WO2013146962A1 - ブロー成形容器及び燃料容器、並びにブロー成形容器の製造方法 - Google Patents
ブロー成形容器及び燃料容器、並びにブロー成形容器の製造方法 Download PDFInfo
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- WO2013146962A1 WO2013146962A1 PCT/JP2013/059152 JP2013059152W WO2013146962A1 WO 2013146962 A1 WO2013146962 A1 WO 2013146962A1 JP 2013059152 W JP2013059152 W JP 2013059152W WO 2013146962 A1 WO2013146962 A1 WO 2013146962A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
- B65D1/0207—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
- B65D1/0215—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features multilayered
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/22—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor using multilayered preforms or parisons
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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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
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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
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/40—Details of walls
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/04—Polymers of ethylene
- B29K2023/08—Copolymers of ethylene
- B29K2023/086—EVOH, i.e. ethylene vinyl alcohol copolymer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/25—Solid
- B29K2105/253—Preform
- B29K2105/258—Tubular
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0065—Permeability to gases
- B29K2995/0067—Permeability to gases non-permeable
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2009/00—Layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/712—Containers; Packaging elements or accessories, Packages
- B29L2031/7158—Bottles
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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
- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
- B32B2307/7265—Non-permeable
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/40—Closed containers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/40—Closed containers
- B32B2439/60—Bottles
-
- 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
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1397—Single layer [continuous layer]
Definitions
- the present invention relates to a blow molded container, a fuel container, and a method for manufacturing a blow molded container.
- An ethylene-vinyl alcohol copolymer (hereinafter sometimes abbreviated as EVOH) is a polymer material excellent in gas shielding properties such as oxygen, oil resistance, and non-charging properties. Therefore, the EVOH-containing resin composition is formed into a container, a film, a sheet, and the like, and is widely used as various packaging materials. In particular, in the field of blow molded containers and the like, a multilayer structure composed of a layer made of the above EVOH-containing resin composition and a layer of other thermoplastic resin having excellent moisture resistance, impact resistance, etc. is widely adopted. .
- melt molding is generally performed, but this melt molding may cause defects such as gels, blisters and streaks, which may impair the appearance of the molded product.
- the gels and blisters not only impair the appearance of the molded product, but also cause performance deterioration, and therefore it is necessary to suppress these occurrences.
- an EVOH-containing resin composition with improved self-purge properties (1) a resin in which a polyolefin resin, a carboxylic acid-modified polyolefin resin, and an alkaline earth metal salt of a lower fatty acid having 9 or less carbon atoms are added to the EVOH resin at a specific ratio Composition (JP-A-5-255554), (2) EVOH-containing resin composition containing a specific viscosity and a carboxylic acid having a molecular weight of less than 75 and an alkaline earth metal salt (JP-A-2001 2001) No. 234008) is known.
- the molded product may be colored, and the self-purge property is not sufficient.
- the EVOH-containing resin composition (1) has the disadvantage that deterioration of hue or long run property occurs due to the addition of the polyolefin resin.
- the present invention has been made based on the circumstances as described above, and its purpose is to provide a blow-molded container excellent in appearance, in which the occurrence of defects such as gels, blisters and streaks due to melt molding and coloring are suppressed. It is to be.
- Another object of the present invention is to provide a blow molded container that has good self-purge properties during production, has sufficient strength and other quality, and can be produced at low cost.
- a blow molded container comprising: The layer (A) contains an unsaturated aldehyde (II), The blow molded container is characterized in that the content of the unsaturated aldehyde (II) in the layer (A) is 0.01 ppm or more and 100 ppm or less.
- the blow molded container of the present invention can prevent the occurrence of defects such as gels, blisters and streaks due to melt molding by providing the (A) layer in which the content of unsaturated aldehyde (II) is in the specific range. And excellent in appearance. Further, since the layer (A) contains the specific amount of the unsaturated aldehyde (II), the self-purge property in the manufacturing process of the blow-molded container is excellent, so that the manufacturing cost of the blow-molded container can be reduced. it can.
- the main component means a component that occupies a majority of the whole, and includes the case where the whole consists of only the main component.
- the unsaturated aldehyde (II) is preferably an unsaturated aliphatic aldehyde (II-1), and is selected from the group consisting of crotonaldehyde, 2,4-hexadienal and 2,4,6-octatrienal. More preferably, it is at least one.
- unsaturated aldehyde (II) that suppresses the generation of fish eyes, gels, and streaks during melt molding is not necessarily clear, but unsaturated aldehyde (II) is more easily oxidized than EVOH (I). For this reason, it is estimated that during heating and melting, the oxidative deterioration of EVOH (I) due to oxygen is suppressed by oxidizing unsaturated aldehyde (II) earlier than EVOH (I).
- the layer (A) preferably contains a conjugated polyene compound, and the content of the conjugated polyene compound in the layer (A) is preferably 0.01 ppm or more and 1,000 ppm or less.
- the layer (A) further contains the above-mentioned specific amount of the conjugated polyene compound, thereby suppressing the occurrence of defects such as gels and blisters, coloring, and the like by suppressing the oxidative deterioration during melt molding. Can be further improved. Moreover, since the (A) layer contains the specific amount of the conjugated polyene compound, the self-purge property is further improved, so that the blow molded container can further reduce the cost.
- the conjugated polyene compound is preferably sorbic acid and / or sorbate.
- sorbic acid and / or sorbate as the conjugated polyene compound, it is possible to more effectively suppress oxidative deterioration during melt molding, and to prevent the occurrence of defects such as gels and blisters and coloring. And appearance can be effectively improved.
- the layer (A) contains sorbic acid and / or sorbate as a conjugated polyene compound, even when melt-molded continuously for a long time, the occurrence of gels and blisters is suppressed, and the impact resistance is improved. An excellent blow molded container can be obtained.
- the blow molded container is (B) A layer mainly composed of a thermoplastic resin (hereinafter referred to as “(B) layer”) which is disposed on the inner surface side and outer surface side of the (A) layer and whose solubility parameter calculated from the Fedors equation is 11 or less. And (C) a layer that is disposed between the (A) layer and the (B) layer and contains a carboxylic acid-modified polyolefin as a main component (hereinafter also referred to as “(C) layer”). It is preferable to provide.
- the blow molded container can further improve the gas shielding property, oil resistance, impact resistance, etc. under high humidity by further including the (B) layer and the (C) layer. it can.
- the blow molded container is (D) ethylene-vinyl alcohol copolymer (I), a thermoplastic resin having a solubility parameter calculated from the Fedors equation of 11 or less, and a layer containing a carboxylic acid-modified polyolefin (hereinafter referred to as “(D) layer”) (Also called) It is preferable to provide.
- the blow molded container can further improve gas shielding properties, impact resistance, and the like under high humidity by further including the (D) layer.
- the (D) layer is formed by using the recovered material of the (A) layer, the (B) layer, and the (C) layer in the blow molding container manufacturing process.
- the layer (D) is formed using the recovered material (A), (B), and (C) in the blow molding container manufacturing process, and is generated in the blow molding container manufacturing process.
- the burrs to be tested, products that have failed the test, etc. are reused in the (D) layer, so that the material resin can be used without waste, and the low cost is improved.
- the layer thickness of the layer (A) is 5.0% or less of the total layer thickness, and the content of the ethylene-vinyl alcohol copolymer in the layer (D) is 9.0 mass. % Or less is preferable.
- the layer thickness of the layer (A) is 5.0% or less of the total layer thickness, and the content of the ethylene-vinyl alcohol copolymer in the layer (D) is 9.0% by weight or less.
- the blow molded container is preferably used as a fuel container.
- the blow molded container is excellent in gas shielding properties, oil resistance and the like, and is also excellent in appearance, and therefore can be suitably used for a fuel container.
- blow molded container is suitably used for blow molded bottles.
- the blow molded container is excellent in gas shielding properties, oil resistance and the like, and also in appearance.
- the preferable manufacturing method of the said blow molded container is Having a step of blow molding using a resin composition mainly composed of ethylene-vinyl alcohol copolymer (I),
- the resin composition contains an unsaturated aldehyde (II), and the content of the unsaturated aldehyde (II) in the resin composition is 0.01 ppm or more and 100 ppm or less.
- the method for producing a blow molded container since the generation and coloring of defects such as gels, blisters, streaks and the like are suppressed, a blow molded container having an excellent appearance can be obtained.
- the resin composition used for the manufacturing method of the said blow molding container is excellent in self purge property, manufacturing cost can be reduced.
- the blow-molded container of the present invention contains a specific amount of unsaturated aldehyde (II) in the (A) layer, so that it is melt-molded. Since the occurrence of defects such as gels, blisters, streaks and coloring due to the coloration is suppressed, the appearance is excellent. Moreover, since the said (A) layer contains the said specific amount of unsaturated aldehyde (II), since the said blow molding container is excellent also in the self purge property in a manufacturing process, the manufacturing cost of the said blow molding container is reduced. be able to. Therefore, the blow molded container is used for various applications, and is particularly suitable as a fuel container or a blow molded bottle container.
