when forming a packaging material, and also has a function of increasing various mechanical strengths such as puncture strength and tensile strength.
  • the content of the ethylene- ⁇ -olefin copolymer resin (c) in the thermal adhesive layer (C) must be more than 50% by mass, preferably 70% by mass or more, more preferably 90% by mass or more, and 95% by mass or more. % by mass or more is more preferable.
  • the density of the ethylene- ⁇ -olefin copolymer resin (c) is 0.880-0.920 g/cm 3 .
  • the lower limit of density is preferably 0.885 g/cm 3 , more preferably 0.890 g/cm 3 , still more preferably 0.895 g/cm 3 .
  • the upper limit of density is preferably 0.915 g/cm 3 , more preferably 0.910 g/cm 3 , still more preferably 0.905 g/cm 3 .
  • the MFR (190° C., under 2.16 kg load) of the ethylene- ⁇ -olefin copolymer resin (c) may be, for example, 0.3 to 4.0 g/10 min, but may be 0.5 to 2.0 g/10 min. 0 g/10 min is preferred.
  • the MFR is within the above range, the ethylene- ⁇ -olefin copolymer resin (c) is excellent in melt processability, and various mechanical strengths such as puncture strength and tensile strength of the resulting multilayer film are improved.
  • the lower limit of MFR is preferably 0.7 g/10 minutes.
  • the upper limit of MFR is preferably 1.5 g/10 minutes, more preferably 1.0 g/10 minutes.
  • MFR is measured at 190°C under a load of 2.16 kg according to JIS K7210 (2014).
  • the total heat of fusion in the melting curve when the ethylene- ⁇ -olefin copolymer resin (c) is heated at 10°C/min with a differential scanning calorimeter (DSC) is preferably 150 J/g or less.
  • the ethylene- ⁇ -olefin copolymer resin (c) has excellent melt processability, and the obtained multilayer film is flexible and can be used in various mechanical applications such as puncture strength and tensile strength. Improves strength.
  • the total heat of fusion is more preferably 125 J/g or less, still more preferably 100 J/g or less, and particularly preferably 90 J/g or less.
  • the lower limit of the total heat of fusion is not particularly limited, it is preferably 70 J/g or more, more preferably 80 J/g or more, from the viewpoint of the handleability and heat resistance of the obtained multilayer film.
  • the total heat of fusion can be adjusted by the type of ⁇ -olefin, the ratio of ethylene and ⁇ -olefin, the distribution in the polymer chain, the degree of polymerization, and the like.
  • the above heat of fusion is preferably 60 J/g or less.
  • the heat of fusion at 100°C or higher is within the above range, the ethylene- ⁇ -olefin copolymer resin (c) has both flexibility and toughness, and various mechanical strengths such as puncture strength and tensile strength are improved. sometimes.
  • the lower limit of the heat of fusion of 100° C. or higher is not particularly limited, it is preferably 5 J/g or higher, more preferably 10 J/g or higher, from the viewpoint of the handleability and heat resistance of the resulting multilayer film.
  • the heat of fusion of 100° C. or higher can be adjusted by the type of ⁇ -olefin, the ratio of ethylene to ⁇ -olefin, the distribution in the polymer chain, the degree of polymerization, and the like.
  • the ratio (percentage) of the heat of fusion at 100° C. or less to the heat is 45% or more.
  • the ratio of the heat of fusion at 100° C. or less is within the above range, the obtained multilayer film is flexible and various mechanical strengths such as puncture strength and tensile strength are improved.
  • the ratio of heat of fusion at 100° C. or less is more preferably 60% or more, and even more preferably 75% or more.
  • the upper limit of the ratio of the heat of fusion at 100° C. or less is not particularly limited, it is preferably 90% or less, more preferably 85% or less, from the viewpoint of the handleability and heat resistance of the resulting multilayer film.
  • the above ratio can be adjusted by the type of ⁇ -olefin, the ratio of ethylene to ⁇ -olefin, the distribution in the polymer chain, the degree of polymerization, and the like.
  • the ethylene- ⁇ -olefin copolymer resin (c) is a resin obtained by polymerizing ethylene and an ⁇ -olefin having 3 or more carbon atoms.
  • ⁇ -olefins having 3 or more carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene and 4-methyl-1-pentene.
  • the ethylene- ⁇ -olefin copolymer resin (c) is preferably a linear low-density polyethylene obtained by polymerizing ethylene and an ⁇ -olefin having 6 or more carbon atoms.
  • it is a linear low-density polyethylene obtained by polymerizing the above ⁇ -olefin.
  • the ⁇ -olefin to be copolymerized with ethylene has a relatively large number of carbon atoms, various mechanical strengths such as puncture strength and tensile strength may be particularly improved.
  • the upper limit of the number of carbon atoms of the ⁇ -olefin constituting the ethylene- ⁇ -olefin copolymer resin (c) is not particularly limited, it may be 14, 12 or 10, for example.
  • a metallocene catalyst as the polymerization catalyst for polymerizing the ethylene- ⁇ -olefin copolymer resin (c).
  • the metallocene catalyst usually has at least one or more ligands having a cyclopentadienyl skeleton, a compound having a transition metal of Group 4 of the periodic table (preferably zirconium) as a central metal atom, an organoaluminum oxy compound, and It is formed from various components added as necessary.
  • a linear low-density polyethylene polymerized using a metallocene catalyst is produced by copolymerizing ethylene and an ⁇ -olefin in the presence of such a metallocene catalyst.
  • Linear low-density polyethylene polymerized using a metallocene catalyst has excellent melt moldability, and the obtained multilayer film has an excellent balance of heat resistance, flexibility and mechanical strength.
