WO1992012202A1 - Structure de moulage en copolymere ethylene et composition de copolymere ethylene - Google Patents
Structure de moulage en copolymere ethylene et composition de copolymere ethylene Download PDFInfo
- Publication number
- WO1992012202A1 WO1992012202A1 PCT/JP1991/001765 JP9101765W WO9212202A1 WO 1992012202 A1 WO1992012202 A1 WO 1992012202A1 JP 9101765 W JP9101765 W JP 9101765W WO 9212202 A1 WO9212202 A1 WO 9212202A1
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- Prior art keywords
- ethylene
- copolymer
- vinyl alcohol
- weight
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- Prior art date
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Classifications
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- 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 atoms other than carbon or hydrogen
- C08L23/0853—Ethene vinyl acetate copolymers
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31913—Monoolefin polymer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31913—Monoolefin polymer
- Y10T428/3192—Next to vinyl or vinylidene chloride polymer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31928—Ester, halide or nitrile of addition polymer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31935—Ester, halide or nitrile of addition polymer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon
Definitions
- the present invention relates to an ethylene-based copolymer molded structure and an ethylene-based copolymer composition, and more particularly, to an ethylene-based copolymer molded structure excellent in gas barrier properties and pinhole resistance.
- the present invention relates to an ethylene copolymer composition excellent in stretchability at the time, film formability, heat stability, and the like.
- An ethylene-vinyl alcohol copolymer containing a high proportion of a vinyl alcohol structural unit is widely used as a packaging material because it exhibits excellent gas barrier properties when formed into a film or the like.
- the ethylene-vinyl alcohol copolymer has problems that it is easy to absorb water, has poor stretchability, is inferior in heat resistance, and is difficult to mold at high temperatures. In this case, the gas barrier property is deteriorated due to water absorption, the impact resistance in a dry state is insufficient, and the pinhole resistance is poor.
- the ethylene-vinyl alcohol copolymer is rarely used simply, and is usually used in combination with other materials.
- An example of this is a multilayer body in which a layer made of the ethylene-vinyl alcohol copolymer is used as an intermediate layer and another material is laminated on the intermediate layer. And a method for use. Further, the copolymer and another resin
- No. 3,004,004 discloses polyolefin and ethylene vinyl alcohol.
- the official gazette contains 60-95% by weight of polyolefin
- the present invention is intended to solve the above-mentioned problems in the conventional technology, and has an object to provide an ethylene-based copolymer molded structure excellent in gas barrier properties, pinhole resistance, and the like. I have. Another object of the present invention is to provide an ethylene copolymer composition which is excellent in stretchability during film formation, film formability, and thermal stability, and is excellent in gas barrier properties and pinhole resistance.
- [A] the amount of ethylene constituent unit is 85 to 65 weight
- the unsaturated ester unit is present in an amount of 15 to 35% by weight
- the amount of ethylene constituent unit is 50 to 20 mol%
- the vinyl alcohol structural unit is present in an amount of 50 to 80 mol%
- the apparent melt viscosity at a shear rate of 100 se 1 is 3 G ⁇ ) to i 0 0 P a ⁇ szj ⁇ from that of the above [A] ethylene / unsaturated ester copolymer, and ,
- [A] the amount of ethylene constituent unit is 85 to 65% by weight
- the unsaturated ester structural unit is present in an amount of 15 to 35% by weight, and the melt flow rate at a load of 190 to 160 g is
- the vinyl alcohol constituent unit is present in an amount of 50 to 80 mol%, and the melt melt rate at 210 ° C. and a load of 210 g is
- the above-mentioned [B] ethylene'vinyl alcohol copolymer has an apparent melt viscosity at 220 ° C and a shear rate of 100 sec- 1 which is 30% lower than that of the [A] ethylene / unsaturated ester copolymer. It is characterized in that it is smaller than 0 to 100 Pas.
