WO2020158803A1 - 多層構造体並びにそれを備える包装材及び縦製袋充填シール袋 - Google Patents

多層構造体並びにそれを備える包装材及び縦製袋充填シール袋 Download PDF

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Publication number
WO2020158803A1
WO2020158803A1 PCT/JP2020/003181 JP2020003181W WO2020158803A1 WO 2020158803 A1 WO2020158803 A1 WO 2020158803A1 JP 2020003181 W JP2020003181 W JP 2020003181W WO 2020158803 A1 WO2020158803 A1 WO 2020158803A1
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Prior art keywords
layer
less
ethylene
acid
multilayer structure
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PCT/JP2020/003181
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English (en)
French (fr)
Japanese (ja)
Inventor
清水　裕司
昌宏 北村
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Kuraray Co Ltd
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Kuraray Co Ltd
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Priority to JP2020569685A priority Critical patent/JP7184932B2/ja
Priority to DE112020000599.2T priority patent/DE112020000599T5/de
Publication of WO2020158803A1 publication Critical patent/WO2020158803A1/ja
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Definitions

  • the present invention is provided with a layer composed of a resin composition in which a resin component substantially consists of an ethylene-vinyl alcohol copolymer (hereinafter sometimes abbreviated as “EVOH”) and an acid-modified ethylene- ⁇ -olefin copolymer.
  • EVOH ethylene-vinyl alcohol copolymer
  • the present invention relates to a multi-layer structure and a vertical bag-making filling seal bag including the multi-layer structure.
  • EVOH has excellent barrier properties against gases such as oxygen, and also has excellent melt moldability, so it is processed into films and widely used as food packaging materials.
  • the EVOH film is rigid because it has high crystallinity, and pinholes sometimes occur due to bending.
  • Patent Document 1 discloses that EVOH having an ethylene unit content of 10 to 32 mol% and an anhydride and/or carboxylic acid functional group having a melt viscosity at 177° C. of less than 50000 cP.
  • a multilayer structure having a barrier layer containing a fluorinated ethylene/alpha-olefin interpolymer is a multilayer structure that exhibits good toughness and enables smooth drawdown, and is useful in thermoforming applications. Is listed.
  • Patent Document 2 describes that a blow-molded container having a pinch-off portion, which has a resin composition layer containing EVOH and a flexible resin as the innermost layer, has excellent impact strength at the side surface, bottom surface, corner portion, and pinch-off portion. ing.
  • the barrier layer described in Patent Document 1 uses an ethylene/ ⁇ -olefin interpolymer having a relatively low melt viscosity, impact strength, in particular, fold strength when impact is applied with the folds (hereinafter, “Folding strength” may be abbreviated) in some cases, and this may cause a problem particularly in packaging material applications where thin film thickness is required.
  • Fusion strength when an ethylene/ ⁇ -olefin interpolymer having a relatively low melt viscosity as described in Patent Document 1 is used or when the content ratio of the soft resin is increased, the appearance of the multilayer structure is deteriorated. There is a tendency.
  • the present invention provides a multilayer structure in which a barrier layer containing an ethylene-vinyl alcohol copolymer is excellent in impact resistance while maintaining high gas barrier properties and transparency, and is excellent in appearance, bending resistance and fold strength of the multilayer structure itself.
  • the present invention also provides a packaging material and a vertical bag-making filling seal bag including the multilayer structure.
  • the present invention is [1] A layer (X) and a layer (consisting of a resin composition (x) in which the resin component consists essentially of the ethylene-vinyl alcohol copolymer (A) and the acid-modified ethylene- ⁇ -olefin copolymer (B).
  • a layer (Y) containing a thermoplastic resin (C) is provided on both sides of (X), and the mass ratio of the acid-modified ethylene- ⁇ olefin copolymer (B) to the ethylene-vinyl alcohol copolymer (A) (B/ A) is 3/97 or more and 17/83 or less, and the melt flow rate of the acid-modified ethylene- ⁇ -olefin copolymer (B) measured at 230° C. under a load of 2160 g is 0.1 g/10 min, measured according to JIS K 7210:2014.
  • Multi-layer structure [2] The multilayer structure of [1], wherein the acid value of the acid-modified ethylene- ⁇ -olefin copolymer (B) is 3.0 mgKOH/g or more and 20 mgKOH/g or less; [3] Melt flow rate of ethylene-vinyl alcohol copolymer (A) at 230° C.
  • JIS K 7210 The multilayer structure of [1] or [2], wherein the absolute value of the difference from the melt flow rate under a load of 2160 g at 230° C.
  • a barrier layer containing an ethylene-vinyl alcohol copolymer is excellent in impact resistance while maintaining high gas barrier properties and transparency, and the multilayer structure itself is excellent in appearance, bending resistance and crease strength. It is possible to provide a vertical bag-making filling seal bag including a structure and a multilayer structure thereof.
  • FIG. 1 is a rear view showing a vertical bag-making filling seal bag according to an embodiment of the present invention.