- the blow molded container 1 has (B) layer 6, (C) layer 5, (A) layer 4, (C) layer 5, and (D) layer from the container inner surface 2 toward the container outer surface 3. 7 and (B) a multilayer structure in which the layers 6 are laminated in this order.
- FIG. 1 is a partial cross-sectional view of the peripheral wall of the blow molded container 1. Hereinafter, each layer will be described.
- the layer 4 is a layer containing EVOH (I) as a main component, and contains 0.01 ppm or more and 100 ppm or less of unsaturated aldehyde (II).
- the blow-molded container 1 includes the (A) layer 4 containing the above-mentioned specific amount of unsaturated aldehyde (II), thereby suppressing the occurrence of defects such as gels, blisters and streaks due to melt molding. Excellent in properties.
- the said (A) layer 4 contains the said specific amount of unsaturated aldehyde (II), since it is excellent also in the self purge property in the manufacturing process of the blow-molded container 1, manufacturing cost can be reduced.
- the (A) layer 4 preferably further contains a conjugated polyene compound. Furthermore, the (A) layer 4 may contain a boron compound, acetic acid and / or acetate, a phosphorus compound, and other optional components as long as the effects of the present invention are not impaired. Hereinafter, each component will be described in detail.
- EVOH (I) used in the present invention is an ethylene-vinyl alcohol copolymer obtained by saponifying an ethylene-vinyl ester copolymer.
- the ethylene content of the EVOH (I) is usually 20 mol% or more and 60 mol% or less, preferably 20 mol% or more and 45 mol% or less, and preferably 24 mol% or more and 45 mol% or less. Preferably, it is 27 mol% or more and 42 mol% or less, and more preferably 27 mol% or more and 38 mol% or less.
- EVOH tends to gel due to a decrease in thermal stability during melt extrusion, and defects such as gels, blisters and streaks are likely to occur.
- the saponification degree of the vinyl ester component of the EVOH (I) is usually 85% or more, preferably 90% or more, more preferably 98% or more, and further preferably 99% or more.
- EVOH may have insufficient thermal stability when the saponification degree of the vinyl ester component of EVOH is less than 85%.
- vinyl ester used for the production of EVOH (I) for example, vinyl acetate can be cited as a typical example, but other fatty acid vinyl esters such as vinyl propionate and vinyl pivalate can be used. it can.
- the EVOH (I) can further use a vinylsilane compound as a copolymer component in addition to ethylene and vinyl ester.
- the content of the vinylsilane compound in the EVOH is 0.0002 to 0.2 mol%.
- vinylsilane compound examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri ( ⁇ -methoxy-ethoxy) silane, and ⁇ -methacryloxypropylmethoxysilane. Of these, vinyltrimethoxysilane and vinyltriethoxysilane are preferred.
- the EVOH (I) may use other monomers as copolymer components other than ethylene, vinyl ester and vinyl silane-based compounds as long as the effects of the present invention are not impaired.
- Examples of the other monomers include unsaturated hydrocarbons such as propylene and butylene; Unsaturated carboxylic acids such as (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate or esters thereof; And vinyl pyrrolidone such as N-vinyl pyrrolidone.
- the EVOH (I) content in the layer (A) 4 is usually 95% by mass or more, preferably 98.0% by mass or more, more preferably 99.0% by mass, 99 More preferably, it is 5% by mass or more.
- the blow molded article is excellent in various gas shielding properties, oil resistance, and the like.
- the (A) layer 4 contains from 0.01 ppm to 100 ppm of unsaturated aldehyde (II) as an essential component together with EVOH (I).
- Unsaturated aldehyde (II) is an aldehyde having a carbon-carbon double bond or triple bond in the molecule, and unsaturated aliphatic aldehyde (II-1) is preferred, crotonaldehyde, 2,4-hexadienal And at least one selected from the group consisting of 2,4,6-octatrienal.
- content of unsaturated aldehyde (II) in the said (A) layer 4 it is 0.01 ppm or more and 100 ppm or less, 0.05 ppm or more and 50 ppm or less are preferable, 0.1 ppm or more and 30 ppm or less are preferable, 0.15 ppm or more 20 ppm or less is more preferable.
- content of the unsaturated aldehyde (II) in the (A) layer 4 is less than 0.01 ppm, the blow molded container 1 may have insufficient self-purge properties during production.
- the unsaturated aldehyde (II) exhibits a crosslinking effect at the time of melt molding, and may cause defects such as gels, blisters, streaks, and coloring, resulting in insufficient appearance.
- the content of the unsaturated aldehyde (II) in the layer (A) 4 is a resin composition (hereinafter referred to as “EVOH-containing resin composition”) containing EVOH (I) that forms the layer 4 (A). It is expressed as a ratio with respect to the total solid mass of the product, and specifically refers to a value obtained by quantifying the unsaturated aldehyde (II) contained in the dried resin composition.
- the unsaturated aldehyde (II) is preferably an unsaturated aliphatic aldehyde (II-1), such as acrylic aldehyde (acrolein), crotonaldehyde, methacrylaldehyde, 2-methyl-2-butenal, 2-butynal, 2-hexenal.
- unsaturated aliphatic aldehyde (II-1) such as acrylic aldehyde (acrolein), crotonaldehyde, methacrylaldehyde, 2-methyl-2-butenal, 2-butynal, 2-hexenal.
- 2,6-nonadienal, 2,4-hexadienal, 2,4,6-octatrienal 2-hexenal, 5-methyl-2-hexenal, and other aldehydes having a carbon-carbon double bond in the molecule
- Aldehydes having a carbon-carbon triple bond such as propioaldehyde, 2-butyn-1-al, 2-pentyne-1-al, etc. are preferred, and those having a straight-chain or branched carbon-carbon double bond are preferred.
- Saturated aliphatic aldehydes are more preferred, crotonaldehyde, 2,4-hexadienal And at least one selected from the group consisting of 2,4,6-octatrienal.
- crotonaldehyde having a high solubility in water and a boiling point of around 100 ° C. It is more preferable because it is easy to remove the excess or add the deficiency as needed in the process.
- the number of carbon atoms including the aldehyde part of the unsaturated aldehyde (II) is preferably 3 to 10, more preferably 4 to 8, and further preferably 4, 6, and 8.
- the (A) layer 4 preferably further contains a conjugated polyene compound, and the content of the conjugated polyene compound is preferably 0.01 ppm or more and 1,000 ppm or less, more preferably 0.1 ppm or more and 1,000 ppm or less. preferable.
- the blow-molded container 1 can suppress oxidative deterioration during melt molding, and generate and color defects such as gels and blisters. Is less likely to occur, so the appearance is better.
- the layer (A) 4 contains the specific amount of the conjugated polyene compound, even when melt-molded continuously for a long time, the occurrence of gels and blisters is suppressed, and blow molding with excellent impact resistance is achieved. A container can be obtained.
- the conjugated polyene compound is a so-called conjugated double bond having a structure in which carbon-carbon double bonds and carbon-carbon single bonds are alternately connected and having two or more carbon-carbon double bonds. It is a compound that has.
- the conjugated polyene compound may be a conjugated diene having two conjugated double bonds, a conjugated triene having three, or a conjugated polyene having more than that number. Further, a plurality of sets of the conjugated double bonds may be present in one molecule without being conjugated with each other. For example, a compound having three conjugated triene structures in the same molecule such as tung oil is also included in the conjugated polyene compound.
- the number of conjugated double bonds is preferably 7 or less.
- the blow molded container 1 may be colored.
- the conjugated polyene compounds include carboxyl groups and salts thereof, hydroxyl groups, ester groups, carbonyl groups, ether groups, amino groups, imino groups, amide groups, cyano groups, diazo groups, nitro groups, sulfones. It may have other functional groups such as a group and a salt thereof, a sulfonyl group, a sulfoxide group, a sulfide group, a thiol group, a phosphate group and a salt thereof, a phenyl group, a halogen atom, a double bond, and a triple bond.
- conjugated polyene compound examples include isoprene, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-t-butyl-1,3-butadiene, 1,3- Pentadiene, 2,3-dimethyl-1,3-pentadiene, 2,4-dimethyl-1,3-pentadiene, 3,4-dimethyl-1,3-pentadiene, 3-ethyl-1,3-pentadiene, 2- Methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene, 2,5-dimethyl-2,4- Hexadiene, 1,3-octadiene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1-phenyl-1,3-butadiene, 1,4-dip
- sorbic acid, sorbic acid ester, sorbate, myrcene and a mixture of any of these are preferable, and sorbic acid, sorbate and a mixture thereof are more preferable.
- Sorbic acid, sorbate and a mixture thereof are highly effective in suppressing oxidative degradation at high temperatures, and are also widely used industrially as food additives, and thus are preferable from the viewpoint of hygiene and availability.