- the second molded structure ⁇ according to the present invention is formed from the above-described ethylene copolymer composition, and the molded structure has [B] an ethylene / vinyl alcohol copolymer dispersed in a thin layer. It is characterized by. BRIEF DESCRIPTION OF THE FIGURES
- FIG. 1 is an electron micrograph showing a cross section of the molded structure according to the present invention.
- the shaded portion is the ethylene-unsaturated ester copolymer [A] as the matrix layer, and the ethylene-vinyl alcohol copolymer [B] is thin and unevenly distributed along the film surface direction. Dispersed without difficulty and observed as a part surrounded by a discontinuous white line ⁇
- the molded structure according to the present invention has such a layered structure.
- the molded structure and the ethylene copolymer composition comprising the ethylene copolymer composition according to the present invention will be specifically described.
- the term "polymer” is sometimes used to mean not only a homopolymer but also a copolymer.
- This ethylene-based copolymer composition comprises [A] an ethylene / unsaturated ester copolymer and [B] an ethylene'vinyl alcohol copolymer.
- the ethylene 'unsaturated ester copolymer [A] used in the present invention is:
- the ethylene unit is contained in an amount of 85 to 65% by weight, preferably 85 to 72% by weight, and the unsaturated ester unit is contained in an amount of 15 to 35% by weight, preferably 15 to 28% by weight. ing.
- the content of the unsaturated ester structural unit is less than 15% by weight, the gas barrier property tends to decrease, while if it exceeds 35% by weight, the strength of the molded structure tends to decrease.
- the ethylene 'unsaturated ester copolymer [A] has a melt flow rate measured at 190 ° C. and a load of 210 g of 0.5 to 20 g Z 10 minutes, preferably 1 to 1 minute. 5 g Z 10 minutes.
- Such an ethylene / unsaturated ester copolymer [A] is obtained by copolymerizing ethylene and an unsaturated ester, and the unsaturated ester used in this case is a unsaturated ester of dicarboxylic acid. And may be any of unsaturated power rubonic esters. Specific examples include vinyl acetate, acrylate, and methacrylate. Examples of the ester component of acrylate or methacrylate include alkyl esters having 1 to 8 carbon atoms, and among them, methyl esters and ethyl esters are preferred.
- the ethylene vinyl alcohol copolymer [B] used in the present invention contains 50 to 20 mol%, preferably 45 to 25 mol%, of the ethylene structural unit and 50 to 50 mol% of the vinyl alcohol structural unit. 8 0 mol good Mashiku 5 5-7 5 molar amounts such this u containing at the: ft polymerization ⁇ [B] is the corresponding ethylene-vinyl acetate copolymer saponification degree 95% or more preferably By saponifying at a rate of more than 99% can get.
- the ethylene 'vinyl alcohol copolymer [B] has a melt flow rate of 0.5 to 30 g / 10 minutes, preferably 1 to 20 g / 0 minutes at 210 and a load of 210 g. is there.
- the ethylene-vinyl alcohol copolymer [B] used in the present invention has an apparent melt viscosity at 220 ° C and a shear rate of 10 Osec which is 3 times lower than that of the ethylene / unsaturated ester copolymer [A]. 00 to 100 Pa'S, preferably 400 to 900 Pa'S is small.
- the ethylene / unsaturated ester copolymer [A] and the ethylene'vinyl alcohol copolymer [B] having such a difference in melt apparent viscosity at such a value form an ethylene copolymer composition.
- the composition comes to form a molded structure having a layered structure in which the copolymer [B] is dispersed in a thin layer without uneven distribution.
- the ethylene-based copolymer composition forming the first molded structure according to the present invention comprises the above-mentioned ethylene 'unsaturated ester copolymer [A] and ethylene' vinyl alcohol copolymer [B]. And ethylene-unsaturated ester copolymer [A] in an amount of 50 to 80% by weight, preferably 55 to 0% by weight, and ethylene 'vinyl alcohol copolymer [B] in an amount of 20 to 5%. 0% by weight, preferably 30 to 45% by weight.