  • the resin component is substantially ethylene-vinyl alcohol copolymer (A) (hereinafter sometimes abbreviated as “EVOH(A)”) and acid-modified ethylene- ⁇ -olefin copolymer ( B) (hereinafter sometimes abbreviated as “polymer (B)”) consisting of a resin composition (x) consisting of a layer (X) and a thermoplastic resin (C) on both sides of the layer (X).
  • A ethylene-vinyl alcohol copolymer
  • B acid-modified ethylene- ⁇ -olefin copolymer
  • the layer (Y) is provided, the mass ratio (B/A) of the polymer (B) to the EVOH (A) is 3/97 or more and 17/83 or less, and the acid-modified ethylene- ⁇ olefin copolymer (B)
  • the melt flow rate (MFR) at 230° C. and 2160 g load measured according to JIS K 7210:2014 is 0.1 g/10 min or more and 10 g/10 min or less, and the total average thickness of all layers is 50 ⁇ m or more and 500 ⁇ m or less.
  • the ratio of the average thickness of the layer (X) to the total average thickness of the layers is 1% or more and 15% or less.
  • the resin component may be a polymer component having one or more structural units.
  • the resin component may be, for example, a compound (polymer) component having a molecular weight of 1,000 or more.
  • the average thickness means an average value of thicknesses measured at arbitrary 5 points in the multilayer structure.
  • the layer (X) is composed of the resin composition (x) in which the resin component substantially consists of EVOH (A) and the polymer (B).
  • the layer (X) is composed of the resin composition (x)
  • the bending resistance, the impact resistance and the crease strength tend to increase while maintaining the transparency.
  • the layer (X) contains a resin component other than the EVOH (A) and the polymer (B)
  • the transparency, impact resistance, crease strength, etc. tend to decrease.
  • the average thickness of the layer (X) is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, still more preferably 6 ⁇ m or more, from the viewpoint of barrier properties.
  • the average thickness of the layer (X) is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, and even more preferably 12 ⁇ m or less, from the viewpoint of bending resistance.
  • the average thickness of the layer (X) means the sum of the average thicknesses of all the layers (X) included in the multilayer structure of the present invention.
  • the ratio of the average thickness of the layer (X) to the average thickness of the multilayer structure of the present invention is 1% or more, preferably 3% or more, 6% or more is more preferable. Further, the ratio of the average thickness of the layer (X) is 15% or less, preferably 12% or less.
  • film surface stability When the ratio of the average thickness of the layer (X) is less than 1%, streak or the like is generated on the film surface of the multilayer structure, and the appearance is deteriorated due to molding failure (hereinafter sometimes referred to as “film surface stability”). It tends to get worse. If the ratio of the average thickness of the layer (X) exceeds 15%, the bending resistance tends to decrease.
  • the film surface means an interface between the layer (X) and the layer (Y), and when the layer (X) and the layer (Y) are laminated via another layer such as an adhesive resin layer. Means an interface between each layer (layer (X) and layer (Y)) and another layer.
  • At least one layer (X) may be included in the multilayer structure of the present invention.
  • each layer (X) is the same. Or they may be different.
  • the upper limit of the number of layers (X) contained in the multilayer structure of the present invention may be, for example, 40 layers, 10 layers or 3 layers. It may be preferable that the layer (X) contained in the multilayer structure of the present invention is one layer.
  • the average thickness of the layer (X) means the total average thickness of the plurality of layers (X) as described above.
  • the average thickness of one layer (X) is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more or 6 ⁇ m or more from the viewpoint of barrier properties. Further, the average thickness of one layer (X) is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less or 12 ⁇ m or less from the viewpoint of bending resistance.
  • EVOH (A) can be usually obtained by saponifying an ethylene-vinyl ester copolymer.
  • the ethylene-vinyl ester copolymer can be produced and saponified by known methods.
  • the vinyl ester is typically vinyl acetate, but other fatty acid vinyls such as vinyl formate, vinyl propionate, vinyl valerate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl pivalate and vinyl versatate. It may be an ester.
  • the ethylene unit content of EVOH (A) is preferably 20 mol% or more, more preferably 22 mol% or more, still more preferably 24 mol% or more. Further, the ethylene unit content of the EVOH (A) is preferably 60 mol% or less, more preferably 55 mol% or less, still more preferably 50 mol% or less. When the ethylene unit content is 20 mol% or more, the melt moldability and the gas barrier property under high humidity tend to be good. On the other hand, when the ethylene unit content is 60 mol% or less, the gas barrier property tends to increase.
  • the ethylene unit content of EVOH (A) can be determined by a nuclear magnetic resonance (NMR) method.
  • the degree of saponification of the vinyl ester component of EVOH (A) is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 99 mol% or more. By setting the saponification degree to 90 mol% or more, the gas barrier property can be enhanced.
  • the degree of saponification of EVOH (A) may be 100 mol% or less, or 99.99 mol% or less.
  • the degree of saponification of EVOH (A) can be calculated by performing 1 H-NMR measurement and measuring the peak area of hydrogen atoms contained in the vinyl ester structure and the peak area of hydrogen atoms contained in the vinyl alcohol structure. When the degree of saponification of EVOH (A) is within the above range, good gas barrier properties tend to be obtained.
  • EVOH (A) may have units derived from other monomers than ethylene, vinyl ester and its saponified product, as long as the object of the present invention is not impaired.
