WO2004069922A1 - Composition de resine et utilisation de ladite composition - Google Patents

Composition de resine et utilisation de ladite composition Download PDF

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Publication number
WO2004069922A1
WO2004069922A1 PCT/JP2004/001251 JP2004001251W WO2004069922A1 WO 2004069922 A1 WO2004069922 A1 WO 2004069922A1 JP 2004001251 W JP2004001251 W JP 2004001251W WO 2004069922 A1 WO2004069922 A1 WO 2004069922A1
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Prior art keywords
resin composition
copolymer
weight
acid
film
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PCT/JP2004/001251
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English (en)
Japanese (ja)
Inventor
Shinta Miyazumi
Keisuke Fujimura
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The Nippon Synthetic Chemical Industry Co., Ltd.
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Application filed by The Nippon Synthetic Chemical Industry Co., Ltd. filed Critical The Nippon Synthetic Chemical Industry Co., Ltd.
Publication of WO2004069922A1 publication Critical patent/WO2004069922A1/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
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate

Definitions

  • the present invention relates to a resin composition containing a saponified copolymer of ethylene, biel acetate and a butylsilane compound, and a multilayer structure using the same. More specifically, the present invention relates to a TD (width) direction during film formation such as inflation molding. The present invention relates to a resin composition of the above-mentioned saponified copolymer in which the variation in the thickness of the resin is suppressed, and a multilayer structure having a layer of the composition.
  • EVOH saponified ethylene-vinyl acetate copolymer
  • EVOH saponified ethylene-vinyl acetate copolymer
  • the molding it is general to extrude EVOH in a molten state from an extruder or other device (die, etc.) with a certain thickness to form a film.
  • the unevenness of cooling and the flow of molten resin The thickness of the extruded film or sheet may be uneven due to unevenness or neck-in.
  • thickness variations are often observed in the TD (width) direction, and these variations cause poor appearance of the formed film or sheet, poor adhesion (lamination) with other films or sheets, and printing on the surface. This results in inconvenience such as failure.
  • the applicant of the present invention added a boron compound, peroxide, polyacid, polyamide compound, copper compound, aluminum compound to EVOH.
  • An EVOH obtained by reacting at least one compound selected from a nickel compound, a titanium compound, a zinc compound, a tin compound, a vanadium compound, and a chromium compound; (See Japanese Patent Application Laid-Open No. 2000-351811) was proposed.
  • the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that copolymers of ethylene, vinyl acetate and vinyl silane compounds (A), magnesium acetate or higher fatty acid salts of divalent metals
  • the present inventors have found that a resin composition containing (B) meets the above object, and have completed the present invention.
  • the present invention is a resin composition containing a saponified copolymer of ethylene, vinyl acetate and a vinylsilane-based compound (A), a higher fatty acid S-borate salt of magnesium acetate or a divalent metal (B) (B).
  • the content of silicon in the saponified copolymer (A) is preferably from 0.001 to 0.1% by weight.
  • the content of the higher fatty acid salt of magnesium acetate or divalent metal (B) is 0.001 to 0.05 part by weight in terms of metal with respect to 100 parts by weight of the copolymer saponified product (A). Is preferred.
  • it preferably contains a boron compound (C).
  • the content of the boron compound (C) is preferably 0.01 to 1 part by weight in terms of boron based on 100 parts by weight of the saponified copolymer (A).
  • the present invention is a multilayer structure including at least one layer composed of the resin composition.
  • the layer composed of the resin composition is composed of a multilayer film arranged on the outermost layer, and another film bonded to the multilayer film.
  • the multilayer structure is preferably manufactured by an inflation molding method.
  • the saponified copolymer (A) used in the resin composition of the present invention is obtained by saponifying a copolymer of ethylene, vinyl acetate and a vinylsilane compound.
  • vinylsilane compounds include vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, pinyltriethoxyquin, vinylisobutyldimethoxysilane, vinylethyldimethoxysilane, vinylmethoxydibutoxysilane, vinyldimethoxybutoxysilane, and vinyltrimethoxysilane.
  • the target copolymer can be obtained by performing a copolymerization reaction in the presence of a polymerization initiator such as azobisisobutyronitrile (AIBN).
  • a polymerization initiator such as azobisisobutyronitrile (AIBN).