- the molecular weight of the conjugated polyene compound is usually 1,000 or less, preferably 500 or less, and more preferably 300 or less. If the molecular weight of the conjugated polyene compound exceeds 1,000, the dispersion state in EVOH is poor, and the appearance after melt molding may be poor.
- the blow-molded container 1 cannot sufficiently obtain an effect of suppressing oxidative deterioration during melt molding, and thus gel and blisters are generated. There is a risk.
- the content of the conjugated polyene compound in the (A) layer 4 exceeds 1,000 ppm, the generation of gels and blisters is promoted, and the blow molded container 1 tends to have a poor appearance.
- the (A) layer 4 preferably further contains a boron compound. Since the blow-molded container 1 includes the (A) layer 4 further containing a boron compound, it is difficult to cause gelation during melt molding, and torque fluctuations of an extrusion molding machine or the like can be suppressed. Excellent appearance. Moreover, since the (A) layer 4 further contains a boron compound, the self-purge property at the time of manufacture is further improved, so that it can be manufactured at a lower cost.
- boron compound examples include boric acids such as orthoboric acid, metaboric acid, and tetraboric acid; Borate esters such as triethyl borate and trimethyl borate; Borate salts such as alkali metal salts or alkaline earth metal salts of borates, borax; Examples thereof include borohydrides.
- boric acids are preferable, and orthoboric acid (hereinafter sometimes simply referred to as “boric acid”) is more preferable.
- the content of the boron compound in the layer (A) 4 is preferably 100 ppm or more and 5,000 ppm or less, more preferably 100 ppm or more and 3,000 ppm or less, and further preferably 1,000 ppm or more and 1,500 ppm or less.
- the blow-molded container 1 can effectively suppress torque fluctuations of an extrusion molding machine or the like during heating and melting in the production process by setting the content of the boron compound in the (A) layer 4 within the specific range. Further, if the content of the boron compound is less than 100 ppm, the above effect cannot be sufficiently achieved, and if it exceeds 5,000 ppm, gelation tends to occur, and the blow-molded container 1 may have insufficient appearance. is there.
- the layer (A) 4 preferably contains acetic acid and / or acetate. Since the blow-molded container 1 includes the (A) layer 4 further containing acetic acid and / or acetate, coloring can be prevented, and thus the appearance is excellent.
- both acetic acid and acetate are preferably used, and acetic acid and sodium acetate are more preferably used.
- the content of acetic acid and / or acetate in the layer (A) 4 is preferably 50 ppm or more and 1,000 ppm or less, more preferably 100 ppm or more and 1,000 ppm or less, further preferably 150 ppm or more and 500 ppm or less, and 200 ppm or more and 400 ppm or less. Is particularly preferred. If the content of acetic acid and / or acetate is less than 50 ppm, a sufficient anti-coloring effect cannot be obtained, and the blow molded container 1 may have insufficient appearance due to yellowing or the like.
- the (A) layer 4 preferably further contains a phosphorus compound.
- the blow-molded container 1 can further suppress the occurrence of defects such as gels and blisters and coloring, and improve the appearance.
- Examples of the phosphorus compound include various phosphoric acids such as phosphoric acid and phosphorous acid, and phosphates.
- the phosphate may be in any form of a first phosphate, a second phosphate and a third phosphate.
- the cation species is not particularly limited, but is preferably an alkali metal salt or an alkaline earth metal salt. Among these, sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate Dipotassium hydrogen phosphate is more preferable, and sodium dihydrogen phosphate and dipotassium hydrogen phosphate are more preferable.
- the content of the phosphorus compound in the layer (A) 4 is preferably 1 ppm to 200 ppm, more preferably 2 ppm to 200 ppm, further preferably 3 ppm to 150 ppm, and particularly preferably 5 ppm to 100 ppm.
- the content of the phosphorus compound in the (A) layer 4 is less than 1 ppm or exceeds 200 ppm, the blow-molded container 1 has reduced thermal stability in the production process, and generation of gels and blisters and coloring It tends to occur and the appearance may be insufficient.
- the (A) layer 4 may contain an alkali metal as another optional component as long as the effects of the present invention are not impaired.
- the alkali metal include lithium, sodium, and potassium.
- the said alkali metal can also be contained as an alkali metal salt.
- the alkali metal salt include a monovalent metal aliphatic carboxylate, aromatic carboxylate, and metal complex. Specific examples include sodium acetate, potassium acetate, sodium stearate, potassium stearate, sodium salt of ethylenediaminetetraacetic acid, and the like. Of these, sodium acetate and potassium acetate are preferred.
- As content in the said (A) layer 4 of the said alkali metal 20 ppm or more and 1,000 ppm or less are preferable, and 50 ppm or more and 500 ppm or less are more preferable.
- the layer (A) 4 includes an antioxidant, an ultraviolet absorber, a plasticizer, an antistatic agent, a lubricant, a colorant, a filler, a heat stabilizer, other resins, and higher aliphatic carboxylic acids.
- the metal salt, hydrotalcite compound and the like may be contained as other optional components.
- the (A) layer 4 may contain one or more of these optional components, and the total content is 1% by mass or less.
- antioxidants examples include 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-p-cresol, 4,4′-thiobis- (6-t-butylphenol), 2, 2′-methylene-bis- (4-methyl-6-tert-butylphenol), octadecyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate, 4,4′-thiobis -(6-t-butylphenol) and the like.
- Examples of the ultraviolet absorber include ethylene-2-cyano-3,3′-diphenyl acrylate, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, and 2- (2′-hydroxy-5′-).
- plasticizer examples include dimethyl phthalate, diethyl phthalate, dioctyl phthalate, wax, liquid paraffin, and phosphate ester.
- antistatic agent examples include pentaerythritol monostearate, sorbitan monopalmitate, sulfated polyolefins, polyethylene oxide, and carbowax.
- Examples of the lubricant include ethylene bisstearamide and butyl stearate.
- colorant examples include carbon black, phthalocyanine, quinacridone, indoline, azo pigment, and bengara.
- filler examples include glass fiber, ballastite, calcium silicate, talc, and montmorillonite.
- heat stabilizer examples include hindered phenol compounds and hindered amine compounds.
- Examples of the other resin include polyamide and polyolefin.
- Examples of higher aliphatic carboxylic acid metal salts include calcium stearate and magnesium stearate.
- the (A) layer 4 can be formed of an EVOH-containing resin composition containing each component.
- unsaturated aldehyde (II) can be uniformly blended in EVOH, and finally obtained (A) layer 4 has an unsaturated content in the range of 0.01 ppm to 100 ppm.
- aldehyde (II) is contained
- a method for producing an ethylene-vinyl alcohol copolymer-containing resin composition comprising: (1) a step of copolymerizing ethylene and a vinyl ester; and (2) a step of saponifying the copolymer obtained in step (1). Because A method for producing a resin composition, wherein the resin composition contains 0.01 ppm or more and 100 ppm or less of unsaturated aldehyde (II), is preferred.
- the method for containing the specific amount of unsaturated aldehyde (II) in the EVOH-containing resin composition is not particularly limited.
- the method of adding the specific amount of unsaturated aldehyde (II) in the step (1), A method of adding a specific amount of unsaturated aldehyde (II) in the step (2), The method etc. which add specific amount unsaturated aldehyde (II) to EVOH obtained by the said process (2) are mentioned.
- the resin obtained In order to contain the desired amount of unsaturated aldehyde (II) in the composition the amount of addition is determined in consideration of the amount consumed in the polymerization reaction in step (1) and the saponification reaction in step (2). There is a need to do more. Further, since the amount consumed varies depending on the reaction conditions of the polymerization reaction and saponification reaction, it is difficult to adjust the content of unsaturated aldehyde (II) in the resin composition. Therefore, a method of adding a specific amount of unsaturated aldehyde (II) to EVOH obtained by the above step (2) after the above step (2) is preferable.
- a method of adding a specific amount of unsaturated aldehyde (II) to EVOH for example, a method in which unsaturated aldehyde (II) is previously blended with EVOH and pellets are granulated, saponification of ethylene-vinyl ester copolymer
- the method of impregnating the unsaturated aldehyde (II) into the strand precipitated in the step of depositing the paste later, the method of impregnating the unsaturated aldehyde (II) after cutting the precipitated strand, and the dry resin composition chip again A method of adding unsaturated aldehyde (II) to a dissolved one, a method of melt-kneading a blend of two components of EVOH and unsaturated aldehyde (II), and an unsaturated aldehyde (II into the EVOH melt from the middle of the extruder ) Feed and contain, a high concentration of unsaturated aldeh
- the unsaturated aldehyde (II) is mixed in advance in EVOH as the above-mentioned unsaturated aldehyde (II) mixing step.