- the ethylene copolymer composition having the above composition has excellent heat stability during molding, stretchability and film moldability.
- the first molded structure according to the present invention is formed from the above ethylene-based copolymer composition.
- the ethylene / vinyl alcohol is used. It has a structure in which the copolymer [B] is dispersed in a thin layer without uneven distribution. More specifically, the copolymer [B] forms a discontinuous thin layer along the surface direction of the molded structure, and substantially the copolymer [ B] has a layered structure that is dispersed without being unevenly distributed. Such a layered structure is shown in the electron micrograph in FIG. 1 above.
- the molded structure according to the present invention has such a layered structure, the molded structure can be obtained from a composition containing the ethylene'pinyl alcohol copolymer [B] in an amount of 50 to 20% by weight. Despite being formed, it has excellent gas barrier properties.
- the molded structure according to the present invention preferably has a shape having a large area and a relatively small thickness, and can take various shapes such as a film, a sheet, and a hollow container.
- the molded structure according to the present invention usually has a thickness of 5 to 100 zm, preferably 20 to 500 m.
- the molded structure exhibits excellent gas barrier properties even in a thin layer having a thickness of about 30 to 50 m.
- Such a molded structure can be obtained by molding the above-mentioned ethylene copolymer composition.
- the above components [A] and [B] may be molded while kneading them, or they may be kneaded and then supplied to a molding machine, but the latter is more preferred. It is preferable that the kneading is usually carried out at a temperature of 17 C to 235, a shear rate of 10 to 200 sec- ', and a residence time of 10 sec to 5 min under stirring.
- the molding may be performed by a method in which the molten ethylene-based copolymer composition flows in the plane direction of the molded structure from which the obtained ethylene-based copolymer composition is obtained.
- the method can be carried out by a method such as an extrusion molding method, a hollow molding method, an injection molding method, an injection-blow molding method, and a vacuum molding method.
- additives depending on the intended use may be added to the above-mentioned ethylene copolymer composition.
- additives include an antioxidant, a heat stabilizer, a desiccant, a nucleating agent, an antistatic agent, and a barrier-imparting filler such as mica.
- Addition of a desiccant is preferable because the tendency of the ethylene-vinyl alcohol copolymer [B] component to absorb water and reduce the gas barrier properties of the molded structure can be reduced. When mica is blended, the gas barrier property can be further improved.
- the ethylene 'vinyl alcohol copolymer [B] has an apparent melt viscosity of the ethylene / unsaturated ester copolymer [A]. ) Is smaller than the apparent viscosity of the copolymer by 300 to 100 OPa ⁇ s, it is estimated that the ethylene / vinyl alcohol copolymer will be dispersed in a thin layer along the surface direction during molding.
- the first molded structure according to the present invention is excellent in gas barrier properties and pinhole resistance as described above, and has a water absorption property of a molded product composed of only an ethylene / vinyl alcohol copolymer [B]. It is remarkably superior to the structure.
- the i-th molded structure according to the wood invention may be used by being laminated with a layer made of a ground material.
- a layer made of a ground material include, for example, high density polyethylene, hollow polyethylene, low density polyethylene, linear low density Polyolefins such as polyethylene, polypropylene, poly-4-methyl-1-pentene, polyesters such as polyethylene terephthalate and polybutylene terephthalate, and polyamides such as nylon-6 and nylon-6,6 Thermoplastic resins, thermosetting resins such as polyurethane, various elastomers, metal materials such as aluminum foil, and paper.
- the molded structure layer of the present invention may include one layer or two or more layers, and the molded structure layer is used as a surface layer of the laminate or as an intermediate layer.
- the ethylene-based copolymer composition according to the present invention is a graph-modified product of the above-mentioned ethylene / unsaturated ester copolymer [A], ethylene-vinyl alcohol copolymer [B], and the following ethylene-olefin copolymer.