  • the ethylene content in the copolymer is preferably from 5 to 60 mol%, more preferably from 25 to 58 mol%, even more preferably from 25 to 55 mol%. If the ethylene content is less than 5 mol%, the gas barrier properties and melt moldability of the finally obtained copolymer saponified product (A) at high humidity are reduced, and conversely, it exceeds 60 mol%. However, it is not preferable because sufficient gas barrier properties cannot be obtained.
  • the content of silicon derived from the Biersilane group in the copolymer is preferably from 0.01 to 0.1% by weight, more preferably from 0.05 to 0.05% by weight. , 0.05 to 0.03% by weight. If the content is less than 0.001% by weight, the effect of the present invention may not be sufficiently obtained. On the other hand, if the content exceeds 0.1% by weight, a gel may be formed on a molded film. Not preferred.
  • a copolymerizable ethylenically unsaturated monomer may be further copolymerized as long as the effects of the present invention are not impaired.
  • monomers include olefins such as propylene, 1-butene, and isobutene, acrylic acid, methacrylic acid, crotonic acid, (anhydrous) phthalic acid, and (anhydrous) maleic.
  • Acid unsaturated acids such as itaconic acid or salts thereof or mono- or dialkyl esters having 1 to 18 carbon atoms, acrylamide, N-alkylacrylamide having 1 to 18 carbon atoms, N, N-dimethylacrylamide, 2-acrylamidopropanesulfonic acid or its salt, acrylamide such as acrylamidopropyldimethylamine or its acid salt or its quaternary salt, methacrylamide, N-alkylmethacrylamide having 1 to 18 carbon atoms, N, N— Methacrylamides such as dimethyl methacrylamide, 2-methylacrylamide propanesulfonic acid or its salt, methacrylamidopropyldimethylamine or its acid salt or its quaternary salt, N-vinylpyrrolidone, N_pinylformamide, N_vinylase N-vinyl such as amide Amides, vinyl cyanides such as acryl nitrile, methacryl nitrile, vinyl ether
  • the copolymer is then saponified to obtain the saponified copolymer (A) used in the present invention.
  • saponification a known method can be adopted.
  • the copolymer is saponified in a methanol solvent with sodium hydroxide, hydroxylated water, sodium methylate, potassium hydroxide or the like, and then neutralized with an acid such as acetic acid.
  • the copolymer saponified product (A) You get it.
  • the saponification degree of the vinyl acetate component of the obtained saponified copolymer (A) is preferably at least 90 mol%, more preferably at least 95 mol%, even more preferably at least 99 mol%. If the degree of saponification of such a vinyl acetate component is less than 90 mol%, the gas barrier properties, thermal stability, moisture resistance, etc. are undesirably reduced.
  • the saponified copolymer (A) preferably has a melt flow rate (MFR) (210 ° C., load 2160 g) of 0.5 to 100 g / 10 min, more preferably 1 to 50 gZl0. Min, more preferably 3 to 35 gZlO min. If the melt flow rate is less than 0.5 gZl O minute, the inside of the extruder may be in a high torque state during molding and extrusion may be difficult. The thickness accuracy of the sheet is undesirably reduced.
  • MFR melt flow rate
  • the saponified copolymer EVOH (A) it is also possible to use two or more different saponified copolymers.
  • the ethylene content is 5 mol% or more (furthermore, 5 mol% or more). ⁇ 25 mol%, especially 8-20 mol%) and / or differ in the degree of gation by more than 1 mol% (further 1-15 mol%, especially 2-10 mol%), and Z or MFR
  • the ratio is preferably 2 or more (more preferably 3 to 20, especially 4 to 15).
  • the resin composition of the present invention contains the above-mentioned copolymer (A) and magnesium acetate or a higher fatty acid salt of a divalent metal (B).
  • the higher fatty acid salt of a divalent metal include fatty acid salts having 8 or more carbon atoms.
  • lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptydecyl acid, Alkaline earth metal salts such as magnesium salt, calcium salt and barium salt of higher fatty acids such as stearic acid, nonadecanoic acid, oleic acid, carboxylic acid, behenic acid and linoleic acid, and zinc metal salts be able to.
  • stearic acid, oleic acid, Alkaline earth metal salts of lauric acid are preferably used.