- the step of granulating the pellet is preferable. Specifically, unsaturated aldehyde (II) is added to a solution in which EVOH is dissolved in a good solvent such as a water / methanol mixed solvent, and the mixed solution is extruded into a poor solvent from a nozzle or the like to precipitate and / or. By solidifying and washing and / or drying, pellets in which the unsaturated aldehyde (II) is uniformly mixed with EVOH can be obtained.
- unsaturated aldehyde (II) can be added simultaneously with the conjugated polyene compound in the subsequent step of the polymerization step.
- the auxiliary function of the conjugated polyene compound is exhibited, and the generation of a substance that is difficult to melt by heat is suppressed. As a result, a film having an excellent appearance can be obtained.
- Examples of the method of containing each component other than the unsaturated aldehyde (II) in the layer (A) 4 include a method in which the pellet is mixed with each component and melt-kneaded. Examples thereof include a method of simultaneously mixing each component together with aldehyde (II), a method of immersing the pellet in a solution containing each component, and the like.
- a ribbon blender, a high-speed mixer, a mixing roll, an extruder, an intensive mixer, or the like can be used.
- the (B) layer 6 is a layer mainly composed of a thermoplastic resin which is disposed on the inner surface side and the outer surface side of the (A) layer 4 and whose solubility parameter calculated from the Fedors equation is 11 or less.
- the solubility parameter calculated from the Fedors equation is a value represented by (E / V) 1/2 .
- a thermoplastic resin having a solubility parameter calculated by this formula of 11 or less is excellent in moisture resistance.
- the thermoplastic resin contained in the (B) layer 6 is not particularly limited as long as the solubility parameter is 11 or less.
- polyethylene linear low-molecular weight having the solubility parameter of 11 or less.
- Density polyethylene low density polyethylene, medium density polyethylene, high density polyethylene, etc.
- ethylene-vinyl acetate copolymer ethylene-propylene copolymer
- polypropylene copolymer of propylene and ⁇ -olefin having 4 to 20 carbon atoms.
- Olefin homopolymers or copolymers such as polybutene and polypentene, polystyrene, polyvinyl chloride, polyvinylidene chloride, acrylic resins, vinyl ester resins, polyurethane elastomers, polycarbonate, chlorinated polyethylene, chlorinated polypropylene, etc. It is done. Of these, polyethylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, polypropylene, and polystyrene are preferable, and high-density polyethylene is more preferable.
- the density of the high-density polyethylene is preferably 0.93 g / cm 3 or more, preferably 0.95 g / cm 3 or more from the viewpoint of rigidity, impact resistance, moldability, drawdown resistance, gasoline resistance, and the like. It is more preferably 98 g / cm 3 or less, further preferably 0.96 g / cm 3 or more and 0.98 g / cm 3 or less.
- the melt flow rate (MFR) of the high-density polyethylene is preferably in the range of 0.01 to 0.5 g / 10 minutes (190 ° C., 2160 g load), preferably 0.01 to 0.1 g / 10. A range of minutes is more preferred.
- the said high-density polyethylene can be used selecting it normally from a commercial item normally.
- the said (B) layer 6 may contain the other arbitrary components similar to the (A) layer 4 unless the effect of this invention is impaired.
- the (C) layer 5 is disposed between the (A) layer 4 and the (B) layer 6 and is a layer mainly composed of a carboxylic acid-modified polyolefin.
- the (C) layer 5 can function as an adhesive layer between the (A) layer 4 and another layer such as the (B) layer 6.
- the carboxylic acid-modified polyolefin is a carboxyl group or an anhydride thereof obtained by chemically bonding an ethylenically unsaturated carboxylic acid or an anhydride thereof to an olefin polymer by an addition reaction, a graft reaction or the like.
- Examples of the ethylenically unsaturated carboxylic acid or its anhydride include monocarboxylic acid, monocarboxylic acid ester, dicarboxylic acid, dicarboxylic acid monoester, dicarboxylic acid diester, and dicarboxylic acid anhydride.
- Specific examples include maleic acid, fumaric acid, itaconic acid, maleic anhydride, itaconic anhydride, maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid diethyl ester, and fumaric acid monomethyl ester.
- dicarboxylic anhydrides such as maleic anhydride and itaconic anhydride are preferred, and maleic anhydride is more preferred.
- the olefin polymer examples include polyolefins such as low density, medium density or high density polyethylene, linear low density polyethylene, polypropylene, and bolibene; Examples thereof include a copolymer of an olefin such as an ethylene-vinyl acetate copolymer and an ethylene-ethyl acrylate copolymer and a comonomer such as a vinyl ester and an unsaturated carboxylic acid ester that can be copolymerized with these olefins.
- polyolefins such as low density, medium density or high density polyethylene, linear low density polyethylene, polypropylene, and bolibene
- examples thereof include a copolymer of an olefin such as an ethylene-vinyl acetate copolymer and an ethylene-ethyl acrylate copolymer and a comonomer such as a vinyl ester and an unsaturated carboxylic acid ester that can be copolymerized
- linear low density polyethylene ethylene-vinyl acetate copolymer having a vinyl acetate content of 5 to 55% by mass
- Polymers are preferred, and linear low density polyethylene and ethylene-vinyl acetate copolymers having a vinyl acetate content of 5 to 55% by mass are more preferred.
- the carboxylic acid-modified polyolefin is prepared by adding the ethylenically unsaturated carboxylic acid or its anhydride to the olefin polymer in the presence of a solvent such as xylene or a catalyst such as peroxide by an addition reaction or a graft reaction. It is obtained by introducing.
- the addition amount or graft amount (modification degree) of the carboxylic acid or anhydride thereof to the olefin polymer is preferably 0.01 to 15% by mass relative to the olefin polymer. More preferred is 02 to 10% by mass.
- the above carboxylic acid-modified polyolefin may be used alone or in combination of two or more.
- the (C) layer 5 may contain other optional components similar to the (A) layer 4 in addition to the carboxylic acid-modified polyolefin as long as the effects of the present invention are not impaired.
- the (D) layer 7 is a layer containing an ethylene-vinyl alcohol copolymer, a thermoplastic resin having a solubility parameter calculated from the Fedors equation of 11 or less, and a carboxylic acid-modified polyolefin.
- the (D) layer 7 is preferably formed using the recovered material of the (A) layer 4, the (B) layer 6, and the (C) layer 5 in the manufacturing process of the blow molded container 1.
- the blow molding container 1 further includes the (D) layer 7 as such a recovery layer, so that such burrs and inaccurate tests are not possible. By reusing the acceptable product, it is possible to reduce the loss of the resin used when the blow molded container 1 is manufactured.
- the (D) layer 7 can be used in place of the above-described (B) layer 6, but in general, the mechanical strength of the (D) layer 7 may be lower than that of the (B) layer 6. Since there are many, it is preferable to laminate
- FIG. When the blow molded container 1 receives an impact from the outside, stress concentration occurs in the container, and the compressive stress against the impact acts on the inner layer side of the container in the stress concentration portion, and there is a possibility that breakage occurs. It is preferable to arrange the recovery layer that is weak to the outer layer side of the (A) layer 4. Further, when a large amount of resin needs to be recycled, such as when burrs are frequently generated, a recovery layer can be disposed as (D) layer 7 on both sides of (A) layer 4.
- the EVOH content in the layer 7 is preferably 9.0% by mass or less. If the EVOH content in the (D) layer 7 exceeds 9% by mass, cracks are likely to occur at the interface with the (B) layer 6, and the entire blow-molded container 1 may be destroyed starting from the cracks. is there.
- the thickness ratio (I / O) when the total thickness of each layer inside the layer 4 is I and (A) the total thickness of each layer outside the layer 4 is O is 1/99 to It is preferably 70/30, more preferably 1/99 to 55/45, and even more preferably 30/70 to 55/45.
- the thickness of the whole layer or each layer of the blow-molded container 1 is obtained by observation with an optical microscope for a sample obtained by cutting a plurality of cross sections from the container body using a microtome, and an average value is obtained for all layers or each layer. Calculate and use the average thickness of all layers or the average thickness of each layer.
- (A) Although it does not specifically limit as average thickness of the layer 4, From viewpoints, such as barrier property and mechanical strength, it is preferable that it is 5.0% or less of all the layer average thickness, 0.5% It is more preferably from 5% to 5%, further preferably from 1.0% to 4.5%, particularly preferably from 1.5% to 4.0%.
- the average thickness of the layer 5 is not particularly limited, but is preferably 0.3% to 12%, more preferably 0.6% to 9% of the average thickness of all layers. 2% to 6% is more preferable. If the thickness of the (C) layer 5 as the adhesive resin layer is too small, the adhesiveness is lowered, and if it is too large, the cost increases, which is not preferable.
- the overall average thickness of the blow molded container 1 is preferably 300 to 10,000 ⁇ m, more preferably 500 to 8,500 ⁇ m, and even more preferably 1,000 to 7,000 ⁇ m. In addition, these whole average thickness says the average thickness in the trunk
- the blow molded container 1 has a step of blow molding using a resin composition containing an ethylene-vinyl alcohol copolymer as a main component, and the resin composition contains an unsaturated aldehyde (II). It is preferable to manufacture by the manufacturing method whose content in the said resin composition of (II) is 0.01 ppm or more and 100 ppm or less.