- Object [C] is a graph-modified product of the above-mentioned ethylene / unsaturated ester copolymer [A], ethylene-vinyl alcohol copolymer [B], and the following ethylene-olefin copolymer.
- the graft modified product [C] of the ethylene-olefin copolymer used in the present invention can be obtained by modifying the ethylene-olefin copolymer with an unsaturated sulfonic acid or its anhydride.
- Such an ethylene-olefin copolymer contains 60 to 90 mol%, preferably 70 to 85 mol, of an ethylene structural unit, and has a structural unit derived from a non-ethylene-free olefin. Is 4 0 ⁇ ! It is contained in an amount of 0 mol%, preferably 30 to i5 mol.
- olefins include one-year-old olefins having about 3 to 8 carbon atoms, preferably propylene, 1-butene, "-
- Such an ethylene-horefin copolymer is low in crystallinity or amorphous. Specifically, the crystallinity by X-ray diffraction is usually 30% or less, preferably 20% or less. is there.
- the copolymer has a melt flow rate at a load of 190 and 210 g, usually 0.3 to 50 gZl 0 minutes, preferably 0.5 to 20 g / 10 minutes. Desirably.
- Unsaturated carboxylic acids or their anhydrides used in the graft modification of such ethylene-olefin copolymers include, specifically, acrylic acid, methacrylic acid, fumaric acid, maleic acid, Examples thereof include diic acid, maleic anhydride, itaconic anhydride, and nadic anhydride. Of these, maleic acid or maleic anhydride is particularly preferred.
- the graft modified product [C] of the ethylene-one-olefin refin copolymer used in the present invention usually has a graft amount of 0.03 to 7% by weight, preferably 0.05 to 5% by weight. It is desirable that it be denatured as described above.
- a graft-modified product other than an ethylene / hydroolefin copolymer for example, an ethylene-vinyl acetate copolymer graft-modified product is known.
- the gas barrier properties of the obtained molded structure may be significantly reduced depending on the amount of the graft-modified product.
- the graft modified product of ethylene / polyolefin copolymer [C] used in the present invention is used in a relatively large amount. Even if it does, the gas barrier property of the obtained molded structure is hardly reduced.
- the ethylene copolymer composition according to the present invention contains ethylene-unsaturated ester copolymer [A] as described above in an amount of 30 to 75% by weight, preferably 40 to 65% by weight, and ethylene.
- ethylene-unsaturated ester copolymer [A] as described above in an amount of 30 to 75% by weight, preferably 40 to 65% by weight, and ethylene.
- the ethylene copolymer composition having the above composition is excellent in thermal stability during stretching, stretchability and film moldability, and forms a molded structure excellent in gas barrier properties and pinhole resistance. Can.
- Such an ethylene-based copolymer composition contains the above-mentioned amount of the ethylene-olefin copolymer-modified graft [C], whereby the extrusion kneading property and the film formability are further improved. ing.
- the molded structure obtained may have a reduced gas barrier property.
- the ethylene-based copolymer composition according to the present invention has , Graft modified products
- [C] is contained in the amount described above, and the gas barrier property of the obtained molded structure is hardly reduced.
- the second molded structure according to the present invention is formed from the first ethylene-based copolymer composition as described above.
- the second molded structure according to the present invention has the same layered structure as the i-th molded structure described above.
- Such a second molded structure is the same as the first molded structure described above. It takes various shapes and is molded in the same manner.
- an extruder having a normal kneading function may be used, and it is not necessary to employ extrusion conditions that cause a laminar flow.
- the sheet may be subjected to secondary forming such as vacuum forming and pressure forming to form a container having a desired shape.
- the first ethylene-based copolymer molded structure provided by the present invention is characterized in that an ethylene / vinyl alcohol copolymer [B], which is dispersed in the molded structure in a thin layer and without uneven distribution, Excellent gas barrier properties.