  • the content of the other monomer unit with respect to all the structural units of the EVOH (A) is preferably 30 mol% or less, and 20 mol% It is more preferably at most, more preferably at most 10 mol% and particularly preferably at most 5 mol %.
  • the lower limit value may be 0.05 mol% or 0.10 mol%.
  • Examples of the other monomer include alkenes such as propylene, butylene, pentene, and hexene; unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, and itaconic acid, or their anhydrides, salts, or mono- or dialkyls. Esters, etc.; Acrylonitrile, methacrylonitrile, etc. Nitriles; Acrylamide, Methacrylamide, etc., Amides; Vinylsulfonic acid, Allylsulfonic acid, Methallylsulfonic acid, etc.
  • alkenes such as propylene, butylene, pentene, and hexene
  • unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, and itaconic acid, or their anhydrides, salts, or mono- or dialkyls.
  • Esters, etc. Acrylonitrile, methacrylonitrile, etc. Nitriles; Acrylamide, Methacrylamide
  • Olefinsulfonic acids or salts thereof Vinyltrimethoxysilane, Vinyltriethoxysilane Vinyl silane compounds such as vinyltri( ⁇ -methoxy-ethoxy)silane and ⁇ -methacryloxypropylmethoxysilane; alkyl vinyl ethers, vinyl ketones, N-vinylpyrrolidone, vinyl chloride, vinylidene chloride and the like.
  • EVOH(A) may be EVOH(A) modified after a procedure such as urethanization, acetalization, cyanoethylation, oxyalkylenation.
  • EVOH(A) As EVOH(A), two or more kinds of EVOH(A) having different ethylene unit content, saponification degree, copolymer component, presence or absence of modification, modification type, etc. may be mixed and used.
  • the MFR of EVOH (A) at 230° C. under a load of 2160 g is preferably 0.1 g/10 min or more, more preferably 0.5 g/10 min or more, still more preferably 1 g/10 min or more.
  • the MFR of EVOH (A) is preferably 50 g/10 min or less, more preferably 30 g/10 min or less, even more preferably 15 g/10 min or less.
  • EVOH (A) may be used alone or in combination of two or more.
  • the acid-modified ethylene- ⁇ -olefin copolymer (B) is a modified product obtained by chemically bonding an unsaturated carboxylic acid or an anhydride thereof to the ethylene- ⁇ -olefin copolymer by an addition reaction or a graft reaction. It means an ethylene- ⁇ olefin copolymer.
  • the resin composition (x) contains the polymer (B), flexibility and crease strength tend to increase.
  • acid modifiers include unsaturated carboxylic acids such as maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, and itaconic anhydride, or anhydrides thereof, but in view of reactivity with EVOH (A) Therefore, maleic anhydride modification is preferable.
  • the polymer (B) is a copolymer having a monomer unit based on ethylene and a monomer unit based on an ⁇ -olefin having 3 to 20 carbon atoms.
  • the ⁇ -olefin having 3 to 20 carbon atoms include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene and the like. More preferred are 1-butene and 1-hexene.
  • the above-mentioned ⁇ -olefin having 3 to 20 carbon atoms may be used alone or in combination of two or more kinds.
  • the content of ethylene-based monomer units in the polymer (B) is usually 50% by mass or more based on the total mass (100% by mass) of the ethylene- ⁇ -olefin copolymer.
  • the content of the monomer unit based on the ⁇ -olefin having 3 to 20 carbon atoms is usually 50% by mass or less based on the total mass (100% by mass) of the ethylene- ⁇ -olefin copolymer.
  • the polymer (B) contains, in addition to the ethylene-based monomer unit and the C 3-20 ⁇ -olefin-based monomer unit, ethylene and C 3 -C 3 within the range that does not impair the effects of the present invention. It may have a monomer unit derived from a monomer other than ⁇ -olefin of 1 to 20, and the monomer may be a conjugated diene such as 1,3-butadiene or 2-methyl-1,3-butadiene.
  • Non-conjugated dienes such as 1,4-pentadiene and 1,5-hexadiene; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, etc. Unsaturated carboxylic acid ester; vinyl ester compounds such as vinyl acetate.
  • polymer (B) ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1- Acids such as octene copolymer, ethylene-1-butene-1-hexene copolymer, ethylene-1-butene-4-methyl-1-pentene copolymer, ethylene-1-butene-1-octene copolymer Examples include modified products. Among them, the acid-modified ethylene-1-butene copolymer or the acid-modified ethylene-propylene copolymer is preferable from the viewpoint of the bending resistance of the obtained multilayer structure.
  • the acid value of the polymer (B) is preferably 3.0 mgKOH/g or more, more preferably 7.0 mgKOH/g or more, and 8.0 mgKOH from the viewpoint of the transparency of the layer (X), and thus the multilayer structure of the present invention. /G or more is more preferable, and 10.0 mgKOH/g or more is particularly preferable.
  • the acid value of the polymer (B) is preferably 20 mgKOH/g or less, more preferably 18 mgKOH/g or less, and even more preferably 15 mgKOH/g or less, from the viewpoint of suppressing the generation of gel lumps.