  • Linear low-density polyethylene obtained by polymerizing ethylene and an ⁇ -olefin having 6 or more carbon atoms using a metallocene catalyst is commercially available as "Evolue (trademark)” (prime polymer (manufactured by Sumitomo Chemical Co., Ltd.), “Sumikasen (trademark)” (manufactured by Sumitomo Chemical Co., Ltd.), “Umerit (trademark)” (manufactured by Ube Maruzen Polyethylene Co., Ltd.), and “Elite (trademark)” (manufactured by Dow Chemical Co., Ltd.).
  • the heat-sealable layer (C) contains 100-7000 ppm of a higher fatty acid amide compound (d) having a melting point of 60-120°C.
  • a higher fatty acid amide compound (d) is, for example, an amide compound of a fatty acid having 6 or more carbon atoms (preferably 10 to 25 carbon atoms).
  • the higher fatty acid amide (d) is, for example, an amide compound having an acyl group with 6 or more carbon atoms (preferably 10 to 25 carbon atoms).
  • the multilayer film of the present invention can reduce the fluctuation of the mechanical strength measurement value regardless of the storage environment or the measurement position, and the mechanical strength can be reduced. can improve the stability of In particular, even when the multilayer film is stored at high temperatures for a long period of time, it is possible to suppress fluctuations in mechanical strength, so reliability as a packaging material can be improved.
  • the lower limit of the content of the higher fatty acid amide compound (d) in the heat sealing layer (C) is 100 ppm, preferably 300 ppm, more preferably 500 ppm, and even more preferably 700 ppm.
  • the upper limit of the content of the higher fatty acid amide compound (d) is 7000 ppm, preferably 5000 ppm, more preferably 3000 ppm, still more preferably 1500 ppm, and may be 1000 ppm.
  • the higher fatty acid amide compound (d) is not particularly limited as long as it has a melting point of 60-120°C.
  • the lower limit of the melting point of the higher fatty acid amide compound (d) is preferably 70°C.
  • the upper limit of the melting point of the higher fatty acid amide compound (d) is preferably 110°C.
  • the melting point can be controlled by the length of the carbon chain, the degree of unsaturation (the number of double bonds in the carbon chain), the number of amide groups, the presence or absence of other substituents, and the like.
  • Examples of the higher fatty acid amide compound (d) include saturated higher fatty acid bisamides, unsaturated higher fatty acid bisamides, saturated higher fatty acid monoamides, unsaturated higher fatty acid monoamides and derivatives thereof, including saturated higher fatty acid monoamides having 10 to 25 carbon atoms and It is preferably at least one selected from the group consisting of unsaturated higher fatty acid monoamides having 10 to 25 carbon atoms.
  • Preferred examples of saturated higher fatty acid monoamides having 10 to 25 carbon atoms include capric acid amide, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, arachidic acid amide, and behenic acid amide.
  • lauric acid amide, stearic acid amide, and behenic acid amide are preferred, and stearic acid amide is more preferred, from the viewpoint of economy and availability.
  • the unsaturated higher fatty acid monoamide having 10 to 25 carbon atoms is preferably a monoene higher fatty acid monoamide having a degree of unsaturation of 1 from the viewpoint of suppressing coloration, such as oleic acid amide, elaidic acid amide, vaccenic acid amide, gadoleic acid amide, Preferred examples include eicosenoic acid amide and erucic acid amide. Among these, oleic acid amide or erucic acid amide is preferable from the viewpoint of economy and availability.
  • the higher fatty acid amide compound (d) may preferably have 12 to 22 carbon atoms. Moreover, the higher fatty acid amide compound (d) may have a substituent such as a hydroxyl group.
  • the higher fatty acid amide compound (d) preferably contains two or more higher fatty acid amide compounds having different melting points.
  • it preferably contains an unsaturated higher fatty acid amide compound (d1) having a melting point of 60°C or higher and lower than 90°C and a saturated higher fatty acid amide compound (d2) having a melting point of 90°C or higher and lower than 120°C.
  • the thermal adhesive layer (C) preferably contains 500 to 5000 ppm of inorganic oxide particles (e) having an average particle size of 1 to 30 ⁇ m. By doing so, it may be possible to improve the handleability in the process of manufacturing and processing the multilayer film, and further improve the stability of the mechanical strength of the multilayer film.
  • the average particle size of the inorganic oxide particles (e) is preferably 2-15 ⁇ m, more preferably 3-10 ⁇ m.
  • the average particle size is the median size measured by a light scattering method while the inorganic oxide particles (e) are dispersed in water or an organic solvent, sufficiently stirred, and then the resulting dispersion is circulated.
  • the content of the inorganic oxide particles (e) is preferably 750-4500 ppm, more preferably 1000-4000 ppm.
  • the shape of the inorganic oxide particles (e) preferably has a small aspect ratio (for example, 2 or less, preferably 1.5 or less) and is nearly spherical.
  • the inorganic oxide particles (e) are preferably at least one selected from the group consisting of silicon oxide particles and metal oxide particles.
  • the metal constituting the metal oxide particles is preferably at least one selected from the group consisting of aluminum, magnesium, zirconium, cerium, tungsten, molybdenum, titanium and zinc.
  • Specific inorganic oxides constituting the inorganic oxide particles (e) include silicon oxide, aluminum oxide, zirconium oxide, magnesium oxide, cerium oxide, tungsten oxide, molybdenum oxide, titanium oxide, zinc oxide, and composites thereof. etc. (a composite of silicon oxide and aluminum oxide, etc.), with silicon oxide being preferred.
  • the heat-sealable layer (C) contains other than the ethylene- ⁇ -olefin copolymer resin (c), the higher fatty acid amide compound (d) and the inorganic oxide particles (e) as long as the effects of the present invention are not impaired.