  • (B) should be blended, but specifically,
  • boron compound (C) is boric acid or a metal salt thereof, such as calcium borate, cobalt borate, zinc borate (zinc tetraborate, zinc metaborate, etc.), aluminum / potassium borate, ammonium borate Ammonia (ammonium metaborate, ammonium tetraborate, ammonium pentaborate Cadmium, ammonium octaborate, etc.), cadmium borate (cadmium orthoborate, cadmium tetraborate, etc.), potassium borate (potassium metaborate, potassium tetraborate, potassium pentaborate, potassium hexaborate, potassium hexaborate, Potassium borohydride, silver borate (silver metaborate, silver tetraborate, etc.), copper borate (cupric boric boric acid or a metal salt thereof, such as calcium borate, cobalt borate, zinc borate (zinc tetraborate, zinc metaborate, etc
  • the content of the boron compound (C) is not particularly limited, but is preferably 0.01 to 1.0 part by weight in terms of boron with respect to 100 parts by weight of the saponified copolymer (A). 0.001 to 0.5 part by weight is more preferable, and 0.01 to 0.2 part by weight is further preferable. If the content is less than 0.001 part by weight, it is difficult to obtain the content effect, and if the content exceeds 1.0 part by weight, the appearance of the resulting film or sheet tends to deteriorate. Preferred Absent.
  • the porous precipitate of the saponified copolymer having a water content of 20 to 80% by weight was prepared by using the water content of the boron compound in the aqueous boron compound solution and the aqueous solution of the boron compound in the saponified copolymer compound. After contacting with a boron compound aqueous solution adjusted to be 0.001 to 1.0 parts by weight with respect to 100 parts by weight of the total amount of water contained therein, Drying by combining fluidized drying and standing drying,
  • Copolymer saponified product obtained by contacting a pellet with an aqueous solution of a boron compound to contain a boron compound, and then drying to a water content of 0.001 to 10% by weight.
  • the resin composition of the present invention containing the saponified copolymer (A) and the metal salt (B), or the saponified copolymer (A), the metal salt (B) and the boron compound (C) is obtained.
  • a saturated aliphatic amine is added to the resin composition as long as the object of the present invention is not impaired.
  • stearic acid amide For example, stearic acid amide), unsaturated fatty acid amide (for example, oleic acid amide), bisfatty acid amide (for example, ethylene bisstearic acid amide), low molecular weight polyolefin (for example, molecular weight 500 to 100,0) Low molecular weight polyethylene of about 0, or low molecular weight polypropylene, etc.
  • unsaturated fatty acid amide for example, oleic acid amide
  • bisfatty acid amide for example, ethylene bisstearic acid amide
  • low molecular weight polyolefin for example, molecular weight 500 to 100,0
  • the extruder is provided with one or more vent holes to remove moisture and by-products (such as pyrolyzed low-molecular-weight products) to prevent suction under reduced pressure and to prevent oxygen from entering the extruder.
  • an inert gas such as nitrogen
  • the resin composition of the present invention is formed into films, sheets, containers, fibers, rods, pipes, and other various molded products by melt molding, and is also used to form these crushed products (for example, when reusing recovered products).
  • melt molding an extrusion molding method ( ⁇ -die extrusion, inflation extrusion, professional molding, melt spinning, profile extrusion, etc.) and an injection molding method are mainly employed, and a melting temperature of 150 to 30 is used. It is often selected from the range of 0 ° C.
  • the inflation molding method refers to a method in which a resin or resin composition melted by an extruder is guided into a cylindrical die (spider die, spiral mandrel die, etc.), and is placed inside a cylindrical film extruded from the die. This is a method in which air is blown to expand, cooled by an air ring or other device, and the resulting film is wound up.
  • inflation molding can be performed using a conventionally known air-cooled multilayer inflation film forming apparatus.
  • the blow-up ratio is 0.75 to 1.0
  • the take-off speed is 15 to 30 m / min
  • the film folding width is The melting temperature of the resin composition of the present invention may be in the range of about 150 to 250 ° C (further, about 180 to 230 ° C). You can choose from.
  • Such a molded article can of course be used as a single layer for various applications, but is also useful as a laminate (multilayer structure), and in particular, a thermoplastic resin layer is formed on at least one side of a layer made of the resin composition. These are preferably used as a laminate obtained by laminating, and a laminate suitable for practical use having water resistance, mechanical properties, heat sealing properties and the like is obtained.