  • the acid value of the polymer (B) means a value measured according to the description of JIS K 2501 using xylene as a solvent.
  • the MFR of the polymer (B) at 230° C. under a load of 2160 g is preferably 0.1 g/10 min or more, more preferably 0.5 g/10 min or more, from the viewpoint of improving the transparency of the layer (X), the crease strength and the like. , 1.0 g/10 min or more is more preferable.
  • the MFR of the polymer (B) is preferably 10 g/10 min or less, more preferably 7 g/10 min or less, still more preferably 5 g/10 min or less, from the viewpoint of improving the appearance and the crease strength.
  • the polymer (B) may be used alone or in combination of two or more.
  • the resin component of the resin composition (x) consists essentially of EVOH (A) and the polymer (B), and the mass ratio (B/A) of the polymer (B) to the EVOH (A) is 3/97 or more. 17/83 or less.
  • the mass ratio (B/A) is preferably 5/95 or more, more preferably 7/93 or more, still more preferably 9/91 or more. Further, the mass ratio (B/A) is preferably 15/85, more preferably 13/87 or less, still more preferably 11/89 or less. If the mass ratio (B/A) is less than 3/97, the bending resistance and the crease strength tend to decrease.
  • the mass ratio (B/A) is more than 17/83, the appearance tends to be deteriorated due to deterioration of the film surface stability due to poor fluidity. If the mass ratio (B/A) is more than 17/83, the transparency of the layer (X) will decrease.
  • the MFR at 210° C. and 2160 g load of the resin composition (x) measured according to JIS K 7210:2014 is preferably 1.2 g/10 min or more, more preferably 1.5 g/10 min or more, and 2.0 g/10 min or more. More preferable. If the MFR at 210° C. under a load of 2160 g is less than 1.2 g/10 min, the fluidity tends to decrease, and the film surface stability tends to decrease. On the other hand, the MFR of the resin composition (x) at 210° C. under a load of 2160 g is preferably 10 g/10 min or less, more preferably 5 g/10 min or less.
  • the absolute value of the difference between the MFR at 230°C and 2160g load measured according to JIS K 7210:2014 of EVOH (A) and the MFR at 230°C and 2160g load measured according to JIS K 7210:2014 of polymer (B) is From the viewpoint of improving appearance, crease strength, impact resistance, etc., 10 g/10 min or less is preferable, 7 g/10 min or less is more preferable, and 4 g/10 min or less is further preferable.
  • 95 mass% or more is preferable, as for the total content of EVOH (A) and polymer (B) with respect to the resin component of resin composition (x), 97 mass% or more is more preferable, 99 mass% or more is further more preferable, 99 It is particularly preferably at least 9% by mass.
  • the content of the resin component with respect to the resin composition (x) is preferably 95% by mass or more, more preferably 97% by mass or more, and further preferably 99% by mass or more.
  • the content of EVOH (A) and polymer (B) in the resin composition (x) is also preferably 95% by mass or more, more preferably 97% by mass or more, and further preferably 99% by mass or more.
  • the resin composition (x) is, for example, a resin other than EVOH (A) and the polymer (B), a carboxylic acid compound, a phosphoric acid compound, a boron compound, a metal salt, as long as it does not impair the effects of the present invention.
  • Other components such as stabilizers, antioxidants, ultraviolet absorbers, plasticizers, antistatic agents, lubricants, colorants, fillers, desiccants, reinforcing agents for various fibers (EVOH (A) and polymers (B Components other than) may be contained.
  • resins other than EVOH (A) and polymer (B) include non-modified polyolefins such as non-modified polyethylene, non-modified polypropylene, and non-modified ethylene- ⁇ -olefin copolymer; polyamide; polyvinyl chloride; polyvinylidene chloride Polyester, polystyrene, epoxy resin, acrylic resin, urethane resin, polyester resin and the like.
  • the non-modified polyolefin is preferable, and the non-modified ethylene- ⁇ olefin copolymer is more preferable, from the viewpoint of excellent compatibility with the polymer (B).
  • the resin composition (x) contains a resin other than EVOH (A) and the polymer (B), its content is preferably 5% by mass or less, and 3% by mass or less, from the viewpoint of not impairing the effects of the present invention. It is more preferably 1% by mass or less, still more preferably 0.1% by mass or less.
  • the resin composition (x) may be in a mode containing no resin other than the EVOH (A) and the polymer (B).
  • the carboxylic acid contained in the resin composition (x) may be a monocarboxylic acid, a polycarboxylic acid, or a combination thereof.
  • the carboxylic acid contained in the resin composition (x) may be an ion, and the carboxylate ion may form a salt with a metal ion.
  • the resin composition (x) contains a phosphoric acid compound, coloring tends to be suppressed during melt molding.
  • the phosphoric acid compound contained in the resin composition (x) is not particularly limited, and various acids such as phosphoric acid and phosphorous acid and salts thereof can be used.
  • the phosphate may be contained in any form of a first phosphate, a second phosphate and a third phosphate, but the first phosphate is preferred.
  • the cation species is also not particularly limited, but an alkali metal salt is preferable. Among these, sodium dihydrogen phosphate and potassium dihydrogen phosphate are preferable.