- the content of the unsaturated aldehyde (II) in the resin composition is preferably 0.01 ppm to 100 ppm, more preferably 0.1 ppm to 30 ppm, and further preferably 0.15 ppm to 20 ppm.
- the hollow container can be used as, for example, a fuel tank or a blow molded bottle container.
- the blow-molded container of the present invention is not limited to the form of FIG. 1 described above, and may be provided with at least the (A) layer. Specifically, the (D) layer or the like as the recovery layer may not be provided. Furthermore, other layers may be laminated. Further, the (C) layer as the adhesive layer may be omitted by selecting a combination of resins having good adhesiveness.
- the layer (B) is preferably disposed as the outermost layer. That is, from the inner surface of the container toward the outer surface of the container, the arrangement is (B) layer / (C) layer / (A) layer / (C) layer / (B) layer (hereinafter referred to as (inner) B / C / A / C / B (outside) is preferable from the viewpoint of impact resistance.
- the (D) layer such as the recovery layer
- (inside) D / C / A / C / D (outside), etc. may be arranged, and the (B) layer may be replaced with the (D) layer.
- the arrangement of (inner) B / C / A / C / D / B (outer) and (inner) B / D / C / A / C / D / B (outer) as in the above-described embodiment Is preferred.
- the resins constituting each layer may be the same or different.
- the fuel container of the present invention includes the above-described blow molded container, and includes, for example, a filter, a fuel gauge, a baffle plate, and the like as necessary. Since the fuel container is provided with the above-described blow-molded container, the fuel container is excellent in appearance, gas shielding properties, oil resistance, and the like, and thus is suitably used as a fuel container.
- the fuel container is a fuel container mounted on an automobile, a motorcycle, a ship, an aircraft, a generator, an industrial or agricultural device, or a portable fuel container for supplying fuel to these fuel containers. Means a container for storing fuel.
- the fuel examples include gasoline, particularly oxygen-containing gasoline blended with methanol, ethanol, MTBE, or the like, but also includes heavy oil, light oil, kerosene, and the like.
- the fuel container is particularly preferably used as a fuel container for oxygen-containing gasoline.
- the amount of unsaturated aldehyde (II) was quantified by quantitatively analyzing the extracted sample by high performance liquid chromatography. For quantification, a calibration curve prepared using a standard obtained by reacting each unsaturated aldehyde (II) with a DNPH preparation solution was used. In addition, in this application, content in the dry resin composition used in order to form the layer was used as content of each component in each layer in a blow molded container.
- sorbic acid After adding sorbic acid to this copolymerization reaction solution, the sorbic acid is supplied to an extraction tower, and unreacted vinyl acetate is removed from the top of the tower by introducing methanol vapor from the bottom of the tower. % Methanol solution was obtained. The ethylene content of this ethylene-vinyl acetate copolymer was 32 mol%.
- This methanol solution of ethylene-vinyl acetate copolymer is charged into a saponification reactor, and caustic soda / methanol solution (80 g / L) is added so as to be 0.4 equivalent to the vinyl ester component in the copolymer. Then, methanol was added to adjust the copolymer concentration to 20%. This solution was heated to 60 ° C.
- Resin such that the content of unsaturated aldehyde (II) and conjugated polyene compound is as shown in Table 1 by adjusting the amount of unsaturated aldehyde (II) added and the concentration of each component of the aqueous solution for immersion treatment A composition was prepared.
- This strand was introduced into a pelletizer to obtain a porous resin composition chip.
- the obtained porous resin composition chip was washed with an aqueous acetic acid solution and ion-exchanged water, and then immersed in an aqueous solution containing acetic acid, sodium acetate, potassium dihydrogen phosphate and boric acid.
- the aqueous solution for immersion treatment and the resin composition chip are separated and drained, and then placed in a hot air dryer, dried at 80 ° C.
- a resin composition (dried Resin composition pellets) were obtained.
- the content of each component in the obtained resin composition was quantified using the above quantification method.
- the resin composition was prepared so that content of each component might become as as described in Table 1 by adjusting the density