  • Other components include, for example, alkali metal ions, polyvalent metal ions, carboxylic acids, phosphoric acid compounds, boron compounds, antioxidants, antioxidants, plasticizers, heat stabilizers (melt stabilizers), photoinitiators, Deodorants, ultraviolet absorbers, antistatic agents, lubricants, colorants, fillers, desiccants, fillers, pigments, dyes, processing aids, flame retardants, antifog agents, and the like.
  • the content of other components in the heat-sealable layer (C) is usually 5% by mass or less, preferably 3% by mass or less, more preferably 1% by mass or less.
  • the heat-sealable layer (C) may further contain a thermoplastic resin other than the ethylene- ⁇ -olefin copolymer resin (c).
  • the thermoplastic resin any of the resins exemplified above as the thermoplastic resin that may be contained in the barrier layer (A) can be used.
  • the content of the thermoplastic resin in the heat-sealable layer (C) is less than 50% by mass, preferably less than 30% by mass, more preferably less than 10% by mass, even more preferably 5% by mass or less, and 1% by mass. It may be below.
  • the ratio of the ethylene- ⁇ -olefin copolymer resin (c) as the resin constituting the thermal adhesive layer (C) is preferably 60% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more. Preferably, it may be 95% by mass or more, 97% by mass or more, or 99% by mass or more, and the resin constituting the heat sealing layer (C) consists only of the ethylene- ⁇ -olefin copolymer resin (c). good too.
  • the ratio of the ethylene- ⁇ -olefin copolymer resin (c) and the higher fatty acid amide compound (d) in the heat-sealable layer (C) is preferably 60% by mass or more, more preferably 80% by mass or more.
  • the heat sealing layer (C) is substantially an ethylene- ⁇ -olefin copolymer resin (c ) and the higher fatty acid amide compound (d) alone.
  • the method for producing the resin composition constituting the thermal adhesive layer (C) is not particularly limited, but the ethylene- ⁇ -olefin copolymer resin (c), the higher fatty acid amide compound (d) and, if necessary, an inorganic oxide It can be produced by melt-kneading other additives such as particles (e).
  • the higher fatty acid amide compound (d) may be blended in a solid state such as powder or as a melt, or may be blended as a solute contained in a solution or a dispersoid contained in a dispersion.
  • Aqueous solutions and aqueous dispersions are suitable as solutions and dispersions, respectively.
  • melt-kneading For melt-kneading, known mixing or kneading devices such as a kneader ruder, an extruder, a mixing roll, and a Banbury mixer can be used.
  • the temperature range during melt-kneading can be appropriately adjusted according to the melting point of the ethylene- ⁇ -olefin copolymer resin (c) used, and is usually 150 to 300°C.
  • the higher fatty acid amide compound (d) and, if necessary, other additives such as inorganic oxide particles (e) are added to the ethylene- ⁇ -olefin copolymer resin (c) at a high concentration.
  • the masterbatch containing in is produced by melt-kneading, and the masterbatch is an ethylene- ⁇ -olefin copolymer that does not substantially contain other additives such as higher fatty acid amide compounds (d) and inorganic oxide particles (e) It can be dry blended with the coalesced resin (c) and used to make multilayer films.
  • the ethylene- ⁇ -olefin copolymer resin (c), the higher fatty acid amide compound (d), and optionally other additives such as inorganic oxide particles (e) are dry blended. It can be used in the production of multilayer films. Dry blending refers to mechanical mixing in the form of powders or pellets. Mixing may be performed using a mixing device such as a tumbler, ribbon mixer, or Henschel mixer, or may be performed by manually stirring, shaking, or the like in a closed vessel. The mixing temperature may be from room temperature to below the melting point of the ethylene- ⁇ -olefin copolymer resin (c), and mixing can be performed in an air atmosphere or a nitrogen atmosphere.
  • a mixing device such as a tumbler, ribbon mixer, or Henschel mixer
  • the thickness of one thermal adhesive layer (C) may be, for example, 5 to 300 ⁇ m, preferably 10 to 200 ⁇ m, more preferably 20 to 100 ⁇ m, and even more preferably 30 to 60 ⁇ m.
  • the multilayer film of the present invention has at least a barrier layer (A), an adhesive layer (B), and a heat-sealable layer (C). It does not have the above metal layers.
  • the multilayer film does not have a layer containing a resin having a melting point of 200° C. or more as a main component and a metal layer having a thickness of 1 ⁇ m or more, so that when the pulverized multilayer film is melt-molded, it does not mix with other components. Non-uniform mixing can be suppressed.
  • a metal layer is a layer which has a continuous and discontinuous surface which consists of metals, such as an aluminum foil, here.
  • barrier layer (A) and adhesive layer (B) are preferably laminated adjacent to each other, more preferably directly laminated.
  • the heat-sealable layer (C) is preferably at least one of the outermost layers in the multilayer film.
  • a conventional co-extrusion method in which resins are extruded from separate dies or from a common die and laminated can be used.
  • the die either an annular die or a T-die can be used.
  • the molding temperature during melt molding may be appropriately adjusted based on the melting point and melt viscosity of the resin to be used, and is often selected from the range of 150 to 300°C.
  • the multilayer film of the present invention may be a coextruded film.
  • the multilayer film of the present invention may be a non-stretched film or a stretched film.
  • the total thickness of the multilayer film of the present invention is preferably 15-300 ⁇ m, more preferably 25-250 ⁇ m, still more preferably 35-200 ⁇ m, and particularly preferably 45-150 ⁇ m.
  • the multilayer film of the present invention is lightweight and flexible, and is preferably used for flexible packaging. Moreover, the amount of resin used in the multilayer film is small, and the environmental load is suppressed.