  • the content of the phosphoric acid compound is preferably 5 ppm or more and 200 ppm or less in terms of phosphate radical.
  • the content of the phosphoric acid compound is 5 ppm or more, the color resistance during melt molding tends to be good.
  • melt moldability tends to be good, and more preferably 160 ppm or less.
  • the boron compound contained in the resin composition (x) is not particularly limited, and examples thereof include boric acid, boric acid ester, borate, and borohydride.
  • examples of the boric acid include orthoboric acid, metaboric acid, tetraboric acid, etc.
  • examples of the borate ester include triethyl borate, trimethyl borate, etc.
  • examples of the borate include the various borate described above. Examples thereof include alkali metal salts of acids, alkaline earth metal salts, and borax.
  • orthoboric acid hereinafter sometimes simply referred to as boric acid is preferable.
  • the content of the boron compound is preferably 20 ppm or more and 2000 ppm or less in terms of elemental boron.
  • the content of the boron compound is 20 ppm or more, torque fluctuation during heating and melting tends to be suppressed, and more preferably 50 ppm or more.
  • the content of the boron compound is 2000 ppm or less, moldability tends to be kept good, and more preferably 1000 ppm or less.
  • the resin composition (x) contains an alkali metal salt
  • the multilayer structure having the layer (X) made of the resin composition (x) interlayer adhesion between the layer (X) and another resin layer is improved. Tends to become.
  • the cation species of the alkali metal salt is not particularly limited, but sodium salt or potassium salt is preferable.
  • the anion species of the alkali metal salt is also not particularly limited. It can be added as a carboxylate, carbonate, hydrogen carbonate, phosphate, hydrogen phosphate, borate, hydroxide or the like.
  • the content of the alkali metal salt is preferably 10 ppm or more and 500 ppm or less in terms of metal element.
  • the interlayer adhesion tends to be good, and more preferably 50 ppm or more.
  • the content of the alkali metal salt is 500 ppm or less, the melt stability tends to be excellent, and more preferably it is 300 ppm or less.
  • the resin composition (x) contains an alkaline earth metal salt, it tends to be possible to suppress deterioration when a molded body is repeatedly melt-molded and to suppress deterioration such as gel.
  • the cation species of the alkaline earth metal salt is not particularly limited, but magnesium salt or calcium salt is preferable.
  • the anionic species of the alkaline earth metal salt is also not particularly limited. It can be added as a carboxylate, carbonate, hydrogen carbonate, phosphate, hydrogen phosphate, borate, hydroxide or the like.
  • stabilizers for improving melt stability and the like include hydrotalcite compounds, hindered phenol-based, hindered amine-based heat stabilizers, metal salts of higher aliphatic carboxylic acids (eg, calcium stearate, magnesium stearate, etc.), etc.
  • the content thereof may be 0.001 mass% or more and 1 mass% or less in the resin composition (x).
  • Antioxidants include 2,5-di-t-butyl-hydroquinone, 2,6-di-t-butyl-p-cresol, 4,4′-thiobis-(6-t-butylphenol), 2,2 '-Methylene-bis-(4-methyl-6-t-butylphenol), octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate, 4,4'-thiobis- (6-t-butylphenol) and the like.
  • ultraviolet absorber ethylene-2-cyano-3′,3′-diphenyl acrylate, 2-(2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(2′-hydroxy-3′-t -Butyl-5'-methylphenyl)5-chlorobenzotriazole, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone and the like.
  • plasticizers include dimethyl phthalate, diethyl phthalate, dioctyl phthalate, wax, liquid paraffin, and phosphoric acid ester.
  • antistatic agent include pentaerythritol monostearate, sorbitan monopalmitate, sulfated polyolefins, polyethylene oxide, carbowax and the like.
  • lubricant include ethylene bis stearamide, butyl stearate and the like.
  • the colorant include carbon black, phthalocyanine, quinacridone, indoline, azo pigments, red iron oxide and the like.
  • the filler include glass fiber, asbestos, ballastonite, calcium silicate and the like.
  • the method for producing the resin composition (x) is not particularly limited, but can be produced, for example, by mixing or kneading the EVOH (A) and the polymer (B) under melting conditions.
  • Mixing or kneading under melting conditions can be carried out using a known mixing device or kneading device such as a kneader ruder, extruder, mixing roll, Banbury mixer or the like.
  • the temperature at the time of mixing or kneading may be appropriately adjusted depending on the melting point of the EVOH (A) used, etc., but a temperature within a temperature range of 160° C. or higher and 300° C. or lower may be adopted.
  • the transparency of the layer (X) can be evaluated by measuring the internal haze of the layer (X).
  • the internal haze of the layer (X) is preferably 15% or less, more preferably 10% or less, still more preferably 5% or less, from the viewpoint of making the appearance of the content clear.
  • the internal haze here is a haze value (cloudiness) measured by applying water to both surfaces of a single-layer film composed of a layer (X) having a thickness of 20 ⁇ m and sandwiching it with a glass plate.
  • the layer (Y) is a layer containing a thermoplastic resin (C), and is arranged at least on both surface sides of the layer (X). If the layer (Y) is not arranged on both surface sides of the layer (X), the bending resistance tends to decrease.