  • thermoplastic resin As such another substrate, a thermoplastic resin is useful. Specifically, linear low-density polyethylene, low-density polyethylene, ultra-low-density polyethylene, medium-density polyethylene, high-density polyethylene, ethylene-vinyl acetate Polymers, ionomers, ethylene-propylene (block or random) copolymers, ethylene-acrylic acid copolymers, ethylene-acrylic acid ester copolymers, ethylene-methacrylic acid copolymers, ethylene-methacrylic acid ester copolymers Copolymer, Polypropylene, Propylene- ⁇ -olefin ( ⁇ -olefin with 4 to 20 carbon atoms) Copolymer, Polybutene, Polypentene, Polymethylene Polyolefin resins, polyester resins, polyamide resins (copolymers) such as homo- or copolymers of olefins, or those obtained by graft-modifying homo- or copo
  • Polyethylene, chlorinated polypropylene, aromatic or aliphatic polyketones, polyalcohols obtained by reducing them, and other ⁇ VOH are also examples of the properties of the laminate (particularly strength and appearance).
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • a base such as a film or sheet of the resin composition of the present invention is extrusion-coated with another base or a film or sheet of another base is laminated with an adhesive, such base is used as the base.
  • Any substrate other than the above-mentioned thermoplastic resin paper, metal foil, uniaxial or biaxially stretched plastic film or sheet and its inorganic deposits, woven fabric, nonwoven fabric, metallic cotton, woody, etc. can be used It is.
  • the layer structure of the laminate, the layer of the resin composition of the present invention is a (al, a2,
  • thermoplastic resin layer is b (bl, b2, ⁇ ⁇ ⁇ ), if it is a film, sheet, or bottle, not only the two-layer structure of a Zb but also b / a / b, aZbZa, a 1 / a 2Zb, aZb lZb 2, b 2/1 / a / 1 / b 2, b2 / / bl / a / bl / a / bl / / / b 2 etc.
  • a regrind layer composed of a mixture of at least a resin composition and a thermoplastic resin is defined as R, b / R / a, b / R / a / b, b / R / a / R / b, It is also possible to use b / a / R / a / b, b / R / a / R / a ZRZb, etc.
  • a and b are bimetallic, core (a) —sheath (b) type Any combination such as a core (b) -sheath (a) type or an eccentric core-sheath type is possible.
  • a laminated structure in which the layer of the resin composition of the present invention is the outermost layer is particularly preferable, and more specifically, the layer Z of the resin composition of the present invention is an adhesive resin.
  • Layer Z Polyolefin resin (preferably poly Ethylene) layer, layer of the resin composition of the present invention / polyamide-based resin layer, and Z polyolefin-based resin (preferably polyethylene) layer are particularly preferable, and more specifically, the layer Z of the resin composition of the present invention is an adhesive resin.
  • Layer Z Polyolefin resin preferably poly Ethylene
  • layer of the resin composition of the present invention / polyamide-based resin layer preferably polyamide-based resin layer
  • Z polyolefin-based resin preferably polyethylene
  • an adhesive resin layer can be provided between each layer as needed, and various adhesive resins can be used as the adhesive resin. It is preferable in that an excellent laminate can be obtained. Although it depends on the type of the resin b and cannot be stated unconditionally, the unsaturated carboxylic acid or its anhydride can be converted into an olefin polymer (the above-mentioned olefin alone or copolymer).
  • Examples include a modified olefin polymer containing a carboxyl group obtained by chemically bonding by an addition reaction, a graft reaction, or the like.
  • maleic anhydride graft-modified polyethylene maleic anhydride graft-modified Polypropylene, maleic anhydride graft-modified ethylene-propylene (block or random) copolymer, maleic anhydride Preferred examples include one or a mixture of two or more selected from a graft-modified ethylene-ethyl acrylate copolymer, a maleic anhydride-graft-modified ethylene-vinyl acetate copolymer, and the like.
  • the amount of the unsaturated carboxylic acid or the anhydride thereof contained in the thermoplastic resin is preferably 0.001 to 3% by weight, more preferably 0.01 to 1% by weight, and particularly preferably. 0.3 to 0.5% by weight. If the amount of modification in the modified product is small, the adhesiveness may be insufficient, while if it is large, a crosslinking reaction may occur and moldability may deteriorate, which is not preferable.