  • the ratio of the thickness of the barrier layer (A) to the total thickness of all layers may be, for example, 0.20 or less or 0.15 or less, but preferably 0.10 or less. When this ratio is within the above range, recyclability and mechanical strength are improved.
  • the lower limit of the ratio of the thickness of the barrier layer (A) to the total thickness of all layers is not particularly limited, it is generally 0.005 or more in order to exhibit sufficient gas barrier properties.
  • the ratio of the thickness of the heat sealing layer (C) to the total thickness of all layers is preferably 0.60 or more, more preferably 0.70 or more, and even more preferably 0.80 or more. . When this ratio is within the above range, recyclability and mechanical strength are improved.
  • Typical layer structures of the multilayer film of the present invention are, for example, (A)/(B)/(C) and (C)/(B)/(A)/(B)/(C). Yes, but may have additional layers. Also, when a plurality of barrier layers (A), adhesive layers (B), and heat-sealable layers (C) are used, different types of resins can be used for each layer.
  • the oxygen transmission rate (OTR) of the multilayer film of the present invention under conditions of 20° C. and 65% RH may be adjusted according to the application and is not particularly limited, but is preferably 5 cc/(m 2 ⁇ day ⁇ atm) or less.
  • a multilayer film having an OTR within this range has excellent gas barrier properties and is suitable for use as a packaging material.
  • the OTR is more preferably 4 cc/(m 2 ⁇ day ⁇ atm) or less, even more preferably 3 cc/(m 2 ⁇ day ⁇ atm) or less, and particularly preferably 2 cc/(m 2 ⁇ day ⁇ atm) or less.
  • OTR is measured according to JIS K7126-2 (isobaric method; 2006), and specifically, the method described in Examples is employed.
  • the multilayer film of the present invention was conditioned at 23° C. and 50% RH for 24 hours, and then under the same conditions, was pierced with a needle having a tip diameter of 1 mm at a speed of 50 mm/min.
  • Elongation is preferably 6 mm or more.
  • a multilayer film having a puncture breaking elongation within the above range has excellent mechanical strength and is less likely to break due to an external impact or the like, and is therefore suitable for use as a packaging material.
  • the puncture elongation is more preferably 8 mm or more, still more preferably 10 mm or more, and particularly preferably 12 mm or more.
  • the multilayer film of the present invention was conditioned at 23° C. and 50% RH for 24 hours, and then under the same conditions, the breaking strength when a needle with a tip diameter of 1 mm was pierced at a speed of 50 mm/min (penetration breaking strength ) is preferably 5N or more.
  • a multilayer film having a puncture strength within this range has excellent mechanical strength and is less likely to break due to external impact or the like, and is therefore suitable for use as a packaging material.
  • the puncture elongation is more preferably 6.0N or more, more preferably 7.0N or more, and particularly preferably 8.0N or more.
  • the multilayer film of the present invention preferably has a coefficient of variation (value obtained by dividing the standard deviation by the average value) of the puncture breaking strength of 0.05 or less.
  • a multilayer film having a coefficient of variation within this range has excellent mechanical strength stability and is less likely to break due to external impact or the like, and is therefore suitable for use as a packaging material.
  • the coefficient of variation is more preferably 0.03 or less, more preferably 0.015 or less, and particularly preferably 0.010 or less.
  • the variation coefficient of the puncture breaking strength is a value based on the measured values of the puncture breaking strength at 10 points.
  • the multilayer film of the present invention itself can be used as a packaging material having gas barrier properties. By doing so, various functions as a packaging material such as heat resistance and design can be imparted.
  • the thermoplastic resin (g) is not particularly limited, and linear low density polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, vinyl ester resin, ethylene-propylene copolymer, polypropylene, propylene- ⁇ -olefin Copolymers ( ⁇ -olefins with 4 to 20 carbon atoms), olefins such as polybutene and polypentene, or their copolymers, polyamides such as nylon 6 and nylon 6,6, polyethylene terephthalate, polybutylene terephthalate, polyethylene nano Polyester such as phthalate, polystyrene, polyvinyl chloride, polyvinylidene chloride, acrylic resin, polycarbonate, chlorinated polyethylene, chlorinated polypropylene and the like can be mentioned.
  • the thermoplastic resin (g) more preferably contains polyethylene resin as a main component, and is more preferably polyethylene resin.
  • Polyethylene resin refers to polyethylene (unmodified polyethylene) and modified polyethylene.
  • the polyethylene resin used for the resin layer (R) may be polyethylene (unmodified polyethylene).
  • the resin layer (R) may be a single layer, or may be a multilayer consisting of multiple layers. Moreover, the resin layer (R) may be unstretched, or may be stretched or rolled uniaxially or biaxially. From the viewpoint of improving mechanical strength, it is preferably a biaxially stretched layer, and from the viewpoint of improving heat sealability, it is preferably a non-stretched layer.
  • the method of forming the resin layer (R) is not particularly limited, it is generally formed by melt extrusion using an extruder.
  • the die either an annular die or a T-die can be used.
  • the method of stretching uniaxially or biaxially is also not particularly limited, and by a conventionally known stretching method such as roll uniaxial stretching, tubular simultaneous biaxial stretching, tenter successive biaxial stretching, and tenter simultaneous biaxial stretching.
  • the film can be produced by stretching in the machine direction and/or in the direction perpendicular to the machine direction, that is, in the width direction.
  • the draw ratio is preferably 8 to 60 times the area from the viewpoint of the uniformity of the thickness of the layer to be obtained and the mechanical strength.
  • the area magnification is more preferably 55 times or less, more preferably 50 times or less. Further, the area magnification 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 be easily broken during stretching.