  • the layer (Y) may be directly laminated on the surface of the layer (X), or may be laminated via another layer (for example, an adhesive resin layer or the like).
  • the average thickness of the layer (Y) is preferably 25 ⁇ m or more, more preferably 30 ⁇ m or more, still more preferably 35 ⁇ m or more, from the viewpoint of bending resistance. Further, the average thickness of the layer (Y) is preferably 499 ⁇ m or less, more preferably 200 ⁇ m or less, further preferably 100 ⁇ m or less, and particularly preferably 80 ⁇ m or less from the viewpoint of bending resistance.
  • the average thickness of the layer (Y) means the sum of the average thicknesses of all the layers (Y) included in the multilayer structure of the present invention.
  • the layer (Y) may be at least two layers in the multilayer structure of the present invention, and each layer (Y) may be the same or different.
  • the upper limit of the number of layers (Y) contained in the multilayer structure of the present invention may be, for example, 41 layers, 11 layers or 4 layers.
  • the layer (X) included in the multilayer structure of the present invention may preferably be two layers.
  • the average thickness of one layer (Y) is preferably 15 ⁇ m or more, more preferably 20 ⁇ m or more, further preferably 25 ⁇ m or more, and particularly preferably 30 ⁇ m or more, from the viewpoint of bending resistance. Further, the average thickness of one layer (Y) is preferably 240 ⁇ m or less, more preferably 150 ⁇ m or less, further preferably 100 ⁇ m or less, and particularly preferably 50 ⁇ m or less from the viewpoint of bending resistance.
  • thermoplastic resin (C) contained in the layer (Y) examples include linear low-density polyethylene, low-density polyethylene, ultra-low-density polyethylene, medium-density polyethylene, high-density polyethylene, and other polyethylene, ethylene-vinyl acetate copolymer.
  • Ionomer ethylene-propylene (block or random) copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, polypropylene, propylene- ⁇ -olefin copolymer, polybutene, Polyolefins such as homo- or copolymers of olefins such as polypentene, or those graft-modified with unsaturated carboxylic acids or their esters; polyesters; polyamides (including co-polyamides); polyvinyl chloride; polyvinylidene chloride; acryl Resin; polystyrene; polyvinyl ester; polyester elastomer; polyurethane elastomer; chlorinated polystyrene; chlorinated polypropylene; aromatic polyketone or aliphatic polyketone, and polyalcohol obtained by reducing these; polyacetal; polycarbonate and the like.
  • thermoplastic resin (C) contained in the layer (Y) may be preferably a resin having substantially no carboxy group. Further, the thermoplastic resin (C) may be preferably a resin other than the adhesive resin.
  • the proportion of the thermoplastic resin (C) in the layer (Y) is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, particularly preferably 95% by mass or more, and 100% by mass. It may be. That is, the layer (Y) may be substantially composed only of the thermoplastic resin (C).
  • the layer structure of the multilayer structure of the present invention is not particularly limited as long as it has the layers (Y) on both sides of the layer (X), but when the adhesive resin layer is represented by Ad, Y/X/Y , Y/X/Ad/Y, Y/Ad/X/Ad/Y, Y/Ad/Y/X/Y/Ad/Y, Y/X/Y/X/Y and the like. Among them, it is preferable that the multilayer structure of the present invention has an adhesive resin layer between the layer (X) and the layer (Y), such as Y/Ad/X/Ad/Y.
  • the bending resistance and the crease strength tend to be extremely good.
  • the multilayer structure of the present invention does not satisfy the constitution of the present invention such as X/Ad/Y, not only the bending resistance is lowered, but also the crease strength is similarly lowered.
  • the layers like Y/Ad/X/Ad/Y When (X) and the layer (Y) are all laminated via the adhesive resin layer, the bending resistance and the like are further improved.
  • thermoplastic resin (C) contained in the layer (Y) is a polyolefin having no polar functional group
  • the layer (X) and the layer (Y) such as Y/Ad/X/Ad/Y are used. It is preferable to have an adhesive resin layer between the above and.
  • the lower limit of the total number of layers constituting the multilayer structure of the present invention is 3 layers, preferably 5 layers.
  • the upper limit of the total number of layers may be, for example, 100 layers, and may be 40 layers, 20 layers, or 10 layers.
  • the method for producing the multilayer structure of the present invention is not particularly limited, and known methods such as extrusion coating, co-extrusion, co-injection, and lamination can be used, and the layer (X) and the layer (Y) are adhesive resins. It may be via a layer.
  • the adhesive resin is not particularly limited as long as it has adhesiveness with the layer (X) and the layer (Y), but a carboxylic acid-modified adhesive resin is preferable, and specifically, an ethylenically unsaturated carboxylic acid is used.
  • An adhesive resin containing a carboxyl group chemically bound to an acid, its ester or its anhydride is preferred.
  • unsaturated carboxylic acid modified products such as polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer are preferable.
  • the average thickness of one adhesive resin layer may be, for example, 1 ⁇ m or more and 20 ⁇ m or less, and preferably 2 ⁇ m or more and 10 ⁇ m or less.