- a twin screw extruder (“2D25W”, manufactured by Toyo Seiki Seisakusho, Ltd .; 25 mm ⁇ , die temperature 220 ° C. And screw pellets were extruded and pelletized under a nitrogen atmosphere.
- this extruded pellet was further extruded and pelletized under the same extruder and under the same conditions, and the same operation was performed 4 times (total of 5 blends in the extruder) to obtain a recovered resin. .
- the blow-molded container of the present invention was excellent in appearance as the occurrence of streaks and coloring were suppressed compared to the comparative example.
- the blow molded container of the present invention was excellent in impact resistance even if it was molded 20 minutes after restarting the molding apparatus. Since the blow molded container of the present invention uses an EVOH-containing resin composition having excellent self-purge properties, the occurrence of gels, blisters, etc. that reduce impact resistance may not occur in a short time after restarting. all right.
- the blow molded container of the present invention has a sufficient gas shielding property and oil resistance as characteristics of EVOH, and in addition to the (A) layer containing a specific amount of unsaturated aldehyde (II), it is melted. Since appearance and coloration of defects such as gels, blisters and streaks due to molding are suppressed, the appearance is excellent.
- the layer (A) contains the specific amount of the unsaturated aldehyde (II)
- the blow-molded container can be manufactured at low cost because it has excellent self-purge properties in the process of manufacturing the blow-molded container. it can. Therefore, the blow molded container is used for various applications, and is particularly suitable as a fuel container.
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Abstract
Description
(A)エチレン-ビニルアルコール共重合体(I)を主成分とする層(以下、「(A)層」ともいう)
を備えるブロー成形容器であって、
上記(A)層が、不飽和アルデヒド(II)を含有し、
この不飽和アルデヒド(II)の(A)層における含有量が0.01ppm以上100ppm以下であることを特徴とするブロー成形容器である。
なお、本発明において主成分とは、全体の過半を占める成分をいい、全体が主成分のみからなる場合も含む意味である。
(B)上記(A)層の内面側及び外面側に配置され、Fedorsの式から算出する溶解性パラメータが11以下である熱可塑性樹脂を主成分とする層(以下、「(B)層」ともいう)、及び
(C)上記(A)層と(B)層との間に配置され、カルボン酸変性ポリオレフィンを主成分とする層(以下、「(C)層」ともいう)
を備えることが好ましい。
(D)エチレン-ビニルアルコール共重合体(I)、Fedorsの式から算出する溶解性パラメータが11以下である熱可塑性樹脂、及びカルボン酸変性ポリオレフィンを含有する層(以下、「(D)層」ともいう)
を備えることが好ましい。
エチレン-ビニルアルコール共重合体(I)を主成分とする樹脂組成物を用いてブロー成形する工程を有し、
上記樹脂組成物が不飽和アルデヒド(II)を含有し、この不飽和アルデヒド(II)の上記樹脂組成物における含有量が0.01ppm以上100ppm以下である。当該ブロー成形容器の製造方法によれば、ゲル・ブツ、ストリーク等の欠陥の発生及び着色が抑制されるため、外観に優れたブロー成形容器を得ることができる。また、当該ブロー成形容器の製造方法に用いる樹脂組成物はセルフパージ性に優れるため、製造コストを低減することができる。
図1のブロー成形容器1は、
(A)エチレン-ビニルアルコール共重合体(I)を主成分とする層4、
(B)上記(A)層の内面側及び外面側に配置され、Fedorsの式から算出する溶解性パラメータが11以下である熱可塑性樹脂を主成分とする層6、
(C)上記(A)層と(B)層との間に配置され、カルボン酸変性ポリオレフィンを主成分とする層5、及び
(D)エチレン-ビニルアルコール共重合体(I)、Fedorsの式から算出する溶解性パラメータが11以下である熱可塑性樹脂、及びカルボン酸変性ポリオレフィンを含有する層7を備える。具体的にブロー成形容器1は、容器内部表面2から容器外部表面3に向かって、(B)層6、(C)層5、(A)層4、(C)層5、(D)層7、(B)層6の順に積層した多層構造を有する。なお、図1はブロー成形容器1の周壁の部分断面図である。以下、各層毎に説明する。
(A)層4は、EVOH(I)を主成分とする層であり、0.01ppm以上100ppm以下の不飽和アルデヒド(II)を含有する。ブロー成形容器1は、上記特定量の不飽和アルデヒド(II)を含有する(A)層4を備えることで、溶融成形によるゲル・ブツ、ストリーク等の欠陥の発生を抑制することができ、外観性に優れる。また、上記(A)層4が上記特定量の不飽和アルデヒド(II)を含有することで、ブロー成形容器1の製造工程におけるセルフパージ性にも優れるため、製造コストを低減することができる。また、上記(A)層4は、共役ポリエン化合物をさらに含有することが好ましい。さらに、上記(A)層4は、本発明の効果を損なわない限り、ホウ素化合物、酢酸及び/又は酢酸塩、リン化合物、その他の任意成分を含有してもよい。以下、各成分について詳述する。
本発明に用いられるEVOH(I)は、エチレン-ビニルエステル共重合体をケン化して得られるエチレン-ビニルアルコール共重合体である。
プロピレン、ブチレン等の不飽和炭化水素;
(メタ)アクリル酸、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル等の不飽和カルボン酸又はそのエステル;
N-ビニルピロリドン等のビニルピロリドン等が挙げられる。
上記(A)層4は、EVOH(I)と共に0.01ppm以上100ppm以下の不飽和アルデヒド(II)を必須成分として含有する。
上記(A)層4は、共役ポリエン化合物をさらに含有することが好ましく、この共役ポリエン化合物の含有量としては、0.01ppm以上1,000ppm以下が好ましく、0.1ppm以上1,000ppm以下がより好ましい。ブロー成形容器1は、上記特定量の共役ポリエン化合物をさらに含有する(A)層4を備えることで、溶融成形時の酸化劣化を抑制することができ、ゲル・ブツ等の欠陥の発生及び着色がより起こり難くなるため、外観性により優れる。また、上記(A)層4が上記特定量の共役ポリエン化合物を含有することで、長時間連続して溶融成形した場合でもゲル・ブツ等の発生が抑制され、耐衝撃性に優れたブロー成形容器を得ることができる。
イソプレン、2,3-ジメチル-1,3-ブタジエン、2,3-ジエチル-1,3-ブタジエン、2-t-ブチル-1,3-ブタジエン、1,3-ペンタジエン、2,3-ジメチル-1,3-ペンタジエン、2,4-ジメチル-1,3-ペンタジエン、3,4-ジメチル-1,3-ペンタジエン、3-エチル-1,3-ペンタジエン、2-メチル-1,3-ペンタジエン、3-メチル-1,3-ペンタジエン、4-メチル-1,3-ペンタジエン、1,3-ヘキサジエン、2,4-ヘキサジエン、2,5-ジメチル-2,4-ヘキサジエン、1,3-オクタジエン、1,3-シクロペンタジエン、1,3-シクロヘキサジエン、1-フェニル-1,3-ブタジエン、1,4-ジフェニル-1,3-ブタジエン、1-メトキシ-1,3-ブタジエン、2-メトキシ-1,3-ブタジエン、1-エトキシ-1,3-ブタジエン、2-エトキシ-1,3-ブタジエン、2-ニトロ-1,3-ブタジエン、クロロプレン、1-クロロ-1,3-ブタジエン、1-ブロモ-1,3-ブタジエン、2-ブロモ-1,3-ブタジエン、オシメン、フェランドレン、ミルセン、ファルネセン、センブレン、ソルビン酸、ソルビン酸エステル、ソルビン酸塩、アビエチン酸等の共役ジエン化合物;
1,3,5-ヘキサトリエン、2,4,6-オクタトリエン-1-カルボン酸、エレオステアリン酸、桐油、コレカルシフェロール、フルベン、トロポン等の共役トリエン化合物;
シクロオクタテトラエン、2,4,6,8-デカテトラエン-1-カルボン酸、レチノール、レチノイン酸等の共役ポリエン化合物等が挙げられる。なお、上記共役ポリエン化合物は1種単独で用いてもよいし、2種以上を併用することもできる。上記共役ポリエン化合物の炭素数としては、4~30が好ましく、4~10がより好ましい。
上記(A)層4は、ホウ素化合物をさらに含有することが好ましい。ブロー成形容器1は、ホウ素化合物をさらに含有する(A)層4を備えることにより、溶融成形の際にゲル化を起こし難くなると共に、押出し成形機等のトルク変動を抑制することができるため、外観性により優れる。また、上記(A)層4がホウ素化合物をさらに含有することで、製造時のセルフパージ性にもさらに優れるため、さらに低コストで製造することができる。
オルトホウ酸、メタホウ酸、四ホウ酸等のホウ酸類;