  • the thickness of the resin layer (R) is preferably 10-200 ⁇ m from the viewpoint of industrial productivity. Specifically, the thickness of the non-stretched layer is more preferably 10 to 150 ⁇ m, and the thickness of the biaxially stretched layer is more preferably 10 to 50 ⁇ m.
  • the total thickness of the multilayer structure of the present invention is preferably 300 ⁇ m or less.
  • the multilayer structure of the present invention is lightweight and flexible, and is preferably used for flexible packaging. Moreover, the amount of resin used in the multilayer structure is small, and the environmental load is suppressed.
  • each layer in the multilayer structure of the present invention may be appropriately adjusted according to the application, but when the pulverized product is melt-molded, coloring can be suppressed, the thermal stability during melt-molding is improved, and the occurrence of pimples. is suppressed, the ratio of the total thickness of the layers containing polyethylene resin as a main component to the total thickness of the multilayer structure is preferably 0.80 or more, more preferably 0.85 or more, and 0.90 or more. More preferably, 0.95 or more is particularly preferable.
  • the multilayer structure of the present invention preferably does not have a layer containing a resin with a melting point of 200°C or more as a main component and a metal layer with a thickness of 1 ⁇ m or more.
  • a layer containing a resin having a melting point of 200° C. or more as a main component and a metal layer having a thickness of 1 ⁇ m or more mixing with other components is impossible when the pulverized product of the multilayer structure is melt-molded. Uniformity can be suppressed.
  • the method of laminating the resin layer (R) on the multilayer film of the present invention is not particularly limited, and examples thereof include extrusion lamination, co-extrusion lamination, and dry lamination.
  • An adhesive layer may be provided when the resin layer (R) is laminated on the multilayer film.
  • the adhesive layer may be the same as the adhesive layer (B), or may be formed by applying a known adhesive and drying.
  • the adhesive is preferably a two-liquid reactive polyurethane adhesive in which a polyisocyanate component and a polyol component are mixed and reacted.
  • the thickness of the adhesive layer is not particularly limited, it is preferably 1 to 5 ⁇ m, more preferably 2 to 4 ⁇ m.
  • the multilayer structure of the present invention may have layers other than those described above as long as the effects of the present invention are not impaired.
  • Examples of other layers include collection layers.
  • Other examples of other layers include, for example, printing layers.
  • the printed layer may be included anywhere in the multilayer structure of the present invention. Examples of the printed layer include a film obtained by applying a solution containing a pigment or dye and, if necessary, a binder resin, followed by drying. Examples of coating methods for the printed layer include gravure printing, as well as various coating methods using a wire bar, a spin coater, a die coater, and the like.
  • the thickness of the printed layer is not particularly limited, it is preferably 0.5 to 10 ⁇ m, more preferably 1 to 4 ⁇ m.
  • the multi-layer film and multi-layer structure of the present invention have excellent appearance, gas barrier properties and recyclability, and also have excellent stability in mechanical properties. It can be suitably used as a material for various packaging. That is, the packaging material of the present invention contains the multilayer film or multilayer structure of the present invention.
  • the packaging material of the present invention may consist of the multilayer film or multilayer structure of the present invention.
  • the multilayer film and multilayer structure of the present invention can be used in a wider range of applications, and are not limited to packaging materials.
  • a preferred embodiment of the packaging material is a package formed by filling the packaging material with contents.
  • Contents that can be filled include beverages such as wine, fruit juice, etc.; foods such as fruits, nuts, vegetables, meat products, infant foods, coffee, jam, mayonnaise, ketchup, edible oil, dressings, sauces, tsukudani, and dairy products. etc.; Others include, but are not limited to, contents that are likely to deteriorate in the presence of oxygen, such as pharmaceuticals, cosmetics, and gasoline.
  • ⁇ Recovery composition and recovery method> It is preferable to collect and reuse edges and defective products generated during the production of the multilayer film or multilayer structure of the present invention. It is also a preferred embodiment to collect and reuse multilayer films and multilayer structures on the market.
  • a method for recovering a multilayer film or multilayer structure comprising a step of pulverizing the multilayer film or multilayer structure of the present invention followed by melt molding, and a recovered composition containing the recovered multilayer film or multilayer structure of the present invention are also provided by the present invention. It is a preferred embodiment of the invention.
  • the recovered multilayer film or multilayer structure of the present invention also includes recovered packaging materials containing the multilayer film or multilayer structure of the present invention.
  • the recovered multilayer film or multilayer structure of the present invention is pulverized.
  • the recovered pulverized material may be directly melt-molded to obtain a recovered composition, or may be melt-molded together with other components as necessary to obtain a recovered composition.
  • Preferred components to be added to the recovered material are polyolefin resins, more preferably polyethylene resins.
  • the recovered pulverized material may be directly used for manufacturing molded articles such as multilayer structures, or the recovered pulverized material may be melt pelletized to obtain pellets made of the recovered composition, and then the pellets may be used as molded articles.
  • Extrusion molding may be used for the production of Extrusion molding, inflation extrusion, blow molding, melt spinning, injection molding and the like can be used as melt molding methods for the recovered composition.
  • the molding temperature during melt molding may be appropriately adjusted based on the melting point and melt viscosity of the resin to be used, and is often selected from the range of 150 to 300°C.
  • the recovered composition may contain unused resin, but the content of the recovered material in the recovered composition is preferably 10% by mass or more, more preferably 20% by mass or more, and 30% by mass or more. may be
  • the content of EVOH (a) in the recovery composition is preferably 20% by mass or less, more preferably 10% by mass or less, and may be 5% by mass or less.
  • Example 1 (1) Preparation of EVOH (a)-containing resin composition for barrier layer (A) Load) 1.6 g/10 minutes, containing 220 ppm of sodium acetate in terms of sodium ions, 30 ppm of phosphate ions in terms of phosphate radicals, 150 ppm of boric acid in terms of boron elements, and no polyvalent metal ions) and magnesium stearate were melt-kneaded so that the content of magnesium ions in the resulting resin composition was 50 ppm, to obtain resin composition pellets for the barrier layer (A).