  • the multilayer structure of the present invention is flexible because the layer (X) maintains high gas barrier properties and transparency and is excellent in impact resistance, and the multilayer structure itself has excellent appearance, bending resistance and crease strength. It is useful as a packaging material.
  • a vertical bag-making filling seal bag can be mentioned.
  • the vertical bag-making filling seal bag can be applied to various applications, but is preferably used as an application requiring a barrier property against oxygen, for example, a bag containing food as a content.
  • the contents of the vertical bag-making filling and sealing bag of the present invention may be daily commodities; chemicals such as agricultural chemicals and medicines; medical equipments; industrial materials such as machine parts and precision materials;
  • Vertical filling bag is often used, for example, for packaging liquids, viscous materials, powders, solid bulk items, or foods and beverages in which these are combined.
  • the vertical bag-making filling and sealing bag including the multilayer structure of the present invention has excellent gas barrier properties and transparency, and maintains the gas barrier properties when subjected to physical stress such as deformation or impact. Further, since it has excellent crease strength, the film is less likely to break even when the contents are filled, and the productivity is excellent.
  • Fig. 1 shows one form of a vertical bag filling seal bag (Vertical form fill seal pouch).
  • the film material 10 is sealed on three sides of the upper end portion 11, the lower end portion 12 and the body portion 15 of the seal bag 1.
  • the body portion 15 is arranged at the center of the back surface extending from the upper end portion 11 to the lower end portion 12 so as to divide the back surface 20 into two.
  • the film material 10 is sealed with its inner surfaces in contact with each other.
  • the form of the seal in the body portion 15 is so-called joint attachment.
  • the front surface of the sealing bag 1 not shown in FIG.
  • the sealed body portion 15 may be arranged at either of the side end portions 21 and 22, and in this case, the back surface is not divided by the sealed portion.
  • one film material 10 having a width that is twice the width of the back surface 20 (the total width of the front surface and the back surface) plus the width required for sealing in the body portion 15 is a vertical type. It is a bag manufactured by being supplied to the bag making and filling machine.
  • the upper end portion 11, the lower end portion 12 and the body portion 15 are each formed as a linear seal portion having no branch.
  • the vertical bag-making filling seal bag is, in one form thereof, an upper end portion corresponding to the upper side of the front surface and the back surface of the bag, a lower end portion corresponding to the lower side, and these end portions from the upper end portion to the lower end portion.
  • One film material is sealed and formed into a bag at three portions of the body portion extending perpendicularly to.
  • the film material 10 comprises the multilayer structure of the present invention.
  • A-1 “Eval (registered trademark) L171B” (EVOH, manufactured by Kuraray Co., Ltd., ethylene unit content: 27 mol %, MFR: 8.0 g/10 min (230° C., 2160 g load))
  • B-1 “Tufmer (trademark) MH7020” (maleic anhydride-modified ethylene-butene copolymer, manufactured by Mitsui Chemicals, Inc., MFR: 1.5 g/10 min (230° C., 2160 g load), acid value 12 mg KOH/g)
  • Acid value of acid-modified ethylene- ⁇ -olefin copolymer (B) According to JIS K 0070:1992, the acid-modified ethylene- ⁇ -olefin copolymer (B) is dissolved in xylene, and phenolphthalein is used as an indicator. Acid value was calculated by dropping 0.05 mol/L potassium hydroxide-ethanol solution.
  • Oxygen transmission rate (gas barrier property evaluation)
  • the 20 ⁇ m thick single-layer films obtained in Examples and Comparative Examples were conditioned at 20° C. and 65% RH for 7 days, and then subjected to JIS K 7126-2 (isobaric method) at 20° C. and 65% RH.
  • the oxygen permeation rate (“OX-TORAN MODEL 2/21” manufactured by Mocon) was measured under the conditions described above.
  • Example 1 95 parts by mass of EVOH (manufactured by Kuraray Co., Ltd., “Eval (registered trademark) L171B”) (A-1), and ethylene-butene copolymer (manufactured by Mitsui Chemicals, Inc., "Tafmer (trademark) MH7020”) (B- 1) 5 parts by mass was dry blended to obtain resin composition pellets under the following extruder conditions.
  • ⁇ Extruder conditions> Equipment: 30mm ⁇ twin-screw extruder L/D: 45.5 Screw: Same direction perfect mesh type extrusion temperature (°C): 220°C Rotation speed: 200 rpm Discharge rate: 20kg/hr
  • a multilayer film (multilayer structure) was produced under the following conditions.
  • LDPE Low density polyethylene
  • LDPE layer (Y)/Ad/resin composition layer (X)/Ad/LDPE layer (Y) 34 ⁇ m/6 ⁇ m/10 ⁇ m/6 ⁇ m/34 ⁇ m (total thickness 90 ⁇ m)
  • Equipment Feed block type 3 layer 5 layer film extruder Mold temperature: 220°C. Cooling roll temperature: 60°C. Collection speed: 5.0 m/min.
  • ⁇ Conditions of LDPE layer extruder> Extruder: 32 ⁇ single-screw extruder (Plastic Engineering Laboratory Co., Ltd.). Rotation speed: 57 rpm.
  • Extrusion temperature: supply part/compression part/measurement part 150° C./200° C./210° C.