ホウ酸トリエチル、ホウ酸トリメチル等のホウ酸エステル;
上記ホウ酸類のアルカリ金属塩又はアルカリ土類金属塩、ホウ砂等のホウ酸塩;
水素化ホウ素類等が挙げられる。これらのうち、ホウ酸類が好ましく、オルトホウ酸(以下、単に「ホウ酸」と称することもある)がより好ましい。
上記(A)層4は、酢酸及び/又は酢酸塩を含有することが好ましい。ブロー成形容器1は、酢酸及び/又は酢酸塩をさらに含有する(A)層4を備えることで、着色を防止することができるため、外観性に優れる。
上記(A)層4は、リン化合物をさらに含有することが好ましい。ブロー成形容器1は、リン化合物をさらに含有する(A)層4を備えることにより、ゲル・ブツ等の欠陥の発生及び着色がより抑制され、外観性を向上させることができる。
上記(A)層4は、本発明の効果を損なわない範囲で、その他の任意成分として、アルカリ金属を含有してもよい。上記アルカリ金属としては、例えばリチウム、ナトリウム、カリウム等が挙げられる。また、上記アルカリ金属は、アルカリ金属塩として含有することもできる。上記アルカリ金属塩とは、例えば一価の金属の脂肪族カルボン酸塩、芳香族カルボン酸塩、金属錯体等である。具体的には酢酸ナトリウム、酢酸カリウム、ステアリン酸ナトリウム、ステアリン酸カリウム、エチレンジアミン四酢酸のナトリウム塩等が挙げられる。これらのうち、酢酸ナトリウム、酢酸カリウムが好ましい。上記アルカリ金属の上記(A)層4における含有量としては、20ppm以上1,000ppm以下が好ましく、50ppm以上500ppm以下がより好ましい。
上記(A)層4は、各成分を含有するEVOH含有樹脂組成物により形成することができる。このEVOH含有樹脂組成物の製造方法としては、EVOH中に不飽和アルデヒド(II)を均一にブレンドでき、最終的に得られる(A)層4において、0.01ppm以上100ppm以下の範囲の不飽和アルデヒド(II)を含有させられる製造方法であれば特に限定されないが、
(1)エチレンとビニルエステルとを共重合させる工程、及び
(2)工程(1)により得られた共重合体をケン化する工程
を有するエチレン-ビニルアルコール共重合体含有樹脂組成物の製造方法であって、
上記樹脂組成物中に0.01ppm以上100ppm以下の不飽和アルデヒド(II)を含有させることを特徴とする樹脂組成物の製造方法が好ましい。
上記工程(1)において特定量の不飽和アルデヒド(II)を添加する方法、
上記工程(2)において特定量の不飽和アルデヒド(II)を添加する方法、
上記工程(2)により得られたEVOHに、特定量の不飽和アルデヒド(II)を添加する方法等が挙げられる。しかし、上記工程(1)において特定量の不飽和アルデヒド(II)を添加する方法、又は上記工程(2)において特定量の不飽和アルデヒド(II)を添加する方法を採用する場合、得られる樹脂組成物中に所望量の不飽和アルデヒド(II)を含有させるためには、上記工程(1)における重合反応、上記工程(2)におけるケン化反応で消費される量を考慮して添加量を多くする必要がある。また、重合反応やケン化反応の反応条件により消費される量が変動するため、樹脂組成物中の不飽和アルデヒド(II)の含有量を調節することが難しい。したがって、上記工程(2)より後に、上記工程(2)により得られたEVOHに、特定量の不飽和アルデヒド(II)を添加する方法が好ましい。
上記(B)層6は、上記(A)層4の内面側及び外面側に配置され、Fedorsの式から算出する溶解性パラメータが11以下である熱可塑性樹脂を主成分とする層である。
上記(C)層5は、上記(A)層4と(B)層6との間に配置され、カルボン酸変性ポリオレフィンを主成分とする層である。上記(C)層5は、(A)層4と(B)層6等の他の層との間の接着層として機能させることができる。なお、上記カルボン酸変性ポリオレフィンとは、オレフィン系重合体に、エチレン性不飽和カルボン酸又はその無水物を、付加反応、グラフト反応等により化学的に結合させて得られる、カルボキシル基又はその無水物基を有するオレフィン系重合体のことをいう。
低密度、中密度又は高密度ポリエチレン、直鎖状低密度ポリエチレン、ポリプロピレン、ボリブテン等のポリオレフィン;
エチレン-酢酸ビニル共重合体、エチレン-アクリル酸エチル共重合体等のオレフィンとこれらのオレフィンと共重合し得るビニルエステル、不飽和カルボン酸エステル等のコモノマーとの共重合体等が挙げられる。これらうち、直鎖状低密度ポリエチレン、酢酸ビニル含有量が5~55質量%であるエチレン-酢酸ビニル共重合体、及びアクリル酸エチル含有量8~35質量%であるエチレン-アクリル酸エチル共重合体が好ましく、直鎖状低密度ポリエチレン及び酢酸ビニル含有量が5~55質量%であるエチレン-酢酸ビニル共重合体がより好ましい。
上記(D)層7は、エチレン-ビニルアルコール共重合体、Fedorsの式から算出する溶解性パラメータが11以下である熱可塑性樹脂、及びカルボン酸変性ポリオレフィンを含有する層である。また、上記(D)層7は、ブロー成形容器1の製造工程における上記(A)層4、(B)層6及び(C)層5の回収物を用いて形成されることが好ましい。特にブロー成形容1の製造工程においては、バリの発生が不可避であるため、ブロー成形容器1がこのような回収層としての(D)層7をさらに有することで、かかるバリや、検定の不合格品を再利用することによって、ブロー成形容器1の製造時に使用される樹脂のロスを低減することが可能となる。
(A)層4の内側にある各層の厚みの合計をIとし、(A)層4の外側にある各層の厚みの合計をOとしたときの厚み比(I/O)が1/99~70/30であることが好ましく、1/99~55/45であることがより好ましく、30/70~55/45であることがさらに好ましい。なお、当該ブロー成形容器1の全層又は各層の厚みは、ミクロトームを用いて容器胴部より複数箇所の断面を切り出したサンプルについて、光学顕微鏡観察により求め、全層又はそれぞれの層について平均値を算出し、全層平均厚み又は各層の平均厚みとする。
ブロー成形容器1は、エチレン-ビニルアルコール共重合体を主成分とする樹脂組成物用いてブロー成形する工程を有し、上記樹脂組成物が不飽和アルデヒド(II)を含有し、この不飽和アルデヒド(II)の上記樹脂組成物における含有量が0.01ppm以上100ppm以下である製造方法により製造することが好ましい。不飽和アルデヒド(II)の上記樹脂組成物における含有量としては、0.01ppm以上100ppm以下が好ましく、0.1ppm以上30ppm以下がより好ましく、0.15ppm以上20ppm以下がさらに好ましい。具体的には、(A)層4を形成する乾燥EVOH含有樹脂組成物ペレット、(B)層5を形成する高密度ポリエチレン樹脂等、(C)層6を形成する接着性樹脂、及び(D)層7を形成する回収樹脂等を用い、ブロー成形機にて100℃~400℃の温度で、例えば(内)B/C/A/C/D/B(外)の4種6層パリソンからブロー成形し、金型内温度10℃~30℃で10秒間~30分間冷却し、全層平均厚み300μm~10,000μmの中空容器を成形することができる。中空容器は、たとえば燃料タンクやブロー成形ボトル容器などとして用いることができる。
本発明のブロー成形容器は、上記図1の形態に限定されず、少なくとも(A)層を備えていればよい。具体的には、回収層としての(D)層等を備えなくてもよい。さらに、他の層が積層されてもよい。また、接着性がよい樹脂の組合せを選択することで、接着層としての(C)層を省略してもよい。
本発明の燃料容器は、上述のブロー成形容器を備えており、必要に応じて、例えばフィルター、残量計、バッフルプレート等が備えられる。当該燃料容器は、上述のブロー成形容器を備えることで、外観性、ガス遮蔽性、耐油性等にも優れるため燃料容器として好適に用いられる。ここで、燃料容器とは、自動車、オートバイ、船舶、航空機、発電機、工業用若しくは農業用機器等に搭載された燃料容器、又はこれら燃料容器に燃料を補給するための携帯用燃料容器、さらには、燃料を保管するための容器を意味する。また、燃料としては、ガソリン、特にメタノール、エタノール又はMTBE等をブレンドした含酸素ガソリン等が代表例として挙げられるが、その他、重油、軽油、灯油等も含まれるものとする。これらうち、当該燃料容器は、含酸素ガソリン用燃料容器として特に好適に用いられる。
DMSO-d6を溶媒とした1H-NMR(日本電子株式会社製「JNM-GX-500型」)により求めた。
50質量%の2,4-ジニトロフェニルヒドラジン(DNPH)溶液200mgに、1,1,1,3,3,3-ヘキサフルオロイソプロパノール(HFIP)50mL、酢酸11.5mL及びイオン交換水8mLを添加し、DNPH調整溶液を作製する。その後、乾燥EVOH含有樹脂組成物ペレット1gをDNPH調整溶液20mLに添加し、35℃にて1時間攪拌溶解させる。この溶液にアセトニトリルを添加してEVOH(I)を沈降させ、溶液を濾過・濃縮し、抽出サンプルを得る。この抽出サンプルを高速液体クロマトグラフィーにて定量分析することで、不飽和アルデヒド(II)の量を定量した。また、定量に際しては、それぞれの不飽和アルデヒド(II)をDNPH調製溶液と反応させて得た標品を用いて作成した検量線を使用した。なお、本願においては、ブロー成形容器における各層中の各成分の含有量として、その層を形成するために用いた乾燥樹脂組成物における含有量を用いた。
乾燥EVOH含有樹脂組成物ペレットを凍結粉砕により粉砕し、呼び寸法0.150mm(100メッシュ)のふるい(JIS規格Z8801-1~3準拠)によって粗大粒子を除去して得た粉砕物10gをソックスレー抽出器に充填し、クロロホルム100mLを用いて48時間抽出処理した。この抽出サンプルを高速液体クロマトグラフィーにて定量分析することで、共役ポリエン化合物の量を定量した。なお、定量に際しては、それぞれの共役ポリエン化合物の標品を用いて作成した検量線を使用した。
乾燥樹脂組成物ペレットを空気中120℃で15時間熱処理したペレット10gを300mlの三角フラスコに取り、水/プロパノール混合溶液(質量比:水/プロパノール=45/55)100mlを加え、75℃で3時間攪拌し、目視にて溶液の透明性と着色を評価した。
乾燥樹脂組成物ペレット60gをラボプラストミル(東洋精機製作所製「20R200」二軸異方向)100rpm、260℃で混練し、混練開始から5分後のトルク値が1.5倍になるまでの所要時間を測定した。
[合成例1]
250Lの加圧反応槽を用いて以下の条件でエチレン-酢酸ビニル共重合体の重合を実施した。
酢酸ビニル83.0kg、
メタノール26.6kg、
2,2‘-アゾビスイソブチルニトリル供給量 1119.5mL/hr
重合温度 60℃
重合槽エチレン圧力 4.93MPa
重合時間 5.0時間