  • these adhesive resins can be blended with the resin composition of the present invention, other rubber / elastomer components such as EV ⁇ H, polyisobutylene, and ethylene-propylene rubber, as well as the resin in layer b. It is. In particular, by blending a polyolefin resin that is different from the polyolefin resin that is the base of the adhesive resin, the adhesiveness is improved. There is useful.
  • each layer of the laminated body cannot be specified unconditionally depending on the layer constitution, the type of b, the use and the form of the container, the required physical properties, etc., but usually the layer a is 5 to 500 m (and 0 ⁇ 200 ⁇ m), b layer is 10 ⁇ 500m (or even 30 ⁇ 100 ⁇ m), adhesive resin layer is 5 ⁇ 400m (or even 10m) ⁇ : L is selected from the range of about 50 m). If the thickness of the layer a is less than 5 m, the gas barrier properties are insufficient and the thickness control becomes unstable. On the other hand, if it exceeds 500 x m, the impact resistance and the like are poor, and it is not economical and is not preferred.
  • the b layer is less than 100 m, the rigidity is insufficient, and if it exceeds 500 m;
  • the thickness of the adhesive resin layer is less than 5 m, the interlayer adhesiveness is insufficient and the thickness control becomes unstable.
  • the thickness exceeds 400 zm, the weight increases, which is not economical and not preferable.
  • the laminate is used as it is in various shapes. However, in order to further improve the physical properties of the laminate and to form a desired container shape, it is preferable to perform a heat-extending treatment.
  • the heat-stretching process refers to a film, sheet, or parison-like laminate that has been uniformly heated by means of chucks, plugs, true aerodynamics, pneumatics, blows, etc., cups, trays, tubes, bottles, films This means that the film may be uniaxially stretched or biaxially stretched. Stretching at the highest possible magnification provides better physical properties. A stretch-formed product excellent in gas barrier properties, free from cracks, stretching unevenness, uneven thickness, and delamination, is obtained.
  • any of a roll stretching method, a tensile stretching method, a tubular stretching method, a stretch blow method, a vacuum forming, a press forming, a vacuum press forming, etc., which has a high draw ratio can be employed.
  • any of a simultaneous biaxial stretching method and a sequential biaxial stretching method can be employed.
  • the stretching temperature is selected from the range of 60 to 170 ° C, preferably about 80 to 160 ° C.
  • After completion of the stretching it is also preferable to perform heat setting.
  • the heat setting can be performed by a well-known means, and the stretched film is heat-treated at 80 to 170 ° C, preferably 100 to 160 ° C for about 2 to 600 seconds while maintaining the stretched state. I do.
  • the shape of the thus obtained laminate may be any shape, and examples thereof include a film, a sheet, a tape, a cup, a tray, a tube, a pottle, a pipe, a filament, and an extrudate of a modified cross section.
  • the obtained laminate can be heat-treated, cooled, rolled, printed, dry-laminated, solution or melt-coated, bag-formed, deep drawn, boxed, tubed, or split as required. And so on.
  • Containers made of cups, trays, tubes, bottles, bottles, bags, bags, etc., and bags and lids made of stretched films obtained as described above, as well as general foods, seasonings such as mayonnaise and dressings, Fermented foods such as miso, oil and fat foods such as salad oil, beverages, cosmetics, pharmaceuticals, detergents, cosmetics, industrial chemicals, agricultural chemicals, fuels, and other containers. This is useful for packaging of foods and pharmaceuticals that make the contents look beautiful.
  • Vinyl acetate and biertrimethoxysilane are dissolved in a methanol solvent and polymerized at a reaction temperature of 60 ° C using 2,2'-azobisisobutyronitrile (AIBN) as an initiator under ethylene pressure (55 kg / cm 2 ). The reaction was carried out until the ratio reached 50% to obtain a silane-containing copolymer.
  • AIBN 2,2'-azobisisobutyronitrile
  • Screw shape Compression part has 100 mm reading disk
  • the obtained resin composition (pellet) was charged into an inflation molding machine, and inflation film formation was performed under the following conditions.
  • the thickness of the obtained film in the TD (width) direction was measured, and the average thickness and the difference between the maximum thickness and the minimum thickness were determined.
  • the measurement was performed at intervals of about lcm in the TD direction and over about lm in the MD (longitudinal) direction.