  • the obtained monolayer film and multilayer film were evaluated for transparency, impact strength, appearance of multilayer film, oxygen permeability, flex resistance and crease strength according to the evaluation methods of (3) to (8) above. .. The results are shown in Table 1.
  • Examples 2 to 7, Comparative Examples 1 to 6) A resin composition was prepared in the same manner as in Example 1 except that the kind of the polymer (B) (and the polymer (B′)) and the mass ratio with the EVOH (A-1) were changed as described in Table 1.
  • a product pellet and a monolayer film were prepared. Further, a multilayer film was produced in the same manner as in Example 1 except that the thickness of all layers was changed as described in Table 1.
  • the thickness of each adhesive resin layer was the same as in Example 1, and the thicknesses of the resin composition layer (X) and the LDPE layer (Y) were changed to adjust the total layer thickness.
  • Example 2 to 7 and Comparative Examples 1 to 4 and 6 the same evaluations as in Example 1 were performed, and for Comparative Example 5, transparency, impact strength, and transparency were evaluated according to the evaluation methods of (3) to (7) above. The appearance, oxygen permeability and flex resistance of the multilayer film were evaluated. The results are shown in Table 1.
  • the obtained monolayer film and multilayer film were evaluated for transparency, impact strength, appearance of multilayer film, oxygen permeability, flex resistance and crease strength according to the evaluation methods of (3) to (8) above. .. The results are shown in Table 1.
  • Example 7 it can be seen that even when the resin other than the EVOH (A) and the polymer (B) is contained, a sufficient effect can be obtained if the content is a trace amount. Then, when Example 2 and Example 7 are compared, it can be seen that the transparency and the impact resistance are further enhanced when the resin other than the EVOH (A) and the polymer (B) is not contained.
  • the multilayer structure of the present invention can be suitably used as a flexible packaging material, and is not limited to the application, and can be applied to a wide range of fields such as foods, pharmaceuticals, industrial chemicals and agricultural chemicals. Particularly, it can be suitably used as a vertical filling seal bag.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
PCT/JP2020/003181 2019-01-30 2020-01-29 多層構造体並びにそれを備える包装材及び縦製袋充填シール袋 Ceased WO2020158803A1 (ja)

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DE112020000599.2T DE112020000599T5 (de) 2019-01-30 2020-01-29 Mehrschichtstruktur sowie Verpackungsmaterial und vertikaler gefüllter und versiegelter Beutel mit dieser

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JP2022123573A (ja) * 2021-02-12 2022-08-24 三井化学株式会社 バイオマス由来原料を含む樹脂組成物およびその用途
CN116761847A (zh) * 2021-01-25 2023-09-15 三菱化学株式会社 乙烯-乙烯醇系共聚物组合物

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BR112021003248A2 (pt) * 2018-09-07 2021-05-18 Kuraray Co., Ltd composição de resina termoplástica

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JP2001080002A (ja) * 1999-09-17 2001-03-27 Nippon Synthetic Chem Ind Co Ltd:The 積層包装材
JP2004090380A (ja) * 2002-08-30 2004-03-25 Kuraray Co Ltd 多層フィルムおよびその製造方法
JP2004268441A (ja) * 2003-03-10 2004-09-30 Dainippon Ink & Chem Inc 紙ラミネート用多層フィルムおよびフィルムラミネート紙容器
WO2015141610A1 (ja) * 2014-03-17 2015-09-24 株式会社クラレ 樹脂組成物、多層構造体、及びバッグインボックス用内容器
JP2016513980A (ja) * 2013-01-18 2016-05-19 サルトリアス ステディム エフエムティー エスエーエス 単回使用ポーチの壁用の、コア層および外層を含む多層フィルム

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EP2851308B1 (en) 2012-05-14 2017-07-12 Kuraray Co., Ltd. Co-extruded blow-molded multilayer container with pinch-off part
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JP2001080002A (ja) * 1999-09-17 2001-03-27 Nippon Synthetic Chem Ind Co Ltd:The 積層包装材
JP2004090380A (ja) * 2002-08-30 2004-03-25 Kuraray Co Ltd 多層フィルムおよびその製造方法
JP2004268441A (ja) * 2003-03-10 2004-09-30 Dainippon Ink & Chem Inc 紙ラミネート用多層フィルムおよびフィルムラミネート紙容器
JP2016513980A (ja) * 2013-01-18 2016-05-19 サルトリアス ステディム エフエムティー エスエーエス 単回使用ポーチの壁用の、コア層および外層を含む多層フィルム
WO2015141610A1 (ja) * 2014-03-17 2015-09-24 株式会社クラレ 樹脂組成物、多層構造体、及びバッグインボックス用内容器

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116761847A (zh) * 2021-01-25 2023-09-15 三菱化学株式会社 乙烯-乙烯醇系共聚物组合物
JP2022123573A (ja) * 2021-02-12 2022-08-24 三井化学株式会社 バイオマス由来原料を含む樹脂組成物およびその用途
JP7658752B2 (ja) 2021-02-12 2025-04-08 三井化学株式会社 バイオマス由来原料を含む樹脂組成物およびその用途

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