  • adhesive resin (b)-containing resin composition for adhesive layer (B) Maleic anhydride-modified polyethylene “Admer (trademark) NF518” (MFR (190 ° C., 2.16 kg load) manufactured by Mitsui Chemicals, Inc. ) 3.1 g/10 min, density 0.91 g/cm 3 , acid value 1.8 mg KOH/g) was used as adhesive resin (b-1). This adhesive resin (b-1) was used as it was as resin composition pellets for the adhesive layer (B).
  • Admer (trademark) NF518” MFR (190 ° C., 2.16 kg load) manufactured by Mitsui Chemicals, Inc. ) 3.1 g/10 min, density 0.91 g/cm 3 , acid value 1.8 mg KOH/g
  • the linear low-density polyethylene (c-1) pellets and the obtained stearic acid amide masterbatch pellets were dry-blended at a mass ratio of 98/2, and the resin composition for the heat sealing layer (C) was obtained.
  • a mixed pellet was obtained.
  • the linear low-density polyethylene (c-1) was heated from 20° C. to 250° C.
  • the total heat of fusion in the melting curve was 86.8 J/g, and the ratio (percentage) of the heat of fusion at 100°C or less to the total heat of fusion was 79.7%.
  • Extrusion temperature of barrier layer (A): feeding section/compression section/measuring section/die 170/220/220/220°C
  • Extrusion temperature of adhesive layer (B): feed section/compression section/measuring section/die 170/220/220/220°C
  • the multilayer film obtained in (4) above was pulverized to a size of 4 mm square or less.
  • the mass ratio (pulverization Material/polyethylene resin) were blended at a ratio of 40/60, and a single layer film having a thickness of 50 ⁇ m was obtained by performing single layer film formation under the extrusion conditions shown below.
  • the thickness of the single-layer film was adjusted by appropriately changing the screw rotation speed and take-up roll speed. As a control, a monolayer film having a thickness of 50 ⁇ m was similarly obtained using only the polyethylene resin.
  • Extrusion temperature: feeding section/compression section/measuring section/die 230/230/230/230°C
  • E is an unacceptable criterion.
  • the multi-layered structure thus obtained is elastic yet flexible, and is excellent in appearance properties, gas barrier properties, and mechanical properties, and therefore can be preferably used as a packaging material.
  • the ratio of the polyethylene-based material exceeds 0.9, it is also preferable for recycling as a so-called monomaterial packaging material. can be provided.
  • Example 2 EVOH (a-2) (ethylene unit content 32 mol%, saponification degree 99.99, MFR (190 ° C., 2.16 kg load) 4.4 g / 10 minutes, sodium acetate instead of EVOH (a-1)
  • EVOH (a-2) ethylene unit content 32 mol%, saponification degree 99.99, MFR (190 ° C., 2.16 kg load) 4.4 g / 10 minutes, sodium acetate instead of EVOH (a-1)
  • a multilayer film was produced in the same manner as in Example 1 except that 220 ppm in terms of sodium ions, 30 ppm in terms of phosphate ions and no polyvalent metal ions were used, and various measurements and evaluations were performed. rice field. Tables 3 and 4 show the results.
  • Example 3 EVOH (a-3) (ethylene unit content 27 mol%, saponification degree 99.99, MFR (190 ° C., 2.16 kg load) 1.5 g / 10 minutes, sodium acetate instead of EVOH (a-1)
  • a multilayer film was produced in the same manner as in Example 1, except that 220 ppm in terms of sodium ions, 30 ppm in terms of phosphate ions, 120 ppm in terms of boron elements, and no polyvalent metal ions were used. It was produced and various measurements and evaluations were performed. Tables 3 and 4 show the results.
  • Example 4 EVOH (a-4) (ethylene unit content 44 mol%, saponification degree 99.99, MFR (190 ° C., 2.16 kg load) 1.7 g / 10 minutes, sodium acetate instead of EVOH (a-1)
  • a multilayer film was produced in the same manner as in Example 1, except that 220 ppm in terms of sodium ions, 30 ppm in terms of phosphate ions, 100 ppm in terms of boron elements, and no polyvalent metal ions were used. It was produced and various measurements and evaluations were performed. Tables 3 and 4 show the results.
  • Example 5 A multilayer film was produced in the same manner as in Example 1, except that EVOH (a-1) was not kneaded with magnesium stearate, and various measurements and evaluations were performed. Tables 3 and 4 show the results.
  • Examples 6-7 A multilayer film was produced in the same manner as in Example 1, except that the amount of magnesium stearate kneaded with EVOH (a-1) was changed as shown in Table 1, and various measurements and evaluations were performed. Tables 3 and 4 show the results.
  • Examples 8-10 A multilayer film was produced in the same manner as in Example 1 except that the magnesium stearate kneaded with EVOH (a-1) was changed to calcium stearate, zinc stearate and magnesium acetate, respectively, and various measurements and evaluations were performed. . Tables 3 and 4 show the results.
  • Example 11 A multilayer film was produced in the same manner as in Example 1 except that the following adhesive resin (b-2) was used instead of the adhesive resin (b-1), and various measurements and evaluations were performed. Tables 3 and 4 show the results.
  • Adhesive resin (b-2) linear low-density polyethylene (c-1) and maleic anhydride-modified polyethylene manufactured by Dow Chemical Co. "Bynel CXA417E10" (MFR (190 ° C., 2.16 kg load) 2.7 g / 10 minutes, density 0.91 g/cm 3 , acid value 10.7 mg KOH/g) at a mass ratio of 93/7.