- an ethylene / vinyl alcohol copolymer [B] which is dispersed in the molded structure in a thin layer and without uneven distribution, Excellent gas barrier properties.
- the gas barrier properties are less dependent on humidity.
- the molded structure molded as a film or the like has excellent pinhole resistance and is useful as various packaging materials such as food packaging.
- the first ethylenic copolymer composition according to the present invention comprises: an ethylene / unsaturated ester copolymer [A] containing a specific amount of an unsaturated ester constituent unit; It consists of an ethylene copolymer with different apparent viscosity at a specific value, a vinyl alcohol copolymer [B], and a graft modified product of an ethylene monoolefin copolymer [C], and has thermal stability and stretchability during molding. In addition to being excellent in extrudability, extrusion kneadability and film formability during molding are further improved.
- the second molded structure provided by the present invention is formed from the first ethylene copolymer-based copolymer composition, and has the same layered structure as the first ethylene copolymer molded structure. .
- Such a second molded structure has excellent gas barrier properties and excellent pinhole resistance.
- the present invention will be described in more detail by way of examples.
- the resin kneading method, the ⁇ shape processing method and evaluation, and the analysis method were performed under the following conditions and methods.
- the measurement was performed according to JISK-1760.
- a predetermined ratio of the resin was melt-kneaded under the following conditions.
- An inflation film was formed on an inflation molding machine comprising a 30-shaft single-screw full-flight extruder under the following conditions.
- Examples 2 and 8 molding was performed while changing the discharge speed from the extruder. These molding conditions are those of a normal inflation film molding method, and do not particularly control the dispersion or flow state of the ethylene-vinyl alcohol resin.
- Table 1 shows the resins used in Examples and Comparative Examples.
- Ethylene EV 1 70 "vinegar» vinyl 3 3wt3 ⁇ 4 5 92-based polymer copolymer
- Table 4 shows the three components listed in Table 1, the ethylene-vinyl acetate copolymer [A], the ethylene • vinyl alcohol copolymer [B], and the modified ethylene-vinyl-olefin copolymer [C]. Kneading was carried out by the method described in the above (3) using the stated amount, and the performance such as extrusion kneading property, film formability, and oxygen permeability was evaluated.
- Table 5 shows the three components of ethylene-vinyl acetate copolymer [A], ethylene • vinyl alcohol copolymer [B], and ethylene-ethylene-olefin copolymer graft modified product [C] listed in Table 1. Kneading was performed by the method described in (3) using the amounts described above, and performances such as extrusion kneading properties, film moldability, and oxygen permeability were evaluated.
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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)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE69125710T DE69125710T2 (de) | 1990-12-27 | 1991-12-26 | Formstruktur und zusammensetzung aus einem ethen-copolymer |
| US07/927,636 US5319022A (en) | 1990-12-27 | 1991-12-26 | Ethylene copolymer molded structure and ethylene copolymer composition |
| EP19920901878 EP0522166B1 (en) | 1990-12-27 | 1991-12-26 | Ethylenic copolymer molding structure and ethylenic copolymer composition |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2/415153 | 1990-12-27 | ||
| JP41515390 | 1990-12-27 | ||
| JP3/12391 | 1991-01-10 | ||