得られた共重合体における酢酸ビニルの重合率は約40%であった。この共重合反応液にソルビン酸を添加した後、追出塔に供給し、塔下部からのメタノール蒸気の導入により未反応酢酸ビニルを塔頂より除去して、エチレン-酢酸ビニル共重合体の41%メタノール溶液を得た。このエチレン-酢酸ビニル共重合体のエチレン含有量は32mol%であった。このエチレン-酢酸ビニル共重合体のメタノール溶液をケン化反応器に仕込み、苛性ソーダ/メタノール溶液(80g/L)を、共重合体中のビニルエステル成分に対して0.4当量となるように添加し、メタノールを加えて共重合体濃度が20%になるように調整した。この溶液を60℃に昇温し、反応器内に窒素ガスを吹き込みながら約4時間反応させた。この溶液を円形の開口部を有する金板から水中に押し出して析出させ、切断することで直径約3mm、長さ約5mmのペレットを得た。得られたペレットを遠心分離機で脱液し、さらに大量の水を加え脱液する操作を繰り返した。
上記脱液したペレット20kgを、180kgの水/メタノール=40/60(質量比)の混合溶媒に入れ、60℃で6時間攪拌し完全に溶解させた。得られた溶液に不飽和アルデヒド(II)、及び共役ポリエン化合物を添加し、さらに1時間攪拌して不飽和アルデヒド(II)及び共役ポリエン化合物を完全に溶解させ、樹脂組成物溶液を得た。この樹脂組成物溶液を直径4mmのノズルより、0℃に調整した水/メタノール=90/10(質量比)の凝固浴中に連続的に押出してストランド状に凝固させた。このストランドをペレタイザーに導入して多孔質の樹脂組成物チップを得た。得られた多孔質の樹脂組成物チップを酢酸水溶液及びイオン交換水を用いて洗浄を行った。この洗浄液と樹脂組成物チップを分離して脱液した後、熱風乾燥機に入れて80℃で4時間乾燥を行い、さらに100℃で16時間乾燥を行って、樹脂組成物(乾燥樹脂組成物ペレット)を得た。得られた樹脂組成物における各成分の含有量を上記定量方法により定量し、(A)層における含有量とした。不飽和アルデヒド(II)の添加量、浸漬処理用水溶液の各成分の濃度を調節することにより、不飽和アルデヒド(II)及び共役ポリエン化合物の含有量が表1に記載の通りとなるように樹脂組成物を調製した。
重合終了後にソルビン酸とクロトンアルデヒドを同時に添加した以外は合成例1と同様に操作し、ペレットを得た。得られたペレット20kgを180kgの水/メタノール=40/60(質量比)の混合溶媒に入れ、60℃で6時間攪拌し完全に溶解させた。得られた溶液に共役ポリエン化合物としてのソルビン酸を添加し、さらに1時間攪拌してソルビン酸を完全に溶解させ、樹脂組成物溶液を得た。この樹脂組成物溶液を直径4mmのノズルより、0℃に調整した水/メタノール=90/10(質量比)の凝固浴中に連続的に押出してストランド状に凝固させた。このストランドをペレタイザーに導入して多孔質の樹脂組成物チップを得た。得られた多孔質の樹脂組成物チップを酢酸水溶液及びイオン交換水を用いて洗浄した後、酢酸、酢酸ナトリウム、リン酸二水素カリウム及びホウ酸を含む水溶液で浸漬処理を行った。この浸漬処理用水溶液と樹脂組成物チップを分離して脱液した後、熱風乾燥機に入れて80℃で4時間乾燥を行い、さらに100℃で16時間乾燥を行って、樹脂組成物(乾燥樹脂組成物ペレット)を得た。得られた樹脂組成物における各成分の含有量は、上記定量方法を用いて定量した。なお、浸漬処理用水溶液の各成分の濃度を調節することにより、各成分の含有量が表1に記載の通りとなるように樹脂組成物を調製した。
このようにして得られた各EVOH含有樹脂組成物について、以下のように評価した。評価結果を表1に合わせて示す。
3時間加熱攪拌した溶液について、目視にて溶液の透明性と着色を下記評価基準により評価した。
「良好(A)」:透明、目視で確認できる浮遊物なし。
「やや良好(B)」:やや白濁、目視で確認できる浮遊物あり。
「不良(C)」:白濁、浮遊物あり。
「良好(A)」:無色
「やや良好(B)」:やや着色
「不良(C)」:著しく着色
加熱状態の粘度変化を以下のように評価した。なお加熱状態での樹脂組成物の粘度は、二次加工時のロングラン性に影響する要因である。
(モータートルク変動の評価基準)
「良好(A)」:60分以上
「やや良好(B)」:40分以上60分未満
「不良(C)」:40分未満
上記乾燥EVOH樹脂ペレット4質量部、高密度ポリエチレン樹脂(三井石油化学製 HZ8200B、190℃-2160g荷重におけるMFR=0.01g/10分)86質量部、及び接着性樹脂(三井化学製ADMER GT-6A(商品名)、190℃-2160gにおけるMFR=0.94g/10分)10質量部をドライブレンド後、二軸押出し機(「2D25W」、株式会社東洋精機製作所製;25mmφ、ダイ温度220℃、スクリュー回転数100rpm)を用い、窒素雰囲気下で押出しペレット化を行った。さらにモデル回収樹脂を得るために、この押出ペレットをさらに同押出機および同条件で押出しペレット化を実施、同作業を4回(押出機でのブレンドは計5回)実施し回収樹脂を得た。
[実施例1~17、比較例1~3]
上記乾燥EVOH樹脂ペレット、上記高密度ポリエチレン樹脂、上記接着性樹脂、及び上記回収樹脂を用い、鈴木製工所製ブロー成形機TB-ST-6Pにて210℃で、(内側)高密度ポリエチレン/接着性樹脂/EVOH/接着性樹脂/回収樹脂/樹脂組成物(外側)の4種6層パリソンを2時間放流し、2時間加熱状態のまま運転を停止させた。その後運転を再開し、各所定時間後に製造したブロー成形容器を評価した。なお、ブロー成形容器の製造においては、金型内温度15℃で20秒間冷却し、全層厚み1000μm((内側)高密度ポリエチレン/接着性樹脂/EVOH/接着性樹脂/回収樹脂/樹脂組成物(外側)=(内側)340/50/40/50/400/120μm(外側))の500mLタンクを成形した。このタンクの底面直径は100mm、高さは400mmであった。なお、実施例1~11、13~17、比較例1~5の乾燥EVOH樹脂ペレットは、上記合成例1によって得た。また、実施例12の乾燥EVOH樹脂ペレットは、上記合成例2によって得た。比較例1の乾燥EVOH樹脂ペレットは、上記合成例1により得ているが、EVOH含有樹脂組成物の調製において不飽和アルデヒド(II)に当たるクロトンアルデヒドは添加しなかった。
このようにして得られた各ブロー成形容器について、以下のように評価した。評価結果を表1に合わせて示す。
再立ち上げ40分後に成形した500mLタンクについて、目視にてストリーク及び着色を下記基準にて評価し、外観性の評価とした。
「良好(A)」:ストリークは認められなかった。
「やや良好(B)」:ストリークが確認された。
「不良(C)」:多数のストリークが確認された。
「良好(A)」:無色
「やや良好(B)」:黄変
「不良(C)」:著しく黄変
再立ち上げ20分後、40分後、及び10時間後にブロー成形した500mLタンクに、エチレングリコールを400mL充填し、開口部をポリエチレン40μm/アルミ箔12μm/ポリエチレンテレフタレート12μm構成のフィルムで熱シールして蓋をした。このタンクを-40℃で3日間冷却し、開口部が上になるように6mの高さから落下させ、破壊した個数で評価した(n=10)。再立ち上げ20分後の耐衝撃性がセルフパージ性の指標となる。
(耐衝撃性の評価基準)
「良好(A)」:3個未満
「やや良好(B)」:3個~6個未満
「不良(C)」:6個以上
2 容器内部表面
3 容器外部表面
4 (A)層
5 (C)層
6 (B)層
7 (D)層
Claims (12)
- (A)エチレン-ビニルアルコール共重合体(I)を主成分とする層
を備えるブロー成形容器であって、
上記(A)層が、不飽和アルデヒド(II)を含有し、
この不飽和アルデヒド(II)の(A)層における含有量が0.01ppm以上100ppm以下であることを特徴とするブロー成形容器。 - 上記不飽和アルデヒド(II)が不飽和脂肪族アルデヒド(II-1)である請求項1に記載のブロー成形容器。
- 上記不飽和アルデヒド(II)が、クロトンアルデヒド、2,4-ヘキサジエナールおよび2,4,6-オクタトリエナールからなる群より選ばれる少なくとも1種である請求項1または2に記載のブロー成形容器。
- 上記(A)層が、共役ポリエン化合物を含有し、
この共役ポリエン化合物の(A)層における含有量が0.01ppm以上1,000ppm以下である請求項1、請求項2又は請求項3に記載のブロー成形容器。 - 上記共役ポリエン化合物が、ソルビン酸及び/又はソルビン酸塩である請求項4に記載のブロー成形容器。
- (B)上記(A)層の内面側及び外面側に配置され、Fedorsの式から算出する溶解性パラメータが11以下である熱可塑性樹脂を主成分とする層、及び
(C)上記(A)層と(B)層との間に配置され、カルボン酸変性ポリオレフィンを主成分とする層
を備える請求項1から請求項5のいずれかに1項に記載のブロー成形容器。 - (D)エチレン-ビニルアルコール共重合体(I)、Fedorsの式から算出する溶解性パラメータが11以下である熱可塑性樹脂、及びカルボン酸変性ポリオレフィンを含有する層を備える請求項6に記載のブロー成形容器。
- 上記(D)層が、ブロー成形容器の製造工程における上記(A)層、(B)層及び(C)層の回収物を用いて形成される請求項7に記載のブロー成形容器。
- 上記(A)層の平均厚みが、全層平均厚みの5.0%以下であり、
かつ上記(D)層におけるエチレン-ビニルアルコール共重合体(I)の含有量が9.0質量%以下である請求項7又は請求項8に記載のブロー成形容器。 - 請求項1から請求項9のいずれか1項に記載のブロー成形容器を備える燃料容器。
- 請求項1から請求項9のいずれか1項に記載のブロー成形容器を備えるブロー成形ボトル容器。
- エチレン-ビニルアルコール共重合体(I)を主成分とする樹脂組成物を用いてブロー成形する工程を有し、
上記樹脂組成物が不飽和アルデヒド(II)を含有し、
この不飽和アルデヒド(II)の上記樹脂組成物における含有量が0.01ppm以上100ppm以下である請求項1から請求項9のいずれか1項に記載のブロー成形容器の製造方法。
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Also Published As
Publication number | Publication date |
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EP2832653B1 (en) | 2017-08-02 |
EP2832653A1 (en) | 2015-02-04 |
JP6039650B2 (ja) | 2016-12-07 |
JPWO2013146962A1 (ja) | 2015-12-14 |
US20150041462A1 (en) | 2015-02-12 |
US9862517B2 (en) | 2018-01-09 |
CN104185596A (zh) | 2014-12-03 |
CN104185596B (zh) | 2016-12-21 |
EP2832653A4 (en) | 2015-10-28 |
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