  • Example 12 A multilayer film was produced in the same manner as in Example 1 except that the following adhesive resin (b-3) was used instead of the adhesive resin (b-1), and various measurements and evaluations were performed. Tables 3 and 4 show the results.
  • Adhesive resin (b-3) linear low-density polyethylene (c-1) and maleic anhydride-modified polyethylene manufactured by Dow Chemical Co. "Binel CXA417E10" (MFR (190 ° C., 2.16 kg load) 2.7 g / 10 minutes, density 0.91 g/cm 3 , acid value 10.7 mg KOH/g) at a mass ratio of 85/15.
  • Example 13 A multilayer film was produced in the same manner as in Example 1 except that the following adhesive resin (b-4) was used instead of the adhesive resin (b-1), and various measurements and evaluations were performed. Tables 3 and 4 show the results.
  • Adhesive resin (b-4) Linear low-density polyethylene (c-1) and maleic anhydride-modified polyethylene manufactured by Dow Chemical Co. "Bynel CXA417E10" (MFR (190 ° C., 2.16 kg load) 2.7 g / 10 minutes, density 0.91 g/cm 3 , acid value 10.7 mg KOH/g) at a mass ratio of 60/40.
  • Examples 20-22 A multilayer film was produced in the same manner as in Example 1 except that lauric acid amide (L1A), oleic acid amide (O1A) and erucic acid amide (E1A) were used instead of stearic acid amide, and various measurements and made an evaluation. Tables 3 and 4 show the results.
  • Example 23 A multilayer film was produced in the same manner as in Example 1 except that stearamide and oleamide were used in a mass ratio of 1/1 instead of stearamide, and various measurements and evaluations were performed. Tables 3 and 4 show the results.
  • the multilayer films of Examples 1, 21 and 23 were separately subjected to the above-mentioned "(8) Stability evaluation of puncture breaking strength of multilayer films" under different conditions.
  • the multilayer film of this example using two or more kinds of higher fatty acid amide compounds having different melting points has a temperature of 60° C. and 90% RH compared to the multilayer films of Examples 1 and 21 using only higher fatty acid amide compounds. Even when stored for a long period of time under harsher conditions such as 85°C and 85% RH, fluctuations in puncture rupture strength were suppressed, and the stability of mechanical properties was excellent.
  • Example 24 A multilayer film was produced in the same manner as in Example 1 except that 10% by mass of spherical silica particles having an average particle size of 3.9 ⁇ m was added to the stearic acid amide masterbatch pellets, and various measurements and evaluations were performed. Tables 3 and 4 show the results.
  • Example 27 Instead of linear low density polyethylene (c-1), linear low density polyethylene (c-2) “Elite (trademark) 5220G” manufactured by Dow Chemical Co. (polymerization of ethylene and 1-octene with a metallocene catalyst, MFR (190° C., 2.16 kg load) 3.5 g/10 minutes, density 0.915 g/cm 3 , DSC measurement results are shown in Table 2), but using the same procedure as in Example 1 to prepare a multilayer film. , various measurements and evaluations were performed. Tables 3 and 4 show the results.
  • Example 28 Linear low density polyethylene (c-3) "Elite (trademark) 5400G” manufactured by Dow Chemical Co. (ethylene and 1-octene polymerized with a metallocene catalyst, MFR (190° C., 2.16 kg load) 1.0 g/10 min, density 0.916 g/cm 3 , DSC measurement results are shown in Table 2) was used, but a multilayer film was produced in the same manner as in Example 1. , various measurements and evaluations were performed. Tables 3 and 4 show the results.
  • Example 29 Linear low density polyethylene (c-4) "Inate (trademark) ST50" manufactured by Dow Chemical Co. (polymerization of ethylene and 1-octene, MFR (190 ° C. , 2.16 kg load) 0.9 g/10 min, density 0.918 g/cm 3 , DSC measurement results are shown in Table 2). and evaluated. Tables 3 and 4 show the results.
  • Example 30 Linear low-density polyethylene (c-5) "Inate (trademark) TH60" manufactured by Dow Chemical Co., Ltd. (polymerization of ethylene and 1-octene, MFR (190 ° C. , 2.16 kg load) 0.9 g/10 min, density 0.912 g/cm 3 , DSC measurement results are shown in Table 2). and evaluated. Tables 3 and 4 show the results.
  • Example 31 Instead of linear low-density polyethylene (c-1), Prime Polymer's linear low-density polyethylene (c-6) "Evolue (trademark) SP1540" (polymerization of ethylene and 1-octene with a metallocene catalyst, MFR (190° C., 2.16 kg load) 3.8 g/10 min, density 0.913 g/cm 3 , DSC measurement results are shown in Table 2) was used, but a multilayer film was produced in the same manner as in Example 1. , various measurements and evaluations were performed. Tables 3 and 4 show the results.
  • Example 32 Instead of linear low-density polyethylene (c-1), Prime Polymer's linear low-density polyethylene (c-7) "Evolue (trademark) SP0540" (polymerization of ethylene and 1-octene with a metallocene catalyst, MFR (190° C., 2.16 kg load) 3.8 g/10 minutes, density 0.903 g/cm 3 , DSC measurement results are shown in Table 2). , various measurements and evaluations were performed. Tables 3 and 4 show the results.
  • Example 33 Instead of linear low-density polyethylene (c-1), Prime Polymer's linear low-density polyethylene (c-8) "Evolue (trademark) SP1510" (polymerization of ethylene and 1-octene with a metallocene catalyst, MFR (190° C., 2.16 kg load) 1.0 g/10 min, density 0.915 g/cm 3 , DSC measurement results are shown in Table 2) was used, but a multilayer film was produced in the same manner as in Example 1. , various measurements and evaluations were performed. Tables 3 and 4 show the results.