| JP1239191 | 1991-01-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1992012202A1 true WO1992012202A1 (fr) | 1992-07-23 |
Family
ID=26348001
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP1991/001765 Ceased WO1992012202A1 (fr) | 1990-12-27 | 1991-12-26 | Structure de moulage en copolymere ethylene et composition de copolymere ethylene |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5319022A (enExample) |
| EP (1) | EP0522166B1 (enExample) |
| DE (1) | DE69125710T2 (enExample) |
| WO (1) | WO1992012202A1 (enExample) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU1046095A (en) * | 1993-11-01 | 1995-05-23 | E.I. Du Pont De Nemours And Company | Multicomponent pellets of barrier resin and compatibilizer for making laminar articles |
| US5849376A (en) * | 1995-08-21 | 1998-12-15 | Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha | Multi-layered laminate comprising hydrolyzed EVOH and use thereof |
| US5972447A (en) * | 1996-09-30 | 1999-10-26 | Kuraray Co., Ltd. | Thermoformable multilayer film and thermoformed container |
| CA2343816C (en) | 1998-09-11 | 2009-04-14 | Nike International Ltd. | Flexible membranes |
| US6127026A (en) * | 1998-09-11 | 2000-10-03 | Nike, Inc. | Flexible membranes |
| US6082025A (en) * | 1998-09-11 | 2000-07-04 | Nike, Inc. | Flexible membranes |
| KR100693388B1 (ko) * | 2000-12-06 | 2007-03-09 | 바프렉스 주식회사 | 산소차단성 수지 조성물 및 이를 포함하는 제품 |
| JP6509109B2 (ja) * | 2013-04-04 | 2019-05-08 | 日本クロージャー株式会社 | 熱可塑性樹脂から成る層を有する成形体 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5311032B2 (enExample) * | 1973-12-06 | 1978-04-18 | ||
| JPS55155042A (en) * | 1979-05-21 | 1980-12-03 | Mitsubishi Chem Ind Ltd | Polymer composition |
| JPS6181448A (ja) * | 1984-09-06 | 1986-04-25 | Kuraray Co Ltd | 耐衝撃性を有する樹脂組成物 |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5130104A (ja) * | 1974-09-04 | 1976-03-15 | Kazuo Yoshida | Morutarufukitsukemennoryokukakoho |
| JPS5311032A (en) * | 1976-07-19 | 1978-02-01 | Toshiba Corp | Detector for remaining toner |
| JPS5512107A (en) * | 1978-07-10 | 1980-01-28 | Toray Ind Inc | Matte coating composition |
| CA1146323A (en) * | 1979-03-06 | 1983-05-17 | Pallatheri M. Subramanian | Laminar articles of polyolefin and a second polymer and process for making them |
| US4410482A (en) * | 1979-03-06 | 1983-10-18 | E. I. Du Pont De Nemours & Co. | Process for making laminar articles of polyolefin and a condensation polymer |
| DE3233693C2 (de) * | 1982-09-10 | 1995-01-05 | American National Can Co | Orientierte Verbundfolie und deren Verwendung |
| US4657972A (en) * | 1985-01-02 | 1987-04-14 | General Electric Company | Polycarbonate compositions |
| DK730288A (da) * | 1988-01-15 | 1989-07-16 | Kuraray Co | Harpikskompositioner og flerlagede strukturer indeholdende disse |
-
1991
- 1991-12-26 WO PCT/JP1991/001765 patent/WO1992012202A1/ja not_active Ceased
- 1991-12-26 US US07/927,636 patent/US5319022A/en not_active Expired - Lifetime
- 1991-12-26 EP EP19920901878 patent/EP0522166B1/en not_active Expired - Lifetime
- 1991-12-26 DE DE69125710T patent/DE69125710T2/de not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5311032B2 (enExample) * | 1973-12-06 | 1978-04-18 | ||
| JPS55155042A (en) * | 1979-05-21 | 1980-12-03 | Mitsubishi Chem Ind Ltd | Polymer composition |
| JPS6181448A (ja) * | 1984-09-06 | 1986-04-25 | Kuraray Co Ltd | 耐衝撃性を有する樹脂組成物 |
Non-Patent Citations (1)
| Title |
|---|
| See also references of EP0522166A4 * |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0522166A4 (enExample) | 1994-04-20 |
| DE69125710T2 (de) | 1997-11-13 |
| DE69125710D1 (de) | 1997-05-22 |
| EP0522166A1 (en) | 1993-01-13 |
| EP0522166B1 (en) | 1997-04-16 |
| US5319022A (en) | 1994-06-07 |
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