  • Example 1 except that magnesium acetate (B) was changed to 0.005 part (0.001 part in terms of magnesium) and boric acid (C) to 0.02 part (0.003 part in terms of boron). In the same manner, a resin composition was obtained in the same manner, and evaluation was similarly performed.
  • Example 3 A resin composition was obtained in the same manner as in Example 1, except that magnesium stearate (B) was used in an amount of 0.025 part (0.001 part in terms of magnesium) in place of magnesium acetate (B). An evaluation was performed.
  • a resin composition was obtained in the same manner as in Example 1 except that magnesium stearate (B) was replaced by 0.02 parts of zinc stearate (B) (0.002 parts in terms of zinc). Was evaluated.
  • a resin composition was obtained in the same manner as in Example 1 except that potassium borate (C) (0.08 part (0.003 part in terms of boron)) was used instead of boric acid (C). Was done.
  • Example 1 inflation molding was performed using only the saponified copolymer (A), and the same evaluation was performed.
  • Table 1 shows the evaluation results of the examples and the comparative examples.
  • the resin composition of the present invention can suppress thickness variation in the TD (width) direction at the time of film formation such as inflation molding, and can obtain a molded product such as a film or sheet having a uniform thickness.
  • the multilayer structure including the formed layer is useful for packaging applications such as foods and pharmaceuticals.

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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)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Composition de résine avec laquelle la dispersion d'épaisseur dans la direction TD (largeur) peut être inhibée lors de la formation du film par gonflage, etc., ce qui permet ainsi d'obtenir un article à forme, telle qu'un film ou une feuille, d'épaisseur uniforme. La présente invention concerne également une structure monocouche ou multicouche produite à partir de ladite composition de résine. En particulier, la présente invention concerne une composition de résine contenant un copolymère d'éthylène, d'acétate de vinyle et de composé vinylsilane ayant été saponifié (A) et de l'acétate de magnésium ou un sel d'acide gras supérieur d'un métal bivalent (B), ainsi qu'une structure multicouche comportant une couche constituée de ladite composition de résine.
PCT/JP2004/001251 2003-02-07 2004-02-06 Composition de resine et utilisation de ladite composition WO2004069922A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
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US10357629B2 (en) 2012-04-05 2019-07-23 Fisher & Paykel Healthcare Limited Respiratory assistance apparatus
US11433210B2 (en) 2014-05-27 2022-09-06 Fisher & Paykel Healthcare Limited Gases mixing and measuring for a medical device
US11666720B2 (en) 2015-12-02 2023-06-06 Fisher & Paykel Healthcare Limited Flow path sensing for flow therapy apparatus

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JP2000000817A (ja) * 1998-06-17 2000-01-07 Nippon Synthetic Chem Ind Co Ltd:The エチレン−酢酸ビニル共重合体ケン化物ペレットの製造法
JP2000043040A (ja) * 1998-07-27 2000-02-15 Nippon Synthetic Chem Ind Co Ltd:The エチレン−酢酸ビニル共重合体ケン化物組成物ペレットの製造法
JP2000044756A (ja) * 1998-07-27 2000-02-15 Nippon Synthetic Chem Ind Co Ltd:The エチレン−酢酸ビニル共重合体ケン化物組成物の製造法
JP2000178397A (ja) * 1998-12-14 2000-06-27 Nippon Synthetic Chem Ind Co Ltd:The 水酸基含有熱可塑性樹脂改質用の樹脂組成物およびその使用法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999005213A1 (fr) * 1997-07-25 1999-02-04 Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha Composition de resine, procede de preparation, et stratifie contenant une couche de ladite composition de resine
JP2000000817A (ja) * 1998-06-17 2000-01-07 Nippon Synthetic Chem Ind Co Ltd:The エチレン−酢酸ビニル共重合体ケン化物ペレットの製造法
JP2000043040A (ja) * 1998-07-27 2000-02-15 Nippon Synthetic Chem Ind Co Ltd:The エチレン−酢酸ビニル共重合体ケン化物組成物ペレットの製造法
JP2000044756A (ja) * 1998-07-27 2000-02-15 Nippon Synthetic Chem Ind Co Ltd:The エチレン−酢酸ビニル共重合体ケン化物組成物の製造法
JP2000178397A (ja) * 1998-12-14 2000-06-27 Nippon Synthetic Chem Ind Co Ltd:The 水酸基含有熱可塑性樹脂改質用の樹脂組成物およびその使用法

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