  • Example 34 Instead of linear low-density polyethylene (c-1), Prime Polymer's linear low-density polyethylene (c-9) "Evolue (trademark) SP0510" (polymerization of ethylene and 1-octene with a metallocene catalyst, MFR (190° C., 2.16 kg load) 1.2 g/10 minutes, density 0.903 g/cm 3 , DSC measurement results are shown in Table 2), but using the same procedure as in Example 1 to prepare a multilayer film. , various measurements and evaluations were performed. Tables 3 and 4 show the results.
  • Comparative example 1 Various measurements and evaluations were performed in the same manner as in Example 1, except that a 100 ⁇ m-thick heat-sealable layer (C) single-layer film was produced instead of the multilayer film. Tables 3 and 4 show the results.
  • Comparative example 2 A multilayer film was produced in the same manner as in Example 1, except that stearic acid amide was not used, and various measurements and evaluations were performed. Tables 3 and 4 show the results.
  • Comparative example 4 A multilayer film was produced in the same manner as in Example 1 except that ethylenebisstearic acid amide (S2A) was used instead of stearic acid amide, and various measurements and evaluations were performed. Tables 3 and 4 show the results.
  • S2A ethylenebisstearic acid amide
  • Comparative example 5 Low-density polyethylene (c-10) "Novatec LD LJ400" manufactured by Nippon Polyethylene Co., Ltd. (MFR (190 ° C., 2.16 kg load) 1.5 g / 10 minutes, instead of linear low-density polyethylene (c-1), A multilayer film was produced in the same manner as in Example 1, except that the density was 0.921 g/cm 3 and the DSC measurement results are shown in Table 2), and various measurements and evaluations were performed. Tables 3 and 4 show the results.
  • Comparative example 7 High-density polyethylene (c-12) "Novatec HD HY540" manufactured by Nippon Polyethylene Co., Ltd. (MFR (190 ° C., 2.16 kg load) 1.0 g / 10 minutes, instead of linear low-density polyethylene (c-1), A multilayer film was produced in the same manner as in Example 1, except that the density was 0.960 g/cm 3 and the DSC measurement results are shown in Table 2), and various measurements and evaluations were performed. Tables 3 and 4 show the results.
  • each multilayer film of Examples is excellent in appearance properties, gas barrier properties and recyclability, and is also excellent in mechanical strength and its stability.
  • the MFR is 0.5 to 2.0 g/10 minutes and the melting point is 100°C or less. It can be seen that Examples 1, 30, 33 and 34 using the ethylene- ⁇ -olefin copolymer resin (c) having a heat ratio of 45% or more are particularly excellent in mechanical strength such as impact strength.

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Abstract

Ce film multicouche comprend : une couche barrière (A) contenant en tant que composant principal un copolymère éthylène-alcool vinylique (a) ayant une teneur en unité éthylène de 20 à 50 % en moles et un degré de saponification d'au moins 90 % en moles ; une couche adhésive (B) contenant en tant que composant principal une résine adhésive (b) ; et une couche de liaison à chaud (C) contenant en tant que composant principal une résine de copolymère d'éthylène-alpha-oléfine (c) qui a une densité de 0,880-0,920 g/cm3. Le film multicouche ne comporte pas : une couche contenant en tant que composant principal une résine ayant un point de fusion de 200 °C ou plus ; ou une couche métallique ayant une épaisseur de 1 µm ou plus. La couche de liaison à chaud (C) contient 100-7 000 ppm d'un composé amide d'acide gras supérieur (d) qui a un point de fusion de 60 à 120 °C.
PCT/JP2022/045916 2021-12-13 2022-12-13 Film multicouche, structure multicouche, matériau d'emballage, composition de récupération et procédé de récupération d'un film multicouche ou d'une structure multicouche WO2023112929A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002173561A (ja) * 2000-09-29 2002-06-21 Sumitomo Chem Co Ltd ポリオレフィン樹脂組成物及びそのフィルム
JP2005220307A (ja) * 2004-02-09 2005-08-18 Tosoh Corp シーラントフィルムおよび積層体
WO2011068105A1 (fr) * 2009-12-01 2011-06-09 株式会社クラレ Structure multicouches et son procédé de production
JP2012245767A (ja) * 2011-05-31 2012-12-13 Kuraray Co Ltd 多層構造体、これを用いた容器及びその製造方法
WO2020071513A1 (fr) * 2018-10-04 2020-04-09 株式会社クラレ Structure multicouche et matériau d'emballage la comprenant

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4005977B2 (ja) 2004-04-09 2007-11-14 日本ポリオレフィン株式会社 フィルムおよびシーラント
BR112019026004B1 (pt) 2017-06-09 2022-11-29 Dow Global Technologies Llc Filme multicamada coextrudado e laminado
EP4173822A1 (fr) 2020-06-25 2023-05-03 Kuraray Co., Ltd. Film multicouche et structure multicouche dans laquelle celui-ci est utilisé

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002173561A (ja) * 2000-09-29 2002-06-21 Sumitomo Chem Co Ltd ポリオレフィン樹脂組成物及びそのフィルム
JP2005220307A (ja) * 2004-02-09 2005-08-18 Tosoh Corp シーラントフィルムおよび積層体
WO2011068105A1 (fr) * 2009-12-01 2011-06-09 株式会社クラレ Structure multicouches et son procédé de production
JP2012245767A (ja) * 2011-05-31 2012-12-13 Kuraray Co Ltd 多層構造体、これを用いた容器及びその製造方法
WO2020071513A1 (fr) * 2018-10-04 2020-04-09 株式会社クラレ Structure multicouche et matériau d'emballage la comprenant

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